JP2012022262A - Toner for developing electrostatic charge image, developer for developing electrostatic charge image, toner cartridge, process cartridge, method for forming image and image forming apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner for developing an electrostatic charge image that suppresses increase in a fixing temperature after storage in a heated state, in comparison with the case of using a dodecenyl succinic acid modified polyester or a styrene-acrylic acid modified polyester as an amorphous polyester to be used together with a crystalline polyester.SOLUTION: A toner for developing an electrostatic charge image contains a crystalline polyester and an amorphous polyester having a modified moiety derived from an acrylic acid of 2 mol% or more and 10 mol% or less.

Description

  The present invention relates to an electrostatic charge image developing toner, an electrostatic charge image developing developer, a toner cartridge, a process cartridge, an image forming method, and an image forming apparatus.

  In recent years, in addition to the increase in image quality required for electrophotography and the increase in process speed, there has been a strong demand for energy saving in production processes from the viewpoint of environmental considerations. For this reason, studies have been actively made from the viewpoints of productivity and low-temperature fixability with respect to the reduction in toner particle size, the increase in speed, and energy saving for high image quality.

For example, Patent Document 1 is obtained by polymerizing styrenes or styrenes and (meth) acrylic acid esters for the purpose of obtaining a toner binder having excellent low-temperature fixability when applied to toner. An electrophotographic toner binder comprising a non-crosslinked resin having a high glass transition temperature and a non-crosslinked amorphous polyester having a low glass transition temperature is disclosed.
In addition, Patent Document 2 discloses a resin having a high glass transition temperature and a polar group having a low glass transition temperature obtained by polymerizing styrenes or styrenes and (meth) acrylic acid esters for the same purpose. An electrophotographic toner binder comprising a chain amorphous resin is disclosed.

Japanese Patent Laid-Open No. 06-194476 Japanese Patent Application Laid-Open No. 07-230186

  An object of the present invention is to develop an electrostatic image that suppresses an increase in fixing temperature after heat storage as compared to a case where dodecenyl succinic acid-modified polyester or styrene / acrylic acid-modified polyester is used as an amorphous polyester used in combination with a crystalline polyester. It is to provide a toner for use.

The above problem is solved by the following means. That is,
The invention according to claim 1
Crystalline polyester,
An amorphous polyester having a modified part derived from acrylic acid of 2 mol% or more and 10 mol% or less;
A toner for developing an electrostatic image.

The invention according to claim 2
The electrostatic image developing toner according to claim 1, wherein the amorphous polyester is a linear molecule.

The invention according to claim 3
An electrostatic charge image developing developer comprising the electrostatic charge image developing toner according to claim 1.

The invention according to claim 4
A toner cartridge which is detached from the image forming apparatus and contains the toner for developing an electrostatic charge image according to claim 1.

The invention according to claim 5
4. A toner image obtained by developing the electrostatic latent image formed on the surface of the electrostatic latent image holding member with the developer, wherein the developer is attached to the image forming apparatus and accommodates the electrostatic charge developing developer according to claim 3. A process cartridge including developing means for forming

The invention according to claim 6
An electrostatic latent image carrier;
Charging means for charging the surface of the electrostatic latent image holding member;
Electrostatic latent image forming means for forming an electrostatic latent image on the surface of the electrostatic latent image holding member;
Developing means for developing the electrostatic latent image with the electrostatic charge developing developer according to claim 3 to form a toner image;
Transfer means for transferring the toner image to a recording medium;
Fixing means for fixing a toner image of the recording medium;
An image forming apparatus.

The invention according to claim 7 provides:
A charging step for charging the surface of the electrostatic latent image holding member;
An electrostatic latent image forming step of forming an electrostatic charge image on the surface of the charged electrostatic latent image holding member;
A developing step of developing the electrostatic latent image with the electrostatic charge developing developer according to claim 3 to form a toner image;
A transfer step of transferring the toner image to a recording medium;
A fixing step of fixing the toner image of the recording medium;
Is an image forming method.

  According to the first aspect of the present invention, as compared with the case where dodecenyl succinic acid-modified polyester or styrene / acrylic acid-modified polyester is used as the amorphous polyester used in combination with the crystalline polyester, an increase in the fixing temperature after heat storage is suppressed. .

  According to the invention which concerns on Claim 2, the amorphous polyester suppresses the raise of the fixing temperature after heat storage compared with the case where it is not a linear molecule.

  According to the invention of claim 3, when the toner for developing an electrostatic charge image containing a crystalline polyester and an amorphous polyester having a modified portion derived from acrylic acid of 2 mol% or more and 10 mol% or less is not used. In comparison, the increase in fixing temperature after heat storage is suppressed.

  According to the invention of claim 4, in the case of not using a toner for developing an electrostatic charge image comprising a crystalline polyester and an amorphous polyester having a modified portion derived from acrylic acid of 2 mol% or more and 10 mol% or less. In comparison, the increase in fixing temperature after heat storage is suppressed.

  According to the invention of claim 5, when the electrostatic charge image developing toner containing the crystalline polyester and the amorphous polyester having a modified part derived from acrylic acid of 2 mol% or more and 10 mol% or less is not used. In comparison, the increase in fixing temperature after heat storage is suppressed.

  According to the invention of claim 6, when the electrostatic charge image developing toner containing the crystalline polyester and the amorphous polyester having a modified portion derived from acrylic acid of 2 mol% or more and 10 mol% or less is not used. In comparison, the increase in fixing temperature after heat storage is suppressed.

  According to the invention of claim 7, when the electrostatic charge image developing toner containing the crystalline polyester and the amorphous polyester having a modified part derived from acrylic acid of 2 mol% or more and 10 mol% or less is not used. In comparison, the increase in fixing temperature after heat storage is suppressed.

1 is a schematic configuration diagram illustrating an example of an image forming apparatus according to an exemplary embodiment. It is a schematic block diagram which shows an example of the process cartridge which concerns on this embodiment.

  Hereinafter, embodiments of the present invention will be described in detail.

<Toner for electrostatic image development>
The toner for developing an electrostatic charge image of the present embodiment (hereinafter sometimes simply referred to as “toner”) includes a crystalline polyester, an amorphous polyester having 2 to 10 mol% of a modified portion derived from acrylic acid, and , Including.
The toner according to the exemplary embodiment has the above-described configuration, and thus suppresses an increase in the fixing temperature after heat storage. The reason why the toner according to the exemplary embodiment exhibits such an effect is not clear, but is presumed to be as follows.

In the case where a crystalline polyester and an amorphous polyester are used in combination as a binder resin component in the toner, if the two are not compatible with each other, that is, if the compatible state is not maintained, the binder resin It is thought that phase separation will occur. That is, it is considered that the amorphous polyester that is less likely to melt than the crystalline polyester is unevenly distributed.
It is considered that the uneven distribution of amorphous polyester is likely to occur when the toner is stored under heat, for example, when the toner is exposed to a glass transition temperature ± 10 ° C. of the resin for a long time. This is thought to be because the amorphous polyester partially exists due to the increased mobility of the binder resin by heating, and as a result, the phase separation of the crystalline polyester and the amorphous polyester proceeds. Conceivable.
In this case, the temperature required to melt the entire binder resin is higher than when the crystalline polyester and the amorphous polyester are compatible, and the temperature required to fix the toner to the recording medium is also higher. It tends to rise.
Therefore, in order to suppress an increase in the fixing temperature, it is conceivable to increase the affinity between the crystalline polyester and the amorphous polyester to facilitate compatibility.

In order to increase the affinity between the crystalline polyester and the amorphous polyester, it is conceivable to introduce a portion having high solubility into a part of the amorphous polyester. For example, it is conceivable to introduce a long-chain alkyl (for example, having 12 carbon atoms) having a low solubility parameter (SP value) into an amorphous polyester. Specifically, for example, it is conceivable to bond dodecenyl succinic acid and amorphous polyester.
In terms of introducing a site having a low solubility parameter into the amorphous polyester, the modified portion derived from acrylic acid has a solubility parameter smaller than that of the long-chain alkyl. Therefore, the amorphous polyester according to this embodiment is derived from dodecenyl succinic acid. It is considered that the compatibility with the crystalline polyester is higher than that of the amorphous polyester having the modified portion.

Further, similarly to the modified part derived from acrylic acid according to the present embodiment, the modified part derived from styrene / acrylic acid is considered as the part having a lower solubility parameter than the long-chain alkyl, and the modified part derived from styrene / acrylic acid. It is considered that the amorphous polyester having a higher compatibility with the crystalline polyester than the amorphous polyester having a modified portion derived from dodecenyl succinic acid.
At this time, since the modified portion derived from acrylic acid does not have a styrene group, steric hindrance is suppressed, so that the affinity between the crystalline polyester and the acid-modified amorphous polyester is considered to be higher.

Furthermore, in the modified part derived from acrylic acid, it is considered that the carboxyl group derived from acrylic acid has affinity with the ester group of the crystalline polyester.
In other words, in addition to the suppression of steric hindrance, the resin molecules approach each other by having affinity with the ester group of the crystalline polyester resulting from the carboxyl group derived from acrylic acid, so that the ester group is free. It is thought that molecular mobility can be suppressed. Therefore, it is considered that even after the toner is heated and stored, phase separation due to the mobility of the ester group is suppressed.
When the modified part derived from acrylic acid in the amorphous polyester is less than 2 mol%, the amorphous polyester and the crystalline polyester are not compatible, and more than 10 mol% is acrylic acid. It is considered that the low-temperature fixability and flexibility characteristic of the polyester resin are impaired because the properties of acrylic acid are strongly expressed when the modified part derived from the polyester resin is present.

  From the above, even after the toner is heated and stored, the compatibility between the crystalline polyester and the amorphous polyester is excellent, and in order to suppress the uneven distribution of the amorphous polyester that is harder to melt than the crystalline polyester, It is considered that the melting temperature of the binder resin can be lowered. As a result, it is considered that an increase in the fixing temperature of the toner can be suppressed.

  The above is presumed to be the reason why the increase in the fixing temperature after heat storage is suppressed in the electrostatic image developing toner according to this embodiment.

