JP5162881B2 - Resin particle dispersion and method for producing the same, electrostatic image developing toner, electrostatic image developer, developing device, cartridge, and image forming apparatus - Google Patents

Description

  The present invention relates to a resin dispersion and a method for producing the same. The present invention also relates to an electrostatic image developing toner using the resin particle dispersion, an electrostatic developer, a developing device using them, a cartridge, and an image forming apparatus.

Preparation of an emulsion dispersion of a polycondensation resin such as polyester usually requires a solvent. If an electrostatic charge image developing toner (toner) is prepared using this, the solvent tends to remain in the toner. Image defects such as filming on the photoconductor are likely to occur.
Various studies have been made on the preparation of emulsion dispersions of polycondensation resins such as polyester resins.
For example, studies have been made on solvent-free emulsification at high temperatures. In Patent Document 1, a toner raw material containing at least a polyester resin is heated and melted to produce a melt of the toner raw material, and the melt is then emulsified in an aqueous medium to form resin fine particles. Then, a method for producing an electrostatic charge image developing toner is disclosed, in which the resin fine particles are aggregated and further fused to produce an aggregate of the resin fine particles.

Further, a means for obtaining a composite resin particle dispersion by dissolving a polycondensation resin in an addition polymerizable monomer and so-called miniemulsion polymerization has been studied.
Conventionally, a method in which a polyester resin having an acidic group is emulsified and dispersed in water in the presence of a basic neutralizing agent, and the dispersed resin fine particles are aggregated and fused to form a toner is known.

  Patent Document 2 has a dispersion stabilizer after dissolving a hydrophobic polycondensable compound in a solution obtained by dissolving and dispersing an electrophotographic toner component in a volatile solvent having a boiling point of 100 ° C. or less. A step of mixing and stirring with water to emulsify, and removing the volatile solvent from the emulsion, and then adding a hydrophilic compound that reacts with the polycondensable compound and substantially interfacial polycondensation. A method for producing a spherical toner is disclosed.

  Patent Document 3 discloses a synthesis in which an aqueous slurry containing colorant-containing synthetic resin particles is produced by heating or heat-pressing a resin kneaded material containing at least a synthetic resin and a colorant that can be granulated in a molten state in water. In the toner manufacturing method including the resin particle generation step and the cooling step of cooling the aqueous slurry containing the colorant-containing synthetic resin particles, the resin kneaded product does not contain an organic solvent, and the water soluble in the synthetic resin particle generation step. Forming a colorant-containing synthetic resin particle in the presence of the polymer dispersant, and an aqueous dispersion containing a poorly water-soluble alkaline earth metal salt in an aqueous slurry containing the colorant-containing synthetic resin particle in the cooling step There is disclosed a method for producing a toner, which is characterized by being added.

JP 2002-351140 A Japanese Patent Laid-Open No. 63-030863 JP 2005-345734 A

  In the toner for developing an electrostatic charge image using a polycondensation resin, the present invention suppresses the fusion (hereinafter referred to as filming) of the toner to the photoreceptor at high temperature and high humidity, and maintains the image quality during long-term continuous use. The purpose is to improve. Another object of the present invention is to provide a resin particle dispersion that can be suitably used for the toner and a method for producing the same. It is another object of the present invention to provide an electrostatic charge image developer containing the toner for developing an electrostatic charge image, a developing device using the toner or the developer, a cartridge, and an image forming apparatus.

The above-described problems of the present invention have been solved by the means described in <1> and <5> to <11> below. It is described below together with <2> to <4> which are preferred embodiments.
<1> The ratio of the hydrophilic monomer unit having at least one polar group selected from the group consisting of an acidic polar group, a basic polar group, and a neutral polar group is 10 mol% or more and 90 mol% or less, And a resin particle dispersion characterized by containing a polymer having a weight average molecular weight of 10,000 or more and containing a polycondensation resin in a resin solid content of 50% by weight or more,
<2> The resin particle dispersion according to <1>, wherein the content of the polymer is 5% by weight or more based on the total amount of the polycondensation resin,
<3> The resin particle dispersion according to <1> or <2>, wherein the polycondensation resin is a polycondensation resin obtained by polycondensation at 150 ° C. or lower using sulfur acid as a catalyst.
<4> The resin particle dispersion according to any one of <1> to <3>, wherein an average particle diameter of the resin particles is 50 nm to 300 nm.
<5> A method for producing a toner for developing an electrostatic charge image, comprising: a step of aggregating the resin particles in a dispersion containing at least a resin particle dispersion to obtain aggregated particles; and a step of heating and coalescing the aggregated particles Wherein the resin particle dispersion is the resin particle dispersion according to any one of <1> to <4>,
<6> Toner for developing an electrostatic charge image produced by the production method according to <5>,
<7> The ratio of the hydrophilic monomer unit having at least one polar group selected from the group consisting of an acidic polar group, a basic polar group, and a neutral polar group is 10 mol% or more and 90 mol% or less, In addition, the method for producing a resin particle dispersion according to any one of <1> to <4>, wherein a polymer having a weight average molecular weight of 10,000 or more, an aqueous medium, and a polycondensation resin are mixed.
<8> An electrostatic image developer containing the electrostatic image developing toner according to <5>,
<9> An image carrier, a developer supply unit that supplies a developer containing the electrostatic charge image developing toner according to <6> on the image carrier, and a developer supplied by the developer supply unit A developing device comprising a charging means for charging
<10> Developing means for forming a toner image by developing the electrostatic latent image formed on the surface of the image carrier with the developer containing the toner according to <6>, an image carrier, and the image carrier A cartridge comprising: at least one selected from the group consisting of a charging means for charging the surface of the toner and a cleaning means for removing the developer remaining on the surface of the image carrier;
<11> The image carrier, a charging unit that charges the surface of the image carrier, a latent image forming unit that forms a latent image on the surface of the image carrier, and the toner according to <6>. An image forming apparatus comprising: a developing unit configured to develop a toner image by developing with a developer including: a transfer unit configured to transfer the toner image onto a recording medium; and a fixing unit configured to fix the toner image onto the recording medium. Forming equipment.

  According to the present invention, in an electrostatic charge image developing toner using a polycondensation resin, the toner can be prevented from being fused (hereinafter referred to as filming) under high temperature and high humidity, and the image quality during long-term continuous use can be reduced. Maintainability can be improved. In addition, according to the present invention, it is possible to provide a resin particle dispersion that can be suitably used for the toner and a method for producing the same. Furthermore, it is possible to provide an electrostatic charge image developer containing the toner for developing an electrostatic charge image, and a developing device, a cartridge, and an image forming apparatus using the toner or the developer.

(1) Resin particle dispersion The resin particle dispersion of the present invention is a hydrophilic monomer having at least one polar group selected from the group consisting of an acidic polar group, a basic polar group, and a neutral polar group. The unit ratio is 10 mol% or more and 90 mol% or less, the polymer contains a polymer having a weight average molecular weight of 10,000 or more, and the polycondensation resin is contained in the resin solid content by 50 wt% or more. And
In the present invention, the ratio of the hydrophilic monomer unit having at least one polar group selected from the group consisting of the above-mentioned “acidic polar group, basic polar group and neutral polar group” is 10 mol% or more and 90 mol% or less. And a polymer having a weight average molecular weight of 10,000 or more is also referred to as “polymer dispersant” or “polymer dispersant of the present invention”.

  In the resin particle dispersion of the present invention, the polycondensation resin is dispersed in an aqueous medium. In the present invention, the aqueous medium means water or a mixed solvent containing 50% by weight or more of water and in which a water-miscible organic solvent may be mixed. The mixing ratio of water in the mixed solvent is preferably 60% by weight or more and 100% by weight or less, and more preferably 70% by weight or more and 100% by weight or less. Examples of the water-miscible organic solvent include ethyl alcohol, methyl alcohol, acetone, and acetic acid, and ethyl alcohol is preferable. The aqueous medium is most preferably water, and soft water or ion exchange water is preferable. These may be used individually by 1 type and may use 2 or more types together.

The resin particle dispersion of the present invention is obtained by dispersing a polycondensation resin using a polymer dispersant, and is preferably substantially solvent-free and dispersed in an aqueous medium. The term “substantially solvent-free” means that the solvent is not dispersed using a volatile substance such as an aromatic group such as toluene, an ester group such as acetate, or a ketone group such as acetone.
By using a resin particle dispersion that does not use a solvent in the step of emulsifying and dispersing the resin, when an electrostatic charge image developing toner is produced using the resin particle dispersion, it can be used under the influence of the solvent remaining in the toner under high temperature and high humidity. This is preferable because the softening behavior of the toner can be suppressed and, in turn, the occurrence of image quality defects due to photoconductor filming can be prevented. At the same time, when a polymer dispersant having a molecular weight above a certain level is used, hydrophobic behavior occurs after the toner is dried, so that softening behavior due to water adsorption is suppressed even under high humidity, and image quality defects due to photoconductor filming. This is preferable because it can prevent the occurrence of.

(Polymer dispersant)
In the present invention, the polymer dispersant is obtained by polymerizing a monomer, and 10 mol% or more and 90 mol% or less of the monomer is selected from the group consisting of an acidic polar group, a basic polar group and a neutral polar group. And a hydrophilic monomer having at least one polar group. That is, at least one polar group selected from the group consisting of an acidic polar group, a basic polar group, and a neutral polar group in which 10 mol% or more and 90 mol% or less of the monomer unit of the polymer dispersant of the present invention is present. It is a hydrophilic monomer unit having
When the hydrophilic monomer unit is less than 10 mol%, sufficient dispersion of the polycondensation resin cannot be obtained. On the other hand, if it exceeds 90 mol%, the final toner has high hygroscopicity, leading to deterioration of filming under high temperature and high humidity.
The hydrophilic monomer unit is preferably 20 mol% or more and 80 mol% or less, and more preferably 30 mol% or more and 70 mol% or less.

  More than a certain number of constituent parts derived from hydrophilic monomers having polar groups selected from the group consisting of acidic polar groups, basic polar groups and neutral polar groups and constituent parts derived from other monomers When the polycondensation resin is emulsified and dispersed in an aqueous medium while heating the polycondensation resin together with the polymer dispersant having a molecular weight, such a polymer dispersant has an effect of increasing the viscosity of the aqueous medium. As a result, the uniform mixing of the aqueous medium and the molten polycondensation resin is promoted. As a result, a resin particle dispersion can be produced by a dispersion treatment at a low temperature for a short time.

In order to obtain the effect of increasing the viscosity of an aqueous medium, the polymer dispersant needs to have a molecular weight of a certain level or more. In the present invention, the polymer dispersant needs to have a weight average molecular weight of 10,000 or more. is there. If the weight molecular weight is less than 10,000, the emulsifying power is reduced and the resin dispersed particle size is increased, or when toner is produced using the resin particle dispersion, filming occurs after conversion to toner. The inhibitory effect on is reduced. The weight average molecular weight is preferably 11,000 or more, and more preferably 12,000 or more.
Although the upper limit of the molecular weight is not as clear as the lower limit, in consideration of dispersibility in an aqueous medium, the weight average molecular weight is preferably 300,000 or less, more preferably 200,000 or less.

In the resin particle dispersion of the present invention, the amount of the polymer dispersant added is preferably 5% by weight or more, more preferably 7% by weight or more based on the total amount of the polycondensation resin. Moreover, it is preferable that it is 20 weight% or less, and it is more preferable that it is 15 weight% or less.
It is preferable that the content of the polymer dispersant is 5% by weight or more based on the total amount of the polycondensation resin because good dispersibility can be obtained. Moreover, it is preferable that it is 20% by weight or less because good dispersibility can be obtained and there is no generation of a bulk solid that is not emulsified.

In the present invention, the polymer dispersant can be obtained by a known method. For example, a monomer such as methyl methacrylate is copolymerized with a hydrophilic monomer such as acrylic acid (an ionic polar group-containing monomer). The polymer can be synthesized by obtaining a polymer having a weight average molecular weight of 10,000 or more.
As an example of the hydrophilic monomer used in the polymer dispersant, first, as a hydrophilic monomer having an acidic polar group, (i) an α, β-ethylenic monomer having a carboxyl group (—COOH) is used. Mention may be made of saturated compounds and (ii) α, β-ethylenically unsaturated compounds having a sulfone group (—SO ₃ H).
(I) Examples of α, β-ethylenically unsaturated compounds having a carboxyl group (—COOH) include acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, cinnamic acid, maleic acid monobutyl ester , Maleic acid monooctyl esters, and metal salts such as Na salts thereof.
(Ii) Examples of α, β-ethylenically unsaturated compounds having a sulfonic acid group (—SO ₃ H) include sulfonated styrene, its Na salt, allylsulfosuccinic acid, allylsulfosuccinic acid octyl, its Na salt and the like. Can be mentioned.

