JP2008152072A - Electrostatic charge image developing toner, method for producing the same, electrostatic charge image developer, and image forming method and image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrostatic charge image developing toner using a binding resin derived from biomass resources, in which the defect in sharpness caused by the generation of filming hardly occurs, to provide an electrostatic charge image developer using the electrostatic charge image developing toner, and to provide an image forming method and an image forming apparatus using them. <P>SOLUTION: The electrostatic charge image developing toner at least contains chemically modified starch as a binding resin, and a method is provided for producing the same. The electrostatic charge image developer using the electrostatic charge image developing toner is provided, and the image forming method and the image forming apparatus using the same are also provided. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a toner for developing an electrostatic charge image, and more particularly to a toner for developing an electrostatic charge image used for developing an electrostatic latent image formed by an electrophotographic method or an electrostatic recording method. The present invention relates to a method, an electrostatic charge image developer, an image forming method, and an image forming apparatus.

In recent years, biomass resources have been actively used from the viewpoints of environmental issues such as global warming, oil depletion, waste problems, and the concept of building a sustainable recycling society.
For example, polylactic acid, which is known as a biomass resource raw material resin, has attracted attention as a biomass material produced from cereals and the like without using any petroleum, and is used in applications such as agricultural sheets and household garbage bags.
In the field of toners, for example, toners using polylactic acid resins as described in Patent Documents 1 to 9 have been proposed.

JP-A-9-281746 JP 2001-22123 A JP 2001-166537 A JP 2002-327047 A JP 2003-12909 A JP 2003-248339 A JP 2004-93829 A JP 2004-151315 A JP 2006-91278 A

  An object of the present invention is to provide a toner for developing an electrostatic charge image using a binder resin derived from biomass resources, which hardly causes image quality defects due to filming, and a method for producing the same. Another object of the present invention is to provide an electrostatic image developer using the electrostatic image developing toner. Another object of the present invention is to provide an image forming method and an image forming apparatus using them.

The above-described problems of the present invention have been solved by means described in the following <1> to <5>.
<1> An electrostatic image developing toner comprising at least a chemically modified starch as a binder resin,
<2> A step of obtaining chemically modified starch particles by particleizing chemically modified starch in an aqueous medium, and aggregating and aggregating these particles in a dispersion containing at least the chemically modified starch particles, colorant particles and release agent particles. A method for producing a toner for developing an electrostatic charge image according to the above <1>, comprising a step of obtaining particles, and a step of heating and coalescing the aggregated particles;
<3> An electrostatic charge image developer comprising the electrostatic charge image developing toner according to <1> and a carrier,
<4> A latent image forming step of forming an electrostatic latent image on the surface of the latent image holding member, and developing the electrostatic latent image formed on the surface of the latent image holding member with a developer containing toner to form a toner image. A development step, a transfer step of transferring the toner image formed on the surface of the latent image holding member to the surface of the transfer target, and a fixing step of thermally fixing the toner image transferred to the surface of the transfer target. An image forming method using the electrostatic image developing toner according to <1> or the electrostatic image developer according to <3> as an agent,
<5> a latent image holding member, a charging unit that charges the latent image holding member, an exposure unit that exposes the charged latent image holding member to form an electrostatic latent image on the latent image holding member, A developing unit that develops the electrostatic latent image with a developer to form a toner image; and a transfer unit that transfers the toner image from the latent image holding member to a recording material. An image forming apparatus using the electrostatic image developing toner according to 1> or the electrostatic image developer according to <3>.

  According to the present invention, it is possible to provide a toner for developing an electrostatic charge image using a binder resin derived from biomass resources and a method for producing the same, which hardly cause image quality defects due to filming. Further, according to the present invention, it is possible to provide an electrostatic image developer using the electrostatic image developing toner. Furthermore, according to the present invention, an image forming method and an image forming apparatus using these can be provided.

  Hereinafter, the present invention will be described in detail.

(Electrostatic image developing toner)
The electrostatic image developing toner of the present invention (hereinafter also simply referred to as “toner”) contains at least a chemically modified starch (hereinafter also referred to as “chemically modified starch resin”) as a binder resin. To do.
In the present invention, “starch” refers to amylose, which is a linear molecule in which D-glucose is bonded by an α (1 → 4) type glycoside bond, and D-glucose is an α (1 → 4) type glycoside bond and α ( Amylopectin, which is a branched molecule linked by a glycoside bond of type 1 → 6), or a mixture of amylose and amylopectin in an arbitrary ratio.
The “chemically modified starch” in the present invention is a starch in which a hydroxyl group present in starch is substituted with a modifying group by esterification or etherification reaction, and also reduces hydrophobicity and hydrogen bonding of starch molecules, and is a substituent. It is preferred that the starch molecular chain is broken by the steric effect of the above to give the starch thermoplasticity.

Chemically modified starch can be easily controlled for melting point, softening point, hydrophilicity / hydrophobicity by modifying starch skeleton with vinyl ester, lactone, etc. Becomes larger. In addition, because it is easy to make submicron by melt emulsification, solvent phase inversion emulsification, etc., it is an environmentally friendly material that can be designed as a material for emulsion polymerization aggregation toner (EA toner) that meets the required toner properties Useful as (eco-material).
As described above, there are a large number of documents describing polylactic acid applied toners. However, the problem of large structural dependence of charge and mechanical properties on humidity can be greatly improved by chemically modified starch having a high degree of freedom.

  The raw material starch (starch) for chemically modified starch includes corn starch, high amylose corn starch, ground starch unmodified starch such as wheat starch, potato starch, tapioca starch and other unmodified starch, and low starch esterification / Preferred examples include modified starch obtained by etherification, oxidation, acid treatment, and dextrinization. Moreover, the raw material starch of chemically modified starch can be used individually or in combination.

In the chemically modified starch, the modifying group introduced into the raw material starch is a group in which the hydroxyl group of the glucose structure in the starch is modified. When the group in which the hydroxyl group (—OH) is modified is defined as —OR, —OR is —OCOR ¹ , —O (CO—R ² —O) _n —H and —O (CO—R ² —O) _n —COR ¹ are preferable.
R ¹ is a monovalent hydrocarbon group which may have a substituent, preferably a monovalent hydrocarbon group having 1 to 17 carbon atoms, and having 1 to 6 carbon atoms. More preferably, it is a monovalent hydrocarbon group.
R ² is a divalent hydrocarbon group which may have a substituent, preferably a divalent hydrocarbon group having 1 to 17 carbon atoms, and having 1 to 6 carbon atoms. The divalent hydrocarbon group is more preferable.
A preferable amount of the modifying group is 0.01 or more and 5.0 or less, more preferably 0.02 or more and 3.0 or less as an average number of substituents per structure of glucose. These substitution degrees are evaluated using FT-IR or elemental analysis.
Examples of the monovalent or divalent hydrocarbon group include an alkyl group, an alkylene group, an alkenyl group, an alkenylene group, an alkynyl group, an alkynylene group, a cycloalkyl group, a cycloalkylene group, an aryl group, an arylene group, and 2 Examples of the monovalent or divalent group combined above can be exemplified.
Examples of the substituent that R ¹ or R ² may have include a hydroxyl group, a halogen atom, an acyl group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an oxy group, an alkyl group, an amino group, an imino group, A phenyl group, a phosphino group, a thioxy group, etc. are mentioned.

As the chemically modified starch, esterified starch, hydroxycarboxylic acid esterified starch, lactone modified starch, hydroxycarboxylic acid esterified starch, and lactone modified esterified starch, acylated starch, acrylic ester modified starch are preferable. More preferred are esterified starch, lactone-modified starch, and lactone-modified esterified starch.
Among them, the most useful in chemically modified starch is lactone-modified esterified starch.
The method of synthesizing lactone-modified esterified starch uses an esterification / lactone-modifying catalyst in a non-aqueous organic solvent using vinyl ester, acid anhydride and / or acid halide as esterification reagent and lactone as lactone-modification reagent. The starch is reacted and polymerized with starch, and esterification and lactone modification reactions are carried out simultaneously or sequentially. In this case, there may be an independent polymer derived from the reagent not bound to starch.
Moreover, when performing esterification and lactone modification | denaturation sequentially, whichever may be preceded, it is free, such as esterification after lactone modification and lactone modification after esterification. Furthermore, commercially available esterified starch, lactone-modified starch, or lactone-modified esterified starch can be lactone-modified or esterified using vinyl ester, acid anhydride, acid halide, and lactone as reagents, respectively.
The hydroxycarboxylic acid or lactone used for hydroxycarboxylic acid oxidation or lactone modification is a hydroxycarboxylic acid having 3 to 18 carbon atoms, a 3- to 8-membered lactone, or an oligomer or derivative thereof. Is preferred, and a 3- to 8-membered lactone is more preferred.
Specific examples of the hydroxycarboxylic acid include lactic acid and lactide.
A specific example of lactone is preferably ε-caprolactone.