  Furthermore, it is considered that the phase separation from the crystalline polyester can be suppressed because the amorphous polyester is a linear molecule. Since the main chain of the amorphous polyester is not branched, the mobility of the amorphous polyester itself can be suppressed compared to the branched molecule, and steric hindrance can be suppressed, improving the affinity with the crystalline polyester. It is thought to do.

Hereinafter, materials, process conditions, evaluation / analysis conditions, and the like used in the present embodiment will be described in detail.
[Binder resin]
In the toner according to the exemplary embodiment, a crystalline polyester and an amorphous polyester having a modified portion derived from acrylic acid are used as a binder resin. Amorphous polyester has a modified part derived from acrylic acid in an amount of 2 mol% to 10 mol%.
If necessary, other binder resins may be used in combination. However, when other binder resins are used in combination, the ratio of the total amount of the amorphous polyester having a modified portion derived from acrylic acid and the crystalline polyester in the total binder resin is, for example, 50% by mass or more. Desirably, it is desirable that it is 70 mass% or more.

  The melting temperature and glass transition temperature of the binder resin are preferably in the range of 45 ° C. or higher and 110 ° C. or lower, and more preferably in the range of 60 ° C. or higher and 90 ° C. or lower.

  The mixing ratio of the amorphous polyester having a modified site derived from acrylic acid and the crystalline polyester is selected in consideration of the relationship between the melting temperature of the crystalline polyester and the glass transition temperature of the amorphous polyester. It is important to select a resin component that does not hinder the low-temperature fixability because the thermal melting characteristics of the component having a large content are generally dominant.

The melting temperature is obtained as the melting peak temperature of input compensated differential scanning calorimetry based on JIS K-7121. The crystalline polyester may show a plurality of melting peaks. In this case, the maximum peak is regarded as the melting temperature.
Further, the glass transition temperature is a value measured by a method (DSC method) defined in ASTM D3418-82.

-Crystalline polyester-
The crystalline polyester is synthesized from a polyvalent carboxylic acid and a polyhydric alcohol. In the present embodiment, a commercially available product may be used as the crystalline polyester, or a synthesized product may be used. Below, the polyvalent carboxylic acid and polyhydric alcohol suitable for the synthesis | combination of crystalline polyester are demonstrated.

  Examples of the polyvalent carboxylic acid 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, etc. Aromatic dicarboxylic acids such as dibasic acids, 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 1,2,3-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, and 1,2,4-naphthalenetricarboxylic acid. And their anhydrides and their lower alkyl esters. These may be used individually by 1 type and may use 2 or more types together.

  Further, as the polyvalent carboxylic acid, in addition to the above-mentioned aliphatic dicarboxylic acid and aromatic dicarboxylic acid, a dicarboxylic acid having a sulfonic acid group may be contained, or a dicarboxylic acid having a double bond is contained. May be.

  The polyhydric alcohol may be an aliphatic diol or a linear aliphatic diol having a main chain portion having 7 to 20 carbon atoms. When the aliphatic diol is branched, the crystallinity of the polyester is lowered and the melting temperature is lowered, so that the toner blocking resistance, the image storage stability, and the low-temperature fixability may be deteriorated. When the number of carbon atoms is less than 7, when the polycondensation with an aromatic dicarboxylic acid is performed, the melting temperature becomes high and fixing at a low temperature may be difficult. On the other hand, when it exceeds 20, it is difficult to obtain a practical material. It is easy to become. The carbon number is 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. Among these, considering availability, 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol are exemplified.

  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.

  Among the polyhydric alcohols, the content of the aliphatic diol component is desirably 80 mol% or more, and more desirably 90% or more. When the content of the aliphatic diol component is less than 80 mol%, the crystallinity of the polyester is lowered and the melting temperature is lowered, so that toner blocking resistance, image storage stability, and low-temperature fixability may be deteriorated. is there.

  If necessary, a monovalent acid such as acetic acid or benzoic acid or a monovalent alcohol such as cyclohexanol or benzyl alcohol may be used for the purpose of adjusting the acid value or the hydroxyl value.

  “Crystallinity” of crystalline polyester means that in differential scanning calorimetry, it has a clear endothermic peak, not a stepwise change in endothermic amount. Specifically, it is measured at a heating rate of 10 ° C./min. It means that the half-value width of the endothermic peak is 6 ° C. or less. On the other hand, a resin having a half-value width exceeding 6 ° C. or a resin having no clear endothermic peak means an amorphous resin, but the amorphous resin used in the present embodiment has a clear endothermic peak. An unrecognized resin may be used.

  In addition, the above-mentioned “crystalline polyester” means a polymer (copolymer) obtained by polymerizing a component constituting polyester and other components in addition to a polymer having 100% polyester structure. . However, in the latter case, the component other than the polyester constituting the polymer (copolymer) is 50% by mass or less.

  The acid value of polyester (mg number of KOH required to neutralize 1 g of resin) is easy to obtain the desired molecular weight distribution, and can easily obtain the granulation property of the toner particles by the emulsion dispersion method. From 1 mgKOH / g to 30 mgKOH / g is desirable because the environmental stability of the toner (stability of chargeability when the temperature and humidity change) is easily maintained. The acid value of the polyester is adjusted by controlling the carboxyl group at the end of the polyester according to the blending ratio and reaction rate of the raw polyhydric carboxylic acid and polyhydric alcohol. Alternatively, trimellitic anhydride is used as the polyvalent carboxylic acid to adjust the polyester main chain to contain a carboxyl group.

  Various definition methods can be considered for the number of ester groups present in the crystalline polyester. In this embodiment, regarding the ester group concentration M, K is the number of ester groups, and A is the number of atoms constituting the polymer chain. As M = K / A.

  The ester group concentration of the crystalline resin used in the present embodiment is preferably in the range of 0.02 to 0.05 in the above definition (M = K / A). When the ester group concentration is higher than 0.05, the number of ester groups increases, and thus the mobility of the ester group cannot be suppressed, and the development / transferability may deteriorate. On the other hand, when the ester group concentration is less than 0.02, the low temperature fixability may be hindered although there is no problem in development / transferability.

-Amorphous polyester-
The amorphous polyester used in the present embodiment is an amorphous polyester having a modified portion derived from acrylic acid.
Here, the modified part derived from acrylic acid refers to an unsaturated bond site (CH ₂ ) between amorphous polyester and acrylic acid (CH ₂ ═CH—COOH) by reacting the side chain of amorphous polyester with acrylic acid. = CH-) refers to a site obtained by bonding. Therefore, the modified part derived from acrylic acid has a carboxyl group.
In addition, the site | part of the amorphous polyester couple | bonded with the unsaturated bond site | part of acrylic acid is not restrict | limited, For example, arbitrary carbon atoms which the hydrogen atom has couple | bonded among amorphous polyesters are mentioned. That is, it is considered that the hydrogen atom bonded to the carbon atom of the amorphous polyester is eliminated, and the carbon atom of the amorphous polyester and one of the two carbon atoms in the unsaturated bond site of acrylic acid are bonded.
The part of the amorphous polyester bonded to the unsaturated bond part of acrylic acid may be the main chain or side chain of the amorphous polyester, but is preferably the main chain.

  That the modified part derived from acrylic acid is 2 mol% or more and 10 mol% or less means that the molar amount (mol%) of the modified part in 1 mol of the amorphous polyester modified with acrylic acid is 2 mol% or more and 10 mol%. This means that it is less than or equal to mol%, and “modification rate” is sometimes used, such as “the modification rate of the amorphous polyester is not less than 2 mol% and not more than 10 mol%”.

Acrylic acid is introduced into the amorphous polyester, and the amorphous polyester has a modified portion derived from acrylic acid, so that the ester group of the crystalline polyester and the modified portion derived from acrylic acid that is a part of the amorphous polyester In addition, affinity can be given.
However, if the modification rate of the amorphous polyester is less than 2 mol, the affinity between the whole amorphous polyester and the crystalline polyester cannot be obtained. If the modification rate of the amorphous polyester exceeds 10 mol%, the properties of acrylic acid are strongly expressed, so that the low-temperature fixability and flexibility specific to the polyester resin are impaired, which is not preferable.
The acrylic acid modification rate of the amorphous polyester is desirably 5 mol% or more and 10 mol% or less, and more desirably 7 mol% or more and 10 mol% or less.
The method for measuring the acrylic acid modification rate of the amorphous polyester will be described in detail later.

  In this embodiment, when an amorphous polyester is used as the amorphous molecule, the resin particle dispersion is easily prepared by emulsifying and dispersing the resin by adjusting the acid value or using an ionic surfactant. This is advantageous. Amorphous polyester used for emulsification dispersion is synthesized by dehydration condensation of polyvalent carboxylic acid and polyhydric alcohol.

  Examples of polycarboxylic acids include terephthalic acid, isophthalic acid, phthalic anhydride, trimellitic anhydride, pyromellitic acid, naphthalenedicarboxylic acid, and other aromatic carboxylic acids, maleic anhydride, fumaric acid, succinic acid, alkenyl Examples thereof include aliphatic carboxylic acids such as succinic anhydride and adipic acid, and alicyclic carboxylic acids such as cyclohexanedicarboxylic acid. You may use 1 type, or 2 or more types of these polyhydric carboxylic acid.

  Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, glycerin, and other aliphatic diols, cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol A And aromatic diols such as bisphenol A ethylene oxide adduct and bisphenol A propylene oxide adduct. One or more of these polyhydric alcohols may be used. Among these polyhydric alcohols, aromatic diols and alicyclic diols may be used, and among these, aromatic diols may be used. 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, monocarboxylic acid and / or monoalcohol is further added to the polyester obtained by polycondensation of polyvalent carboxylic acid and polyhydric alcohol to esterify the hydroxyl group and / or carboxyl group at the polymerization terminal, You may adjust the acid value of polyester. Examples of the monocarboxylic acid include acetic acid, acetic anhydride, benzoic acid, trichloroacetic acid, trifluoroacetic acid, and propionic anhydride. Examples of the monoalcohol include methanol, ethanol, propanol, octanol, 2-ethylhexanol, trifluoroethanol, trichloroethanol, hexafluoroisopropanol, and phenol.