Examples of the hydrophilic monomer having a basic polar group include (i) an aliphatic alcohol having 1 to 12 carbon atoms, preferably 2 to 8 carbon atoms, particularly preferably 2 having an amine group or a quaternary ammonium group. (Meth) acrylic acid ester, (ii) (meth) acrylic acid amide or (meth) acrylic acid amide optionally mono- or di-alkyl-substituted with an alkyl group having 1 to 18 carbon atoms, Examples thereof include iii) vinyl compounds substituted with a heterocyclic group having N as a ring member, and (iv) N, N-diallylalkylamine or a quaternary ammonium salt thereof. Among them, (i) (meth) acrylic acid esters of aliphatic alcohols having an amine group or a quaternary ammonium group are preferred as hydrophilic monomers having a basic polar group.
(I) Examples of (meth) acrylic acid esters of aliphatic alcohols having amine groups or quaternary ammonium groups include dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, and four of the above four compounds. Examples thereof include a quaternary ammonium salt, 3-dimethylaminophenyl acrylate, 2-hydroxy-3-methacryloxypropyltrimethylammonium salt, and the like.
(Ii) (Meth) acrylic acid amide or optionally mono- or di-alkyl substituted (meth) acrylic acid amide on N includes acrylamide, N-butylacrylamide, N, N-dibutylacrylamide, piperidylacrylamide, methacrylic Examples thereof include amide, N-butylmethacrylamide, N, N-dimethylacrylamide, N-octadecylacrylamide and the like.
Examples of the vinyl compound substituted with a heterocyclic group having N as a ring member in (iii) include vinylpyridine, vinylpyrrolidone, vinyl N-methylpyridinium chloride, vinyl N-ethylpyridinium chloride and the like.
Examples of (iv) N, N-diallylalkylamine include N, N-diallylmethylammonium chloride and N, N-diallylethylammonium chloride.

In the present invention, the neutral polar group means a non-acidic and non-basic polar group.
Examples of hydrophilic monomers having neutral polar groups include at least one hydroxy group, non-acidic polar group and / or non-basic polar group, most preferably one or more hydroxy and / or ether groups Mention may be made of monomers containing (eg PEG functionality and / or alkylene glycol alkyl ethers).
As a polymer dispersant having a neutral polar group, polyvinyl alcohol is expected to have the same effect. In this case, the degree of saponification is preferably in the range of 10% to 90%, and the molecular weight is the same as above. It is important that it is 10,000 or more.

In the present invention, the polymer dispersant is not limited to the above-described addition polymerizable resin, and may be a polycondensable resin. Specifically, a resin obtained by a dehydration reaction or a transesterification reaction between a polycarboxylic acid and a polyol can be exemplified.
As a synthesis method, it is preferable to select a known method as appropriate. However, as a polycondensation catalyst, a metal catalyst, a hydrolase type catalyst, a basic catalyst, etc., which will be described later, are used. Is preferred.

The following can be illustrated as a hydrophilic monomer.
Among the hydrophilic monomers having an acidic polar group, examples of the polycarboxylic acid include dicarboxylic acids having a sulfone group.
Examples of the dicarboxylic acid having a sulfone group include, but are not limited to, 2-sulfoterephthalic acid sodium salt, 5-sulfoisophthalic acid sodium salt, and sulfosuccinic acid sodium salt. Moreover, these lower alkyl esters, acid anhydrides, etc. are also mentioned. Among these, 5-sulfoisophthalic acid sodium salt is preferable from the viewpoint of cost.
Among the hydrophilic monomers having an acidic polar group, examples of the polyol include a diol having a sulfone group.

Among the hydrophilic monomers having a basic polar group, examples of the polycarboxylic acid include amine, amide, and dicarboxylic acid having an ammonium group.
Among the hydrophilic monomers having a basic polar group, examples of the polyol include amines, amides, and diols having an ammonium group.

(Polycondensation resin)
The resin particle dispersion of the present invention contains 50% by weight or more of a polycondensation resin in the resin solid content.
In the present invention, the polycondensation resin is obtained by polycondensation of at least one selected from the group consisting of polycondensable monomers, oligomers and prepolymers, and among these, polycondensable monomers are used. It is preferable to do.
Examples of the polycondensable monomer used for polycondensation include polycarboxylic acids, polyols, and polyamines. As the polycondensation resin, for example, polyester, polyamide and the like can be preferably exemplified. In particular, the polycondensation resin is a polyester obtained by using a polycondensable monomer containing a polycarboxylic acid and a polyol. preferable. Among these, in the present invention, it is preferable to use a polycondensable monomer as the polycondensation component, particularly to use a dicarboxylic acid as the polyvalent carboxylic acid, and to use a diol as the polyol.

  In the present invention, the polycarboxylic acid includes aliphatic, alicyclic and aromatic polycarboxylic acids and alkyl esters thereof, and the polyol includes polyhydric alcohols, ester compounds thereof, hydroxycarboxylic acids and the like. The polyester resin and the polyamide resin can be produced by polycondensation by direct esterification reaction, transesterification reaction or the like using a polycondensable monomer. In this case, the polyester resin to be polymerized may take any form such as amorphous (amorphous / amorphous) polyester, crystalline polyester, or a mixed form thereof.

  In particular, in the present invention, the polycondensation resin preferably contains at least an amorphous polyester having a glass transition point (Tg) of 30 ° C. or more and 100 ° C. or less, and the amorphous polyester having a Tg of 50 ° C. or more and 80 ° C. or less. It is more preferable to contain at least. The amorphous polyester having a Tg of 30 ° C. or more and 100 ° C. or less is preferably contained in an amount of 5.0% by weight or more, and more preferably 10.0% by weight or more and 90.0% by weight or less of the entire resin particles.

  The polycarboxylic acid used as a monomer used for polycondensation is a compound containing two or more carboxyl groups in one molecule. Among these, a divalent carboxylic acid is a compound containing two carboxyl groups in one molecule. For example, oxalic acid, succinic acid, maleic acid, adipic acid, glutaric acid, β-methyladipic acid, azelaic acid, Sebacic acid, suberic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, fumaric acid, citraconic acid, diglycolic acid, glutaconic acid, n-dodecylsuccinic acid, n-dodecenylsuccinic acid, isododecylsuccinic acid , Isododecenyl succinic acid, n-octyl succinic acid, cyclohexane dicarboxylic acid, cyclohexane-3,5-diene-1,2-dicarboxylic acid, malic acid, citric acid, hexahydroterephthalic acid, malonic acid, pimelic acid , Tartaric acid, mucous acid, phthalic acid, isophthalic acid, terephthalic acid, Lachlorophthalic acid, chlorophthalic acid, nitrophthalic acid, p-carboxyphenylacetic acid, p-phenylenediacetic acid, m-phenylenediglycolic acid, p-phenylenediglycolic acid, o-phenylenediglycolic acid, diphenylacetic acid, diphenyl-p, p Examples include '-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, anthracene dicarboxylic acid, and the like. Examples of the polyvalent carboxylic acid other than the divalent carboxylic acid include trimellitic acid, pyromellitic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, pyrenetricarboxylic acid, and pyrenetetracarboxylic acid. Furthermore, these lower ester etc. are mentioned. Furthermore, the acid chloride is not limited to this. These may be used alone or in combination of two or more. Furthermore, in addition to the aliphatic dicarboxylic acid and aromatic dicarboxylic acid described above, a dicarboxylic acid component having a double bond can also be contained.

  The polyol as a monomer in the production method of the present invention is a compound containing two or more hydroxyl groups in one molecule. Among these, a divalent polyol is a compound containing two hydroxyl groups in one molecule. For example, ethylene glycol, propylene glycol, butanediol, butenediol, neopentylglycol, pentanediol, hexanediol, cyclohexanediol, cyclohexane Dimethanol, diethylene glycol, triethylene glycol, dipropylene glycol, octanediol, nonanediol, decanediol, dodecanediol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A, bisphenol Z, hydrogenated bisphenol A, etc. Can do. Examples of polyols other than divalent polyols include glycerin, pentaerythritol, hexamethylol melamine, hexaethylol melamine, tetramethylol benzoguanamine, and tetraethylol benzoguanamine. These may be used alone or in combination of two or more.

Also, a polyamine and a polyol can be used as the polycondensable monomer, and a similar resin particle dispersion can be produced using polyamide.
Polyamines used to obtain polyamides include ethylenediamine, diethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,4-butenediamine, 2,2-dimethyl. -1,3-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,4-cyclohexanediamine, 1,4-cyclohexanebis (methylamine) and the like can be mentioned.

In addition, an amorphous resin or a crystalline resin can be easily obtained by a combination of these polycondensable monomers.
As the polyvalent carboxylic acid used to obtain the crystalline polyester, among the above carboxylic acids, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, Aliphatic dicarboxylic acids such as 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid, sebacic acid, malee Acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, n-dodecyl succinic acid, n-dodecenyl succinic acid, isododecyl succinic acid, isododecenyl succinic acid, n-octyl succinic acid, n-octenyl succinic acid, these An acid anhydride, a lower ester, or an acid chloride can be mentioned. Moreover, the polyvalent carboxylic acid more than bivalence mentioned later can also be used together.

  Examples of the diol used to obtain the crystalline polyester include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, and 1,4-butenediol. Neopentyl glycol, 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-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,14-eicosandecanediol, diethylene glycol, triethylene glycol, dipropylene Glycol Polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, can also be mentioned polytetramethylene glycol. A dihydric or higher polyhydric alcohol can also be used in combination. Examples thereof include glycol, pentaerythritol, hexamethylol melamine, hexaethylol melamine, tetramethylol benzoguanamine, and tetraethylol benzoguanamine.

  Examples of such a crystalline polycondensation resin include polyesters obtained by reacting 1,9-nonanediol and 1,10-decanedicarboxylic acid, or cyclohexanediol and adipic acid, and 1,9-nonanediol and sebacin. Polyester obtained by reacting acid, polyester obtained by reacting 1,6-hexanediol and sebacic acid, polyester obtained by reacting ethylene glycol and succinic acid, reacting ethylene glycol and sebacic acid And polyester obtained by reacting 1,4-butanediol with succinic acid. Among these, polyesters obtained by reacting 1,9-nonanediol and 1,10-decanedicarboxylic acid, 1,9-nonanediol and sebacic acid, and 1,6-hexanediol and sebacic acid are particularly preferred. This is preferable but not limited to this.

In addition, as the polyvalent carboxylic acid used to obtain the non-crystalline polyester in the present invention, among the above polyvalent carboxylic acids, as the dicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, Chlorphthalic acid, nitrophthalic acid, malonic acid, mesaconic acid, p-carboxyphenylacetic acid, p-phenylene diacetic acid, m-phenylene diglycolic acid, p-phenylene diglycolic acid, o-phenylene diglycolic acid, diphenylacetic acid, diphenyl- p, p'-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, anthracene dicarboxylic acid, cyclohexanedicarboxylic acid, cyclohexene dicarboxylic acid, norbornene-2 , 3-Dicarboxylic acid, Adama And ntandicarboxylic acid and adamantanediacetic acid. Examples of the polyvalent carboxylic acid other than dicarboxylic acid include trimellitic acid, pyromellitic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, pyrenetricarboxylic acid, and pyrenetetracarboxylic acid. Moreover, you may use what derived the carboxyl group of these carboxylic acid into the acid anhydride, the acid chloride, or ester.
Among these, it is preferable to use terephthalic acid, its lower ester, phenylenediacetic acid, cyclohexanedicarboxylic acid and the like. The lower ester refers to an ester of an aliphatic alcohol having 1 to 8 carbon atoms.

The polyol used for obtaining the non-crystalline polyester in the present invention is, among the above-mentioned polyols, in particular, polytetramethylene glycol, bisphenol A, bisphenol Z, bisphenol S, biphenol, naphthalenediol, adamantanediol, adamantane di It is preferable to use methanol, hydrogenated bisphenol A, cyclohexanedimethanol or the like. The bisphenol is also preferably an alkylene oxide adduct, and examples of the alkylene oxide group include, but are not limited to, an ethylene oxide group, a propylene oxide group, and a butylene oxide. Preferred are ethylene oxide and propylene oxide.
Among these, the polyol used to obtain the amorphous polyester is preferably an alkylene oxide adduct of bisphenol A, and more preferably an ethylene oxide adduct and a propylene oxide adduct of bisphenol A. The alkylene oxide is preferably added in an amount of 2 mol or more and 4 mol or less, more preferably 2 mol or 4 mol in terms of both ends. This range is preferable because the viscoelasticity and glass transition temperature of the polyester to be produced can be appropriately controlled for use as a toner.
In order to produce one type of polycondensation resin, each of the polyvalent carboxylic acid and polyol may be used alone or in combination of two or more, each of which may be used alone or in combination of two or more. You may use each. Moreover, when using hydroxycarboxylic acid in order to produce 1 type of polycondensation resin, 1 type may be used individually, 2 or more types may be used, and polyvalent carboxylic acid and a polyol may be used together.

  Amorphous polycondensation resin includes a bisphenol A propylene oxide 2 mol adduct (2 mol adduct in terms of both ends), a 4 mol adduct (4 mol adduct in terms of both ends) and dimethyl terephthalate. Condensate, polycondensate of ethylene oxide 2 mol adduct of bisphenol A (2 mol adduct in terms of both ends), 4 mol adduct (4 mol adduct in terms of both ends) and cyclohexanedicarboxylic acid, ethylene of bisphenol A Particularly preferred is a polycondensate of 2 mol addition of oxide or propylene oxide (2 mol adduct in terms of both ends) or 4 mol adduct (4 mol adduct in terms of both ends) and phenylene diacetic acid or phenylene dipropionic acid. .

  In the present invention, when crystalline polyester is used as the polycondensation resin, the crystalline melting point Tm is preferably 50 ° C. or higher and 120 ° C. or lower, and more preferably 55 ° C. or higher and 90 ° C. or lower. It is preferable that Tm is 50 ° C. or higher because the peelability is improved and the offset can be reduced. Further, it is preferable that Tm is 120 ° C. or lower because fixing can be performed at a lower temperature.