The vinyl ester as the esterification reagent is preferably a vinyl ester excluding a vinyl group (that is, an acyl group moiety bonded to a hydroxyl group as a modifying group) having 2 to 18 carbon atoms. More preferably, it is 2 or more and 7 or less. Moreover, vinyl ester can be used individually or in combination of two or more. When the carbon number of the vinyl ester is 2 or more and 18 or less, the reaction efficiency is excellent. Moreover, when the number of carbon atoms of the vinyl ester is 2 or more and 7 or less, it is preferable because a high level can be maintained in terms of reaction efficiency.
Specifically, the following can be exemplified, but among them, vinyl acetate and vinyl propionate are particularly preferable from the viewpoint of high reaction efficiency.
Saturated aliphatic carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl palmitate, vinyl caproate, vinyl caprylate, vinyl butanoate, vinyl laurate, vinyl stearate, or vinyl oleate, vinyl crotonate And unsaturated aliphatic carboxylic acid vinyl esters such as vinyl acrylate and vinyl isocrotonate, and vinyl esters of aromatic carboxylic acids such as vinyl benzoate and vinyl p-methylbenzoate.

  The acid anhydride / acid halide is preferably an acid anhydride / acid halide of an organic acid having 2 to 18 carbon atoms, and an acid anhydride / acid halide of an organic acid having 2 to 8 carbon atoms. It is more preferable that For example, acetic anhydride / propionic anhydride / butyric anhydride or a halide of acetic acid / propionic acid / butyric acid can be suitably used.

Another method of synthesis in a non-aqueous organic solvent is when a vinyl ester is used as the organic solvent.
In this case, a special solvent recovery step in the purification step is not necessary. In addition, in the esterification reaction using the conventional vinyl ester, such a reaction form is not employ | adopted. Further, in this embodiment, the effect of preventing the reduction in molecular weight and the reaction efficiency of vinyl ester are improved, but the vinyl ester is limited to a liquid form including the time of heating and melting. Preferred examples of the vinyl ester that can be used for this purpose include the above vinyl esters.
Another method of the non-aqueous organic solvent is a case where a vinyl ester as a reaction reagent cannot be used as the non-aqueous organic solvent or is not used. Regardless of the type of esterification reaction reagent, it has the advantage that the reaction solution concentration and reaction rate can be easily adjusted. Compared to the use of vinyl ester as a non-aqueous organic solvent, the reaction uniformity is high. It requires separation and recovery of the chemical reaction reagent and the solvent. As the non-aqueous organic solvent in this case, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), a starch-soluble polar solvent such as pyridine, or starch insoluble such as ethyl acetate / acetone, Polar solvents that are soluble in vinyl ester, acid anhydride, acid halide, and formed esterified starch (but not reactive with vinyl ester, acid anhydride, and acid halide) can be used alone or in combination. .
In particular, starch-soluble nonaqueous organic solvents such as DMSO, DMF, and pyridine are preferable from the viewpoints of reaction efficiency and reaction uniformity.

Examples of esterification catalysts include hydroxides, mineral salts, organic acid salts, or carbonates or metal alkoxides belonging to any of alkali metals, alkaline earth metals, and amphoteric metals, phase transfer catalysts, and Bronsted. It is preferable to use either an acid catalyst or an amino compound selected from each group. Specifically, the following compounds can be preferably exemplified.
Alkali metal hydroxides such as caustic soda, caustic potash and lithium hydroxide; alkali metal organic acid salts such as sodium acetate and sodium propionate; alkaline earth metal hydroxides such as barium hydroxide and calcium hydroxide; calcium acetate and propion Alkaline earth metal organic acid salts such as calcium oxide, barium p-toluenesulfonate; mineral salts such as sodium phosphate, calcium phosphate, sodium bisulfite, potassium sulfate, sodium aluminate, potassium zincate, aluminum hydroxide, water Acidic salts and hydroxides of amphoteric metals such as zinc oxide, carbonates such as sodium carbonate, sodium bicarbonate, potassium bicarbonate, sodium alcoholates such as sodium methylate and sodium ethylate, trimethylated salts such as aluminum isopropylate and aluminum ethylate Alkoxy aluminum compounds, aluminum Alkoxy-series aluminum chelate compounds such as ethyl acetate diisopropylate, dimethylaminopyridine, amino compounds such as diethylaminoethyl acetate.
Quaternary ammonium compounds such as N-trimethyl-N-propylammonium chloride and N-tetraethylammonium chloride can also be used.
Also, a Bronsted acid catalyst can be used. For example, dodecylbenzenesulfonic acid, isopropylbenzenesulfonic acid, p-toluenesulfonic acid, alkylbenzenesulfonic acid such as camphorsulfonic acid, alkylsulfonic acid, alkyldisulfonic acid, alkylphenolsulfonic acid, alkylnaphthalenesulfonic acid, alkyltetralinsulfonic acid, Alkyl allyl sulfonic acid, petroleum sulfonic acid, alkyl benzimidazole sulfonic acid, higher alcohol ether sulfonic acid, alkyl diphenyl sulfonic acid, monobutyl phenyl phenol sulfuric acid, dibutyl phenyl phenol sulfuric acid, higher fatty acid sulfuric acid ester such as dodecyl sulfuric acid, higher alcohol sulfuric acid ester , Higher alcohol ether sulfate, higher fatty acid amide alkylol sulfate, higher fatty acid amide alkylated sulfate ester Tellurium, naphthenyl alcohol sulfuric acid, sulfated fat, sulfosuccinate, various fatty acids, sulfonated higher fatty acids, higher alkyl phosphates, resin acids, resin acid alcohol sulfuric acid, naphthenic acid, niobic acid, and all their salt compounds However, it is not limited to this.
Moreover, these catalysts may have a functional group in the structure. A plurality of these catalysts may be combined as necessary.
As the Bronsted acid catalyst, sulfur acid can be more preferably mentioned, and dodecylbenzenesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and camphor sulfonic acid can be more preferred. .

The glass transition point or melting point of the chemically modified starch resin is preferably 50 ° C. or higher and 80 ° C. or lower, more preferably 50 ° C. or higher and 70 ° C. or lower, and further preferably 50 ° C. or higher and 65 ° C. or lower.
The chemically modified starch resin that can be used in the present invention has a melt index (MI value) measured at 135 ° C. of preferably 4 g or more and 40 g or less, and more preferably 15 g or more and 35 g or less. When the melt index (MI value) is 4 g or more and 40 g or less, when the toner containing the chemically modified starch resin is fixed, it receives heat from the heating body and becomes appropriate viscoelasticity to form a smooth image. The glossiness of can be improved.
The melt index (MI value) can be measured by a manual cutting method using an apparatus described in JIS K7210. The measurement conditions are: measurement temperature: 135 ° C., load: 1.2 kg, sample filling amount: 5 g to 10 g. In addition, a measured value is converted into a 10 minute value.

In order to use the resin obtained here as a binder resin to form a toner by a dissolution suspension method or an emulsion polymerization aggregation method, a conventionally known production method can be used.
These chemically modified starches can be used alone as a binder resin, or can be used by mixing resins by conventional emulsion polymerization.

Examples of other resins that can be used as the binder resin in the toner of the present invention include polycondensation resins and addition polymerization resins described below.
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 thereof, and is preferably a polyester.
Among these, it is preferable to use a polycondensable monomer. Examples of the polycondensable monomer used for polycondensation include polycarboxylic acids and polyols.
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 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.
Among these, in the present invention, it is preferable to use a dicarboxylic acid as the polyvalent carboxylic acid and a diol as the polyol.

  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.

  In the present invention, among the above polyvalent carboxylic acids, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decamethylenedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,12-dodecane It is preferable to use dicarboxylic acid, terephthalic acid, trimellitic acid, pyromellitic acid or the like. Since these polyvalent carboxylic acids are hardly soluble or insoluble in water, the ester synthesis reaction proceeds in a suspension in which the polyvalent carboxylic acid is dispersed in water, which is preferable.

  A polyol used as a monomer used for polycondensation 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.