  The amorphous polyester used in this embodiment may be produced by subjecting the polyhydric alcohol and the polyvalent carboxylic acid to a condensation reaction according to a conventional method. For example, the above polyhydric alcohol and polyvalent carboxylic acid, if necessary, a catalyst, and blended in a reaction vessel equipped with a thermometer, a stirrer, a flow-down condenser, and in the presence of an inert gas (such as nitrogen gas), Heating at 150 ° C or higher and 250 ° C or lower, continuously removing low-molecular compounds produced as a secondary product from the reaction system, stopping the reaction when it reaches a predetermined acid value, cooling, Is obtained.

  Examples of the catalyst used for the synthesis of the amorphous polyester include esterification catalysts such as organic metals such as dibutyltin dilaurate and dibutyltin oxide, and metal alkoxides such as tetrabutyl titanate. The addition amount of the catalyst is used in the range of 0.01% by mass to 1.00% by mass with respect to the total amount of raw materials.

Furthermore, in order to make an amorphous polyester into a polyester having a modified part derived from acrylic acid, 2 mol% or more and 10 mol% or less of acrylic acid may be addition-polymerized with respect to 1 mol of the amorphous polyester. The addition polymerization of acrylic acid opens the unsaturated bond of acrylic acid and bonds the acrylic acid to the polyester.
The amount (modification rate) of the modified part derived from acrylic acid in the amorphous polyester can be controlled by the amount of acrylic acid used in the addition polymerization reaction.

The amorphous polyester is preferably a linear molecule.
The term “linear molecule” means that the main chain of the amorphous polyester has a chain structure that does not have a branched structure and is not a cyclic structure.
In order to use amorphous polyester as a linear molecule, polyhydric alcohol and polyhydric carboxylic acid not having a branched structure and polyhydric carboxylic acid not having a branched structure are used as the polyhydric alcohol and polycarboxylic acid used for the synthesis of the polyester. That's fine.

Examples of the polyhydric alcohol having no branched structure include a bisphenol A ethylene oxide adduct, a bisphenol A propylene oxide adduct, a bisphenol A butylene oxide adduct, and the like. Among them, bisphenol A ethylene oxide adduct and bisphenol A propylene Oxide adducts are preferred.
Examples of the polyvalent carboxylic acid not having a branched structure include terephthalic acid, fumaric acid, isophthalic acid, trimellitic acid, and the like. Among these, terephthalic acid, fumaric acid, and trimellitic acid are preferable.

  In the present embodiment, together with the amorphous polyester, other amorphous resins other than the amorphous polyester may be used in combination. Examples of other amorphous resins used in the toner according to the exemplary embodiment include conventionally known thermoplastic binder resins, and specific examples include styrene, parachlorostyrene, α-methylstyrene, and the like. Styrene homopolymer or copolymer (styrene resin); methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, Homopolymers or copolymers of vinyl groups such as ethyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, etc .; vinyl nitriles such as acrylonitrile and methacrylonitrile Homopolymers or copolymers (vinyl resins); vinyl methyl ether Homopolymers or copolymers of vinyl ethers such as vinyl isobutyl ether (vinyl resins); Homopolymers or copolymers of vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone, vinyl isopropenyl ketone (vinyl type) Resins); Homopolymers or copolymers of olefins such as ethylene, propylene, butadiene, and isoprene (olefin resins); non-vinyl condensation resins such as epoxy resins, polyurethane resins, polyamide resins, cellulose resins, and polyether resins , And graft polymers of these non-vinyl condensation resins and vinyl monomers.

  These other amorphous resins may be used alone or in combination of two or more. Among these resins, vinyl resins may be used.

[Colorant]
The toner according to the exemplary embodiment may include a colorant.
Examples of the colorant include carbon black, aniline blue, caryl blue, chrome yellow, ultramarine blue, dupont oil red, quinoline yellow, methylene blue chloride, phthalocyanine blue, malachite green oxalate, lamp black, rose bengal, 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 97, C.I. I. Pigment yellow 17, C.I. I. Pigment blue 15: 1, C.I. I. Pigment Blue 15: 3 is a typical example.

〔Release agent〕
The toner according to the exemplary embodiment may include a release agent.
Examples of the release agent include natural waxes such as carnauba wax, rice wax, and candelilla wax, low molecular weight polypropylene, low molecular weight polyethylene, sazol wax, microcrystalline wax, Fischer-Tropsch wax, paraffin wax, and montan wax. Synthetic or mineral / petroleum waxes, fatty acid esters, ester waxes such as montanic acid esters, and the like.

  The melting temperature of the release agent used in this embodiment is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, from the viewpoint of storage stability. Further, from the viewpoint of offset resistance at low temperatures, it is preferably 145 ° C. or lower, more preferably 135 ° C. or lower.

[Other additives]
If necessary, various internal additives such as a charge control agent, inorganic powder (inorganic particles), and organic particles, and external additives may be added to the toner according to the exemplary embodiment.

-Internal additive-
The internal additive can be added mainly by a wet method, and examples thereof include metals such as ferrite, magnetite, reduced iron, cobalt, nickel, and manganese, alloys, or magnetic materials such as compounds containing these metals. .

Examples of the charge control agent include quaternary ammonium salt compounds, nigrosine compounds, dyes containing 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, the inorganic powder is used as an external additive on the toner surface such as silica, alumina, titania, calcium carbonate, magnesium carbonate, calcium phosphate, cerium oxide and the like. All inorganic particles are mentioned.

The charge control agent is preferably made of a material that is difficult to dissolve in water in terms of controlling ionic strength that affects the stability of the aggregated particle forming process and the fusion process and reducing wastewater contamination.

-External additive-
Examples of the external additive added to the toner particle surface by a dry method include inorganic particles and organic particles.

  Examples of inorganic particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, cerium chloride, Examples include Bengala, chromium oxide, cerium oxide, antimony trioxide, magnesium oxide, zirconium oxide, silicon carbide, and silicon nitride. Among these, silica particles and titanium oxide particles are desirable, and particles subjected to hydrophobic treatment are more desirable.

  Inorganic particles are generally used for the purpose of improving fluidity. The primary particle size of the inorganic particles is desirably 1 nm or more and less than 200 nm, and the addition amount is desirably 0.01 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the toner particles.

  Further, the organic particles are generally used for the purpose of improving the cleaning property and the transfer property. Examples of the organic particles include polystyrene, polymethyl methacrylate, polyvinylidene fluoride, and the like.

[Various properties of toner]
The melting temperature of the toner is not particularly limited, but is preferably within a range of 45 ° C. or higher and 110 ° C. or lower, and more preferably within a range of 60 ° C. or higher and 90 ° C. or lower.

  This melting temperature is obtained as the melting peak temperature of input compensated differential scanning calorimetry based on JIS K-7121.

  The volume average particle size of the toner according to the exemplary embodiment is desirably 1 μm or more and 20 μm or less, and more desirably 2 μm or more and 8 μm or less. The number average particle size is preferably 1 μm or more and 20 μm or less, and more preferably 2 μm or more and 8 μm or less.

  Here, the volume average particle diameter and the number average particle diameter are measured using Coulter Multisizer II (manufactured by Coulter), and the electrolyte is measured using ISOTON-II (manufactured by Coulter).

In the measurement, a measurement sample is added in a range of 0.5 mg to 50 mg in 2 ml of a 5% by weight aqueous solution of a surfactant such as sodium alkylbenzenesulfonate as a dispersant. This is added to 100 ml to 150 ml of electrolyte.
The electrolytic solution in which the sample is suspended is subjected to a dispersion process for 1 minute with an ultrasonic disperser, and a particle size distribution of particles in the range of 2 μm to 50 μm is measured using a 100 μm aperture with a Coulter Multisizer type II. . The number of particles to be sampled is 50,000.

  For the particle size range (channel) divided on the basis of the particle size distribution measured in this way, the cumulative distribution is drawn from the small diameter side for the volume and number, respectively, and the cumulative particle size is 16% cumulative. D16v, cumulative number average particle diameter D16p, cumulative volume average particle diameter D50v, cumulative volume average particle diameter D50p, cumulative number average particle diameter D50p, cumulative volume average particle diameter D84v, cumulative number average particle diameter It is defined as D84p.

  Here, the volume average particle diameter is determined as the cumulative volume average particle diameter D50v, and the number average particle diameter is determined as the cumulative number average particle diameter D50p.

[Toner Production Method]
The toner according to the exemplary embodiment is prepared by preparing toner particles by using a known method such as a dry method or a wet method with the above-described toner constituents, and further, if necessary, adding silica particles to the toner particles. Etc. are added to complete the final toner.
Examples of the dry method include a mechanical pulverization method in which a resin lump in which toner constituents are dispersed is pulverized and classified to prepare toner particles. As a wet method, for example, a monomer is polymerized while taking in raw materials. And a polymerization method for producing particles and an emulsion aggregation / unification method.

Specifically, for example, when a toner is prepared by an emulsion aggregation / unification method, a dispersion (resin particle dispersion, etc.) in which each material constituting the toner is dispersed in an aqueous dispersion is prepared (emulsification). Process). Subsequently, a resin particle dispersion and other various dispersions (colorant dispersion, release agent dispersion, etc.) used as necessary are mixed to prepare a raw material dispersion.
Next, toner particles are obtained through an aggregated particle forming step for forming aggregated particles and a fusion step for fusing the aggregated particles in the raw material dispersion. In addition, when producing a so-called core-shell structure type toner having core particles and a shell layer covering the core particles, the resin particle dispersion is added to the raw material dispersion after the aggregated particle formation step. Then, a coating layer forming step is performed in which resin particles are attached to the surface of aggregated particles (which become core particles when converted to toner) to form a coating layer (which becomes a shell layer when converted to toner), and then fused. Perform the process. In addition, although the resin component used for a coating layer formation process may be the same as that of the resin component which comprises a core particle, or different, Usually, an amorphous resin is used.