  Here, for the measurement of the melting point of the crystalline polyester resin, a differential scanning calorimeter (DSC) was used, and JIS K-7121: 87 when the measurement was performed at a temperature rising rate of 10 ° C. per minute from room temperature to 150 ° C. The melting peak temperature of the input compensation differential scanning calorimetry shown in FIG. The crystalline polyester resin may show a plurality of melting peaks, but in the present invention, the maximum peak is regarded as the melting point.

On the other hand, when an amorphous polyester resin is used as the polycondensation resin, the glass transition point (Tg) of the amorphous polyester is preferably 30 ° C or higher, more preferably 30 ° C or higher and 100 ° C or lower, More preferably, the temperature is 50 ° C. or higher and 80 ° C. or lower. When the glass transition point (Tg) of the polycondensation resin is 30 ° C. or higher, the toner particles are not agglomerated due to heat and pressure received during ejection, and may adhere to and accumulate on the site because of the glassy state in use. This is preferable because it provides an effect that stable ejection can be obtained over a long period of time.
Here, the glass transition point of the non-crystalline resin refers to a value measured by a method (DSC method) defined in ASTM D3418-82.
Moreover, the measurement of the glass transition point in this invention can be measured by "DSC-20" (made by Seiko Electronics Co., Ltd.), for example according to the differential scanning calorimetry (DSC), for example, specifically, about 10 mg of samples. Is heated at a constant rate of temperature increase (10 ° C./min), and a glass transition point can be obtained from the intersection of the baseline and the endothermic peak tilt line.

In the present invention, when a crystalline polyester resin is used as the polycondensation resin, the weight average molecular weight is 1,000 to 60, as measured by the gel permeation chromatography (GPC) method of the tetrahydrofuran (THF) soluble content. 000 or less, more preferably 1,500 or more and 50,000 or less, and further preferably 2,000 or more and 40,000 or less.
Moreover, when using an amorphous polyester resin as the polycondensation resin, the weight average molecular weight is preferably 1,000 or more and 60,000 or less by the molecular weight measurement by the GPC method of THF-soluble matter, and 3,000 It is more preferably 50,000 or more and 50,000 or less, and further preferably 5,000 or more and 40,000 or less.
It is preferable that the weight average molecular weight is within the above range since both image strength and fixability can be achieved.
In the present invention, the molecular weight of the resin is measured with a THF solvent using a THF soluble material, such as TSK-GEL, GMH (manufactured by Tosoh Corporation), etc. Can be used to calculate the molecular weight.

  Here, in the present invention, “crystallinity” in “crystalline polyester resin” means that it has a clear endothermic peak, not a step-like endothermic change in differential scanning calorimetry (DSC). Means that the half-value width of the endothermic peak when measured at a heating rate of 10 ° C./min is within 15 ° C. On the other hand, a resin having a half-value width of an endothermic peak exceeding 15 ° C. or a resin in which no clear endothermic peak is observed means non-crystalline (amorphous).

In the present invention, the polycondensation step may include a polymerization reaction between the polycarboxylic acid and polyol, which are the aforementioned polycondensation monomers, and an oligomer and / or prepolymer prepared in advance. The prepolymer is not limited as long as it is a polymer that can be melted or uniformly mixed with the monomer.
Furthermore, in the present invention, the resin particles are a homopolymer of the above-mentioned polycondensation component, a copolymer in which two or more monomers containing the above-mentioned polycondensation component are combined, or a mixture, graft polymer, one It may have a partial branching or a crosslinked structure.

In the present invention, the polycondensation resin is obtained by polycondensation of a polycondensation component, preferably a polycondensable monomer, and is particularly preferably a polycondensation resin obtained by polycondensation under a catalyst. In the present invention, it is preferable that sulfur acid (Bronsted acid containing a sulfur atom) is included as a polycondensation catalyst. The polycondensation catalyst will be described below.
<Catalyst>
In this invention, it is preferable to use a sulfuric acid (Bronsted acid containing a sulfur atom) as a polycondensation catalyst.
(Sulfur acid)
Sulfur acid is a Bronsted acid containing a sulfur atom, and examples of the sulfur acid include inorganic sulfur acids and organic sulfur acids. Examples of the inorganic sulfur acid include sulfuric acid, sulfurous acid, and salts thereof, and examples of the organic sulfur acid include sulfonic acids such as alkyl sulfonic acid, aryl sulfonic acid, and salts thereof, alkyl sulfuric acid, Organic sulfuric acids such as aryl sulfuric acid and salts thereof are mentioned.
The sulfur acid is preferably an organic sulfur acid, and more preferably an organic sulfur acid having a surface active effect. The acid having a surface-active effect has a chemical structure composed of a hydrophobic group and a hydrophilic group, has an acid structure in which at least a part of the hydrophilic group is composed of protons, and has both an emulsifying function and a catalytic function. A compound.
Examples of the organic sulfur acid having a surface active effect include alkylbenzene sulfonic acid, alkyl sulfonic acid, alkyl disulfonic acid, alkyl phenol sulfonic acid, alkyl naphthalene sulfonic acid, alkyl tetralin sulfonic acid, alkyl allyl sulfonic acid, petroleum sulfonic acid, alkyl benzoic acid. Imidazole sulfonic acid, higher alcohol ether sulfonic acid, alkyl diphenyl sulfonic acid, long chain alkyl sulfate, higher alcohol sulfate, higher alcohol ether sulfate, higher fatty acid amide alkylol sulfate, higher fatty acid amide alkylated sulfate, sulfate Fat, sulfosuccinic acid ester, resin acid alcohol sulfuric acid, and all salt compounds thereof may be mentioned, and a plurality of them may be combined as necessary. Among these, a sulfonic acid having an alkyl group or an aralkyl group, a sulfate ester having an alkyl group or an aralkyl group, or a salt compound thereof is preferable, and the alkyl group or the aralkyl group has 7 to 20 carbon atoms. It is more preferable that Specifically, dodecylbenzenesulfonic acid, pentadecylbenzenesulfonic acid, isopropylbenzenesulfonic acid, camphor sulfonic acid, p-toluenesulfonic acid, monobutylphenylphenol sulfate, dibutylphenylphenol sulfate, dodecyl sulfate, naphthenyl alcohol Examples include sulfuric acid. These sulfur acids may have some functional group in the structure.

The amount of sulfur acid (sulfur acid containing a sulfur atom) that can be used in the present invention is preferably 0.05% by weight or more and 20% by weight or less based on the total weight of the polycondensation component. It is more preferable that the content is 10% by weight or more.
It is preferable that the amount of sulfur acid used be within the above range since sufficient catalytic activity can be exhibited. In particular, by adding it to the aqueous medium together with the polycondensation component, the stability of the particles is maintained, the polycondensation reaction is further increased, and the polycondensation reaction is performed at a low temperature (preferably 150 ° C. or less, more preferably 130 ° C. or less. And more preferably 100 ° C. or lower).

Other polycondensation catalysts generally used can be used together with the above-mentioned sulfur acid catalyst or alone. Specifically, an acid having a surface active effect, a metal catalyst, a hydrolase type catalyst, and a basic catalyst can be exemplified.
(Acid having surface-active effect)
Examples of the acid having a surface active effect include various fatty acids, higher alkyl phosphate esters, resin acids, and all salt compounds thereof, and a plurality of them may be combined as necessary.

(Metal catalyst)
Examples of the metal catalyst include, but are not limited to, the following. Examples thereof include organic tin compounds, organic titanium compounds, organic antimony compounds, organic beryllium compounds, organic strontium compounds, organic germanium compounds, organic tin halide compounds, and rare earth-containing catalysts.
Specific examples of the rare earth-containing catalyst include scandium (Sc), yttrium (Y), and lanthanoid elements such as lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), and europium. (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), etc. are effective. is there. Of these, alkylbenzene sulfonates, alkyl sulfate esters, and those having a triflate structure are particularly effective. Examples of the triflate include X (OSO ₂ CF ₃ ) _{3 in} the structural formula. Here, X is a rare earth element, and among these, X is preferably scandium (Sc), yttrium (Y), ytterbium (Yb), samarium (Sm), or the like.
The lanthanoid triflate is described in detail in Journal of Synthetic Organic Chemistry, Vol. 53, No. 5, p44-54.

When using a metal catalyst as a catalyst, it is preferable to make the metal content derived from the catalyst in the resin obtained into 10 ppm or less. More preferably, it is 7.5 ppm or less, and further preferably 5.0 ppm or less. Therefore, it is preferable not to use a metal catalyst or to use a very small amount even when a metal catalyst is used.
It is preferable that the metal content in the resin is 10 ppm or less because the stability of the resin particles in the resin particle dispersion is improved.

(Hydrolytic enzyme type catalyst)
The hydrolase type catalyst is not particularly limited as long as it catalyzes an ester synthesis reaction. Examples of the hydrolase in the present invention include EC (enzyme number) 3.1 group such as carboxyesterase, lipase, phospholipase, acetylesterase, pectinesterase, cholesterol esterase, tannase, monoacylglycerol lipase, lactonase, lipoprotein lipase and the like. (See Maruo and Tamiya's "Enzyme Handbook" Asakura Shoten, (1982), etc.) Hydrolase enzymes classified into EC 3.2 group that act on glycosyl compounds such as esterases, glucosidases, galactosidases, glucuronidases, xylosidases ECs that act on peptide bonds such as hydrolase, aminopeptidase, chymotrypsin, trypsin, plasmin, subtilisin, etc. classified into EC 3.3 group such as epoxide hydrase Hydrolase classified .4 group, mention may be made of hydrolytic enzymes such as classified into EC3.7 group such as furo retinoic hydrolase.
Among the above esterases, enzymes that hydrolyze glycerol esters to liberate fatty acids are called lipases, but lipases are highly stable in organic solvents, catalyze ester synthesis reactions in high yields, and are available at a lower price. There are advantages such as what you can do. Therefore, in the present invention, it is preferable to use lipase from the viewpoint of yield and cost.
Lipases of various origins can be used, but preferred are Pseudomonas genus, Alcaligenes genus, Achromobacter genus, Candida genus, Aspergillus genus, Rhizopus Examples include lipases obtained from microorganisms such as (Rhizopus) genus and Mucor genus, lipases obtained from plant seeds, lipases obtained from animal tissues, pancreatin, and steapsin. Among these, it is preferable to use lipases derived from microorganisms of the genus Pseudomonas, Candida, and Aspergillus.

(Basic catalyst)
Examples of the basic catalyst include, but are not limited to, general organic basic compounds, nitrogen-containing basic compounds, and tetraalkyl or arylphosphonium hydroxides such as tetrabutylphosphonium hydroxide. As organic base compounds, ammonium hydroxides such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and nitrogen-containing basic compounds as amines such as triethylamine and dibenzylmethylamine, pyridine, methylpyridine, methoxypyridine, Quinolin, imidazole, alkali metals such as sodium, potassium, lithium, cesium, and alkaline earth metals such as calcium, magnesium, barium, hydroxides, hydrides, amides, alkalis, alkaline earth metals and acids And salts with carbonates, phosphates, borates, carboxylates and phenolic hydroxyl groups.
Moreover, a compound with an alcoholic hydroxyl group, a chelate compound with acetylacetone, and the like can be exemplified, but the invention is not limited thereto.

The total amount of the catalyst added is preferably 0.05% by weight or more and 20% by weight or less, and more preferably 0.1% by weight or more and 10% by weight or less with respect to the polycondensation component. One or a plurality of them can be added in the above ratio.
It is preferable that the total addition amount of the catalyst is within the above range because the polycondensation reactivity can be sufficiently obtained, while reverse reactions and side reactions can be suppressed.

<Polycondensation reaction>
Next, the polycondensation reaction will be described.
In the present invention, it is preferable to obtain a polycondensation resin by polycondensation reaction at a temperature lower than the conventional reaction temperature, and the reaction temperature is preferably 70 ° C. or higher and 150 ° C. or lower. More preferably, it is 75 degreeC or more and 130 degrees C or less, Most preferably, they are 80 degreeC or more and 100 degrees C or less.
When the reaction temperature is 70 ° C. or higher, the reactivity of the polycondensation component, preferably the polycondensable monomer, is not reduced due to the decrease in the catalytic activity and the increase in the molecular weight is suppressed. This is preferable because there is not. Moreover, since it can manufacture with low energy as reaction temperature is 150 degrees C or less, it is preferable. Further, it is preferable because coloring of the obtained resin and decomposition of the produced polycondensation resin do not occur.

Manufacturing the polycondensation resin at a low temperature of 150 ° C. or less while avoiding the conventional high energy consumption manufacturing method reduces the manufacturing energy of the resin in the total sense and the manufacturing energy of the electrostatic charge image developing toner. Is extremely important. Conventionally, the polycondensation reaction has been performed at a high temperature exceeding 200 ° C., but in order to perform polymerization at a low temperature of 150 ° C. or lower, which is several tens of degrees Celsius to several tens of degrees Celsius, a sulfur acid catalyst is used. Is preferred. This is because conventional metal catalysts such as Sn-based and Ti-based metals exhibit high catalytic activity especially at 200 ° C. or higher, and very low activity at low temperatures of 150 ° C. or lower.
Sulfuric acid has a catalytic activity that decreases as the temperature rises at a high temperature of 160 ° C. or higher. However, since the reaction proceeds due to the nucleophilic addition of the catalytic acid, the polymerization temperature is about 70 ° C. or higher. The catalyst activity is high in a low temperature range of 150 ° C. or lower and can be suitably used for a polycondensation reaction at 150 ° C. or lower. Therefore, in the present invention, it can be suitably used as a polycondensation catalyst.