In the polyester production method, it is preferable to use divalent polyols such as 1,8-octanediol, 1,10-decanediol, and 1,12-dodecanediol among the above-mentioned polyols.
Since these polyols are hardly soluble or insoluble in water, the ester synthesis reaction proceeds in a suspension in which the polyol is dispersed in water, which is preferable.

A crystalline resin or an amorphous 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, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid (1,10-decane dicarboxylic acid), 1,12-dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid, etc. Aliphatic dicarboxylic acid, sebacic acid, maleic 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, acid anhydrides, lower esters or acid salts thereof Mention may be made of things. 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, polytetramethylene glycol, bisphenol A, bisphenol Z, bisphenol C Bisphenol E, bisphenol F, bisphenol P, bisphenol S, bisphenol Z, biphenol, naphthalene diol, adamantanediol, adamantane dimethanol, hydrogenated bisphenol A and the like can also be mentioned. 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.
The bisphenols preferably have at least one alkylene oxide group. Examples of the alkylene oxide group include, but are not limited to, an ethylene oxide group, a propylene oxide group, and butylene oxide. Preferred are ethylene oxide and propylene oxide, and the number of moles added is preferably 1 to 3. When it is within this range, the viscoelasticity and glass transition temperature of the produced polyester can be appropriately controlled for use as a toner.

  Examples of such a crystalline polycondensable resin include 1,9-nonanediol and 1,10-decanedicarboxylic acid, polyester obtained by reacting cyclohexanediol and adipic acid, 1,9-nonanediol, Polyester obtained by reacting sebacic acid, polyester obtained by reacting 1,6-hexanediol and sebacic acid, polyester obtained by reacting ethylene glycol and succinic acid, ethylene glycol and sebacic acid Mention may be made of polyesters obtained by reaction, polyesters obtained by reacting 1,4-butanediol and 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, Chlorophthalic acid, nitrophthalic acid, malonic acid, mesaconic acid, p-carboxyphenylacetic acid, p-phenylenediacetic acid, m-phenylenediglycolic acid, p-phenylenediglycolic acid, o-phenylenediglycolic 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 or its lower ester, diphenylacetic acid, cyclohexanedicarboxylic acid, or 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 polyvalent carboxylic acid and polyol may be used alone or in combination of two or more, each of which is used alone or in combination of two or more to produce one type of polyester resin. May be used. Moreover, when using hydroxycarboxylic acid in order to produce 1 type of polycondensable 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.

  Non-crystalline polyester resins include bisphenol A propylene oxide 2-mole adduct (added 1 mol each on both ends) and dimethyl terephthalate polycondensate, bisphenol A ethylene oxide 2-mole adduct (both ends) And a polycondensate of cyclohexanedicarboxylic acid, a 2-condensate of ethylene oxide of bisphenol A (one mole added to both ends) and a polycondensate of phenylenediacetic acid are particularly preferred.

  In the present invention, when a crystalline polyester is used as the polyester 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 polyester resin, the glass transition point (Tg) of the amorphous polyester is preferably 40 ° C. or higher and 100 ° C. or lower, more preferably 50 ° C. or higher and 80 ° C. or lower. It is. When the Tg is within the above range, the cohesive force of the binder resin itself in the high temperature range is good, so that hot offset hardly occurs at the time of fixing, and further sufficient melting is obtained, and the minimum fixing temperature is increased. It is difficult to do.
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 polyester resin, the weight average molecular weight is 1,000 or more and 60,000 by molecular weight measurement by gel permeation chromatography (GPC) method of tetrahydrofuran (THF) soluble content. 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 polyester resin, the weight average molecular weight is preferably 1,000 or more and 60,000 or less, and 3,000 or more, as measured by molecular weight measurement by THF GPC. It is more preferably 50,000 or less, and further preferably 5,000 or more and 40,000 or less.
It is preferable for the weight average molecular weight to be in the above range since offset resistance is improved.
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., and a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample is obtained. Can be used to calculate the molecular weight.

In the present invention, both the non-crystalline polyester resin and the crystalline polyester resin can be used as the polyester resin, but it is preferable that at least the non-crystalline polyester resin is included. It is preferable to use an amorphous polyester as the polyester resin because the viscoelasticity of the toner can be controlled.
Moreover, although a polyester resin can also be used individually by 1 type, it is also preferable to use combining two or more.

  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, as a polycondensation step for producing a polyester resin, a polymerization reaction between the polycarboxylic acid and polyol, which are the aforementioned polycondensable monomers, and an oligomer and / or prepolymer prepared in advance. Can also be included. 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 binder resin is 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 thereof, a graft polymer, It may have a partly branched or crosslinked structure.

In the present invention, the polyester resin is obtained by polycondensation of a polycondensation component, preferably a polycarboxylic acid and a polyol, more preferably a dicarboxylic acid and a diol, which are polycondensable monomers. It is preferable that it is the polyester resin obtained by this. In this invention, it is preferable that the above-mentioned alkylbenzenesulfonic acid is included as a polycondensation catalyst.
In the present invention, when alkylbenzenesulfonic acid is used as the polycondensation catalyst, the amount of alkylbenzenesulfonic acid used is preferably 0.001 wt% or more and 1.0 wt% or less based on the total weight of the polycondensation component, More preferably, the content is 0.01% by weight or more and 0.5% by weight or less. More preferably, it is 0.1 wt% or more and 0.5 wt% or less. If the amount of alkylbenzene sulfonic acid used is within the above range, the stability of the particles in the aqueous medium is maintained, the polycondensation reactivity is higher, and the chargeability of the toner can be appropriately maintained. preferable. Moreover, by making the usage-amount of alkylbenzenesulfonic acid 0.001 weight% or more and 1.0 weight% or less, the obtained polyester resin is neutralized with a metal salt, and alkylbenzenesulfonic acid is changed to alkylbenzenesulfonic acid metal salt. In this case, the alkylbenzenesulfonic acid metal salt content that can be suitably used in the present invention can be obtained, which is preferable.

Other polycondensation catalysts will be described below.
In the present invention, sulfur acid can be used as the polycondensation catalyst.
The sulfur acid is a Bronsted acid containing sulfur, 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 alkylsulfonic acid, arylsulfonic acid, and salts thereof, alkylsulfuric 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 organic sulfur acids having a surface active effect include alkyl sulfonic acids, alkyl disulfonic acids, alkyl phenol sulfonic acids, alkyl naphthalene sulfonic acids, alkyl tetralin sulfonic acids, alkyl allyl sulfonic acids, petroleum sulfonic acids, alkyl benzimidazole sulfonic acids, 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, sulfated fat, sulfo Examples include acid esters, resin acid alcohol sulfuric acid, and all salt compounds thereof, 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. More preferably. Specific examples include camphor sulfonic acid, monobutylphenylphenol sulfate, dibutylphenylphenol sulfate, dodecyl sulfate, and naphthenyl alcohol sulfate. These sulfur acids may have some functional group in the structure.

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.
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.

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.

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 desirable 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, steapsin and the like. Among these, it is desirable to use lipases derived from microorganisms of the genus Pseudomonas, Candida, and Aspergillus.

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. Examples of the organic base compound include ammonium hydroxides such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and examples of the nitrogen-containing basic compound include 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 0.001% by weight to 40% by weight and more preferably 0.01% by weight to 20% by weight 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 is sufficiently high, while reverse reaction and side reaction can be suppressed.

Next, the polycondensation reaction will be described.
In the present invention, the binder resin can be obtained even if the polycondensation reaction is performed at a temperature lower than the conventional reaction temperature. The reaction temperature is preferably 70 ° C or higher and 150 ° C or lower. More preferably, it is 75 ° C. or higher and 130 ° C. or lower.
When the reaction temperature is 70 ° C. or higher, the solubility of the polycondensation component (preferably polycondensable monomer) and the reactivity due to the decrease in the catalytic activity do not occur, and the increase in molecular weight is suppressed. This is preferable because there is nothing. 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 it does not cause coloring of the resin or decomposition of the generated polycondensable resin.

Producing polycondensable resins at a low temperature of 150 ° C or less while avoiding conventional high energy consumption manufacturing methods is extremely important in reducing the total manufacturing energy of resins and toners. It is. Conventionally, a polycondensation reaction has been performed at a high temperature exceeding 200 ° C. However, 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, alkylbenzene sulfonic acid is used as a catalyst. It is preferred to use. 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.
Alkylbenzenesulfonic acid has a catalytic activity that decreases with increasing temperature at a temperature of 160 ° C. or higher. However, since the reaction proceeds by the nucleophilic addition of the catalytic acid, the polymerization temperature is 70 ° C. or higher and 150 ° C. The catalyst activity is high in a low temperature range of not higher than ° C., and can be suitably used for a polycondensation reaction at 150 ° C. or lower.