-Developer for developing electrostatic image-
The developer for developing an electrostatic charge image according to the exemplary embodiment (hereinafter sometimes simply referred to as “developer”) is not particularly limited as long as it includes the toner according to the exemplary embodiment. Any of two-component developers may be used. When used as a two-component developer, a toner and a carrier are mixed and used.
The carrier that can be used in the two-component developer is not particularly limited, and a known carrier is 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.

  The mixing ratio (mass ratio) of toner and carrier in the two-component developer is preferably in the range of toner: carrier = 1: 100 to 30: 100, and more preferably in the range of 3: 100 to 20: 100. .

<Image Forming Apparatus and Image Forming Method>
Next, an image forming apparatus and an image forming method according to this embodiment using the toner of this embodiment will be described.
The image forming apparatus according to the present embodiment forms an electrostatic latent image on the surface of the electrostatic latent image holding member, charging means for charging the surface of the electrostatic latent image holding member, and the electrostatic latent image holding member. An electrostatic latent image forming means, a developing means for developing the electrostatic latent image by the electrostatic charge developing developer of the present embodiment to form a toner image, and a transfer means for transferring the toner image to a recording medium; And a fixing means for fixing the toner image of the recording medium.

  According to the image forming apparatus according to the present embodiment, the charging process for charging the surface of the electrostatic latent image holding member and the electrostatic latent image forming for forming an electrostatic charge image on the charged surface of the electrostatic latent image holding member. A developing step of developing the electrostatic latent image by the electrostatic charge developing developer of the present embodiment to form a toner image, a transferring step of transferring the toner image to a recording medium, and a toner of the recording medium And an image forming method having a fixing step of fixing the image.

  Image formation in the image forming apparatus of this embodiment is performed, for example, as follows when an electrophotographic photosensitive member is used as the electrostatic latent image holding member. First, the surface of the electrophotographic photosensitive member is charged by a corotron charger, a contact charger or the like and then exposed to form an electrostatic charge image. Next, the toner is attached to the electrostatic latent image in contact with or in proximity to a developing roll having a developer layer formed on the surface, thereby forming a toner image on the electrophotographic photosensitive member. The formed toner image is transferred onto the surface of a recording medium such as paper using a corotron charger or the like. Further, the toner image transferred to the surface of the recording medium is fixed by a fixing device, and an image is formed on the recording medium.

  As the electrophotographic photoreceptor, generally, an inorganic photoreceptor such as amorphous silicon or selenium, or an organic photoreceptor using polysilane, phthalocyanine or the like as a charge generation material or a charge transport material is used. In particular, as an electrophotographic photoreceptor, from the viewpoint of wear resistance, an amorphous silicon photoreceptor if an inorganic photoreceptor, and a resin having a cross-linked structure such as a melamine resin, a phenol resin, or a silicone resin on the outermost layer if an organic photoreceptor. A photoreceptor having a so-called overcoat layer having a layer is desirable.

  The fixing device may be any fixing device that performs fixing by heating, pressurization, or light. When the electrophotographic toner of this embodiment is used as a light fixing toner, an optical fixing device (flash fixing device) is used. In other cases, a hot roll fixing device, an oven fixing device, or the like is preferably used.

  As the heat roll fixing device, a heating roll type fixing device is generally used in which a pair of fixing rolls are pressed against each other. As a pair of fixing rolls, a heating roll and a pressure roll are provided facing each other, and a nip is formed by pressure contact. The heating roll has a metal hollow core with a heater lamp inside, and a surface layer made of an oil- and heat-resistant elastic body layer (elastic layer) and a fluororesin, etc. are sequentially formed. Accordingly, an oil- and heat-resistant elastic body layer and a surface layer are sequentially formed on a metal hollow core metal core having a heater lamp inside. An unfixed toner image is fixed by passing a recording medium on which an unfixed toner image is formed through a nip region formed by the heating roll and the pressure roll.

On the other hand, the light source used in the optical fixing device includes a normal halogen lamp, a mercury lamp, a flash lamp, an infrared laser, and the like. It is desirable emission energy of the flash lamp is in the range of 1.0 J / cm ² to 7.0J / cm ^2, and more desirably in the range of 2J / cm ² to 5 J / cm ^2.

  Hereinafter, although an example of the image forming apparatus of this embodiment is shown, it is not necessarily limited to this. In addition, the main part shown to a figure is demonstrated and the description is abbreviate | omitted about others.

  The image forming apparatus shown in FIG. 1 is a quadruple tandem full-color image forming apparatus. The image forming apparatus shown in FIG. 1 is a first to first electrophotographic method that outputs yellow (Y), magenta (M), cyan (C), and black (K) images based on color-separated image data. Fourth image forming units 10Y, 10M, 10C, and 10K (image forming means) are provided. These image forming units (hereinafter simply referred to as “units”) 10Y, 10M, 10C, and 10K are juxtaposed at a predetermined distance in the horizontal direction. The units 10Y, 10M, 10C, and 10K may be process cartridges that are detachable from the main body of the image forming apparatus.

Above each of the units 10Y, 10M, 10C, and 10K, an intermediate transfer belt 20 as an intermediate transfer member is extended through each unit. The intermediate transfer belt 20 is provided by being wound around a driving roller 22 and a support roller 24 that are in contact with the inner surface of the intermediate transfer belt 20 that are spaced apart from each other from the left to the right in the drawing. It is designed to travel in the direction toward 10K. The support roller 24 is biased in a direction away from the drive roller 22 by a spring or the like (not shown), and a predetermined tension is applied to the intermediate transfer belt 20 wound around both. Further, an intermediate transfer member cleaning device 30 is provided on the side of the image carrier of the intermediate transfer belt 20 so as to face the driving roller 22.
Further, each of the developing devices (developing means) 4Y, 4M, 4C, and 4K of the units 10Y, 10M, 10C, and 10K includes yellow, magenta, cyan, and black contained in the toner cartridges 8Y, 8M, 8C, and 8K. The four colors of toner are supplied.

  Since the first to fourth units 10Y, 10M, 10C, and 10K described above have the same configuration, here, the first unit that forms a yellow image disposed on the upstream side in the intermediate transfer belt traveling direction. 10Y will be described as a representative. Note that the second to fourth units are denoted by reference numerals with magenta (M), cyan (C), and black (K) instead of yellow (Y) in the same parts as the first unit 10Y. Description of 10M, 10C, 10K is omitted.

The first unit 10Y has a photoreceptor 1Y that functions as an image holding member. Around the photoreceptor 1Y, an electrostatic charge image is formed by exposing the surface of the photoreceptor 1Y to a predetermined potential with a charging roller 2Y and the charged surface with a laser beam 3Y based on the color-separated image signal. An exposure device 3; a developing device (developing means) 4Y for supplying the charged toner to the electrostatic image and developing the electrostatic image; a primary transfer roller 5Y (primary) for transferring the developed toner image onto the intermediate transfer belt 20; A transfer unit) and a photoconductor cleaning device (cleaning unit) 6Y for removing toner remaining on the surface of the photoconductor 1Y after the primary transfer with a cleaning blade.
The primary transfer roller 5Y is disposed inside the intermediate transfer belt 20, and is provided at a position facing the photoreceptor 1Y. Further, a bias power source (not shown) for applying a primary transfer bias is connected to each of the primary transfer rollers 5Y, 5M, 5C, and 5K. Each bias power source varies the transfer bias applied to each primary transfer roller under the control of a control unit (not shown).

Hereinafter, an operation of forming a yellow image in the first unit 10Y will be described. First, prior to the operation, the surface of the photoreceptor 1Y is charged to a potential of about −600V to −800V by the charging roller 2Y.
The photoreceptor 1Y is formed by laminating a photosensitive layer on a conductive substrate. This photosensitive layer usually has a high resistance (a resistance equivalent to that of a general resin), but has a property that the specific resistance of the portion irradiated with the laser beam changes when irradiated with the laser beam 3Y. Therefore, a laser beam 3Y is output to the surface of the charged photoreceptor 1Y via the exposure device 3 in accordance with yellow image data sent from a control unit (not shown). The laser beam 3Y is applied to the photosensitive layer on the surface of the photoreceptor 1Y, whereby an electrostatic charge image of a yellow print pattern is formed on the surface of the photoreceptor 1Y.

The electrostatic charge image is an image formed on the surface of the photoreceptor 1Y by charging, and the specific resistance of the irradiated portion of the photosensitive layer is lowered by the laser beam 3Y, and the charged charge on the surface of the photoreceptor 1Y flows. On the other hand, this is a so-called negative latent image formed by the charge remaining in the portion not irradiated with the laser beam 3Y.
The electrostatic image formed on the photoreceptor 1Y in this way is rotated to a predetermined development position as the photoreceptor 1Y travels. At this development position, the electrostatic charge image on the photoreceptor 1Y is visualized (developed) by the developing device 4Y.

  For example, yellow toner is accommodated in the developing device 4Y. The yellow toner is triboelectrically charged by being agitated inside the developing device 4Y, and has a charge of the same polarity (negative polarity) as the charged charge on the photoreceptor 1Y, and a developer roll (developer holder). Is held on. As the surface of the photoreceptor 1Y passes through the developing device 4Y, the yellow toner is electrostatically attached to the latent image portion on the surface of the photoreceptor 1Y, and the latent image is developed with the yellow toner. . The photoreceptor 1Y on which the yellow toner image is formed continues to run at a predetermined speed, and the toner image developed on the photoreceptor 1Y is conveyed to a predetermined primary transfer position.

When the yellow toner image on the photoreceptor 1Y is conveyed to the primary transfer, a predetermined primary transfer bias is applied to the primary transfer roller 5Y, and the electrostatic force directed from the photoreceptor 1Y to the primary transfer roller 5Y generates a toner image. The toner image on the photoreceptor 1 </ b> Y is transferred onto the intermediate transfer belt 20. The transfer bias applied at this time is a (+) polarity opposite to the polarity (−) of the toner, and is controlled to about +10 μA by the control unit (not shown) in the first unit 10Y, for example.
On the other hand, the toner remaining on the photoreceptor 1Y is removed and collected by the cleaning device 6Y.