  This polycondensation reaction can be carried out by a general polycondensation method such as bulk polymerization, emulsion polymerization, suspension polymerization, or other underwater polymerization, solution polymerization, interfacial polymerization, etc., but bulk polymerization and underwater polymerization are preferably used. . Among these, it is preferable to obtain a polycondensation resin by directly polycondensing a polycondensable monomer by bulk polymerization.

(Bulk polymerization)
In the case of bulk polymerization, the reaction is possible under atmospheric pressure, but general conditions such as reduced pressure and nitrogen flow can be used for the purpose of increasing the molecular weight of the resulting polycondensation resin.
A polycondensable monomer is preferably used as the polycondensation component, polycarboxylic acid and polyol are preferably used as the polycondensable monomer, and dicarboxylic acid and diol are particularly preferably used. Moreover, it is preferable to use a sulfur acid (Bronsted acid containing a sulfur atom) as a catalyst, and it is preferable that polycondensation is performed at 150 degrees C or less as mentioned above.
That is, it is preferable to directly polymerize a polycondensable monomer at a low temperature of 150 ° C. or lower using sulfur acid (Bronsted acid containing a sulfur atom) as a catalyst.

In addition, an addition polymerizable monomer described later, particularly a vinyl monomer such as styrene or acrylate, is added to the obtained polycondensation resin, and this is emulsified and dispersed to initiate a polymerization initiator, particularly radical polymerization. It is also preferable to polymerize the addition polymerizable monomer using an agent. In this case, the polymerization initiator can be added to the mixture containing the polycondensation resin and the addition polymerizable monomer before emulsification and dispersion, but is preferably added to the aqueous medium.
Further, an addition polymerizable monomer may be added to the polycondensation component, polycondensed under a catalyst, emulsified and dispersed in an aqueous medium, and addition polymerization may be performed using a polymerization initiator.
When the resin particles contain an addition polymerization type polymer, a hybrid resin (particles thereof) with a polycondensation resin can be obtained. These addition polymerizable monomers can also be polymerized by adding a new monomer after the polymerization of the polycondensation component.

In the present invention, as described above, the polycondensation reaction can be performed in the presence of an addition polymerizable monomer, and the addition polymerizable monomer can be mixed after the polycondensation reaction. . Finally, addition polymerization of an addition polymerizable monomer can be performed to give composite particles of a polycondensation resin and an addition polymerization type polymer.
The addition polymerizable monomer that can be used in the present invention includes a radical polymerizable monomer, a cationic polymerizable monomer, or an anion polymerizable monomer, and is a radical polymerizable monomer. It is preferable.

  The addition amount of the addition polymerizable monomer is preferably 1.0 part by weight or more and 50.0 parts by weight or less, and 3.0 parts by weight or more and 30 parts by weight or less with respect to 100 parts by weight of the polycondensation resin or polycondensation component. More preferably, it is 0.0 parts by weight or less. It is preferable that the addition amount of the addition polymerizable monomer is within the above range because an ink excellent in fixing property and particle forming property can be obtained.

  Specific examples of the radical polymerizable monomer include α-substituted styrene such as styrene, α-methylstyrene, α-ethylstyrene, m-methylstyrene, p-methylstyrene, and 2,5-dimethylstyrene. Nuclear aromatic styrene such as p-chlorostyrene, p-bromostyrene, and vinyl aromatics such as halogen-substituted halogenated styrene such as dibromostyrene, (meth) acrylic acid ("(meth) acryl" means acrylic And the same shall apply hereinafter.), Unsaturated carboxylic acids such as crotonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (Meth) acrylate, butyl (meth) acrylate (n-butyl (meth) acrylate, isobutyl (meth) Acrylate, etc.), pentyl (meth) acrylate, hexyl (meth) acrylate, dodecyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, Unsaturated carboxylic acid esters such as 2-chloroethyl (meth) acrylate, phenyl (meth) acrylate and α-chloromethyl (meth) acrylate, unsaturated carboxylic acids such as (meth) acrylaldehyde, (meth) acrylonitrile and (meth) acrylamide Acid derivatives, N-vinyl compounds such as N-vinylpyridine, N-vinylpyrrolidone, vinyl esters such as vinyl formate, vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, vinyl fluoride, vinyl chloride , Vinyl halides such as vinyl bromide and vinylidene chloride, vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidone N-vinyl compounds such as N-methylol acrylamide, N-ethylol acrylamide, N-propanol acrylamide, N-methylol maleamic acid, N-methylol maleamic acid ester, N-methylol maleimide, N-ethylol maleimide, etc. N-substituted unsaturated amides, conjugated dienes such as butadiene and isoprene, polyfunctional vinyl compounds such as divinylbenzene, divinylnaphthalene and divinylcyclohexane, ethylene glycol di (meth) acrylate , Diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hexamethylene glycol di (meth) acrylate, trimethylolpropane di (meth) Acrylate, trimethylolpropane tri (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, di Pentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (me ) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate, sorbitol penta (meth) acrylate, sorbitol hexa (meth) acrylate, etc. Examples include polyfunctional acrylates. Among these, N-substituted unsaturated amides, conjugated dienes, polyfunctional vinyl compounds, polyfunctional acrylates, and the like can also cause a crosslinking reaction in the produced polymer. These can be used alone or in combination.

In addition, as a polymerization method of the radical polymerizable monomer, a known polymerization method such as a method using a radical polymerization initiator, a heat self-polymerization method, a method using ultraviolet irradiation, or the like can be employed. In this case, as a method using a radical polymerization initiator, radical polymerization initiators include oil-soluble and water-soluble ones, but both initiators can be used.
As the radical polymerization initiator, a known radical polymerization initiator can be appropriately selected and used.
Specifically, for example, 2,2′-azobis (2-methylpropionitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobisisobutyronitrile, 2 , 2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), 1,1'-azobis (cyclohexanecarbonitrile), 2,2 Azobisnitriles such as' -azobis (2-amidinopropane) hydrochloride, acetyl peroxide, octanoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, decanoyl peroxide, lauroyl peroxide, benzoyl peroxide Diacyl peroxide such as oxide, di-t-butyl peroxide, t-butyl-α-cumyl peroxy And dialkyl peroxides such as dicumyl peroxide, t-butyl peroxyacetate, α-cumyl peroxypivalate, t-butyl peroxyoctoate, t-butylperoxyneodecanoate, t-butylperoxy Peroxyesters such as laurate, t-butylperoxybenzoate, di-t-butylperoxyphthalate, di-t-butylperoxyisophthalate, t-butylhydroperoxide, 2,5-dimethylhexane-2, Hydroperoxides such as 5-dihydroperoxide, cumene hydroperoxide, di-isopropylbenzene hydroperoxide, organic peroxides such as peroxycarbonate such as t-butylperoxyisopropyl carbonate, inorganic such as hydrogen peroxide Peroxides, Examples include radical polymerization initiators such as persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate. A redox polymerization initiator may be used in combination.
The polymerization initiator can be added to a mixture containing a polycondensable monomer or a polycondensation resin, but can also be added to an aqueous medium. Moreover, it can also add to both. It can also be added before emulsification dispersion and can also be added after emulsification dispersion.

The addition polymerizable resin obtained by polymerizing the addition polymerizable monomer is preferably a vinyl resin. The glass transition point of the addition polymerizable resin is preferably 18.0 ° C or higher, more preferably 20.0 ° C or higher and 80.0 ° C or lower, and 22.0 ° C or higher and 70.0 ° C or lower. Is more preferable. It is preferable that Tg is within the above range since both image storage properties and fixing properties can be achieved.
Moreover, the weight average molecular weight (Mw) of the resulting addition polymerizable resin is preferably 1,500 or more and 50,000 or less, and more preferably 2,000 or more and 40,000 or less. The number average molecular weight (Mn) is preferably from 1,000 to 10,000, and more preferably from 2,000 to 60,000. It is preferable that the weight average molecular weight and the number average molecular weight are in the above ranges since both image storage properties and fixing properties can be achieved.

In the present invention, the resin particles of the resin particle dispersion preferably have an average particle size of 50 nm to 1,000 nm, more preferably 50 nm to 500 nm, and further preferably 50 nm to 300 nm. preferable.
When the average particle diameter of the resin particles is within the above range, the toner for developing an electrostatic charge image produced using the resin particle has a uniform composition, which is preferable.
Here, the average particle diameter means a volume average particle diameter. The volume average particle diameter can be measured using a laser diffraction particle size distribution measuring device or the like.

(Method for producing resin particle dispersion)
In the present invention, the method for producing the resin particle dispersion may be appropriately selected from the above mixing methods characterized by mixing the polymer dispersant of the present invention, a polycondensable resin, and an aqueous medium.
Production methods that can be suitably used in the present invention include (I) batch emulsification method and (II) continuous emulsification method. Each will be described below.

(I) Batch emulsification method In the batch emulsification method, after preparing a dispersion in water of a polymer dispersant and heating it, the same is added to the heated polycondensation resin under stirring, and after performing melt phase inversion emulsification, An example is a method of cooling to produce a resin particle dispersion.
For example, a polymer having a weight average molecular weight of 10,000 or more is obtained by copolymerizing a monomer such as methyl methacrylate and a hydrophilic monomer (ionic polar group-containing monomer) such as acrylic acid. Make a dispersant and disperse a certain amount in water.
Furthermore, in a high-viscosity stirrer such as a desktop kneader, a polyvalent acid (polycarboxylic acid) and a polyhydric alcohol (polyol) are melt-mixed to use sulfur acid (Bronsted acid containing a sulfur atom) as a catalyst. Polycondensation is carried out under reduced pressure at a temperature of from 150 ° C. to 150 ° C. (eg, 120 ° C.) for about 4 to 20 hours (eg, 8 hours) to produce a polycondensation resin.
After cooling the obtained polycondensation resin as necessary (for example, 100 ° C.), the aqueous dispersion of the above-described polymer dispersant is heated (for example, 95 ° C.) while stirring the polycondensation resin to, for example, 15 RPM. Stirring speed is increased while gradually putting into a kneader (30 RPM), melt phase inversion emulsification is performed, and then an emulsion dispersion of cooling and polycondensation resin is prepared.
The present invention is not limited to this, and in the batch emulsification method, the polycondensation temperature, the polycondensation time, the temperature of the aqueous dispersion of the polycondensation resin and the polymer dispersant, the stirring speed, the stirring time, etc. are appropriately selected. be able to.

In the batch emulsification method, the dispersion of the polymer dispersant added to the polycondensation resin preferably contains 2% to 50% by weight of the polymer dispersant, preferably 5% to 40% by weight. It is more preferable to contain 10% by weight or more and 30% by weight or less.
It is preferable that the content of the polymer dispersant is within the above range because the polycondensation resin has good dispersibility.

(II) Continuous emulsification method As a method of dispersing and emulsifying the polycondensation resin, a batch-type kneader such as the above kneader may be used, but the resin particle dispersion is obtained by a continuous emulsification method in which emulsification is continuously performed. It is also preferable to manufacture.
FIG. 1 shows an example of a process schematic diagram of the continuous emulsification method.
An example of a continuous emulsification method that can be suitably used in the present invention will be described with reference to FIG. In this example, the polycondensation reaction is carried out in an ordinary reactor to obtain a polycondensation resin, and then the above-mentioned polymer dispersant dispersion is mixed while kneading the polycondensation resin using a biaxial extruder. In this method, the mixture is heated to 95 ° C. and injected into the kneading zone of the single screw extruder, and further diluted water is injected into the subsequent process to dilute and stabilize. In this case, a continuous non-solvent emulsification process can be realized, and extremely efficient production can be realized.
In addition, this invention is not limited to this, The temperature of polycondensation resin, the temperature of the dispersion liquid of a polymer dispersing agent, extrusion conditions, etc. can be selected suitably.

(2) Toner for developing electrostatic image <Method for producing toner>
In the present invention, a method for producing a toner for developing an electrostatic image (in the present invention, “electrostatic image developing toner” is also simply referred to as “toner”) includes a method for producing the toner in a dispersion containing at least a resin particle dispersion. A method for producing a toner for developing an electrostatic image comprising a step of aggregating resin particles to obtain aggregated particles (aggregation step) and a step of fusing the aggregated particles by heating (fusion step) is preferable. And in this manufacturing method called emulsion polymerization aggregation method, it is preferable to apply said resin particle dispersion as a dispersion in which resin particles are dispersed.

More specifically, the resin particle dispersion obtained as described above is mixed with a colorant particle dispersion, a release agent liquid particle dispersion, etc., if necessary, and a flocculant is added to form heteroaggregation. By forming aggregated particles having a toner diameter by causing the toner particles to be fused and coalesced by heating to a temperature above the glass transition point or the melting point of the resin particles, and further washing and drying. can get.
The toner shape is preferably from an indeterminate shape to a spherical shape.
In addition to surfactants, inorganic salts and divalent or higher metal salts can be suitably used as the flocculant. In particular, when a metal salt is used, it is desirable in terms of cohesion control and toner charging characteristics.