Also, in terms of mechanical strength, a resin produced using alkylbenzenesulfonic acid as a catalyst is superior to a resin produced using a metal catalyst. When alkylbenzene sulfonic acid is used as a catalyst, the polymerization proceeds by the nucleophilic addition reaction mechanism, so the possibility of contamination is low. On the other hand, a resin produced using a Sn-based or Ti-based metal catalyst is a reaction mechanism in which acid and alcohol are collected on the surface of the catalyst metal, so that the catalyst metal is easily taken into the resin. When a conductive metal is taken into the resin, the resin charge is likely to leak. When such a resin is used for the toner, especially when printing under high temperature and high humidity, it is easy to leak the charge, so that the charge amount is low and the background fogging that the toner is scattered to the non-image portion is likely to occur. May cause problems. The incorporated metal tends to cause minute structural defects in the resin.
However, when alkylbenzene sulfonic acid is used as a catalyst, it is preferable because such metal elements can be prevented from being mixed in, and charge leakage hardly occurs even under high temperature and high humidity, and background fogging hardly occurs. Also in this respect, it is preferable to use alkylbenzenesulfonic acid rather than using a metal catalyst.

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

In the case of bulk polymerization, the reaction can be performed under atmospheric pressure. However, for the purpose of increasing the molecular weight of the resulting polyester molecule and controlling the molecular weight distribution, use general conditions such as reduced pressure and nitrogen flow. Can do.
In the present invention, when polycondensation component (preferably polycondensable monomer) is polycondensed by bulk polymerization method, a method of polycondensation by adding alkylbenzene sulfonic acid to the polycondensation component can be exemplified. Moreover, after polycondensing the polycondensation component (preferably polycondensable monomer) preferably in the presence of a catalyst, a method of adding alkylbenzenesulfonic acid and / or metal alkylbenzenesulfonic acid can be exemplified. Among these, it is preferable to perform polycondensation in the presence of alkylbenzenesulfonic acid. A resin particle dispersion for an electrostatic charge image developing toner that can be suitably used for an electrostatic charge image developing toner excellent in particle size distribution can be efficiently produced at low energy, which is preferable.

  In the present invention, a polyester resin in which the area ratio of the weight average molecular weight of 500 or less in gel permeation chromatography measurement is 5% or more and 10% or less of the total area can be obtained, for example, by changing the polymerization conditions during the polymerization. it can. More specifically, there are exemplified methods such as raising the polymerization temperature during the polymerization, adding a catalyst during the polymerization, and adding a polymerizable monomer that does not easily proceed from the middle.

A resin particle dispersion can be obtained by emulsifying and dispersing the polycondensable resin obtained as described above in an aqueous medium.
The polycondensable resin is preferably emulsified and dispersed by adding a base (basic compound). The base is preferably dissolved in water and added to the polycondensable resin with stirring. The base is not particularly limited, and known bases such as sodium hydroxide, potassium hydroxide, ammonia, and various amines can be used. As described above, it is preferable to use a base having a pKb of 4 or less. Examples thereof include sodium hydroxide, potassium hydroxide, lithium hydroxide, barium hydroxide, and diethylamine. Among these, sodium hydroxide and potassium hydroxide are preferable.
The addition amount of the base can be appropriately selected within a range in which good dispersion in the aqueous medium is performed, but is preferably 0.001 mol / L or more and 1 mol / L or less, preferably 0.01 mol / L or more and 0.0. More preferably, it is 8 mol / L or less.
That is, it is preferable to polycondensate the polycondensable monomer in the presence of alkylbenzene sulfonic acid, and then emulsify by adding a base to prepare a resin particle dispersion. After the polycondensation in the presence of the catalyst, an alkylbenzene sulfonic acid and / or an alkyl benzene sulfonic acid metal salt are mixed, and further, a base is added and emulsified to prepare a resin particle dispersion.

In the present invention, the cumulative volume average particle diameter (median diameter) D ₅₀ of the resin particles in the polycondensation resin particle dispersion is preferably 80 nm or more and 500 nm or less, and more preferably 80 nm or more and 300 nm or less. It is preferable to set the median diameter within the above range because a toner having a narrower particle size distribution can be obtained.
The cumulative volume average particle diameter (median diameter) can be measured with a dynamic light scattering measuring instrument (for example, LA920 manufactured by Horiba, Ltd.).

The particle size distribution of the resin particles in the polycondensation resin particle dispersion is preferably narrow. A narrow particle size distribution means that more uniform resin particles can be obtained. As a result, the particle size distribution of the electrostatic charge image developing toner produced using the polycondensation resin particle dispersion becomes narrow. Therefore, it is preferable.
The particle size distribution is represented by GSDv, and the GSDv of the resin particles in the polycondensation resin particle dispersion is preferably from 1.00 to 1.30, more preferably from 1.00 to 1.25. More preferably, it is 0.000 or more and 1.20 or less. When the GSDv is in the above range, the particle size distribution of the obtained toner is narrow and the charge amount uniformity is excellent.

The GSDv of the resin particles in the polycondensation resin particle dispersion can be measured using the above-mentioned dynamic light scattering method measuring instrument (for example, LA920 manufactured by Horiba, Ltd.).
Particles with a cumulative distribution of 16% from the small-diameter side of the particle size range (channel) divided based on the particle size distribution measured by the dynamic light scattering measuring instrument (LA920) described above. The diameter is defined as volume D ₁₆ , the particle size at 50% cumulative is defined as cumulative volume average particle size D ₅₀ , and the particle size at 84% cumulative is defined as volume D ₈₄ . Using these, the volume average particle size distribution index (GSDv) is calculated as (D ₈₄ / D ₁₆ ) ^1/2 .

Moreover, addition polymerization resins are also useful as other binder resins that can be used in the present invention. Examples of the addition polymerizable monomer for producing the addition polymerization resin include a radical polymerizable monomer, a cationic polymerizable monomer, and an anion polymerizable monomer, and the radical polymerizable monomer. Is preferable, and an ethylenically unsaturated monomer is more preferable. Preferred examples of the radical polymerization resin include styrene resins and (meth) acrylic resins, particularly styrene- (meth) acrylic copolymer resins.
Examples of the styrene- (meth) acrylic copolymer resin include 60 to 90 parts by weight of an aromatic monomer (styrene monomer) having an ethylenically unsaturated group, ethylenically unsaturated carboxylic acid ester. A monomer mixture comprising 10 parts by weight or more and 40 parts by weight or less of a monomer ((meth) acrylic acid ester monomer) and 1 part by weight or more and 3 parts by weight or less of an ethylenically unsaturated acid monomer is polymerized. A latex obtained by dispersing and stabilizing the copolymer obtained with a surfactant can be preferably used. The glass transition point of the copolymer is preferably 50 ° C. or higher and 70 ° C. or lower.

The polymerizable monomers that can be suitably used in the production of other binder resins that can be used in the present invention will be described below.
Examples of the styrene monomer include styrene, vinyl naphthalene, alkyl having an alkyl chain such as 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene. Examples include halogen-substituted styrene such as substituted styrene, 2-chlorostyrene, 3-chlorostyrene, and 4-chlorostyrene, and fluorine-substituted styrene such as 4-fluorostyrene and 2,5-difluorostyrene. Styrene is preferred as the styrene monomer.

Examples of (meth) acrylic acid ester monomers include n-methyl (meth) acrylate, n-ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, ( N-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, n-decyl (meth) acrylate, n (meth) acrylate -Dodecyl, n-lauryl (meth) acrylate, n-tetradecyl (meth) acrylate, n-hexadecyl (meth) acrylate, n-octadecyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acryl Isobutyl acid, t-butyl (meth) acrylate, isopentyl (meth) acrylate, amyl (meth) acrylate, (meth) acrylic acid Pentyl, isohexyl (meth) acrylate, isoheptyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, biphenyl (meth) acrylate, (meth) acryl Diphenylethyl acid, t-butylphenyl (meth) acrylate, terphenyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, (meth Examples thereof include diethylaminoethyl acrylate, methoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, β-carboxyethyl (meth) acrylate, (meth) acrylonitrile, (meth) acrylamide and the like. As the (meth) acrylic acid ester monomer, n-butyl acrylate is preferable.
Here, the notation of “(meth) acrylic acid ester” is an abbreviated notation indicating that both structures of methacrylic acid ester and acrylic acid ester can be taken.