Further, the primary transfer bias applied to the primary transfer rollers 5M, 5C, and 5K after the second unit 10M is also controlled according to the first unit.
Thus, the intermediate transfer belt 20 onto which the yellow toner image has been transferred by the first unit 10Y is sequentially conveyed through the second to fourth units 10M, 10C, and 10K, and the toner images of the respective colors are superimposed and transferred in a multiple manner.

  The intermediate transfer belt 20 onto which the four color toner images have been transferred through the first to fourth units is arranged on the image transfer surface side of the intermediate transfer belt 20 and the support roller 24 in contact with the inner surface of the intermediate transfer belt 20. The secondary transfer roller (secondary transfer means) 26 is connected to a secondary transfer portion. On the other hand, the recording medium P is fed at a predetermined timing into a gap where the secondary transfer roller 26 and the intermediate transfer belt 20 are pressed against each other via a supply mechanism, and a predetermined secondary transfer bias is applied to the support roller 24. The The transfer bias applied at this time is a (−) polarity that is the same polarity as the polarity (−) of the toner, and an electrostatic force from the intermediate transfer belt 20 toward the recording medium P is applied to the toner image, so The toner image is transferred onto the recording medium P. Note that the secondary transfer bias at this time is determined according to the resistance detected by a resistance detecting means (not shown) for detecting the resistance of the secondary transfer portion, and is voltage-controlled.

Thereafter, the recording medium P is sent to a fixing device (fixing means) 28, the toner image is heated, and the color-superposed toner image is melted and fixed on the recording medium P. The recording medium P on which the color image has been fixed is unloaded to the discharge unit, and a series of color image forming operations is completed.
The image forming apparatus exemplified above is configured to transfer the toner image to the recording medium P via the intermediate transfer belt 20, but is not limited to this configuration, and the toner image is directly transferred from the photoconductor. It may be a structure that is transferred to a recording sheet.

[Process cartridge]
The process cartridge according to the present embodiment is detached from the image forming apparatus, accommodates the developer, and develops the electrostatic latent image formed on the surface of the electrostatic latent image holding member (photoconductor) with the developer. Development means for forming a toner image is provided. The developer according to the above embodiment is applied as the developer.

FIG. 2 is a schematic configuration diagram illustrating an example of a process cartridge according to the present embodiment. The process cartridge shown in FIG. 2 includes a photosensitive member 107, a charging roller 108, a developing device 111, and a unit provided with a photosensitive member cleaning device (cleaning means) 113, an opening 118 for exposure, and a discharge exposure. It is combined with and integrated with a housing 119 provided with an opening 117 and a mounting rail 116.
The process cartridge is detachable from the main body of the image forming apparatus including the transfer device 112, the fixing device 115, and other components not shown, and forms an image together with the main body of the image forming apparatus. It constitutes a device. P is a recording medium.

  The process cartridge shown in FIG. 2 includes a photoreceptor 107, a charging device 108, a developing device 111, and a cleaning device (cleaning means) 113. These devices are selectively combined. Specifically, for example, in the process cartridge of the present embodiment, in addition to the developing device 111, at least one selected from the group consisting of the photosensitive member 107, the charging device 108, and the cleaning device (cleaning means) 113 is used. Prepare.

[Toner cartridge]
Next, the toner cartridge of this embodiment will be described. The toner cartridge according to the present exemplary embodiment is a cartridge that is detached from the image forming apparatus and stores electrostatic charge image developing toner. The electrostatic image developing toner according to the embodiment is applied as the electrostatic image developing toner.

  The image forming apparatus shown in FIG. 1 is an image forming apparatus having a configuration in which toner cartridges 8Y, 8M, 8C, and 8K are attached and detached, and the developing devices 4Y, 4M, 4C, and 4K are each developing devices (colors). ) And a toner supply pipe (not shown). Further, when the amount of toner stored in the toner cartridge is low, the toner cartridge is replaced.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. Unless otherwise specified, “part” and “%” are based on mass.

[Confirmation of modification of amorphous polyester]
Acrylic acid modification, dodecenyl succinic acid modification, and styrene / acrylic acid modification of amorphous polyester were confirmed by the following method.

-Acrylic acid modification-
A toner produced by the method described later is heated and stored (after storage for 2 weeks under conditions of a temperature of 50 ° C. and a humidity of 50% RH), and then a mixed solvent 1 of water and alcohol (for example, ethyl alcohol) (alcohol concentration of 70%). ) And added to 60 ° C. to extract components. With such a formulation, the crystalline polyester and dodecenyl succinic acid in the binder resin can be separated from the amorphous polyester modified with acrylic acid. The crystalline polyester and dodecenyl succinic acid are not extracted into the mixed solvent 1.
Next, the component extracted into the mixed solvent 1 was dried to obtain a powder. The endothermic peak of the obtained powder was measured using a differential scanning calorimeter (DSC). The endothermic peak is considered to be due to the presence of a compatible part of the binder resin. In the above component extraction, crystalline polyester and dodecenyl succinic acid are not extracted into the mixed solvent 1, so that it is confirmed that the endothermic peak is caused by a modified portion derived from acrylic acid.

  Next, the powder is subjected to 1H-NMR measurement to confirm that amorphous polyester is detected, and acrylic acid that can contribute to the compatibility of the crystalline polyester and the amorphous polyester is the amorphous polyester. It was confirmed that it was introduced in some areas. If the amorphous polyester is not modified with acrylic acid, the amorphous polyester is not detected by 1H-NMR measurement, and only acrylic acid is detected.

-Dodecenyl succinic acid modification-
The toner prepared by the method described later is heated and stored (after storage for 2 weeks under the conditions of a temperature of 50 ° C. and a humidity of 50% RH), and then the H-NMR measurement of the toner powder is performed, and the dodecenyl part of dodecenyl succinic acid is measured. From the detected signal, it was confirmed that the amorphous polyester was modified with dodecenyl succinic acid.

-Styrene / acrylic acid modification-
The toner prepared by the method described later is heated and stored (after storage for 2 weeks under the conditions of a temperature of 50 ° C. and a humidity of 50% RH), and then the H-NMR measurement of the toner powder is performed, and the dodecenyl part of dodecenyl succinic acid is measured. From the detected signal, it was confirmed that the amorphous polyester was modified with styrene / acrylic acid.

[Measurement of modification rate of acid modification]
Each modification rate in acrylic acid modification, dodecenyl succinic acid modification, and styrene / acrylic acid modification of amorphous polyester was measured by neutralization titration using an aqueous sodium hydroxide solution.

[Crystalline resin particle dispersion]
-Preparation of crystalline resin particle dispersion 1-
In a heat-dried three-necked flask, 250 parts of 1,10-dodecanedioic acid, 150 parts of 1,9-nonanediol, and 0.4 part of dibutyltin oxide as a catalyst were added, and then the air in the three-necked flask was removed by depressurization. The reaction was allowed to proceed under an inert atmosphere by replacing with nitrogen at 180 ° C. for 5 hours by mechanical stirring and refluxing. During the reaction, water produced in the reaction system was distilled off. Thereafter, the temperature was gradually raised to 230 ° C. under reduced pressure, and when the mixture became viscous after stirring for 3 hours, the molecular weight was confirmed by GPC (gel permeation chromatography; converted to polystyrene), and the weight average molecular weight was 25000. At that point, the reaction was stopped to obtain a crystalline polyester resin (crystalline resin 1).

  Next, 350 parts of this crystalline polyester resin, 210 parts of methyl ethyl ketone, and 61.8 parts of isopropyl alcohol were placed in a separable flask and thoroughly mixed and dissolved at 40 ° C. Then, 16.24 parts of a 10% aqueous ammonia solution was dropped. did. The heating temperature is lowered to 65 ° C., and ion-exchanged water is added dropwise with stirring using a liquid feeding pump at a liquid feeding speed of 8 g / min. After the liquid is uniformly clouded, the liquid feeding speed is increased to 12 g / min. When the liquid volume reached 1400 parts, the dropping of ion exchange water was stopped. Thereafter, the solvent was removed under reduced pressure to prepare a crystalline resin particle dispersion 1. The obtained crystalline polyester resin particles had a volume average particle size of 164 nm and a solid content concentration of the resin particles of 30%.

-Preparation of crystalline resin particle dispersion 2-
In the preparation of the crystalline resin particle dispersion 1, 1,10-dodecanedioic acid was replaced with 1,8-octanedioic acid, and 1,9-nonanediol was replaced with 1,6-hexanediol. Crystalline resin particle dispersion 2 in which the volume average particle diameter of the crystalline polyester resin (crystalline resin 2) particles is 162 nm and the solid content concentration of the resin particles is 40% is obtained.

[Amorphous resin particle dispersion]
-Preparation of amorphous resin particle dispersion 1-
615 parts of bisphenol A propylene oxide 2 mol adduct, 540 parts of bisphenol A ethylene oxide 2 mol adduct, 394 parts of terephthalic acid, and 14 parts of acrylic acid were placed in a heat-dried three-necked flask, and then the air in the container was removed by decompression. The pressure was reduced, and the atmosphere was inerted with nitrogen gas. The mixture was reacted at 230 ° C. and normal pressure (101.3 kPa) for 10 hours by mechanical stirring, and further reacted at 8 kPa for 1 hour. After cooling to 180 ° C. and adding 278 parts of fumaric acid and 1.5 parts of hydroquinone, heating up to 210 ° C. over 4 hours, reacting for 1 hour, until the softening point becomes 110 ° C. at 8 kPa By reacting, an amorphous polyester resin (amorphous resin 1) was obtained.

Next, 350 parts of an amorphous polyester resin (amorphous resin 1) after removing insolubles, 245 parts of methyl ethyl ketone, 70 parts of isopropyl alcohol, and 11.2 parts of 10% aqueous ammonia solution are placed in a separable flask. After mixing and dissolving, ion-exchanged water was dropped with a liquid feed pump at a liquid feed speed of 8 g / min while heating and stirring at 40 ° C. After the liquid became cloudy uniformly, the liquid feeding speed was increased to 12 g / min to cause phase inversion, and the dropping was stopped when the liquid feeding amount reached 1050 parts. Thereafter, the solvent was removed under reduced pressure to obtain an amorphous resin particle dispersion 1.
The obtained polyester resin particles had a volume average particle size of 165 nm and the resin particles had a solid content concentration of 40%. Further, the acrylic acid modification rate of the amorphous polyester was 2 mol%.