In the agglomeration step, the resin particle dispersion prepared as described above is mixed with the release agent particle dispersion and, if necessary, the colorant particle dispersion and the like, and an aggregating agent is added to heteroaggregate these particles. As a result, aggregated particles having a toner diameter can be formed.
In the present invention, other surfactants can be used in addition to the polymer dispersant when dispersing the resin particles.
The surfactant used here is an anionic surfactant such as sulfate ester, sulfonate, phosphate, or soap; a cationic surfactant such as amine salt or quaternary ammonium salt; polyethylene Nonionic surfactants such as glycol-based, alkylphenol ethylene oxide adduct-based, polyhydric alcohol-based, and various graft polymers can be exemplified and are not particularly limited.

  Further, after forming the first aggregated particles by aggregation in this manner, the resin particle dispersion of the present invention or another resin particle dispersion is further added to form the second shell layer on the surface of the first particles. It is also possible. In this example, the colorant dispersion is prepared separately. However, when the colorant is previously blended with the polycondensation resin particles, the colorant dispersion is not necessary.

Here, as a flocculant, besides a surfactant, an inorganic salt or a divalent or higher metal salt can be suitably used. In particular, when a metal salt is used, it is preferable in characteristics such as cohesion control and toner chargeability. Further, for example, the above-described surfactants can be used for resin emulsion polymerization, pigment dispersion, resin particle dispersion, release agent dispersion, aggregation, and aggregation particle stabilization.
As a dispersing means, a general means such as a rotary shear type homogenizer, a ball mill having a media, a sand mill, a dyno mill, or the like can be used.

In the present invention, the aggregating method is not particularly limited, and the aggregating method conventionally used in the emulsion polymerization aggregating method of electrostatic charge image developing toner, for example, temperature increase, pH change, salt addition For example, a method in which the stability of the emulsion is reduced by, for example, stirring with a disperser or the like is used.
Further, after the agglomeration treatment, the particle surface may be cross-linked by heat treatment or the like for the purpose of suppressing leaching of the colorant from the particle surface. In addition, you may remove the used surfactant etc. by water washing | cleaning, acid washing | cleaning, or alkali washing | cleaning as needed.

In the method for producing the toner for developing an electrostatic image of the present invention, various known internal additives such as a charge control agent, an antioxidant, and an ultraviolet absorber used for this type of toner are used as necessary. May be.
The charge control agent can be added either during preparation of the emulsified dispersion (oil phase), during emulsification dispersion, or during aggregation. The charge control agent is preferably added as an aqueous dispersion or the like. The amount of the charge control agent added is preferably 1 part by weight or more and 25 parts by weight or less, more preferably 100 parts by weight of the oil phase. It is preferable to add so that it may become 5 to 15 weight part.
Here, the oil phase is a component that contains at least a polycondensable resin and is emulsified and dispersed in an aqueous medium in the case of bulk polymerization.

  Examples of the charge control agent include positive charge control agents such as nigrosine dyes, quaternary ammonium salt compounds, triphenylmethane compounds, imidazole compounds, and polyamine resins, or chromium, cobalt, aluminum, and iron. Metal-containing azo dyes such as, salicylic acid or metal salts and metal complexes of hydroxycarboxylic acids such as acrylic acid, benzylic acid such as chromium, zinc, and aluminum, amide compounds, phenol compounds, naphthol compounds, phenolamide compounds, etc. Known charge control agents can be used.

<Release agent>
Further, in the method for producing an electrostatic charge image developing toner of the present invention, if necessary, waxes may be used as a release agent used for this type of toner. Can be added at the time of preparation of the oil phase, at the time of emulsification dispersion, at the time of aggregation or the like. The release agent is preferably added as an aqueous dispersion or the like. The amount of the release agent added is preferably 1 part by weight or more and 25 parts by weight or less, more preferably 100 parts by weight of the oil phase. It is preferably added so as to be 5 parts by weight or more and 15 parts by weight or less.

  In this invention, a well-known component can be used as a mold release agent. Specific examples of such release agents include olefinic waxes such as low molecular weight polyethylene, low molecular weight polypropylene, copolymerized polyethylene, grafted polyethylene, and grafted polypropylene, behenyl behenate, montanate, stearyl stearate, Such as ester waxes having long chain aliphatic groups such as hydrogenated castor oil, plant waxes such as carnauba wax, ketones having long chain alkyl groups such as distearyl ketone, silicone waxes having alkyl groups and phenyl groups, stearin Higher fatty acids such as acids, higher fatty acid amides such as oleic acid amide and stearic acid amide, long chain fatty acid alcohols, long chain fatty acid polyhydric alcohols such as pentaerythritol, and partial ester forms thereof, paraffinic wax, Fischer Tropschwa Box, etc. are exemplified.

  The release agent particle dispersion preferably has a median diameter of 1 μm or less, more preferably 0.1 μm or more and 0.8 μm or less. By controlling the median diameter of the release agent particles within the above range, it becomes easier to control the cohesiveness during particle formation and the particle size distribution as a toner, and the release temperature and the temperature at which offset occurs at the time of fixing appropriately. It is preferable because it can be maintained.

  The release agent is preferably in the range of 5% by weight to 30% by weight, and more preferably in the range of 5% by weight to 25% by weight with respect to the total weight of the toner solids. In order to ensure the peelability of the fixed image in the oilless fixing system, it is preferable to be within the above range.

<Colorant>
The electrostatic image developing toner of the present invention preferably contains a colorant.
Examples of the colorant used in the toner of the present invention include carbon black, chrome yellow (CI No. 14090), Hansa yellow, benzidine yellow, sren yellow, quinoline yellow (CI No. 47005), and permanent orange GTR. , Pyrazolone Orange, Vulcan Orange, Watch Young Red, Permanent Red, Brilliantamine 3B, Brilliantamine 6B, DuPont Oil Red (CI No. 26105), Pyrazolone Red, Resol Red, Rhodamine B Lake, Lake Red C, Rose Bengal (C.I.No. 45435), aniline blue (C.I.No. 50405), ultramarine blue (C.I.No. 77103), calco oil blue (C.I.No. azoic Blue 3) ), Methylene blue chloride (C.I.No. 52015), phthalocyanine blue (C.I.No. 74160), phthalocyanine green, malachite green oxalelate (C.I.No. 42000), titanium black, lamp black (C Various pigments such as I. No. 77266), acridine, xanthene, azo, benzoquinone, azine, anthraquinone, thioindico, dioxazine, thiazine, azomethine, indico, thioindico, Phthalocyanine series, aniline black series, polymethine series, triphenylmethane series, diphenylmethane series, thiazine series, thiazole series, xanthene series, nigrosine series dyes (CI. No. 50415B), etc. Or two or more It is possible to use Te.

As a method for dispersing these colorants, any method, for example, a general dispersion method such as a rotary shear homogenizer, a ball mill having media, a sand mill, or a dyno mill can be used, and is not limited at all. . Moreover, these colorant particles may be added together with other particle components in the mixed solvent at once, or may be divided and added in multiple stages.
The amount of the colorant used is preferably 0.1 to 20 parts by weight and more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the toner.

The electrostatic image developing toner of the present invention may contain a magnetic material as necessary.
As the magnetic material, ferrite, magnetite and other iron, cobalt, nickel and other metals or alloys exhibiting ferromagnetism, compounds containing these elements, or ferromagnetic elements which are not subjected to appropriate heat treatment An alloy that exhibits ferromagnetism, for example, a type of alloy called Heusler alloy containing manganese and copper, such as manganese-copper-aluminum, manganese-copper-tin, or chromium dioxide, and the like can be given. For example, in the case of obtaining a black toner, it is particularly preferable to use magnetite which is black in itself and also functions as a colorant. In the case of obtaining a color toner, a toner having a small blackness such as metallic iron is preferable. Some of these magnetic materials also function as a colorant, and in that case, they may also be used as a colorant. When the magnetic toner is used, the content of these magnetic materials is preferably 20 parts by weight or more and 70 parts by weight or less, more preferably 40 parts by weight or more and 70 parts by weight or less per 100 parts by weight of the toner.

Further, the toner of the present invention is preferably used by mixing inorganic particles for a fluidity improver or the like.
The inorganic particles used in the present invention are particles having a primary particle diameter of preferably 5 nm to 2 μm, more preferably 5 nm to 500 nm. Also it is preferable that the specific surface area by BET method is less than 20 m ² / g or more 500m ² / g. The proportion mixed with the toner is preferably 0.01 wt% or more and 5 wt% or less, more preferably 0.01 wt% or more and 2.0 wt% or less.
Examples of such inorganic powder include silica powder, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, Examples thereof include chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. Silica powder is particularly preferable.

The silica powder here is a powder having a Si—O—Si bond, and includes both those produced by a dry method and a wet method. In addition to anhydrous silicon dioxide, any of aluminum silicate, sodium silicate, potassium silicate, magnesium silicate, zinc silicate and the like may be used, but those containing SiO _{2 in an amount} of 85% by weight or more are preferable.

  Specific examples of these silica powders include various commercially available silicas, but those having a hydrophobic group on the surface are preferable. For example, AEROSIL R-972, R-974, R-805, R-812 (manufactured by Aerosil Co., Ltd.) ), Thalax 500 (manufactured by Tarco) and the like. In addition, silica powder treated with a silane coupling agent, a titanium coupling agent, silicon oil, silicon oil having an amine in the side chain, or the like can be used.

<Toner for electrostatic image development>
The cumulative volume average particle diameter D ₅₀ of the toner obtained by the method for producing an electrostatic charge image developing toner of the present invention is preferably 3.0 μm or more and 9.0 μm or less, more preferably 3.0 μm or more and 7.0 μm or less. More preferably, it is 3.0 μm or more and 5.0 μm or less. It is preferable for D _{50 to} be in the above-mentioned range since adhesion is strong and developability is good. Further, it is preferable because the resolution of the image is good.

  Further, the volume average particle size distribution index GSDv of the obtained toner is preferably 1.30 or less. It is preferable that GSDv is 1.30 or less because resolution is good and image loss such as toner scattering and fogging does not occur.

Here, the cumulative volume average particle diameter D ₅₀ and the volume average particle size distribution index can be measured by a measuring instrument such as Coulter Counter TAII (manufactured by Nikka Kisha Co., Ltd.), Multisizer II (manufactured by Nikka Kisha Co., Ltd.), or the like. A cumulative distribution is drawn from the smaller diameter side to the particle size range (channel) divided based on the particle size distribution, and the particle diameter that becomes 16% cumulative is the volume D _16v , the number D _16P , and the cumulative 50%. The particle diameter is _defined as a volume D _50v and a number D _50P , and the particle diameter at a cumulative 84% is defined as a volume D _84v and a number D _84P . Using these, the volume average particle size distribution index (GSDv) is calculated as (D _84v / D _16V ) ^1/2 and the number average particle size distribution index (GSDp) is calculated as (D _84P / D _16P ) ^1/2 .

  The shape factor SF1 of the obtained toner is preferably 100 or more and 140 or less, more preferably 110 or more and 135 or less from the viewpoint of image formability. The shape factor SF1 is obtained as follows. First, an optical microscope image of the toner spread on the slide glass is taken into a Luzex image analyzer through a video camera, SF1 is obtained for 50 or more toners, and an average of these is obtained. SF1 is defined as follows.

ここでＭＬ：トナ−粒子の絶対最大長、Ａ：トナ−粒子の投影面積である。

Here, ML: absolute maximum length of toner particles, and A: projected area of toner particles.

  The obtained toner is dried in the same manner as a normal toner for the purpose of imparting fluidity and improving cleaning properties, and then inorganic particles such as silica, alumina, titania and calcium carbonate, and resins such as vinyl resins, polyesters and silicones. The particles can be added to the surface of the toner particles while being sheared in a dry state.

  In addition, when adhering to the toner surface in an aqueous medium, examples of inorganic particles include silica, alumina, titania, calcium carbonate, magnesium carbonate, tricalcium phosphate, etc. Can be used by dispersing with an ionic surfactant, polymer acid, or polymer base.

(3) Electrostatic Image Developer The toner obtained by the method for producing an electrostatic image developing toner of the present invention described above is used as an electrostatic image developer. The developer is not particularly limited except that it contains the toner for developing an electrostatic image, and can have an appropriate component composition depending on the purpose. When the electrostatic image developing toner is used alone, it is prepared as a one-component electrostatic image developer, and when used in combination with a carrier, it is prepared as a two-component electrostatic image developer.

The carrier is not particularly limited, but usually, magnetic particles such as iron powder, ferrite, iron oxide powder, nickel, etc .; the magnetic particles as a core material and the surface thereof as a styrene resin, vinyl resin, ethylene resin, rosin Resin-coated carrier formed by coating a resin such as a resin based on polyester, polyester or melamine, or a wax such as stearic acid, and forming a resin coating layer; a magnetic material obtained by dispersing magnetic particles in a binder resin Examples include a distributed carrier. Among them, the resin-coated carrier is particularly preferable because the chargeability of the toner and the resistance of the entire carrier can be controlled by the configuration of the resin coating layer.
The mixing ratio of the toner of the present invention and the carrier in the two-component electrostatic image developer is preferably 2 parts by weight or more and 10 parts by weight or less with respect to 100 parts by weight of the carrier. Moreover, the preparation method of a developing agent is not specifically limited, For example, the method of mixing with a V blender etc. is mentioned.