The ethylenically unsaturated acid monomer is an ethylenically unsaturated monomer containing an acidic group such as a carboxyl group, a sulfonic acid group, or an acid anhydride.
When the carboxyl group is contained in the styrene resin, (meth) acrylic acid ester resin and styrene- (meth) acrylic acid ester copolymer resin, it is copolymerized with a polymerizable monomer having a carboxyl group. Obtainable.

  Specific examples of such carboxyl group-containing polymerizable monomers include acrylic acid, aconitic acid, atropic acid, allylmalonic acid, angelic acid, isocrotonic acid, itaconic acid, 10-undecenoic acid, elaidic acid, erucic acid, olein. Acid, ortho-carboxycinnamic acid, crotonic acid, chloroacrylic acid, chloroisocrotonic acid, chlorocrotonic acid, chlorofumaric acid, chloromaleic acid, cinnamic acid, cyclohexenedicarboxylic acid, citraconic acid, hydroxycinnamic acid, dihydroxysilicic acid Cinnamic acid, tiglic acid, nitrocinnamic acid, vinyl acetic acid, phenyl cinnamic acid, 4-phenyl-3-butenoic acid, ferulic acid, fumaric acid, brassic acid, 2- (2-furyl) acrylic acid, bromocinnamic acid, Bromofumaric acid, bromomaleic acid, benzylidene malonic acid, benzo Examples include acrylic acid, 4-pentenoic acid, maleic acid, mesaconic acid, methacrylic acid, methylcinnamic acid, methoxycinnamic acid, etc., and acrylic acid, methacrylic acid, maleic acid, cinnamic acid due to the ease of polymer formation reaction, etc. Acid, fumaric acid and the like are preferable, and acrylic acid is more preferable.

The weight average molecular weight of the addition polymerization resin used as the binder resin is preferably 5,000 or more and 50,000 or less, and more preferably 8,000 or more and 40,000 or less.
When the molecular weight is within the above range, it is preferable because the powder characteristics of the toner at normal temperature can be kept good and offset of the fixed image can be prevented at high temperature fixing.

The glass transition point of the addition polymerization resin is preferably 45 ° C. or higher and 65 ° C. or lower, and more preferably 50 ° C. or higher and 65 ° C. or lower.
When the glass transition point is within the above range, it is preferable because deterioration of the powder characteristics due to the release agent can be prevented, and bleeding of the release agent during fixing can be facilitated.

In the present invention, a polycondensation or polymerization reaction between a monomer and a prepolymer of a monomer prepared in advance can also be included. The prepolymer is not limited as long as it is a polymer that can be melted or uniformly mixed with the monomer.
Furthermore, the binder resin that can be used in the present invention is a homopolymer of the above-described monomer, a copolymer obtained by combining two or more monomers including the above-described monomer, or a mixture or graft thereof. The polymer may have a partially branched or crosslinked structure.

  In the present invention, when the polycondensable monomer and the radical polymerizable monomer are polymerized, the radical polymerizable monomer is previously mixed with the polycondensation monomer at the time of polymerization in an aqueous medium. It is also possible to obtain hybrid particles of these polymers through polycondensation and radical polymerization.

  Furthermore, in the polycondensation reaction, low molecular weight polymers can be formed in advance by bulk polymerization, solution polymerization, etc., and these can be emulsified or dispersed in an aqueous medium, and further polycondensation can be performed to reach the final molecular weight. In this case as well, the radical polymerizable monomer can be emulsified and dispersed after mixing with the low molecular weight polycondensation resin or with the low molecular weight polycondensation resin and the polycondensation monomer.

  In the polycondensation and / or polymerization in the aqueous medium according to the present invention, the acid value of the resin affects the final molecular weight and the polymerization rate. Therefore, a polycondensation of a radically polymerizable vinyl monomer having low solubility in the aqueous medium is performed. In addition, the polycondensable monomer is prepared in advance into a low molecular weight body (or medium molecular weight body) that does not hinder emulsification and dispersion, and after adjusting the acid value to a lower state, You may use the method of obtaining the final high molecular weight body in an aqueous medium, or the combined use of these both methods, ie, the method of using together the prepolymerization method of a radically polymerizable monomer and a polycondensable monomer.

  Similarly, in the polymerization in the present invention, a plurality of polymerizations can be carried out simultaneously or sequentially. For example, as a monomer component for polymerization, a radical polymerizable monomer is mixed with a polycondensation monomer, and radical polymerization and polycondensation reaction are performed simultaneously, or radical polymerization is performed after the polycondensation reaction, or On the contrary, the polycondensation reaction can be carried out after radical polymerization. At this time, the polycondensation catalyst can be added to either the aqueous medium or the monomer component. Further, regarding the radical polymerizable catalyst (radical polymerization initiator), the monomer mixture (oil phase) or the aqueous medium. It can be added to any of them. Further, it is possible to add a radical polymerization initiator before or during polycondensation or after polycondensation.

  In the polycondensation or polymerization in the aqueous medium in the present invention, general polymerization such as monomer components before polycondensation and fixing aids such as a colorant and a release agent, other charging aids, chain extenders, etc. Components necessary for reaction and toner production may be mixed in advance.

Other binder resins that can be used in the present invention can use a chain transfer agent during the polymerization.
Although there is no restriction | limiting in particular as a chain transfer agent, The compound which has a thiol component can be used preferably. Specifically, alkyl mercaptans such as hexyl mercaptan, heptyl mercaptan, octyl mercaptan, nonyl mercaptan, decyl mercaptan, dodecyl mercaptan can be preferably exemplified. Use of a chain transfer agent is preferable because the molecular weight distribution in the binder resin is narrowed, so that the storage stability of the toner at high temperatures is improved.

If necessary, a crosslinking agent may be added to the addition polymerization resin to form a crosslinked resin. A typical cross-linking agent is a polyfunctional monomer having two or more ethylenically unsaturated groups in the molecule.
Specific examples of such crosslinking agents include aromatic polyvinyl compounds such as divinylbenzene and divinylnaphthalene; divinyl phthalate, divinyl isophthalate, divinyl terephthalate, divinyl homophthalate, divinyl trimesate / trivinyl, naphthalene dicarboxylate Polyvinyl esters of aromatic polyvalent carboxylic acids such as divinyl acid and diphenyl biphenyl carboxylate; Divinyl esters of nitrogen-containing aromatic compounds such as divinyl pyridine dicarboxylate; Vinyl pyromutate, vinyl furan carboxylate, pyrrole-2- Vinyl esters of unsaturated heterocyclic compounds such as vinyl carboxylate and vinyl thiophenecarboxylate; butanediol methacrylate, hexanediol acrylate, octanediol methacrylate, decanediol acrylate (Meth) acrylic acid esters of linear polyhydric alcohols such as dodecanediol methacrylate; branches such as neopentylglycol dimethacrylate and 2-hydroxy-1,3-diacryloxypropane; ) Acrylic acid esters; Polyethylene glycol di (meth) acrylate, Polypropylene polyethylene glycol di (meth) acrylates; Divinyl succinate, divinyl fumarate, vinyl / divinyl maleate, divinyl diglycolate, vinyl / divinyl itaconate, acetone Divinyl dicarboxylate, divinyl glutarate, divinyl 3,3′-thiodipropionate, trans-aconite divinyl / trivinyl, divinyl adipate, divinyl pimelate, divinyl suberate, dibi azelate Le, sebacate, divinyl dodecanedioate divinyl, the polyvinyl esters of polycarboxylic acids such as oxalic acid divinyl and the like.

In the present invention, these crosslinking agents may be used alone or in combination of two or more. Among the above crosslinking agents, the crosslinking agent in the present invention includes (meth) acrylic acid esters of linear polyhydric alcohols such as butanediol methacrylate, hexanediol acrylate, octanediol methacrylate, decanediol acrylate, and dodecanediol methacrylate. Branched chains such as neopentyl glycol dimethacrylate and 2-hydroxy-1,3-diacryloxypropane, (meth) acrylic acid esters of substituted polyhydric alcohols; polyethylene glycol di (meth) acrylate, polypropylene polyethylene glycol di ( It is preferable to use (meth) acrylates.
The content of the crosslinking agent is preferably in the range of 0.05% by weight or more and 5% by weight or less, more preferably in the range of 0.1% by weight or more and 1.0% by weight or less of the total amount of the polymerizable monomers.