-Preparation of amorphous resin particle dispersion 2-
Amorphous polyester resin (noncrystalline resin 2) was prepared in the same manner as in the preparation of the amorphous resin particle dispersion 1, except that 332 parts of terephthalic acid, 232 parts of fumaric acid, and 72 parts of acrylic acid were replaced. Got.
Next, 350 parts of an amorphous polyester resin (amorphous resin 2) after removing insolubles, 245 parts of methyl ethyl ketone, 70 parts of isopropyl alcohol, and 11.2 parts of a 10% aqueous ammonia solution are placed in a separable flask. After mixing and dissolving, ion-exchanged water was dropped with a liquid feed pump at a liquid feed speed of 8 g / min while heating and stirring at 40 ° C. After the liquid became cloudy uniformly, the liquid feeding speed was increased to 12 g / min to cause phase inversion, and the dropping was stopped when the liquid feeding amount reached 1050 parts. Thereafter, the solvent was removed under reduced pressure to obtain an amorphous resin particle dispersion 2.
The obtained polyester resin particles had a volume average particle size of 165 nm and the resin particles had a solid content concentration of 40%. Moreover, the acrylic acid modification rate of amorphous polyester was 10 mol%.

-Preparation of amorphous resin particle dispersion 3-
Amorphous polyester resin (Amorphous Resin 3) was prepared in the same manner as in Preparation of Amorphous Resin Particle Dispersion 1 except that 374 parts of terephthalic acid, 261 parts of fumaric acid and 36 parts of acrylic acid were replaced. Got.
Next, 350 parts of an amorphous polyester resin (amorphous resin 3) after removing insolubles, 245 parts of methyl ethyl ketone, 70 parts of isopropyl alcohol, and 11.2 parts of 10% aqueous ammonia solution are placed in a separable flask. After mixing and dissolving, ion-exchanged water was dropped with a liquid feed pump at a liquid feed speed of 8 g / min while heating and stirring at 40 ° C. After the liquid became cloudy uniformly, the liquid feeding speed was increased to 12 g / min to cause phase inversion, and the dropping was stopped when the liquid feeding amount reached 1050 parts. Thereafter, the solvent was removed under reduced pressure to obtain an amorphous resin particle dispersion 3.
The obtained polyester resin particles had a volume average particle size of 165 nm and the resin particles had a solid content concentration of 40%. Moreover, the acrylic acid modification rate of amorphous polyester was 5 mol%.

-Preparation of amorphous resin particle dispersion 4-
Amorphous polyester resin (noncrystalline resin 4) was prepared in the same manner as in the preparation of the amorphous resin particle dispersion 1, except that 349 parts of terephthalic acid, 244 parts of fumaric acid, and 58 parts of acrylic acid were replaced. Got.
Next, 350 parts of an amorphous polyester resin (amorphous resin 4) after removing insolubles, 245 parts of methyl ethyl ketone, 70 parts of isopropyl alcohol, and 11.2 parts of a 10% aqueous ammonia solution are placed in a separable flask. After mixing and dissolving, ion-exchanged water was dropped with a liquid feed pump at a liquid feed speed of 8 g / min while heating and stirring at 40 ° C. After the liquid became cloudy uniformly, the liquid feeding speed was increased to 12 g / min to cause phase inversion, and the dropping was stopped when the liquid feeding amount reached 1050 parts. Thereafter, the solvent was removed under reduced pressure to obtain an amorphous resin particle dispersion 4.
The obtained polyester resin particles had a volume average particle size of 165 nm and the resin particles had a solid content concentration of 40%. Moreover, the acrylic acid modification rate of the amorphous polyester was 8 mol%.

-Preparation of amorphous resin particle dispersion 5-
In a three-necked flask obtained by heating and drying 525 parts of bisphenol A propylene oxide 2 mol adduct, 225 parts of bisphenol A ethylene oxide 2 mol adduct, 375 parts of terephthalic acid, 20 parts of fumaric acid, 300 parts of dodecenyl succinic acid, 6 parts of dibutyltin oxide After being put in, the pressure in the container is reduced by a decompression operation, and further an inert atmosphere is created with nitrogen gas, and the reaction is performed at 230 ° C. and normal pressure (101.3 kPa) for 10 hours by mechanical stirring, and further at 8 kPa The reaction was carried out for 1 hour. After cooling to 210 ° C. and adding 75 parts of trimellitic anhydride and reacting for 1 hour, the reaction was continued at 8 kPa until the softening point was 120 ° C., and an amorphous polyester resin (amorphous resin 5) was added. Obtained.
The softening point of the resin was a flow tester (Shimadzu Corporation, CFT-5000). While heating a 1 g sample at a heating rate of 6 ° C./min, a load of 1.96 MPa was applied by a plunger, the diameter was 1 mm, Extrusion was performed from a nozzle having a length of 1 mm, and a temperature at which half of the sample flowed out.

  Next, 350 parts of an amorphous polyester resin (amorphous resin 5) after removing insolubles, 175 parts of methyl ethyl ketone, 61.8 parts of isopropyl alcohol, and 12.3 parts of a 10% aqueous ammonia solution were separated. After mixing and dissolving, ion-exchanged water was added dropwise at a liquid feed rate of 8 g / min using a liquid feed pump while stirring with heating at 40 ° C. After the liquid became cloudy uniformly, the liquid feeding speed was increased to 12 g / min to cause phase inversion, and the dropping was stopped when the liquid feeding amount reached 1050 parts. Thereafter, the solvent was removed under reduced pressure to obtain an amorphous resin particle dispersion 5. The obtained polyester resin particles had a volume average particle size of 165 nm and the resin particles had a solid content concentration of 40%. The amorphous polyester had a dodecenyl succinic acid modification rate of 2 mol%.

-Preparation of amorphous resin particle dispersion 6-
Amorphous polyester resin (amorphous resin) was prepared in the same manner as in the preparation of the amorphous resin particle dispersion 5, except that 332 parts of terephthalic acid, 232 parts of fumaric acid, and 281 parts of dodecenyl succinic anhydride were replaced. 6) was obtained.
Next, 350 parts of an amorphous polyester resin (amorphous resin 6) after removing insolubles, 245 parts of methyl ethyl ketone, 70 parts of isopropyl alcohol, and 11.2 parts of 10% aqueous ammonia solution are placed in a separable flask. After mixing and dissolving, ion-exchanged water was dropped with a liquid feed pump at a liquid feed speed of 8 g / min while heating and stirring at 40 ° C. After the liquid became cloudy uniformly, the liquid feeding speed was increased to 12 g / min to cause phase inversion, and the dropping was stopped when the liquid feeding amount reached 1050 parts. Thereafter, the solvent was removed under reduced pressure to obtain an amorphous resin particle dispersion 6.
The obtained polyester resin particles had a volume average particle size of 165 nm and the resin particles had a solid content concentration of 40%. The amorphous polyester had a dodecenyl succinic acid modification rate of 10 mol%.

-Preparation of amorphous resin particle dispersion 7-
Amorphous polyester resin (amorphous resin) was prepared in the same manner as in the preparation of the amorphous resin particle dispersion 5, except that 166 parts of terephthalic acid, 116 parts of fumaric acid, and 843 parts of dodecenyl succinic anhydride were replaced. 7) was obtained.
Next, 350 parts of an amorphous polyester resin (amorphous resin 7) after removing insolubles, 245 parts of methyl ethyl ketone, 70 parts of isopropyl alcohol, and 11.2 parts of a 10% aqueous ammonia solution are placed in a separable flask. After mixing and dissolving, ion-exchanged water was dropped with a liquid feed pump at a liquid feed speed of 8 g / min while heating and stirring at 40 ° C. After the liquid became cloudy uniformly, the liquid feeding speed was increased to 12 g / min to cause phase inversion, and the dropping was stopped when the liquid feeding amount reached 1050 parts. Thereafter, the solvent was removed under reduced pressure to obtain an amorphous resin particle dispersion 7.
The obtained polyester resin particles had a volume average particle size of 165 nm and the resin particles had a solid content concentration of 40%. The amorphous polyester had a dodecenyl succinic acid modification rate of 30 mol%.

-Preparation of amorphous resin particle dispersion 8-
After putting 615 parts of bisphenol A propylene oxide 2 mol adduct, 540 parts of bisphenol A ethylene oxide 2 mol adduct, 398 parts of terephthalic acid, 278 parts of fumaric acid, and 35 parts of styrene / acryl copolymer monomer into a heat-dried three-necked flask. The pressure in the container is reduced by depressurization, and an inert atmosphere is created with nitrogen gas. The reaction is performed at 230 ° C. and normal pressure (101.3 kPa) for 10 hours with mechanical stirring, and further for 1 hour at 8 kPa. I let you. After cooling to 210 ° C and adding 75 parts of trimellitic anhydride and reacting for 1 hour, the reaction was continued at 8 kPa until the softening point was 120 ° C, and an amorphous polyester resin (amorphous resin 8) was added. Obtained.
The softening point of the resin was a flow tester (Shimadzu Corporation, CFT-5000). While heating a 1 g sample at a heating rate of 6 ° C./min, a load of 1.96 MPa was applied by a plunger, the diameter was 1 mm, Extrusion was performed from a nozzle having a length of 1 mm, and a temperature at which half of the sample flowed out.