(4) Toner Cartridge, Process Cartridge, Image Forming Apparatus The electrostatic image developing toner and electrostatic image developer of the present invention can be used in a developing apparatus, cartridge, and image forming apparatus.
The developing device of the present invention includes an image holding member, a developer supplying unit that supplies the developer containing the toner of the present invention on the image holding member, and a charging that charges the developer supplied by the developer supplying unit. Means.
Further, the cartridge of the present invention essentially includes developing means for developing the electrostatic latent image formed on the surface of the image carrier with the developer containing the toner of the present invention to form a toner image, and the image carrier, At least one selected from the group consisting of a charging means for charging the surface of the image carrier and a cleaning means for removing the developer remaining on the surface of the image carrier. The cartridge of the present invention is preferably a process cartridge.
Further, the image forming apparatus of the present invention comprises an image carrier, a charging unit for charging the surface of the image carrier, a latent image forming unit for forming a latent image on the surface of the image carrier, and the latent image. A developing unit that forms a toner image by developing with the developer containing the toner of the present invention; a transfer unit that transfers the toner image to a recording medium; and a fixing unit that fixes the toner image to the recording medium. Features.

Hereinafter, a description will be given with reference to FIGS.
FIG. 2 is a sectional view schematically showing a basic configuration of a preferred embodiment of the image forming apparatus of the present invention. An image forming apparatus 200 shown in FIG. 2 includes an electrophotographic photosensitive member 207, a charging device 208 that charges the electrophotographic photosensitive member 207, a power source 209 connected to the charging device 208, and an electrophotographic image that is charged by the charging device 208. An exposure device 210 that exposes the photosensitive member 207 to form an electrostatic latent image, a developing device 211 that develops the electrostatic latent image formed by the exposure device 210 with toner, and forms a toner image, and a developing device 211 The image forming apparatus includes a transfer device 212 that transfers the formed toner image to a transfer medium (image output medium) 500, a cleaning device 213, a static eliminator 214, and a fixing device 215. In this case, the static eliminator 214 may not be provided.

  Here, the charging device 208 is of a type (contact charging type) in which the surface of the electrophotographic photosensitive member 207 is brought into contact with a charging roll as a conductive member to charge the surface of the photosensitive member 207.

  In the present invention, when the photosensitive member is charged using the charging roll, a voltage is applied to the charging roll. The applied voltage may be a DC voltage or a DC voltage in which an AC voltage is superimposed.

  As the exposure apparatus 210, an optical system apparatus that can expose a light source such as a semiconductor laser, an LED (light emitting diode), and a liquid crystal shutter on the surface of the electrophotographic photosensitive member in a desired image-like manner can be used.

As the developing device 211, a conventionally known developing device using a regular or reversal developer such as a one-component system or a two-component system can be used.
As the one-component developer, the electrostatic image developing toner of the present invention can be used as a developer, and the electrostatic image developing toner and carrier of the present invention are used as a two-component developer. You can also.

  Examples of the transfer device 212 include a roller-type contact charging member, a contact transfer charger using a belt, a film, a rubber blade, or the like, or a scorotron transfer charger or a corotron transfer charger using corona discharge. It is done.

  The transfer device 212 can supply a current having a predetermined current density to the electrophotographic photosensitive member when the toner image formed on the electrophotographic photosensitive member 207 is transferred to the transfer medium 500. Is preferred.

  The cleaning device 213 is for removing residual toner adhering to the surface of the electrophotographic photosensitive member after the transfer process. The cleaned electrophotographic photosensitive member is repeatedly used for the image forming process described above. . As the cleaning device, brush cleaning, roll cleaning, and the like can be used in addition to the cleaning blade. Among these, it is preferable to use the cleaning blade. Examples of the material for the cleaning blade include urethane rubber, neoprene rubber, and silicone rubber.

  Further, the image forming apparatus of the present invention may further include a light irradiation device as the static eliminator 214 as shown in FIG. As a result, when the electrophotographic photosensitive member is repeatedly used, the phenomenon that the residual potential of the electrophotographic photosensitive member is brought into the next cycle is prevented, so that the image quality can be further improved.

  FIG. 3 is a sectional view schematically showing the basic configuration of another preferred embodiment of the image forming apparatus of the present invention. The image forming apparatus 201 shown in FIG. 3 transfers the toner image formed on the electrophotographic photosensitive member 207 to the primary transfer member 212a and then supplies it between the primary transfer member 212a and the secondary transfer member 212b. A transfer device of an intermediate transfer system for transferring to a transfer medium (image output medium) 500 to be transferred, and at the time of such transfer, a current having a predetermined current density from the primary transfer member 212a toward the electrophotographic photosensitive member. Can be supplied. Although not shown in FIG. 3, the image forming apparatus 201 may further include a static eliminator in the same manner as the image forming apparatus 200 illustrated in FIG. 2. Other configurations of the image forming apparatus 201 are the same as those of the image forming apparatus 200.

  In such an image forming apparatus 201, when a toner image formed on the electrophotographic photosensitive member 207 is transferred to the primary transfer member 212a, a predetermined current density is transferred from the primary transfer member 212a toward the electrophotographic photosensitive member 207. By supplying this current, fluctuations in the transfer current due to the type and material of the transfer medium 500 can be suppressed, so that the amount of charge flowing into the electrophotographic photosensitive member 207 can be accurately controlled. Become. As a result, it is possible to achieve higher image quality and reduced environmental burden at a higher level.

  FIG. 4 is a sectional view schematically showing the basic configuration of another preferred embodiment of the image forming apparatus of the present invention. An image forming apparatus 220 shown in FIG. 4 is an intermediate transfer type image forming apparatus. In the housing 400, four electrophotographic photoreceptors 401a to 401d (for example, the electrophotographic photoreceptor 401a is yellow and the electrophotographic photoreceptor 401b is magenta). The electrophotographic photosensitive member 401c can form an image of cyan and the electrophotographic photosensitive member 401d can form a black color) are arranged in parallel along the intermediate transfer belt 409. Here, the electrophotographic photoreceptors 401a to 401d mounted on the image forming apparatus 220 are respectively electrophotographic photoreceptors.

  Each of the electrophotographic photosensitive members 401a to 401d can be rotated in a predetermined direction (counterclockwise on the paper surface), and the charging rolls 402a to 402d, the developing devices 404a to 404d, and the primary transfer roll 410a along the rotation direction. 410d and cleaning blades 415a to 415d are arranged. Each of the developing devices 404a to 404d can be supplied with toners of four colors of black, yellow, magenta and cyan accommodated in toner cartridges 405a to 405d. Further, the primary transfer rolls 410a to 410d are in contact with the electrophotographic photosensitive members 401a to 401d via the intermediate transfer belt 409, respectively.

  Further, a laser light source (exposure device) 403 is disposed at a predetermined position in the housing 400, and the surfaces of the electrophotographic photoreceptors 401a to 401d after charging are irradiated with laser light emitted from the laser light source 403. Is possible. Accordingly, charging, exposure, development, primary transfer, and cleaning are sequentially performed in the rotation process of the electrophotographic photoreceptors 401a to 401d, and the toner images of the respective colors are transferred onto the intermediate transfer belt 409 in an overlapping manner.

  The intermediate transfer belt 409 is supported with a predetermined tension by a drive roll 406, a backup roll 408, and a tension roll 407, and can rotate without causing deflection due to the rotation of these rolls. Further, the secondary transfer roll 413 is disposed so as to contact the backup roll 408 via the intermediate transfer belt 409. The intermediate transfer belt 409 passing between the backup roll 408 and the secondary transfer roll 413 is cleaned by, for example, a cleaning blade 416 disposed in the vicinity of the drive roll 406 and then repeatedly used for the next image forming process. Is done.

  A tray (transfer medium tray) 411 is provided at a predetermined position in the housing 400, and the transfer medium 500 such as paper in the tray 411 is transferred to the intermediate transfer belt 409 and the secondary transfer roll by the transfer roll 412. Then, the paper is sequentially transferred between the two fixing rolls 414 that are in contact with each other and the two fixing rolls 414, and then discharged to the outside of the housing 400.

  In the above description, the case where the intermediate transfer belt 409 is used as the intermediate transfer member has been described. However, the intermediate transfer member may have a belt shape like the intermediate transfer belt 409 or a drum shape. There may be. Conventionally known resins can be used as the resin material used as the base material of the intermediate transfer member in the belt shape. For example, polyimide resin, polycarbonate resin (PC), polyvinylidene fluoride (PVDF), polyalkylene terephthalate (PAT), ethylenetetrafluoroethylene copolymer (ETFE) / PC, ETFE / PAT, PC / PAT blend material, polyester Resin materials such as polyether ether ketone and polyamide, and resin materials using these as main raw materials. Furthermore, a resin material and an elastic material can be blended and used.

  As an elastic material, polyurethane, chlorinated polyisoprene, NBR, chloropyrene rubber, EPDM, hydrogenated polybutadiene, butyl rubber, silicone rubber, or the like can be used, or a material obtained by blending two or more kinds can be used. If necessary, a conductive agent imparting electronic conductivity or a conductive agent having ionic conductivity is added to the resin material and elastic material used for these base materials in combination of one kind or two or more kinds. Among these, it is preferable to use a polyimide resin in which a conductive agent is dispersed from the viewpoint of excellent mechanical strength. As the conductive agent, a conductive polymer such as carbon black, metal oxide, or polyaniline can be used.

  When a belt-shaped configuration such as the intermediate transfer belt 409 is adopted as the intermediate transfer member, generally the thickness of the belt is preferably 50 μm or more and 500 μm or less, more preferably 60 μm or more and 150 μm, but it is appropriately selected according to the hardness of the material can do.

  For example, a belt made of a polyimide resin in which a conductive agent is dispersed is used as a conductive agent in a solution of polyamic acid, which is a polyimide precursor, as described in JP-A-63-311263. After dispersing carbon black of less than% by weight, casting the dispersion on a metal drum and drying it, the film peeled off from the drum is stretched at a high temperature to form a polyimide film, and then cut into an appropriate size. Can be manufactured by using an endless belt.

  The film forming is generally performed by injecting a polyamic acid solution film-forming stock solution in which a conductive agent is dispersed into a cylindrical mold and heating at 100 ° C. or higher and 200 ° C. or lower while rotating at 500 rpm or higher and 2,000 rpm or lower. The film is formed into a film by a centrifugal molding method while rotating the cylindrical mold with a number, and then the obtained film is demolded in a semi-cured state and covered with an iron core, and is polyimideized at a high temperature of 300 ° C. or higher. It can be carried out by allowing the reaction (ring-closing reaction of polyamic acid) to proceed and main curing. Also, the stock solution is cast on a metal sheet to a uniform thickness and heated to 100 ° C. or higher and 200 ° C. or lower in the same manner as described above to remove most of the solvent, and then gradually increased to a high temperature of 300 ° C. or higher. There is also a method of forming a polyimide film by raising the temperature. Further, the intermediate transfer member may have a surface layer.

  When a drum-shaped configuration is adopted as the intermediate transfer member, it is preferable to use a cylindrical substrate formed of aluminum, stainless steel (SUS), copper, or the like as the substrate. If necessary, an elastic layer can be coated on the cylindrical substrate, and a surface layer can be formed on the elastic layer.

  FIG. 5 is a sectional view schematically showing a preferred embodiment of the cartridge of the present invention. The cartridge 300, together with the developing device 211 of the present invention, includes an electrophotographic photosensitive member 207, a charging device 208 having a charging roll, a cleaning device (cleaning means) 213, an opening 218 for exposure, and an opening for static elimination exposure. The parts 217 are combined and integrated using the mounting rails 216.

  The cartridge 300 is detachable from an image forming apparatus main body including a transfer device 212, a fixing device 215, and other components not shown. The image forming apparatus is mounted together with the image forming apparatus main body. It constitutes.

In the present invention, a method for isolating and extracting a binder resin from an electrostatic charge image developer or toner for developing an electrostatic charge image, the weight percent of the polycondensation resin in the binder resin, and the polymer dispersant of the present invention A method for detecting the will be described below.
As a method for isolating and extracting the binder resin from the electrostatic charge image developer, the developer is fixed with a magnet or the like, blown with compressed air, and the toner is collected, and then the toner is washed with a hydrophobic organic solvent such as toluene. The binder resin can be extracted by collecting the supernatant from which the pigments and inorganic additives have been removed with a centrifuge. It can also be extracted by filtration. However, the present invention is not limited to this.
In addition, as a method for evaluating the weight percent of the polycondensation resin in the binder resin, the isolated binder resin is analyzed by infrared absorption (IR), and the components are clarified, followed by high-resolution nuclear magnetic resonance. The weight fraction of the polycondensation resin can be measured by quantifying the condensed ester component by the method (NMR).
Furthermore, the polymer dispersant can be extracted by adding ion-exchanged water to a binder resin dissolved in a hydrophobic organic solvent, shaking in a separatory funnel, and separating the components separated in water by dry separation. It is possible to extract a polymer dispersant having a wide range of compositions by dissolving alcohol or the like in water as required. In addition, the organic solvent solution of the binder resin is added to an alcohol such as methyl alcohol or a mixture of ion-exchanged water and alcohol while stirring, and the polymer dispersant is added to the alcohol or a mixture of ion-exchanged water and alcohol. Can also be extracted.
The ratio of the hydrophilic monomer in the polymer dispersant (ratio of the hydrophilic monomer unit) is analyzed by infrared absorption (IR), and the components are clarified, and then the high resolution nuclear magnetic resonance (NMR) ) By quantifying the copolymer component.

EXAMPLES Hereinafter, although this invention is explained in full detail based on an Example, this invention is not limited to this.
In the following examples, “parts” means “parts by weight” unless otherwise specified.

(Preparation of polymer dispersant)
<Preparation of Polymer Dispersant PD1: Examples>
Methyl methacrylate 50 parts by weight (41.9 mol%)
50 parts by weight of acrylic acid (58.1 mol%)
After mixing 2 parts by weight or more of dodecanethiol in a glass flask container, hold it for 1 hour while blowing nitrogen into the flask. The temperature was raised and held for 5 hours.
After the obtained polymer was dissolved in 300 parts by weight of a 1: 1 mixed solvent of THF and acetone, it was put into 500 parts by weight of methyl alcohol, the precipitate was filtered, and the same operation was repeated again. Finally, the polymer was dried with a hot air dryer and pulverized with a sample mill to obtain a finely divided polymer dispersant PD1.
When PD1 was analyzed by GPC, which is a normal molecular weight measuring means, the weight average molecular weight was 14,000 and the number average molecular weight was 4,500.

Here, the weight average molecular weight and the number average molecular weight of the polymer dispersant were measured as follows. HLC-8220GPC (Tosoh Corporation) was used as the GPC device. 5 mg of the obtained resin was dissolved in 1 ml of THF, and the soluble component was used as a sample.
As an analytical column, TSKgel SuperHM-M manufactured by Tosoh Corp. was used, and the temperature of the column oven and the inlet oven was set to 40 ° C., and the measurement was performed.

<Preparation of Polymer Dispersant PD2: Examples>
20 parts by weight of styrene (14.7 mol%)
80 parts by weight of acrylic acid (85.3 mol%)
After mixing 1.5 parts by weight or more of dodecanethiol in a glass flask container, the mixture was held for 1 hour while blowing nitrogen into the flask. The temperature was raised to 0 ° C. and held for 5 hours.
After the obtained polymer was dissolved in 300 parts by weight of a 1: 1 mixed solvent of THF and acetone, it was put into 500 parts by weight of methyl alcohol, the precipitate was filtered, and the same operation was repeated again. Finally, the polymer was dried with a hot air dryer and pulverized with a sample mill to obtain a finely divided polymer dispersant PD2.
When PD2 was analyzed by GPC, which is a normal molecular weight measuring means, the weight average molecular weight was 26,000 and the number average molecular weight was 6,600.

<Preparation of Polymer Dispersant PD3: Examples>
70 parts by weight of styrene (65.8 mol%)
30 parts by weight of methacrylic acid (34.2 mol%)
1.0 parts by weight or more of dodecanethiol were mixed in a glass flask container, and held for 1 hour while blowing nitrogen into the flask. Further, 0.5 parts by weight of benzoyl peroxide was added, and the mixture was stirred while stirring. The temperature was raised to 0 ° C. and held for 5 hours.
After the obtained polymer was dissolved in 300 parts by weight of a 1: 1 mixed solvent of THF and acetone, it was put into 500 parts by weight of methyl alcohol, the precipitate was filtered, and the same operation was repeated again. Finally, the polymer was dried with a hot air dryer and pulverized with a sample mill to obtain a finely divided polymer dispersant PD3.
When PD3 was analyzed by GPC, which is a normal molecular weight measuring means, the weight average molecular weight was 39,000 and the number average molecular weight was 10,300.

<Preparation of Polymer Dispersant PD4: Examples>
Methyl methacrylate 50 parts by weight (56.5 mol%)
50 parts by weight of hydroxyethyl methacrylate (43.5 mol%)
After mixing 2 parts by weight or more of dodecanethiol in a glass flask container, hold it for 1 hour while blowing nitrogen into the flask. The temperature was raised and held for 5 hours.
The obtained polymer was dissolved in 300 parts by weight of a 1: 1 mixed solvent of THF and acetone, and then poured into 500 parts by weight of methyl alcohol. After filtering the precipitate, the same operation was repeated again, Finally, the polymer was dried with a hot air dryer and pulverized with a sample mill to obtain a finely divided polymer dispersant PD4.
When PD4 was analyzed by GPC which is a normal molecular weight measuring means, the weight average molecular weight was 18,000 and the number average molecular weight was 7,500.

<Preparation of Polymer Dispersant PD5: Examples>
Methyl methacrylate 50 parts by weight (52.6 mol%)
50 parts by weight of vinylpyrrolidone (47.4 mol%)
After mixing 2 parts by weight or more of dodecanethiol in a glass flask container, hold it for 1 hour while blowing nitrogen into the flask. The temperature was raised and held for 5 hours.
After the obtained polymer was dissolved in 300 parts by weight of a 1: 1 mixed solvent of THF and acetone, it was put into 500 parts by weight of methyl alcohol, the precipitate was filtered, and the same operation was repeated again. Finally, the polymer was dried with a hot air dryer and pulverized with a sample mill to obtain a finely divided polymer dispersant PD5.
When PD5 was analyzed by GPC, which is a normal molecular weight measuring means, the weight average molecular weight was 17,000 and the number average molecular weight was 6,300.

<Preparation of Polymer Dispersant PD6: Example>
p-Toluenesulfonic acid 0.5 part by weight Sodium 5-sulfoisophthalate 89.4 parts by weight (50 mol%)
1,9-nonanediol 53.4 parts by weight (50 mol%)
Mix in a 1 L table kneader (Irie Shokai PBV-1), then heat to 120 ° C., melt the mixture, depressurize with stirring at 15 RPM, and hold at 90 ° C. for 8 hours. It became a melt.
After the obtained polymer was dissolved in 300 parts by weight of a 1: 1 mixed solvent of THF and acetone, it was put into 500 parts by weight of methyl alcohol, the precipitate was filtered, and the same operation was repeated again. Finally, the polymer was dried with a hot air dryer and pulverized with a sample mill to obtain a finely divided polymer dispersant PD6.
When PD6 was analyzed by GPC, which is a normal molecular weight measuring means, the weight average molecular weight was 21,000 and the number average molecular weight was 8,100.

<Production of Polymer Dispersant PD7: Comparative Example>
Methyl methacrylate 10 parts by weight (7.4 mol%)
90 parts by weight of acrylic acid (92.6 mol%)
After mixing 2 parts by weight or more of dodecanethiol in a glass flask container, hold it for 1 hour while blowing nitrogen into the flask. The temperature was raised and held for 5 hours.
The obtained polymer was dissolved in 300 parts by weight of a 1: 1 mixed solvent of THF and acetone, and then poured into 500 parts by weight of methyl alcohol. After filtering the precipitate, the same operation was repeated again, Finally, the polymer was dried with a hot air dryer and pulverized with a sample mill to obtain a finely divided polymer dispersant PD7.
When PD7 was analyzed by GPC, which is a normal molecular weight measuring means, the weight average molecular weight was 11,000 and the number average molecular weight was 2,500.

<Production of Polymer Dispersant PD8: Comparative Example>
95 parts by weight of styrene (92.9 mol%)
Acrylic acid 5 parts by weight (7.1 mol%)
After mixing 2 parts by weight or more of dodecanethiol in a glass flask container, hold it for 1 hour while blowing nitrogen into the flask. The temperature was raised and held for 5 hours.
The obtained polymer was dissolved in 300 parts by weight of a 1: 1 mixed solvent of THF and acetone, and then poured into 500 parts by weight of methyl alcohol. After filtering the precipitate, the same operation was repeated again, Finally, the polymer was dried with a hot air dryer and pulverized with a sample mill to obtain a finely divided polymer dispersant PD8.
When PD8 was analyzed by GPC which is a normal molecular weight measuring means, the weight average molecular weight was 21,000 and the number average molecular weight was 7,500.

<Preparation of Polymer Dispersant PD9: Comparative Example>
50 parts by weight of styrene (45.6 mol%)
50 parts by weight of acrylic acid (54.4 mol%)
4 parts by weight or more of dodecanethiol After mixing in a glass flask container, hold for 1 hour while blowing nitrogen into the flask. The temperature was raised and held for 5 hours.
After the obtained polymer was dissolved in 300 parts by weight of a 1: 1 mixed solvent of THF and acetone, it was put into 500 parts by weight of methyl alcohol, the precipitate was filtered, and the same operation was repeated again. Finally, the polymer was dried with a hot air dryer and pulverized with a sample mill to obtain a finely divided polymer dispersant PD9.
When PD9 was analyzed by GPC which is a normal molecular weight measuring means, the weight average molecular weight was 9,200 and the number average molecular weight was 2,400.

  The polymer dispersants (PD1 to PD9) are summarized in the following table.

(Preparation of resin particle dispersion)
<Preparation of crystalline resin particle dispersion (C1)>
p-Toluenesulfonic acid 0.7 parts by weight 1,6-hexanediol 59 parts by weight Sebacic acid 101 parts by weight 1 L In a table kneader (Irie Shokai PBV-1), then heated to 120 ° C. to melt the mixture Then, the pressure was reduced with stirring at 15 RPM, and the contents became a viscous melt when held at 90 ° C. for 8 hours.
16 parts by weight of the polymer dispersant PD1 (10% by weight with respect to the polycondensation resin component) is dispersed in 64 parts by weight of ion-exchanged water, stirred for 10 minutes, and then emulsified with a homogenizer (manufactured by IKA, Ultra Tarrax) for 1 minute. Thereafter, the mixture was heated to 95 ° C., and the melt in the table kneader was added to the table kneader for 3 minutes with stirring at 30 RPM, resulting in a white emulsion. Further, the stirring speed was increased to 40 RPM, and 160 parts by weight of ion-exchanged water heated to 60 ° C. was added over 5 minutes, then held for 10 minutes and further cooled to room temperature.
As a result, a crystalline resin particle dispersion (C1) having a volume average particle diameter (center diameter) of 210 nm, a melting point of 69 ° C., a weight average molecular weight of 12,000, and a solid content of 40% was obtained.

The volume average particle diameter (center diameter) of the fine particles in the resin particle dispersion was measured with a laser diffraction / scattering particle size distribution analyzer LA920 (manufactured by Horiba, Ltd.).
The melting point of the crystalline polyester resin was measured according to JIS K-7121 measured using a DSC-60 differential scanning calorimeter (DSC) manufactured by Shimadzu Corporation at a heating rate of 10 ° C. per minute from room temperature to 150 ° C. : It calculated | required as a melting peak temperature of the input compensation differential scanning calorimetry shown to 87. The crystalline polyester resin may show a plurality of melting peaks, but the maximum peak was regarded as the melting point. Moreover, the glass transition temperature was measured by the method (DSC method) prescribed | regulated to ASTMD3418-82.
The weight average molecular weight of the resin was measured by GPC in the same manner as the method for measuring the weight average molecular weight of the polymer dispersant.

<Preparation of Amorphous Resin Particle Dispersion (A1)>
1,4-cyclohexanedicarboxylic acid 175 parts by weight Bisphenol A 1 ethylene oxide adduct 380 parts by weight (both ends equivalent 2 mol adduct)
Dodecylbenzenesulfonic acid 0.5 parts by weight 1 L In a table top kneader (Irie Shokai PBV-1), heated to 120 ° C., melted, then depressurized with stirring at 15 RPM, and then heated to 100 ° C. The contents became a viscous melt when kept for a while.
44 parts by weight of the polymer dispersant PD2 (6% by weight based on the polycondensation resin component) is dispersed in 230 parts by weight of ion-exchanged water, stirred for 10 minutes, and then emulsified for 1 minute with a homogenizer (manufactured by IKA, Ultra Tarrax). Thereafter, the mixture was heated to 95 ° C., and the melt in the table kneader was added to the table kneader for 3 minutes with stirring at 30 RPM, resulting in a white emulsion. Further, the stirring speed was increased to 40 RPM, and 550 parts by weight of ion-exchanged water heated to 95 ° C. was added over 5 minutes, then held for 10 minutes, and further cooled to room temperature.
As a result, an amorphous resin particle dispersion (A1) having a fine particle center diameter of 250 nm, a glass transition point of 55 ° C., a weight average molecular weight of 16,000, and a solid content of 40% was obtained.

<Preparation of Amorphous Resin Particle Dispersion (A2)>
1,4-cyclohexanedicarboxylic acid 175 parts by weight Bisphenol A 1 ethylene oxide adduct 380 parts by weight (both ends equivalent 2 mol adduct)
0.5 parts by weight of dodecylbenzenesulfonic acid 50 L Mix in a 50 L vacuum reactor, then heat to 120 ° C., melt the mixture, depressurize with stirring and hold at 100 ° C. for 8 hours, the contents become viscous A melt was obtained.
This polycondensation resin melt was transferred to a hopper of a twin-screw co-directional kneading extruder.
Separately, 44 parts by weight of polymer dispersant PD3 was dispersed in 230 parts by weight of ion-exchanged water, stirred for 10 minutes, and then emulsified for 1 minute with a homogenizer (manufactured by IKA, Ultra Turrax) to prepare an aqueous polymer dispersant solution. .
A viscous melt is continuously supplied to the kneading extruder from the hopper of a biaxial co-directional kneading extruder (manufactured by Nippon Steel Works, Ltd., Supertex 44α). An aqueous dispersant solution (10% by weight with respect to the polycondensation resin component) is maintained at 80 ° C., and is press-fitted by a plunger pump and continuously supplied. By press-fitting and diluting, a resin particle dispersion of the polycondensation resin was continuously obtained.
As a result, an amorphous resin particle dispersion (A2) having a fine particle center diameter of 270 nm, a glass transition point of 55 ° C., a weight average molecular weight of 15,500, and a solid content of 40% was obtained.

<Preparation of Amorphous Resin Particle Dispersion (A3)>
An amorphous resin particle dispersion (A3) was prepared in the same manner as in the amorphous resin particle dispersion (A2) except that PD4 was used instead of the polymer dispersant PD3.
The center diameter was 190 nm, the glass transition point was 56 ° C., the weight average molecular weight was 16,500, and the solid content was 40%.

<Preparation of Amorphous Resin Particle Dispersion (A4)>
An amorphous resin particle dispersion (A4) was prepared in the same manner as in the amorphous resin particle dispersion (A2) except that PD5 was used instead of the polymer dispersant PD3.
The center diameter was 220 nm, the glass transition point was 55 ° C., the weight average molecular weight was 16,200, and the solid content was 40%.

<Preparation of Amorphous Resin Particle Dispersion (A5)>
An amorphous resin particle dispersion (A5) was prepared in the same manner as in the amorphous resin particle dispersion (A2) except that PD6 was used instead of the polymer dispersant PD3.
The center diameter was 250 nm, the glass transition point was 55 ° C., the weight average molecular weight was 16,800, and the solid content was 40%.

<Production / Comparative Example of Amorphous Resin Particle Dispersion (A6)>
In the preparation of the amorphous resin particle dispersion (A1), the non-crystalline resin was prepared under the same conditions as the amorphous resin particle dispersion (A1) except that PD7 was used instead of the polymer dispersant PD2. A particle dispersion (A6) was prepared.
The center diameter was 190 nm, the glass transition point was 55 ° C., the weight average molecular weight was 15,700, and the solid content was 40%.

<Production / Comparative Example of Amorphous Resin Particle Dispersion (A7)>
The amorphous resin particle dispersion (A1) was prepared in the same manner as the amorphous resin particle dispersion (A1) except that PD8 was used instead of the polymer dispersant PD2. A particle dispersion (A7) was prepared.
The center diameter was 200 nm, the glass transition point was 55 ° C., the weight average molecular weight was 16,100, and the solid content was 40%.

<Amorphous resin particle dispersion (A8) / Comparative Example>
In the preparation of the amorphous resin particle dispersion (A1), the same conditions as in the amorphous resin particle dispersion (A1) were used except that PD9 was used instead of the polymer dispersant PD2. A dispersion (A8) was prepared.
The center diameter was 190 nm, the glass transition point was 55 ° C., the weight average molecular weight was 15100, and the solid content was 40%.

(Preparation of release agent particle dispersion (W1))
Anionic surfactant (Daiichi Kogyo Seiyaku, Neogen R) 2 parts by weight Ion-exchanged water 800 parts by weight Carnauba wax 200 parts by weight After mixing the above ingredients, heating to 100 ° C and melting, homogenizer (manufactured by IKA) Then, emulsification was carried out at 100 ° C. using a gorin homogenizer.
As a result, a release agent fine particle dispersion (W1) having a fine particle central diameter of 250 nm, a melting point of 83 ° C., and a solid content of 20% was obtained.

(Preparation of colorant particle dispersion (P1))
Cyan pigment (manufactured by Dainichi Seika Co., Ltd., copper phthalocyanine B15: 3) 50 parts by weight Anionic surfactant (Daiichi Kogyo Seiyaku, Neogen R) 5 parts by weight Ion-exchanged water 200 parts by weight (IKA, Ultra Turrax) Dispersed for 5 minutes by an ultrasonic bath for 10 minutes to obtain a Sian colorant particle dispersion (P1) having a center diameter of 190 nm and a solid content of 21.5%.

(Preparation of colorant particle dispersion (P2))
In the preparation of the colorant particle dispersion (1), except that a magenta pigment (manufactured by Dainichi Ink Chemical Co., PR122) was used instead of the cyan pigment, it was prepared in the same manner as the colorant particle dispersion (1). A magenta colorant particle dispersion (P2) having a center diameter of 165 nm and a solid content of 21.5% was obtained.

(Production of toner)
<Example 1 (Toner No. 1)>
(Preparation of toner particles)
Crystalline resin fine particle dispersion (C1) 25 parts by weight (resin 10 parts by weight)
Amorphous resin fine particle dispersion (A1) 125 parts by weight (resin 50 parts by weight)
Colorant particle dispersion (P1) 40 parts by weight (8.6 parts by weight of pigment)
Release agent particle dispersion (W1) 40 parts by weight (release agent 8.6 parts by weight)
Polyaluminum chloride 0.15 parts by weight Deionized water 400 parts by weight The above components were thoroughly mixed and dispersed in a round stainless steel flask with a homogenizer (IKA, Ultra Turrax T50), and then heated in an oil bath for heating. The mixture was heated to 40 ° C. with stirring and held at 40 ° C. for 60 minutes, and then 62.5 parts by weight (25 parts by weight of resin) of the resin fine particle dispersion (A1) was added and gently stirred.
Thereafter, the pH in the system was adjusted to 6.5 with a 0.5 mol / liter sodium hydroxide aqueous solution, and then heated to 85 ° C. while stirring was continued.
A sodium hydroxide aqueous solution was further added dropwise, and the pH was maintained so as not to be 5.5 or less. After completion of the reaction, the mixture was cooled, filtered, sufficiently washed with ion exchange water, and then solid-liquid separated by Nutsche suction filtration. Then, it was redispersed in 3 liters of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This washing operation was repeated 5 times, followed by solid-liquid separation by Nutsche suction filtration, and then freeze-drying for 10 hours to obtain toner particles. When the particle size of the toner particles was measured with a Coulter counter, the cumulative volume average particle size D ₅₀ was 4.9 μm and the volume average particle size distribution index GSDv was 1.20. In addition, the toner particle shape factor SF1 obtained by shape observation with Luzex was 130.

<Preparation of external toner>
This is a reaction product of silica (SiO ₂ ) fine particles having a primary particle average particle size of 40 nm and surface hydrophobized with hexamethyldisilazane (hereinafter sometimes abbreviated as “HMDS”), metatitanic acid and isobutyltrimethoxysilane. Metatitanic acid compound fine particles having an average primary particle diameter of 20 nm were added in an amount of 1% by weight and mixed with a Henschel mixer to prepare a Sian externally added toner.

<Creation of carrier>
A methanol solution containing 0.1 part by weight of γ-aminopropyltriethoxysilane was added to 100 parts by weight of Cu—Zn ferrite fine particles having a volume average particle diameter of 40 μm and coated with a kneader. The silane compound was completely cured by heating at 0 ° C. for 2 hours. To this particle, a perfluorooctylethyl methacrylate-methyl methacrylate copolymer (copolymerization ratio 40:60) dissolved in toluene was added, and perfluorooctylethyl methacrylate-methyl was added using a vacuum reduced pressure kneader. A resin-coated carrier was produced so that the coating amount of the methacrylate copolymer was 0.5% by weight.

<Production of developer>
5 parts by weight of each toner prepared as described above was mixed with 100 parts by weight of the obtained resin-coated carrier for 20 minutes in a V blender to prepare an electrostatic charge image developer. This was used as a developer in the following evaluation.

(Evaluation of toner)
Using the developer described above, a modified DocuCenterColor500 manufactured by Fuji Xerox Co., Ltd. in a normal laboratory environment has good developability and transferability, high image quality and good initial image quality (◯). It was.
In the modified machine, seasoning was carried out by leaving it overnight in a laboratory environment under conditions of high temperature and high humidity of 30 ° C. and 80% (summer environmental conditions).
Furthermore, 100,000 continuous printing tests were conducted under this summer environment condition, but the image quality was well maintained and no image defects such as streaks or spots due to filming were observed.
In Example 2, the non-crystalline resin particle dispersion was changed to A2, and in Example 3, the non-crystalline resin particle dispersion was changed to A3 and the colorant particle dispersion was changed to P2. In Examples 2 and 3, the non-crystalline resin particle dispersion was changed to A4, A5, A6, A7, and A8 for Example 1, and toners (Toner Nos. 2 to 6) were similarly prepared and evaluated. .
The following table was prepared by preparing and evaluating the same toner as described above.

The results of the printing test were evaluated according to the following criteria.
Print test result evaluation criteria:
○: Image quality defects such as streaks and dots are not generated up to 100,000 sheets. △: Slightly observed but acceptable.

It is process drawing which shows an example of the process schematic of the continuous emulsification method which can be used conveniently for this invention. 1 is a cross-sectional view schematically showing a basic configuration of a preferred embodiment of an image forming apparatus of the present invention. It is sectional drawing which shows schematically the basic composition of other suitable one Embodiment of the image forming apparatus of this invention. It is sectional drawing which shows schematically the basic composition of other suitable one Embodiment of the image forming apparatus of this invention. 1 is a cross-sectional view schematically showing a preferred embodiment of a cartridge of the present invention.

Explanation of symbols

200 Image forming apparatus 201 Image forming apparatus 207 Electrophotographic photoreceptor 208 Charging apparatus 209 Power supply 210 Exposure apparatus 211 Developing apparatus 212 Transfer apparatus 212a Primary transfer member 212b Secondary transfer member 213 Cleaning apparatus 214 Static eliminator 215 Fixing apparatus 216 Mounting rail 217 Opening part 218 for static elimination exposure Opening part 220 for exposure Image forming apparatus 300 Cartridge 400 Housings 401a, 401b, 401c, 401d Electrophotographic photosensitive members 402a, 402b, 402c, 402d Charging roll 403 Laser light source (exposure apparatus)
404a, 404b, 404c, 404d Developing devices 405a, 405b, 405c, 405d Toner cartridge 406 Drive roll 407 Tension roll 408 Backup roll 409 Intermediate transfer belt 410a, 410b, 410c, 410d Primary transfer roll 411 Tray (transfer medium tray)
412 Transfer roll 413 Secondary transfer roll 414 Fixing rolls 415a, 415b, 415c, 415d Cleaning blade 416 Cleaning blade 500 Transfer medium (image output medium)

Claims (17)

A step of aggregating the resin particles in a dispersion containing at least a resin particle dispersion and an aggregating agent to obtain aggregated particles;
A method for producing a toner for developing an electrostatic charge image comprising a step of heating and aggregating the aggregated particles,
The resin particles of the resin particle dispersion have a volume average particle diameter of 50 nm or more and 1,000 nm or less,
The resin particle dispersion has a ratio of hydrophilic monomer units having at least one polar group selected from the group consisting of an acidic polar group, a basic polar group, and a neutral polar group in a range of 10 mol% to 90 mol%. And a polymer having a weight average molecular weight of 10,000 or more, and
A method for producing a toner for developing an electrostatic charge image, wherein the solid resin contains a polycondensation resin in an amount of 50% by weight or more.   The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein the content of the polymer is 5% by weight or more based on the total amount of the polycondensation resin.   The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein the polycondensation resin is a polycondensation resin obtained by polycondensation at 150 ° C. or less using sulfur acid as a catalyst.   The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 3, wherein an average particle diameter of the resin particles is 50 nm or more and 300 nm or less.   5. The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein the ratio of the hydrophilic monomer is 30 mol% or more and 70 mol% or less.   The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 5, wherein the polymer has a weight average molecular weight of 10,000 or more and 200,000 or less.   7. The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein the content of the polymer is 5 wt% or more and 15 wt% or less with respect to the total amount of the polycondensation resin.   The method for producing a toner for developing an electrostatic image according to claim 1, wherein the polar group is an acidic polar group.   The hydrophilic monomer is (i) an α, β-ethylenically unsaturated compound having a carboxyl group or (ii) an α, β-ethylenically unsaturated compound having a sulfone group. A method for producing a toner for developing an electrostatic charge image according to any one of the above.   The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 9, wherein the polycondensation resin has a weight average molecular weight of 1,000 or more and 60,000 or less.   The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 10, wherein the polycondensable resin is a polycondensable resin obtained by using a dicarboxylic acid and a diol.   An electrostatic charge image developing toner produced by the production method according to claim 1.   In the resin particle dispersion, the ratio of hydrophilic monomer units having at least one polar group selected from the group consisting of acidic polar groups, basic polar groups, and neutral polar groups is 10 mol% or more and 90 mol%. The toner for developing an electrostatic charge image according to any one of claims 1 to 11, which is produced by mixing a polymer having a weight average molecular weight of 10,000 or more, an aqueous medium, and a polycondensation resin. Manufacturing method.   An electrostatic image developer comprising the electrostatic image developing toner according to claim 12. An image carrier,
Developer supplying means for supplying a developer containing the electrostatic charge image developing toner according to claim 12 on the image carrier;
And a charging unit that charges the developer supplied by the developer supply unit. Developing means for developing the electrostatic latent image formed on the surface of the image carrier with the developer containing toner according to claim 12 to form a toner image;
And at least one selected from the group consisting of an image carrier, a charging unit for charging the surface of the image carrier, and a cleaning unit for removing the developer remaining on the surface of the image carrier. Characteristic cartridge. An image carrier,
Charging means for charging the surface of the image carrier;
Latent image forming means for forming a latent image on the surface of the image carrier;
Developing means for developing the latent image with a developer containing the toner according to claim 12 to form a toner image;
Transfer means for transferring the toner image to a recording medium;
An image forming apparatus comprising: fixing means for fixing the toner image to a recording medium.

Images