Among the other binder resins that can be used in the toner of the present invention, those that can be produced by radical polymerization of a polymerizable monomer can be polymerized using a radical polymerization initiator.
There is no restriction | limiting in particular as an initiator for radical polymerization used here. Specifically, hydrogen peroxide, acetyl peroxide, cumyl peroxide, tert-butyl peroxide, propionyl peroxide, benzoyl peroxide, chlorobenzoyl peroxide, dichlorobenzoyl peroxide, bromomethylbenzoyl peroxide, lauroyl peroxide Ammonium persulfate, sodium persulfate, potassium persulfate, diisopropyl peroxycarbonate, tetralin hydroperoxide, 1-phenyl-2-methylpropyl-1-hydroperoxide, tert-butyl hydroperoxide pertriphenyl acetate, tert-butyl formate, Peroxides such as tert-butyl peracetate, tert-butyl perbenzoate, tert-butyl perphenylacetate, tert-butyl permethoxyacetate, tert-butyl perN- (3-toluyl) carbamate, 2,2 '-Azobispro Bread, 2,2′-dichloro-2,2′-azobispropane, 1,1′-azo (methylethyl) diacetate, 2,2′-azobis (2-amidinopropane) hydrochloride, 2,2 ′ -Azobis (2-amidinopropane) nitrate, 2,2'-azobisisobutane, 2,2'-azobisisobutyramide, 2,2'-azobisisobutyronitrile, 2,2'-azobis-2- Methyl methylpropionate, 2,2′-dichloro-2,2′-azobisbutane, 2,2′-azobis-2-methylbutyronitrile, dimethyl 2,2′-azobisisobutyrate, 1,1′-azobis (1 -Methylbutyronitrile-3-sodium sulfonate), 2- (4-methylphenylazo) -2-methylmalonodinitrile, 4,4'-azobis-4-cyanovaleric acid, 3,5-dihydroxymethylphenyl Zo-2-methylmalonodinitrile, 2- (4-bromophenylazo) -2-allylmalonodinitrile, 2,2'-azobis-2-methylvaleronitrile, 4,4'-azobis-4-cyanoyoshi Dimethyl herbate, 2,2′-azobis-2,4-dimethylvaleronitrile, 1,1′-azobiscyclohexanenitrile, 2,2′-azobis-2-propylbutyronitrile, 1,1′-azobis-1 -Chlorophenylethane, 1,1'-azobis-1-cyclohexanecarbonitrile, 1,1'-azobis-1-cycloheptanenitrile, 1,1'-azobis-1-phenylethane, 1,1'-azobiscumene, 4-Nitrophenylazobenzylcyanoacetate, phenylazodiphenylmethane, phenylazotriphenylmethane, 4-nitrophenylazotrif Nylmethane, 1,1′-azobis-1,2-diphenylethane, poly (bisphenol A-4,4′-azobis-4-cyanopentanoate), poly (tetraethylene glycol-2,2′-azobisiso) Azo compounds such as butyrate), 1,4-bis (pentaethylene) -2-tetrazene, 1,4-dimethoxycarbonyl-1,4-diphenyl-2-tetrazene and the like.

<Release agent>
Further, in the method for producing a toner for developing an electrostatic charge image of the present invention, if necessary, waxes may be used as a release agent used for this type of toner. Can be added either at the time of emulsification dispersion or at the time of aggregation. The release agent is preferably added as an aqueous dispersion or the like, and the amount of the release agent added is preferably 1 part by weight or more and 25 parts by weight with respect to 100 parts by weight of the total amount of resin such as chemically modified starch. It is preferably added so as to be 5 parts by weight or less, more preferably 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 wax having a long chain aliphatic group, hydrogenated castor oil, plant wax such as carnauba wax, ketone having a long chain alkyl group such as distearyl ketone, alkyl group, silicone wax having a phenyl group, Higher fatty acids such as stearic acid, 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 esters thereof, paraffinic wax, Fischer-Tropsch 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 setting 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 appropriately set the release property and the temperature at which offset occurs during fixing. 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 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 dispersion method of these colorants, any method such as a general dispersion method such as a rotary shear type 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 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 that 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.

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, and 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.

(Method for producing toner for developing electrostatic image)
The method for producing a toner for developing an electrostatic charge image of the present invention comprises a step of obtaining chemically modified starch particles by granulating chemically modified starch in an aqueous medium (hereinafter also referred to as “starch particle producing step”), and the chemically modified starch particles. A step of aggregating these particles in a dispersion containing at least colorant particles and release agent particles to obtain aggregated particles (hereinafter also referred to as “aggregation step”), and heating the aggregated particles for fusion It is preferable to include a step (hereinafter also referred to as “fusion step”).

As the starch particle production process, chemically modified starch can be granulated in an aqueous medium by a known apparatus or method, but it is preferably granulated in an aqueous medium by a melt emulsification method or a phase inversion emulsification method. It is more preferable to form particles in an aqueous medium by a phase inversion emulsification method.
Examples of the aqueous medium that can be used in the present invention include water such as distilled water and ion exchange water, and alcohols such as ethanol and methanol. Among these, ethanol and water are preferable, and water such as distilled water and ion-exchanged water is particularly preferable. These may be used individually by 1 type and may use 2 or more types together.
The aqueous medium may contain a water-miscible organic solvent. Examples of the water-miscible organic solvent include acetone and acetic acid.

As the agglomeration step, for example, a chemically modified starch particle dispersion is mixed with a colorant particle dispersion, a release agent particle dispersion or the like as necessary, and a flocculant is added to cause heteroaggregation. Aggregated particles having a toner diameter are formed, and then heated to a temperature equal to or higher than the glass transition point or the melting point of the resin particles to fuse and coalesce the aggregated particles, and further, washed and dried. In the aggregating step in the present invention, it is important to produce agglomerated particles using at least chemically modified starch particles, but it is preferable to further use colorant particles and release agent particles, using other resin particles. Also good.
The toner shape is preferably from irregular to spherical.
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 preferable in terms of aggregation control and toner charging characteristics.

  In the aggregation step, the chemically modified starch particle dispersion is mixed with the release agent particle dispersion and, if necessary, the colorant particle dispersion and the like. Aggregated particles can be formed. The medium of each dispersion is preferably an aqueous medium.

  In addition, after forming the first aggregated particles by aggregation in this way, the above-mentioned resin particle dispersion or another resin particle dispersion may be further added to form the second shell layer on the surface of the first particles. Is possible. In this example, the colorant dispersion is prepared separately. However, when the colorant is mixed in advance with the polycondensable 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, a surfactant can be used for emulsion polymerization of resin, dispersion of pigment, dispersion of resin particles, dispersion of release agent, aggregation, stabilization of aggregated particles, and the like.
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 fusing step, the binder resin in the aggregated particles melts at a temperature equal to or higher than its melting point or glass transition point, and the aggregated particles change from an indeterminate shape to a more spherical shape. Thereafter, the aggregate is separated from the aqueous medium, and washed and dried as necessary to form toner particles.

  After completion of the aggregation step and the fusion step, a desired toner may be obtained through an arbitrary washing step, solid-liquid separation step, and drying step. In the washing step, it is preferable to sufficiently perform substitution washing with ion-exchanged water from the viewpoint of chargeability. The solid-liquid separation step is not particularly limited, but suction filtration, pressure filtration, and the like are preferably used from the viewpoint of productivity. Further, although the drying process is not particularly limited, freeze drying, flash jet drying, fluidized drying, vibration fluidized drying and the like are preferably used from the viewpoint of productivity.

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 preferably added so as to be 5 parts by weight or more and 15 parts by weight or less.
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. In the case of polymerization in water, it is a component that contains at least a polycondensation component and is emulsified and dispersed in an aqueous medium.

  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.

(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 usually 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.

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

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

(Image forming device)
The image forming apparatus of the present invention is an image forming apparatus using the electrostatic charge image developing toner of the present invention or the electrostatic charge image developer of the present invention, and includes an electrostatic latent image holding body and the electrostatic latent image holding body. Charging means for charging the surface of the substrate, exposure means for forming an electrostatic latent image on the surface of the holder charged by the charging means according to image information, and the electrostatic latent image The image forming apparatus includes a developing unit that forms a toner image by developing with a developer, and a transfer unit that transfers the toner image from the holder to a recording material, and fixes the toner image on the fixing base as necessary. Fixing means. In the transfer unit, the transfer may be performed twice or more using an intermediate transfer member.