  Next, 350 parts of amorphous polyester resin (amorphous resin 8) after removal of insolubles, 175 parts of methyl ethyl ketone, 61.8 parts of isopropyl alcohol, and 12.3 parts of 10% aqueous ammonia solution were separated. After mixing and dissolving, ion-exchanged water was added dropwise at a liquid feed rate of 8 g / min using a liquid feed pump while stirring with heating at 40 ° C. After the liquid became cloudy uniformly, the liquid feeding speed was increased to 12 g / min to cause phase inversion, and the dropping was stopped when the liquid feeding amount reached 1050 parts. Thereafter, the solvent was removed under reduced pressure to obtain an amorphous resin particle dispersion 8. The obtained polyester resin particles had a volume average particle size of 165 nm and the resin particles had a solid content concentration of 40%. Further, the styrene / acrylic acid modification rate of the amorphous polyester was 2 mol%.

-Preparation of amorphous resin particle dispersion 9-
Amorphous polyester resin (non-crystalline polyester resin) was prepared in the same manner as in the preparation of the amorphous resin particle dispersion 8, except that 332 parts of terephthalic acid, 232 parts of fumaric acid, and 177 parts of styrene / acryl copolymer monomer were used. Resin 9) was obtained.
Next, 350 parts of an amorphous polyester resin (amorphous resin 9) after removing insolubles, 245 parts of methyl ethyl ketone, 70 parts of isopropyl alcohol, and 11.2 parts of a 10% aqueous ammonia solution are placed in a separable flask. After mixing and dissolving, ion-exchanged water was dropped with a liquid feed pump at a liquid feed speed of 8 g / min while heating and stirring at 40 ° C. After the liquid became cloudy uniformly, the liquid feeding speed was increased to 12 g / min to cause phase inversion, and the dropping was stopped when the liquid feeding amount reached 1050 parts. Thereafter, the solvent was removed under reduced pressure to obtain an amorphous resin particle dispersion 9.
The obtained polyester resin particles had a volume average particle size of 165 nm and the resin particles had a solid content concentration of 40%. Further, the styrene / acrylic acid modification rate of the amorphous polyester was 10 mol%.

-Preparation of amorphous resin particle dispersion 10-
Amorphous polyester resin (non-crystalline polyester resin) was prepared in the same manner as in the preparation of the amorphous resin particle dispersion 8, except that 166 parts of terephthalic acid, 116 parts of fumaric acid, and 531 parts of styrene / acrylic copolymerization monomer were used. Resin 10) was obtained.
Next, 350 parts of an amorphous polyester resin (amorphous resin 10) after removal of insolubles, 245 parts of methyl ethyl ketone, 70 parts of isopropyl alcohol, and 11.2 parts of a 10% aqueous ammonia solution are placed in a separable flask. After mixing and dissolving, ion-exchanged water was dropped with a liquid feed pump at a liquid feed speed of 8 g / min while heating and stirring at 40 ° C. After the liquid became cloudy uniformly, the liquid feeding speed was increased to 12 g / min to cause phase inversion, and the dropping was stopped when the liquid feeding amount reached 1050 parts. Thereafter, the solvent was removed under reduced pressure to obtain an amorphous resin particle dispersion 10.
The obtained polyester resin particles had a volume average particle size of 165 nm and the resin particles had a solid content concentration of 40%. Further, the styrene / acrylic acid modification rate of the amorphous polyester was 30 mol%.

-Preparation of amorphous resin particle dispersion 11-
Amorphous polyester resin (amorphous resin 11) was obtained in the same manner except that 407 parts of terephthalic acid, 284 parts of fumaric acid, and 7 parts of acrylic acid were used in preparation of the amorphous resin particle dispersion 1. .
Next, 350 parts of an amorphous polyester resin (amorphous resin 11) after removing insolubles, 245 parts of methyl ethyl ketone, 70 parts of isopropyl alcohol, and 11.2 parts of a 10% aqueous ammonia solution are placed in a separable flask. After mixing and dissolving, ion-exchanged water was dropped with a liquid feed pump at a liquid feed speed of 8 g / min while heating and stirring at 40 ° C. After the liquid became cloudy uniformly, the liquid feeding speed was increased to 12 g / min to cause phase inversion, and the dropping was stopped when the liquid feeding amount reached 1050 parts. Thereafter, the solvent was removed under reduced pressure to obtain an amorphous resin particle dispersion 11.
The obtained polyester resin particles had a volume average particle size of 165 nm and the resin particles had a solid content concentration of 40%. Moreover, the acrylic acid modification rate of the amorphous polyester was 1 mol%.

-Preparation of amorphous resin particle dispersion 12-
Amorphous polyester resin (amorphous resin 12) was obtained in the same manner except that 315 parts of terephthalic acid, 231 parts of fumaric acid, and 86 parts of acrylic acid were used in the preparation of amorphous resin particle dispersion 1. .
Next, 350 parts of an amorphous polyester resin (amorphous resin 12) after removal of insolubles, 245 parts of methyl ethyl ketone, 70 parts of isopropyl alcohol, and 11.2 parts of a 10% aqueous ammonia solution are placed in a separable flask. After mixing and dissolving, ion-exchanged water was dropped with a liquid feed pump at a liquid feed speed of 8 g / min while heating and stirring at 40 ° C. After the liquid became cloudy uniformly, the liquid feeding speed was increased to 12 g / min to cause phase inversion, and the dropping was stopped when the liquid feeding amount reached 1050 parts. Thereafter, the solvent was removed under reduced pressure to obtain an amorphous resin particle dispersion 12.
The obtained polyester resin particles had a volume average particle size of 165 nm and the resin particles had a solid content concentration of 40%. Further, the acrylic acid modification rate of the amorphous polyester was 12 mol%.

-Preparation of release agent dispersion 1-
・ Unicid 350 (manufactured by Toyo Adre): 50 parts ・ Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK): 5 parts ・ Ion-exchanged water: 170 parts The above was heated to 110 ° C. and homogenizer (IKA Co., Ltd .: Ultra Turrax T50) is used to disperse, then a Manton Gorin high-pressure homogenizer (Gorin Co., Ltd.) is dispersed to disperse a mold release agent having an average particle size of 0.180 μm. Agent dispersion 1 (release agent concentration: 31%) was prepared.

-Preparation of colorant dispersion 1-
Carbon black # 25 (Mitsubishi Chemical Co., Ltd.): 100 parts Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK): 15 parts Ion exchange water: 900 parts The dispersion was carried out for about 1 hour using a type disperser Ultimateizer (HJP30006, manufactured by Sugino Machine Co., Ltd.) Furthermore, 1 part of a carbodiimide compound (Nisshinbo Carbodilite V02L2) was added and held at 50 ° C. for 1 hour to obtain a colorant dispersion 1. The concentration of the colorant in the colorant dispersion was adjusted to 25%.

-Production of Toner 1-
-Crystalline resin particle dispersion 1 57 parts-Amorphous resin particle dispersion 1 155 parts-Colorant dispersion 1 62 parts-Anionic surfactant (Dowfax2A1 20% aqueous solution) 15 parts-Release agent dispersion 1 77 parts

  In a polymerization kettle equipped with a pH meter, stirring blades, and thermometer, among the above raw materials, crystalline resin particle dispersion 1, amorphous resin particle dispersion 1, anionic surfactant and 250 parts of ion exchange water are placed. The surfactant was blended with the polyester resin particle dispersion while stirring at 130 rpm for 15 minutes. Colorant dispersion 1 and release agent dispersion 1 were added and mixed with this, and then a 0.3 M nitric acid aqueous solution was added to the raw material mixture to adjust the pH to 4.8. Subsequently, 13 parts of a 10% nitric acid aqueous solution of aluminum sulfate was added dropwise as a flocculant while applying a shearing force at 3000 rpm with an ultra turrax. Since the viscosity of the raw material mixture increased during the dropping of the flocculant, when the viscosity increased, the dropping speed was slowed so that the flocculant was not biased to one place. When the dropping of the flocculant was completed, the rotation speed was further increased to 5000 rpm, and the mixture was stirred for 5 minutes to sufficiently mix the flocculant and the raw material mixture.

  Subsequently, the raw material mixture was stirred at 500 rpm while being heated to 25 ° C. with a mantle heater. After stirring for 10 minutes, it was confirmed that a primary particle size was formed using a Coulter Multisizer II (aperture diameter: 50 μm; manufactured by Coulter, Inc.), and then 43 ° C. at 0.1 ° C./min for growing aggregated particles. The temperature was raised to. The growth of aggregated particles is confirmed at any time using a Coulter Multisizer. Depending on the aggregation rate, the aggregation temperature and the number of rotations of stirring were changed.

  On the other hand, for coating the aggregated particles, 85 parts of the amorphous resin particle dispersion 1 and 85 parts of the amorphous resin particle dispersion 2 are used, and 118 parts of ion-exchanged water and anionic surfactant (Dowfax 2A1 20% aqueous solution) are used. ) 8.2 parts was added and mixed, and the pH was adjusted to 3.8 in advance to obtain a resin particle dispersion for coating. When the aggregated particles grew to 5.2 μm in the aggregation step, a coating resin particle dispersion prepared in advance was added and held for 20 minutes with stirring. Thereafter, in order to stop the growth of the coated aggregated particles, 1.5 pph of EDTA was added, and then a 1M sodium hydroxide aqueous solution was added to control the pH of the raw material mixture to 7.6. Subsequently, in order to fuse the aggregated particles, the temperature was raised to 85 ° C. at a temperature raising rate of 1 ° C./min while adjusting the pH to 7.6. After reaching 85 ° C., the pH is adjusted to 7.6 or less in order to proceed with the fusion, and after confirming that the aggregated particles have fused with an optical microscope, ice water is used to stop the growth of the particle size. Was injected and quenched at a temperature lowering rate of 10 ° C./min.

  Subsequently, the obtained particles were sieved once with a 15 μm mesh for the purpose of washing. Thereafter, approximately 10 times the amount of ion-exchanged water (30 ° C.) was added to the solid content, stirred for 20 minutes, and then once filtered. Further, the solid content remaining on the filter paper was dispersed in a slurry, repeatedly washed with ion exchange water at 30 ° C. four times, and dried to obtain toner particles 1 having a volume average particle diameter of 5.8 μm.

To toner particles 1 (100 parts) prepared above, 1.2 parts of titania powder (manufactured by Soken Chemical Co., Ltd.) was added and externally added with a stirring mixer to obtain toner 1.
The volume average particle diameter of the toner 1 is 5.8 μm.