As the electrostatic latent image holding member and each of the above-described means, the configurations described in the respective steps of the image forming method can be preferably used.
Any of the above-described means can be a known means in the image forming apparatus. Further, the image forming apparatus used in the present invention may include means and devices other than the above-described configuration. Further, the image forming apparatus used in the present invention may simultaneously perform a plurality of the above-described means.

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

(Chemically modified starch resin synthesis example 1)
<Preparation of chemically modified starch resin particle aqueous dispersion (A)>
High amylose corn starch 100 parts by weight Sodium bicarbonate 20 parts by weight Dimethyl sulfoxide (DMSO) 800 parts by weight A mixture of the above composition was heated to 80 ° C. in a stainless steel reactor, and 120 parts by weight of ε-caprolactone was added while stirring. Further, 0.5 parts by weight of sodium methylate (CH ₃ ONa) was added and maintained under reduced pressure for 3 hours, and then the pressure was returned to atmospheric pressure. In this state, 40 parts by weight of vinyl acetate was added, and 80 ° C. for 3 hours. And the reaction was terminated. Thereafter, the above solution was put into 2,000 parts by weight of ion-exchanged water, and the precipitated chemically modified starch resin (Resin 1) was filtered and collected.
The melting point was 58 ° C. as measured with a differential scanning calorimeter (DSC).
The MI value was 20 g.

Resin 1 was pulverized with a sample mill to form powder, and then 100 parts by weight of this resin powder was put into a table kneader (manufactured by Irie Shokai Co., Ltd.), 100 parts by weight of methyl ethyl ketone was added, and the mixture was stirred up to 60 ° C. Heated and melt mixed.
After adding 1 part by weight of sodium dodecylbenzenesulfonate to this resin solution and further mixing, when 400 parts by weight of ion-exchanged water was gradually added while stirring, the mixture phase-inverted to obtain an emulsion. . While maintaining the temperature at 60 ° C., the inside of the table kneader was decompressed to remove the solvent, thereby obtaining an aqueous dispersion of resin 1 (chemically modified starch resin particle aqueous dispersion (A)). The solid content concentration was 20% by weight, and the median diameter measured by LA920 was 210 nm.

(Chemically modified starch resin synthesis example 2)
<Preparation of chemically modified starch resin particle aqueous dispersion (B)>
High amylose corn starch 100 parts by weight Sodium bicarbonate 20 parts by weight Dimethyl sulfoxide (DMSO) 800 parts by weight A mixture of the above composition was heated to 80 ° C. in a stainless steel reactor, and 100 parts by weight of L-lactide was added while stirring. Further, 0.3 parts by weight of aluminum ethylate (Al (OC ₂ H ₅ ) ₃ ) was added and kept under reduced pressure for 3 hours. Then, the pressure was returned to atmospheric pressure, and in this state, 100 parts by weight of vinyl acetate was added. The temperature was maintained at 80 ° C. for 3 hours to complete the reaction. Thereafter, the above solution was put into 2,000 parts by weight of ion-exchanged water, and the precipitated chemically modified starch resin (Resin 2) was filtered and collected.
The melting point was 52 ° C. as measured with a differential scanning calorimeter (DSC).
The MI value was 29 g.

Resin 2 is pulverized with a sample mill to form powder, and then 100 parts by weight of this resin powder is put into a table kneader (manufactured by Irie Shokai Co., Ltd.), 100 parts by weight of methyl ethyl ketone is added, and the mixture is stirred to 60 ° C. Heated and melt mixed.
To this resin solution, 0.5 parts by weight of sodium dodecylbenzenesulfonate is added, and after further mixing, when 400 parts by weight of ion-exchanged water is gradually added while stirring, the mixture phase inverts to obtain an emulsion. It was. While maintaining the temperature at 60 ° C., the inside of the table kneader was decompressed to remove the solvent, whereby an aqueous dispersion of resin 2 (chemically modified starch resin particle water acid solution (B)) was obtained. The solid content concentration was 20% by weight, and the median diameter measured by LA920 was 250 nm.

(Chemically modified starch resin synthesis example 3)
<Preparation of chemically modified starch resin particle aqueous dispersion (C)>
High amylose corn starch 100 parts by weight Sodium bicarbonate 20 parts by weight Dimethyl sulfoxide (DMSO) 800 parts by weight A mixture of the above composition was heated to 80 ° C. in a stainless steel reactor, and 100 parts by weight of L-lactide was added while stirring. Further, 0.3 part by weight of aluminum ethylate (Al (OC ₂ H ₅ ) ₃ ) was added and held under reduced pressure for 3 hours. Then, the pressure was returned to atmospheric pressure, and in this state, 50 parts by weight of vinyl acetate and ε -120 parts by weight of caprolactone was added and maintained at 80 ° C for 3 hours to complete the reaction. Thereafter, the above solution was put into 2,000 parts by weight of ion-exchanged water, and the precipitated chemically modified starch resin (Resin 3) was filtered and collected.
The melting point was 54 ° C. as measured with a differential scanning calorimeter (DSC).
The MI value was 25 g.

Resin 3 is pulverized with a sample mill to form powder, and then 100 parts by weight of this resin powder is put into a table kneader (manufactured by Irie Shokai Co., Ltd.), 100 parts by weight of methyl ethyl ketone is added, and the mixture is stirred to 60 ° C Heated and melt mixed.
To this resin solution, 1.0 part by weight of sodium dodecylbenzenesulfonate is added, and after further mixing, when 400 parts by weight of ion-exchanged water is gradually added while stirring, the mixture phase inverts to obtain an emulsion. It was. While maintaining the temperature at 60 ° C., the inside of the table kneader was decompressed to remove the solvent, whereby an aqueous dispersion of resin 3 (chemically modified starch resin particle aqueous dispersion (C)) was obtained. The solid content concentration was 20% by weight, and the median diameter measured by LA920 was 180 nm.

(Resin synthesis example 4)
<Preparation of crystalline resin particle aqueous dispersion (D)>
0.36 parts by weight of dodecylbenzenesulfonic acid 59 parts by weight of 1,6-hexanediol 101 parts by weight of sebacic acid The contents became a viscous melt when kept at 80 ° C. for 6 hours while degassing.
The melting point of this resin was 69 ° C. and the weight average molecular weight was 8,100.

Similarly, an aqueous solution for neutralization in which 5 parts by weight of 1N NaOH solution was dissolved in 628 parts by weight of ion-exchanged water heated to 90 ° C. was put into a flask and emulsified with a homogenizer (IKA Corporation, Ultra Tarrax) for 3 minutes. The flask was cooled with room temperature water.
As a result, a crystalline resin particle dispersion (D) having a center diameter of resin particles of 220 nm and a solid content of 20% was obtained.

(Chemically modified starch resin synthesis example 5)
<Preparation of chemically modified starch resin particle aqueous dispersion (E)>
Azuki starch 100 parts by weight Sodium bicarbonate 20 parts by weight Dimethyl sulfoxide (DMSO) 800 parts by weight A mixture of the above composition was heated to 80 ° C. in a stainless steel reactor, 100 parts by weight of L-lactide was added with stirring, and aluminum was further added. After adding 0.3 parts by weight of ethylate (Al (OC ₂ H ₅ ) ₃ ) and maintaining under reduced pressure for 3 hours, the pressure is returned to atmospheric pressure, and 100 parts by weight of vinyl acetate is added in that state. The time was maintained at 80 ° C. to complete the reaction. Thereafter, the above solution was put into 2,000 parts by weight of ion-exchanged water, and the precipitated chemically modified starch resin (Resin 5) was filtered and collected.
The melting point was 50 ° C. as measured by a differential scanning calorimeter (DSC).
The MI value was 33 g.

The resin 5 is pulverized with a sample mill to form a powder, and then 100 parts by weight of the resin powder is put into a table kneader (manufactured by Irie Shokai Co., Ltd.), 100 parts by weight of methyl ethyl ketone is added, and the mixture is stirred to 60 ° C. Heated and melt mixed.
To this resin solution, 0.5 parts by weight of sodium dodecylbenzenesulfonate is added, and after further mixing, when 400 parts by weight of ion-exchanged water is gradually added while stirring, the mixture phase inverts to obtain an emulsion. It was. While maintaining the temperature at 60 ° C., the inside of the table kneader was depressurized to remove the solvent, whereby an aqueous dispersion of resin 5 (chemically modified starch resin particle water acid solution (D)) was obtained. The solid content concentration was 20% by weight, and the median diameter measured by LA920 was 230 nm.

(Starch resin particle dispersion comparative example 1)
<Preparation of chemically modified starch resin particle aqueous dispersion (F)>
High amylose corn starch is pulverized in a sample mill to form powder, and then 100 parts by weight of this resin powder is put into a table kneader (manufactured by Irie Shokai Co., Ltd.), 100 parts by weight of methyl ethyl ketone is added, and the mixture is stirred for 60 Heated to 0 ° C. and melt mixed.
To this resin solution, 0.5 parts by weight of sodium dodecylbenzenesulfonate was added, and after further mixing, 400 parts by weight of ion-exchanged water was gradually added while stirring, but an emulsion could be obtained until the end. First, the production of the resin particle dispersion was abandoned.

<Preparation of Colorant Particle Dispersion (P1)>
Cyan pigment (manufactured by Dainichi Seika Co., Ltd., copper phthalocyanine CI Pigment Blue 15: 3) 50 parts by weight Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK) 5 parts by weight Ion-exchanged water 200 parts by weight The above components were mixed and dissolved, dispersed for 5 minutes with a homogenizer (IKA, Ultra Tarrax) for 5 minutes and an ultrasonic bath, and a Sian colorant particle dispersion (P1) having a center diameter of 190 nm and a solid content of 21.5% was obtained. Obtained.

<Preparation of Colorant Particle Dispersion (P2)>
It was prepared in the same manner as the colorant particle dispersion (P1) except that a magenta pigment (Dai Nippon Ink Chemical Co., Ltd., CI Pigment Red 122) was used instead of the cyan pigment, and the center diameter was 165 nm and the solid content was 21. A 5% magenta colorant particle dispersion (P2) was obtained.

<Preparation of release agent particle dispersion (W1)>
Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen R) 2 parts by weight Ion-exchanged water 800 parts by weight Carnauba wax 200 parts by weight were mixed, heated to 100 ° C. and melted, and then homogenizer (IKA) Manufactured by Ultra Turrax) and emulsified at 100 ° C. using a gorin homogenizer.
As a result, a release agent particle dispersion (W1) having a particle central diameter of 170 nm, a melting point of 83 ° C., and a solid content of 20% was obtained.

(Toner Example 1)
<Preparation of toner particles>
-Chemically modified starch resin particle water dispersion (A) 210 parts by weight (42 parts by weight of resin)
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 8.0 parts by weight)
-Polyaluminum chloride 0.15 parts by weight-Ion-exchanged water 300 parts by weight According to the above composition, the above ingredients were thoroughly mixed and dispersed in a round stainless steel flask with a homogenizer (IKA, Ultra Turrax T50). Heat to 42 ° C while stirring the flask in a heating oil bath and hold at 42 ° C for 60 minutes, then slowly add 84 parts by weight of chemically modified starch resin particle aqueous dispersion (A) (21 parts by weight of resin). Was stirred.
Thereafter, the pH in the system was adjusted to 6.0 with a 0.5 mol / liter aqueous sodium hydroxide solution, and then heated to 95 ° C. while stirring was continued. During the period up to 95 ° C., an aqueous sodium hydroxide solution was added dropwise so that the pH did not become 5.0 or less. Hold at 95 ° C. for 3 hours.
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. And it re-dispersed in 3 liters of ion-exchanged 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 vacuum drying for 12 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 4.8 μm, and the volume average particle size distribution index GSDv was 1.22. The shape factor SF1 of the toner particles obtained from the shape observation by Luzex was 131 potato shapes.

2 parts by weight of hydrophobic silica (manufactured by Cabot, TS720) was added to 50 parts by weight of the toner particles, and mixed with a sample mill to obtain an externally added toner.
Then, using a ferrite carrier having an average particle diameter of 50 μm coated with 1% of polymethyl methacrylate (manufactured by Soken Chemical Co., Ltd.), the externally added toner is weighed so that the toner concentration becomes 5%. A developer was prepared by stirring and mixing for a minute.

<Evaluation of toner>
Using the above developer, Fuji Xerox's DocuCentreColor f450 modified machine was subjected to a continuous print test of 50,000 sheets in a laboratory environment of 30 ° C. and 80% RH. The image quality defects such as dots and streaks were not seen, and good image quality was maintained until the end. (Continuous test maintenance: ○)

(Toner Example 2)
The chemically modified starch resin particle aqueous dispersion (A) is changed to the chemically modified starch resin particle aqueous dispersion (B), the polyaluminum chloride is replaced with aluminum sulfate, and the pH when the temperature is raised to 95 ° C. is set to 7.0. A toner was prepared and evaluated in the same manner as in Toner Example 1.
Although a continuous print test of 50,000 sheets was performed in a laboratory environment of 30 ° C. and 80% RH, no image defects such as streaks and streaks due to toner filming on the photoreceptor were observed, and good image quality at the initial stage of generation was observed. Maintained until the end. (Continuous test maintenance: ○)

(Toner Example 3)
Toner except that the chemically modified starch resin particle aqueous dispersion (A) was changed to the chemically modified starch resin particle aqueous dispersion (C) and the colorant particle dispersion (P1) was changed to the colorant particle dispersion (P2). A toner was prepared and evaluated in the same manner as in Example 1.
Although a continuous print test of 50,000 sheets was performed in a laboratory environment of 30 ° C. and 80% RH, no image defects such as streaks and streaks due to toner filming on the photoreceptor were observed, and good image quality at the initial stage of generation was observed. Maintained until the end. (Continuous test maintenance: ○)

(Toner Example 4)
Half of the chemically modified starch resin particle aqueous dispersion (A) added first is changed to the chemically modified starch resin particle aqueous dispersion (C), and the other half is chemically modified starch resin particle aqueous dispersion (D). ), The colorant particle dispersion (P1) is changed to the colorant particle dispersion (P2), and the resin particle dispersion added in the middle of aggregation is changed to a chemically modified starch resin particle aqueous dispersion (D). The toner was prepared and evaluated in the same manner as in Toner Example 1.
Although a continuous print test of 50,000 sheets was performed in a laboratory environment of 30 ° C. and 80% RH, no image defects such as streaks and streaks due to toner filming on the photoreceptor were observed, and good image quality at the initial stage of generation was observed. Maintained until the end. (Continuous test maintenance: ○)

(Toner Example 5)
The half amount of the chemically modified starch resin particle aqueous dispersion (A) to be added first is changed to the chemically modified starch resin particle aqueous dispersion (E), and the other half amount is chemically modified starch resin particle aqueous dispersion (D). ), The colorant particle dispersion (P1) is changed to the colorant particle dispersion (P2), and the resin particle dispersion added in the middle of the aggregation is a chemically modified starch resin particle aqueous dispersion (D). Were produced and evaluated in the same manner as in Toner Example 1.
Although a continuous print test of 50,000 sheets was performed in a laboratory environment of 30 ° C. and 80% RH, no image defects such as streaks and streaks due to toner filming on the photoreceptor were observed, and good image quality at the initial stage of generation was observed. Maintained until the end. (Continuous test maintenance: ○)

Claims (5)

An electrostatic charge image developing toner comprising at least a chemically modified starch as a binder resin. A step of granulating chemically modified starch in an aqueous medium to obtain chemically modified starch particles;
Aggregating these particles in a dispersion containing at least the chemically modified starch particles, colorant particles and release agent particles to obtain aggregated particles; and
The method for producing a toner for developing an electrostatic charge image according to claim 1, comprising a step of fusing the aggregated particles by heating.   An electrostatic charge image developer comprising the electrostatic charge image developing toner according to claim 1 and a carrier. A latent image forming step for forming an electrostatic latent image on the surface of the latent image holding member;
A developing step of forming a toner image by developing the electrostatic latent image formed on the surface of the latent image holding member with a developer containing toner;
A transfer step of transferring the toner image formed on the surface of the latent image holding member to the surface of the transfer target; and
Including a fixing step of thermally fixing the toner image transferred to the surface of the transfer target,
An image forming method using the electrostatic image developing toner according to claim 1 or the electrostatic image developer according to claim 3 as the developer. A latent image carrier,
Charging means for charging the latent image carrier;
Exposure means for exposing the charged latent image carrier to form an electrostatic latent image on the latent image carrier;
Developing means for developing the electrostatic latent image with a developer to form a toner image;
Transfer means for transferring the toner image from the latent image holding member to a recording material;
An image forming apparatus using the electrostatic image developing toner according to claim 1 or the electrostatic image developer according to claim 3 as the developer.