-Production of Toner 2-
In the production of the toner 1, the same operation was performed except that the amorphous resin particle dispersion 2 was used instead of the amorphous resin particle dispersion 1 to obtain a toner 2 having a volume average particle diameter of 6.0 μm.

-Production of Toner 3-
In the production of the toner 1, the same operation was performed except that the crystalline resin particle dispersion 2 was used in place of the crystalline resin particle dispersion 1, whereby a toner 3 having a volume average particle diameter of 6.0 μm was obtained.

-Production of Toner 4-
In the production of the toner 2, the same operation was performed except that the crystalline resin particle dispersion 2 was used in place of the crystalline resin particle dispersion 1, whereby a toner 4 having a volume average particle diameter of 6.0 μm was obtained.

-Production of Toner 5-
In the production of the toner 1, the same operation was performed except that the amorphous resin particle dispersion 3 was used in place of the amorphous resin particle dispersion 1, whereby a toner 5 having a volume average particle diameter of 6.0 μm was obtained.

-Production of Toner 6-
In the production of the toner 1, the same operation was performed except that the amorphous resin particle dispersion 4 was used in place of the amorphous resin particle dispersion 1, whereby a toner 6 having a volume average particle diameter of 6.0 μm was obtained.

-Production of Toner 101-
In the production of the toner 1, the same operation was performed except that the amorphous resin particle dispersion 5 was used in place of the amorphous resin particle dispersion 1, whereby a toner 101 having a volume average particle diameter of 6.0 μm was obtained.

-Production of Toner 102-
In the production of the toner 1, the same operation was performed except that the amorphous resin particle dispersion 6 was used in place of the amorphous resin particle dispersion 1, and a toner 102 having a volume average particle diameter of 6.0 μm was obtained.

-Production of Toner 103-
In the production of the toner 1, the same operation was performed except that the amorphous resin particle dispersion liquid 7 was used instead of the amorphous resin particle dispersion liquid 1 to obtain a toner 103 having a volume average particle diameter of 6.0 μm.

-Production of Toner 104-
In the production of the toner 1, the same operation was performed except that the amorphous resin particle dispersion 8 was used in place of the amorphous resin particle dispersion 1, and a toner 104 having a volume average particle diameter of 6.0 μm was obtained.

-Production of Toner 105-
In the production of the toner 1, the same operation was performed except that the amorphous resin particle dispersion 9 was used in place of the amorphous resin particle dispersion 1, and a toner 105 having a volume average particle diameter of 6.0 μm was obtained.

-Production of toner 106-
In the production of the toner 1, the same operation was performed except that the amorphous resin particle dispersion 10 was used instead of the amorphous resin particle dispersion 1 to obtain a toner 106 having a volume average particle diameter of 6.0 μm.

-Production of Toner 107-
In the production of the toner 1, the same operation was performed except that the amorphous resin particle dispersion liquid 11 was used instead of the amorphous resin particle dispersion liquid 1 to obtain a toner 107 having a volume average particle diameter of 6.0 μm.

-Production of Toner 108-
In the production of the toner 1, the same operation was performed except that the amorphous resin particle dispersion 12 was used in place of the amorphous resin particle dispersion 1, and a toner 108 having a volume average particle diameter of 6.0 μm was obtained.

<Example 1>
Toner having a volume average particle diameter of 35 μm coated with 1% of polymethyl methacrylate resin (Mw: 80000, manufactured by Soken Chemical Co., Ltd.) is weighed so that the toner concentration is 5%, and 5% by a ball mill. Developer 1 was prepared by stirring and mixing for a minute.

[Evaluation]
The obtained developer or photofixing toner was used to evaluate the fixability. Note that the developer and the photofixing toner used for the evaluation of the fixing property and the charging property were those stored after heating (after storage for two weeks under conditions of a temperature of 50 ° C. and a humidity of 50% RH).

-Fixability evaluation (minimum fixing temperature)-
As an image forming apparatus, a color copying machine DocuCenter II-C3300 manufactured by Fuji Xerox Co., Ltd. modified so that the fixing temperature can be changed every 5 ° C. from 100 ° C. to 200 ° C. was used.
Using this modified machine, an image was formed under the conditions of a toner applied amount of 15.0 g / m ² and a process speed of 250 mm / s, and a fixed image was evaluated from the viewpoint of the minimum fixing temperature.
A good fixed image with no image defect due to mold release failure is folded using a constant load weight (0.5 kg), and the degree of image defect in the bent part is observed, and some peeling of the image is observed. The fixing temperature at which the level at which it is determined that there is no problem above is the minimum fixing temperature, and is used as an index for low-temperature fixing property.
Specifically, the allowable range of the minimum fixing temperature is 142 ° C. or lower, and preferably 140 ° C. or lower.
The results obtained are shown in the table.

<Example 2>
Evaluation was performed in the same manner as in Example 1 except that toner 2 was used instead of toner 1. The results obtained are shown in the table.

<Example 3>
Evaluation was performed in the same manner as in Example 1 except that toner 3 was used instead of toner 1. The results obtained are shown in the table.

<Example 4>
Evaluation was performed in the same manner as in Example 1 except that toner 4 was used instead of toner 1. The results obtained are shown in the table.

<Example 5>
Evaluation was performed in the same manner as in Example 1 except that toner 5 was used instead of toner 1. The results obtained are shown in the table.

<Example 6>
Evaluation was performed in the same manner as in Example 1 except that toner 6 was used instead of toner 1. The results obtained are shown in the table.

<Comparative Example 1>
In Example 1, evaluation was performed in the same manner except that the toner 101 was used instead of the toner 1. The results obtained are shown in the table.

<Comparative example 2>
In Example 1, the evaluation was performed in the same manner except that the toner 102 was used instead of the toner 1. The results obtained are shown in the table.

<Comparative Example 3>
In Example 1, evaluation was performed in the same manner except that the toner 103 was used instead of the toner 1. The results obtained are shown in the table.

<Comparative example 4>
In Example 1, evaluation was performed in the same manner except that the toner 104 was used instead of the toner 1. The results obtained are shown in the table.

<Comparative Example 5>
In Example 1, evaluation was performed in the same manner except that the toner 105 was used instead of the toner 1. The results obtained are shown in the table.

<Comparative Example 6>
Evaluation was performed in the same manner as in Example 1 except that the toner 106 was used instead of the toner 1. The results obtained are shown in the table.

<Comparative Example 7>
In Example 1, evaluation was performed in the same manner except that the toner 107 was used instead of the toner 1. The results obtained are shown in the table.

<Comparative Example 8>
Evaluation was performed in the same manner as in Example 1 except that the toner 108 was used instead of the toner 1. The results obtained are shown in the table.

  In the table, “CC10 · 9” of “Seeds” in the “Crystalline Polyester” column uses “1,10-dodecanedioic acid” and “1,9-nonanediol” as the raw materials for the crystalline polyester. Represents that “CC8.6” indicates that the crystalline polyester uses “1,8-octanedioic acid” and “1,6-hexanediol” as raw materials.

  From Table 1, when the toner containing the acrylic acid-modified amorphous polyester of the example was used, the minimum fixing temperature was lower than that of the comparative example, and the increase of the fixing temperature after heat storage was suppressed. On the other hand, the toner containing the acid-modified amorphous polyester of Comparative Example could not suppress an increase in fixing temperature. That is, even if the modification rate is in the range of 2 mol to 10 mol%, if the acrylic acid is not modified, the increase in the fixing temperature after heat storage is not suppressed, and the modified portion is derived from acrylic acid. It can be seen that if the modification rate is not in the range of 2 mol or more and 10 mol%, an increase in the fixing temperature after heat storage is not suppressed.

1Y, 1M, 1C, 1K Photoconductor 2Y, 2M, 2C, 2K Charging roller 3Y, 3M, 3C, 3K Laser beam 3 Exposure device 4Y, 4M, 4C, 4K Developing device 5Y, 5M, 5C, 5K Primary transfer Rollers 6Y, 6M, 6C, 6K Cleaning devices 8Y, 8M, 8C, 7K Toner cartridges 10Y, 10M, 10C, 10K Image forming unit 20 Intermediate transfer belt 22 Drive roller 24 Support roller 26 Secondary transfer roller 28 Fixing device 30 Intermediate transfer Body cleaning device 107 Photoconductor 108 Charging roller 108 Charging device 111 Developing device 112 Transfer device 115 Fixing device 116 Mounting rail 117 Opening 118 Opening 119 Housing

Claims (7)

Crystalline polyester,
An amorphous polyester having a modified part derived from acrylic acid of 2 mol% or more and 10 mol% or less;
A toner for developing an electrostatic charge image.   The electrostatic image developing toner according to claim 1, wherein the amorphous polyester is a linear molecule.   An electrostatic charge image developing developer comprising the electrostatic charge image developing toner according to claim 1.   A toner cartridge which is detached from an image forming apparatus and contains the electrostatic charge image developing toner according to claim 1.   4. A toner image obtained by developing the electrostatic latent image formed on the surface of the electrostatic latent image holding member with the developer, wherein the developer is attached to the image forming apparatus and accommodates the electrostatic charge developing developer according to claim 3. A process cartridge comprising developing means for forming An electrostatic latent image carrier;
Charging means for charging the surface of the electrostatic latent image holding member;
Electrostatic latent image forming means for forming an electrostatic latent image on the surface of the electrostatic latent image holding member;
Developing means for developing the electrostatic latent image with the electrostatic charge developing developer according to claim 3 to form a toner image;
Transfer means for transferring the toner image to a recording medium;
Fixing means for fixing a toner image of the recording medium;
An image forming apparatus comprising: A charging step for charging the surface of the electrostatic latent image holding member;
An electrostatic latent image forming step of forming an electrostatic charge image on the surface of the charged electrostatic latent image holding member;
A developing step of developing the electrostatic latent image with the electrostatic charge developing developer according to claim 3 to form a toner image;
A transfer step of transferring the toner image to a recording medium;
A fixing step of fixing the toner image of the recording medium;
An image forming method comprising: