JP5091012B2 - Toner for electrostatic image development - Google Patents

Description

  The present invention relates to an electrostatic charge image developing toner used for electrophotography, electrostatic recording, electrostatic printing, and the like, and a method for producing a negative charge image developing toner.

As a method for producing an electrostatic image developing toner having a uniform particle size and excellent image quality, an emulsion aggregation method in which the particle size and shape are intentionally controlled has been proposed (Patent Document 1). In addition, it has been conventionally known that a polyester resin is used as a binder for the purpose of improving the low-temperature fixing performance of the electrostatic image developing toner, and a polyester resin having a high acid value is contained for the purpose of further improving the fixing property. A method has been proposed (Patent Document 2, etc.).
Japanese Patent Laid-Open No. 63-282275 JP 2004-294735 A

In recent years, demand for fixing at a lower temperature has increased due to a demand for reducing the environmental load, and a toner for developing an electrostatic charge image having both blocking resistance and low-temperature fixability has been demanded. However, even the electrostatic image toner obtained by the emulsion aggregation method containing the polyester resin of Patent Document 2 does not reach a satisfactory level.
An object of the present invention is to provide an electrostatic image developing toner having a uniform particle size and further excellent low-temperature fixability and blocking resistance.

  As a result of intensive studies to solve the above problems, the present inventors have reached the present invention. That is, the present invention relates to an electrostatic charge image developing toner including at least a toner resin composition and a toner particle containing a colorant, wherein the toner particle contains at least a resin particle having a volume average particle diameter of 1 μm or less in water. Particles having a volume average particle size of 3 to 10 μm formed from a step including a step of dispersing the resin particles and a step of aggregating the resin particles, and the non-linear polyester (A1) and, if necessary, a linear polyester in the toner resin composition The polyester resin (A) containing (A2) and the ester group-containing additive (B) are contained, the number average molecular weight of the tetrahydrofuran (THF) -soluble component of (B) is 1000 or less, and the glass of (B) A toner for developing electrostatic images, wherein the transition temperature [Tg] (° C.) and the flow softening point [Tm] (° C.) satisfy the relationship [Tm] − [Tg] ≦ 38 (° C.) -; And a method for producing a toner for developing an electrostatic charge image comprising toner particles containing at least a resin composition for a toner and a colorant, wherein at least a resin particle having a volume average particle diameter of 1 μm or less is dispersed in water. A step of aggregating the resin particles, and a step of fusing the agglomerated resin particles to obtain toner particles having a volume average particle size of 3 to 10 μm, and if necessary, the non-linear polyester (A1) and the toner resin composition in the toner resin composition Containing the polyester resin (A) containing the linear polyester (A2) and the ester group-containing additive (B), the tetrahydrofuran (THF) -soluble number average molecular weight of (B) is 1000 or less, (B) The glass transition temperature [Tg] (° C.) and the flow softening point [Tm] (° C.) satisfy the relationship [Tm] − [Tg] ≦ 38 (° C.). A method for producing an image toner.

  By using the toner for developing an electrostatic charge image of the present invention obtained by the production method of the present invention, a toner having a uniform particle size and excellent low-temperature fixability can be obtained, and the toner has good blocking resistance.

The present invention is described in detail below.
The toner for developing an electrostatic charge image of the present invention comprises a resin used to form toner particles containing at least a resin composition for a toner and a colorant [polyester containing a non-linear polyester (A1) and, if necessary, a linear polyester (A2). The resin (A) and the ester group-containing additive (B)] are dispersed in water at 1 μm or less, the aggregated particle diameter is adjusted by agglomerating the water-dispersed resin, and the aggregated particles are melted and fused. , Obtained by granulating.
The volume average particle size is determined by laser type particle size distribution measuring apparatus LA-920 (manufactured by Horiba, Ltd.), Multisizer III (manufactured by Coulter), ELS-800 (manufactured by Otsuka Electronics Co., Ltd.) using a laser Doppler method as an optical system, and the like. Can be measured. If there is a difference in the measured value of the particle diameter between the measuring devices, the measured value by ELS-800 is adopted.

  The polyester resin (A) used for the toner resin composition in the toner for developing an electrostatic charge image of the present invention comprises, for example, one or more types of polyol component (x) and one or more types of polycarboxylic acid component (y). Polyol component (x) obtained by polycondensation includes diol (x1) and / or polyol (x2) having 3 to 8 or more valences. Examples of the polycarboxylic acid component (y) include a dicarboxylic acid (y1) and / or a polycarboxylic acid (y2) having 3 to 6 or more valences.

Examples of the diol (x1) include alkylene glycols having 2 to 36 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, and 1,6-hexane. Diol etc.); C4-C36 alkylene ether glycol (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol etc.); C6-C36 alicyclic diol ( 1,
4-cyclohexanedimethanol and hydrogenated bisphenol A, etc.); (poly) oxyalkylene of the above alicyclic diol (the number of carbon atoms of the alkylene group is 2 to 4, the same applies to the following polyoxyalkylene groups) ether [oxyalkylene units (hereinafter 1-30 of AO units); and polyoxyalkylene ethers (AO units) of dihydric phenols [monocyclic dihydric phenols (for example, hydroquinone) and bisphenols (such as bisphenol A, bisphenol F, and bisphenol S)]. 2-30) and the like.

  Among these (X1), preferred are alkylene glycols having 2 to 12 carbon atoms, polyoxyalkylene ethers of bisphenols (number of AO units 2 to 30), and combinations thereof. More preferred are polyoxyalkylene ethers of bisphenols (particularly bisphenol A) (2 and / or 3 carbon atoms of the alkylene group, 2 to 8 AO units), alkylene glycols of 2 to 12 carbon atoms (particularly ethylene glycol). , 1,2-propylene glycol), and combinations thereof (weight ratio 100: 0 to 20:80).

  Examples of the trivalent to octavalent or higher polyol (x2) include trihydric to octavalent or higher aliphatic polyhydric alcohols having 3 to 36 carbon atoms (alkane polyol and intramolecular or intermolecular dehydrates such as Glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, polyglycerin, and dipentaerythritol; sugars and derivatives thereof such as sucrose and methylglucoside); (poly) oxyalkylenes of the above aliphatic polyhydric alcohols Ether (number of AO units 1-30); polyoxyalkylene ether of trisphenols (trisphenol PA, etc.) (number of AO units 2-30); novolak resin (phenol novolak, cresol novolac, etc.) average degree of polymerization 3 60) Etc. (the number 2 to 30 of AO units) polyoxyalkylene ether.

  Among these (X2), preferred are 3 to 8 or higher aliphatic polyhydric alcohols and polyoxyalkylene ethers of novolac resins (number of AO units: 2 to 30), and particularly preferred are novolak resins. It is a polyoxyalkylene ether (number of AO units 2 to 30).

  Examples of the dicarboxylic acid (y1) include alkane dicarboxylic acids having 4 to 36 carbon atoms (for example, succinic acid, adipic acid, and sebacic acid); alicyclic dicarboxylic acids having 6 to 40 carbon atoms [for example, dimer acid (dimerized linoleic acid) )]; Alkene dicarboxylic acid having 4 to 36 carbon atoms (alkenyl succinic acid such as dodecenyl succinic acid, maleic acid, fumaric acid, citraconic acid, and mesaconic acid); aromatic dicarboxylic acid having 8 to 36 carbon atoms (phthalic acid, Isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, etc.); and ester-forming derivatives thereof (for example, anhydrides, lower alkyl (carbon number 1-4) esters (methyl esters, ethyl esters, isopropyl esters, etc.), The same applies to ester-forming derivatives]; Among these (y1), preferred are alkene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms and ester-forming derivatives thereof.

Examples of the tricarboxylic acid having a valence of 3 to 6 or more (y2) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic, pyromellitic acid, etc.), and aliphatics having 6 to 36 carbon atoms (alicyclic rings). And polycarboxylic acids (including hexanetricarboxylic acid and decanetricarboxylic acid), and ester-forming derivatives thereof.
Of these (y2), trimellitic acid and pyromellitic acid, and ester-forming derivatives thereof are preferred.

The polyester resin (A) in the present invention can be produced in the same manner as in an ordinary polyester production method. For example, the reaction can be carried out in an inert gas (nitrogen gas or the like) atmosphere at a reaction temperature of preferably 150 to 280 ° C, more preferably 160 to 250 ° C, particularly preferably 170 to 235 ° C. The reaction time is preferably 30 minutes or longer, particularly 2 to 40 hours from the viewpoint of reliably performing the polycondensation reaction. It is also effective to reduce the pressure in order to improve the reaction rate at the end of the reaction.
At this time, an esterification catalyst can be used as needed. Examples of the esterification catalyst include a tin-containing catalyst (for example, dibutyltin oxide), antimony trioxide, and a titanium-containing catalyst [for example, titanium alkoxide, potassium oxalate titanate, titanium terephthalate, a catalyst described in JP 2006-243715 A [Titanium dihydroxybis (triethanolaminate), titanium monohydroxytris (triethanolaminate), and intramolecular polycondensates thereof], and catalysts described in JP-A No. 2007-11307 (titanium tributoxyterephthalate) , Titanium triisopropoxy terephthalate, titanium diisopropoxy diterephthalate, etc.)], zirconium-containing catalysts (for example, zirconyl acetate), zinc acetate, and the like. Among these, a titanium-containing catalyst is preferable.

  The polyester resin (A) used in the present invention contains a non-linear polyester (A1) and, if necessary, a linear polyester (A2) from the viewpoint of achieving both low-temperature fixability and offset resistance.

  The non-linear polyester (A1) used in the present invention is usually the above dicarboxylic acid (y1) and diol (x1) together with the above-mentioned 3-6 or higher polycarboxylic acid (y2) and / or trivalent-8 octavalent. Alternatively, it can be obtained by reacting more polyol (x2). The reaction ratio between the polyol component and the polycarboxylic acid component is preferably 2/1 to 1/2, more preferably 1.5 / 1 to 1/1 / as the equivalent ratio [OH] / [COOH] of the hydroxyl group to the carboxyl group. 1.3, particularly preferably 1.3 / 1 to 1 / 1.2.

  The ratio of (y2) and (x2) when obtaining (A1) is preferably such that the sum of the number of moles is the sum of the number of moles of all polyol components (x) and polycarboxylic acid components (y). Is from 0.1 to 40 mol%, more preferably from 1 to 25 mol%, particularly preferably from 3 to 20 mol%.

  The glass transition temperature [Tg] of (A1) is preferably 45 ° C to 75 ° C, more preferably 50 ° C to 70 ° C. When [Tg] is 75 ° C. or lower, the low-temperature fixability is improved. Further, when [Tg] is 45 ° C. or higher, the blocking resistance is good.

  Moreover, in the above and below, glass transition temperature [Tg] is measured by the method (DSC method) prescribed | regulated to ASTM D3418-82 using Seiko Denshi Kogyo Co., Ltd. DSC20, SSC / 580.

  The flow softening point [Tm] of (A1) is not particularly limited, but is preferably 100 ° C to 180 ° C, more preferably 120 ° C to 170 ° C. When [Tm] is 100 ° C. or higher, the hot offset resistance is good, and when it is 180 ° C. or lower, the fixability is good.

In the above and the following, the flow softening point [Tm] is a temperature at which the flow rate is raised at a constant speed under the following conditions using a flow tester, and the outflow amount becomes 1/2.
Apparatus: Flow tester CFT-500D manufactured by Shimadzu Corporation
Load: 20kg
Die: 1mmΦ-1mm
Temperature increase rate: 6 ° C./min.

The number average molecular weight (hereinafter referred to as Mn) of the tetrahydrofuran (THF) soluble part of the nonlinear polyester (A1) is preferably 2000 to 9500, and more preferably 2500 to 9000. When Mn is 2000 or more, the resin strength necessary for fixing is expressed, and when it is 9500 or less, the low-temperature fixability is good.
Moreover, the peak top molecular weight (hereinafter referred to as Mp) of the THF-soluble component of (A1) is preferably 2000 to 50000, more preferably 2500 to 30000, from the viewpoint of the balance between resin strength and low-temperature fixability.

In the present invention, the Mn and Mp of the THF soluble content of the toner resin are measured using gel permeation chromatography (GPC) under the following conditions.
Device (example): HLC-8120 manufactured by Tosoh Corporation
Column (example): TSK GEL GMH6 2 [Tosoh Corp.]
Measurement temperature: 40 ° C
Sample solution: 0.25 wt% THF solution Solution injection amount: 100 μl
Detection device: Refractive index detector Reference material: Tosoh standard polystyrene (TSK standard POLYSYRENE) 12 points (Molecular weight 500 1050 2800 5970 9100 18100 37900 96400 190000 355000 1090000 2890000)
The molecular weight showing the maximum peak height on the obtained chromatogram is referred to as peak top molecular weight (Mp).

The THF insoluble matter in the non-linear polyester (A1) is preferably 3 to 50% from the viewpoint of low-temperature fixability. More preferably, it is 5 to 40%, and particularly preferably 10 to 35%. When the THF-insoluble content is 50% or less, the glossiness (gloss) of the image is good. In the above and the following, “%” means “% by weight” unless otherwise specified.
The THF-insoluble matter in the present invention is determined by the following method.
Add 50 ml of THF to 0.5 g of the sample and stir to reflux for 3 hours. After cooling from the reflux temperature to 20 ° C., the insoluble matter is filtered off with a glass filter, and the resin content on the glass filter is dried under reduced pressure at 80 ° C. for 3 hours. The insoluble matter is calculated from the weight of the dried resin content on the glass filter and the weight ratio of the sample. In addition, this filtrate is used for GPC measurement as a THF soluble part.

The acid value of the non-linear polyester (A1) is preferably 10 to 70 (mg KOH / g, the same shall apply hereinafter), more preferably 13 to 60, and particularly preferably 15 to 50. When the acid value is 70 or less, the water-dispersed resin is easily agglomerated, and the resulting electrostatic charge image developing toner has good charging characteristics.
Further, the hydroxyl value of (A1) (mgKOH / g, the same shall apply hereinafter) is preferably 0 to 50, more preferably 0 to 45, and particularly preferably 0 to 40. When the hydroxyl value is 50 or less, the hot offset resistance becomes better.
The acid value and hydroxyl value in the present invention are measured by the method defined in JIS K0070.

  The acid value of the polyester resin is usually derived from a carboxyl group, but in the method for producing an electrostatic charge image developing toner of the present invention, in order to disperse resin particles of 1 μm or less in water, the non-linear polyester (A1) and the below-mentioned At least a part of the carboxyl group of the linear polyester (A2) may be neutralized with a base. The neutralization rate of the carboxyl group is preferably 20 to 100 equivalent%, more preferably 40 to 100 equivalent%.

Examples of the base that forms the neutralized salt include ammonia, monoamines having 1 to 30 carbon atoms, quaternary ammonium, alkali metals (sodium, potassium, etc.), and alkaline earth metals (calcium, magnesium, etc.). .
Examples of the monoamine having 1 to 30 carbon atoms include primary and / or secondary amines having 1 to 30 carbon atoms (ethylamine, n-butylamine, isobutylamine, etc.), and tertiary amines having 3 to 30 carbon atoms (trimethylamine, triethylamine). , Lauryldimethylamine, etc.). Examples of the quaternary ammonium include trialkylammonium having 4 to 30 carbon atoms (such as lauryltrimethylammonium).
Among these, preferred are alkali metals, quaternary ammoniums, and monoamines, more preferred are sodium and monoamines having 1 to 20 carbon atoms, and particularly preferred are tertiary monoamines having 3 to 20 carbon atoms. It is.

The polyester resin (A) in the toner for developing an electrostatic charge image of the present invention may contain a linear polyester (A2) as necessary in addition to the nonlinear polyester (A1). When (A2) is contained, the low-temperature fixability becomes better.
The linear polyester (A2) used in the present invention is obtained, for example, by polycondensation of the diol (x1) and the dicarboxylic acid (y1), and the molecular terminal is further converted to the polycarboxylic acid component (y) (trivalent). The above may be modified with an anhydride or the like. In these, what modified | denatured the molecular terminal with the anhydride of (y) is preferable. The reaction ratio between the polyol component and the polycarboxylic acid component is preferably 3/1 to 1/3, more preferably 2.5 / 1 to 1/1 / as the equivalent ratio [OH] / [COOH] of the hydroxyl group to the carboxyl group. 2.5, particularly preferably 2/1 to 1/2.

  The acid value of the linear polyester (A2) used in the present invention is preferably 2 to 200. The acid value is more preferably 50 to 180, particularly preferably 58 to 160. When the acid value is 2 or more, it is easy to disperse in water to 1 μm or less, and the low-temperature fixability of the obtained toner for developing an electrostatic image is better. Aggregation is easy, and the resulting electrostatic charge image developing toner has good charging characteristics.

  (A2) preferably has a difference ([Tm]-[Tg]) between the flow softening point [Tm] (° C.) and the glass transition temperature [Tg] (° C.) of 38 ° C. or less. ([Tm] − [Tg]) is more preferably 35 ° C. or less, particularly preferably 34 ° C. or less. When ([Tm] − [Tg]) is 38 ° C. or lower, the low-temperature fixability is better.

  The glass transition temperature [Tg] of (A2) is preferably 40 ° C to 75 ° C, more preferably 45 ° C to 70 ° C. When [Tg] is 75 ° C. or lower, the low-temperature fixability is improved. Further, when [Tg] is 40 ° C. or higher, the blocking resistance is good.

  The flow softening point [Tm] of (A2) is not particularly limited, but is preferably 70 ° C to 120 ° C, more preferably 75 ° C to 100 ° C. When [Tm] is 70 ° C. or higher, the hot offset resistance is good, and when it is 120 ° C. or lower, the fixability is good.

  The hydroxyl value of (A2) is preferably 25 to 125, more preferably 30 to 100. When the hydroxyl value is 25 or more, the compatibility with (A1) is good, and the glossiness (gloss) after fixing is good. Further, when the hydroxyl value is 125 or less, the hot offset resistance becomes better.

Mn of the THF soluble part of linear polyester (A2) used for this invention becomes like this. Preferably it is 1050-4000, More preferably, it is 1100-3000. When Mn is 1050 or more, the resin strength necessary for fixing is expressed, and when it is 4000 or less, the low-temperature fixability is good.
Moreover, Mp of the THF soluble part of (A2) is preferably 1600 to 7000, more preferably 1700 to 5000, from the viewpoint of the balance between the resin strength and the low temperature fixability.

  The THF insoluble content in the linear polyester (A2) is preferably 5% or less from the viewpoint of low-temperature fixability. More preferably, it is 4% or less, and particularly preferably 3% or less.

  The weight ratio [(A1) / (A2)] of the non-linear polyester (A1) and the linear polyester (A2) in the polyester resin (A) is preferably 100 in terms of both low-temperature fixability and hot offset resistance. / 0 to 5/95, more preferably 90/10 to 10/90, and particularly preferably 85/15 to 20/80.

The toner resin composition used in the toner for developing an electrostatic charge image of the present invention contains an ester group-containing additive (B) in addition to the polyester resin (A).
The ester group-containing additive (B) used in the present invention has a number average molecular weight of 1000 or less in THF-soluble matter, and the flow softening point [Tm] and the glass transition temperature [Tg] satisfy the above relationship. The reaction product is not particularly limited as long as it is a reaction product of a polyol and a polycarboxylic acid, or a reaction product of an epoxy group-containing compound and a polycarboxylic acid, more preferably a reaction product of a polyol and an acid anhydride. preferable.

As said polyol, the thing similar to the said polyol component (x) is mentioned.
Preferred as the polyol is the diol (x1), more preferably an alkylene glycol having 2 to 9 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol. And 1,6-hexanediol, etc.) and bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.)] and the polyoxyalkylene ether (number of AO units 2-5), particularly preferably ethylene glycol, 1,2-propylene glycol, bisphenol A ethylene oxide (hereinafter referred to as EO) 2 to 5 mol adduct, bisphenol A propylene oxide (hereinafter referred to as PO) 2 to 5 mol adduct, and the like.
As said polycarboxylic acid, the thing similar to the said polycarboxylic acid component (y) is mentioned. However, in the case of a reaction product with a polyol, from the viewpoint of reactivity, an acid anhydride is preferable, and trimellitic anhydride, phthalic anhydride, maleic anhydride, succinic anhydride, and pyroanhydride are more preferable. It is merit acid.
The epoxy group-containing compound is not particularly limited as long as it is a compound containing one or more epoxy groups in one molecule. For example, polyglycidyl ether [ethylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, bisphenol A Diglycidyl ether, bisphenol F diglycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether, phenol novolac (average degree of polymerization 3 to 60) glycidyl ether, etc.]; Is mentioned. Of these, bisphenol A diglycidyl ether is preferred. The number of epoxy groups per molecule is preferably 2-8, more preferably 2-6.
The reaction molar ratio of polyol and polycarboxylic acid is preferably 2/1 to 1/2, more preferably 1/1 to 1/2.
The reaction molar ratio between the epoxy group-containing compound and the polycarboxylic acid is preferably 2/1 to 1/2, and more preferably 1/1 to 1/2.

Specific examples of the ester group-containing additive (B) include the following (1) to (6).
(1) A reaction product of ethylene glycol and (anhydrous) trimellitic acid.
(2) A reaction product of 1,2-propylene glycol and (anhydrous) trimellitic acid.
(3) A reaction product of 1,3-propylene glycol and (anhydrous) trimellitic acid.
(4) A reaction product of an EO adduct of bisphenol A (number of added moles: any one of 2 to 5) and (anhydrous) trimellitic acid.
(5) Reaction product of PO adduct of bisphenol A (added mole number: any one of 2 to 5) and (anhydrous) trimellitic acid.
(6) A reaction product of bisphenol A diglycidyl ether and terephthalic acid.
In the above, (anhydrous) trimellitic acid means trimellitic acid and / or trimellitic anhydride.

As an example of the production method of the ester group-containing additive (B), for example, in an inert gas (nitrogen gas or the like) atmosphere, the polyol component (x) is preferably 100 to 200 ° C., more preferably 110 to 200 ° C. It is dissolved at 190 ° C, particularly preferably at 120 to 180 ° C. The acid anhydride in the polycarboxylic acid component (y) is added thereto, and the reaction temperature is preferably 100 to 200 ° C, more preferably 110 to 190 ° C, and particularly preferably 120 to 180 ° C. It can be carried out. The reaction time is preferably 30 minutes or more, particularly preferably 1 to 3 hours from the viewpoint of reliably performing the reaction.
At this time, the esterification catalyst may be used as necessary.

Mn of the THF soluble part of the ester group-containing additive (B) is 1000 or less, preferably 200 to 950. When Mn exceeds 1000, the low-temperature fixability deteriorates.
Moreover, Mp of the THF soluble part of (B) is preferably 1500 or less, more preferably 300 to 1400, from the viewpoint of the balance between resin strength and low temperature fixability.

  The difference ([Tm]-[Tg]) between the flow softening point [Tm] (° C.) and the glass transition temperature [Tg] (° C.) of the ester group-containing additive (B) is 38 ° C. or less. ([Tm] − [Tg]) is preferably 37 ° C. or lower, more preferably 35 ° C. or lower, and particularly preferably 33 ° C. or lower. When ([Tm] − [Tg]) exceeds 38 ° C., the low-temperature fixability deteriorates.

  The glass transition temperature [Tg] of the ester group-containing additive (B) is preferably 40 ° C to 75 ° C, more preferably 41 ° C to 70 ° C, and particularly preferably 45 ° C to 65 ° C. When [Tg] is 75 ° C. or lower, the low-temperature fixability is improved. Further, when [Tg] is 40 ° C. or higher, the blocking resistance is good.

  The flow softening point [Tm] of (B) is not particularly limited, but is preferably 60 ° C to 110 ° C, and more preferably 70 ° C to 100 ° C. When [Tm] is 60 ° C. or higher, the hot offset resistance is good, and when it is 110 ° C. or lower, the fixability is good.

  The acid value of the ester group-containing additive (B) used in the present invention is preferably 100 to 1000. More preferably, it is 110-950, Most preferably, it is 170-900. When the acid value is 100 or more, the low-temperature fixability becomes better. On the other hand, when it is 1000 or less, the water-dispersed resin is easily aggregated, and the charging characteristics of the resulting electrostatic image developing toner are improved.

  The acid value of the ester group-containing additive (B) is usually derived from a carboxyl group, but in order to disperse resin particles of 1 μm or less in water in the process for producing an electrostatic charge image developing toner of the present invention, a carboxyl group is used. May be at least partially neutralized with a base. The neutralization rate of the carboxyl group is preferably 20 to 100 equivalent%, more preferably 40 to 100 equivalent%. Examples of the base that forms the neutralized salt include those described above.

  The hydroxyl value of (B) is preferably 500 or less. More preferably, it is 450 or less. When the hydroxyl value is 500 or less, the hot offset resistance is good.

  The THF insoluble content in (B) is preferably 5% or less from the viewpoint of low-temperature fixability. More preferably, it is 4% or less, particularly preferably 3% or less.

  The number of ester groups (B) is preferably 1 to 3 on average per molecule. More preferably, it is 1-2. When the number of ester groups is 1 or more, blocking resistance is good, and when it is 3 or less, fixability is good. The number (average) of ester groups means a calculated value obtained from a reaction molar ratio when (B) is a reaction product of a polyol and an acid anhydride.

  In the toner resin composition in the toner for developing an electrostatic charge image of the present invention, the polyester resin (A) [containing a non-linear polyester (A1) and, if necessary, a linear polyester (A2). ] And the ester group-containing additive (B) in the weight ratio [(A) / (B)] are preferably 10/90 to 95/5, and more preferably in terms of both low-temperature fixability and hot offset resistance. Is 15/85 to 90/10, particularly preferably 20/80 to 80/20.

  As the toner resin composition in the toner for developing an electrostatic charge image of the present invention, in addition to the polyester resin (A) and the ester group-containing additive (B), it is usually used as a toner resin within a range that does not impair its properties. Other resins may be contained. Examples of other resins include polyester resins other than (A1) and (A2) with Mn of 1,000 to 1,000,000, styrene resins, resins having a structure in which a vinyl resin is grafted on a polyolefin resin, epoxy resins, and polyurethane resins. Can be mentioned. Other resins may be blended with (A1), (B), and (A2) if necessary, or may be partially reacted. The content of other resins is preferably 10% or less, more preferably 5% or less.

In the method for producing a toner for developing an electrostatic charge image according to the present invention, a resin having a volume average particle diameter of 1 μm or less containing a polyester resin (A) in water (including a mixed solvent of water and a small amount of a water-soluble organic solvent). The method for dispersing the particles is not particularly limited, but the following [1] to [7] can be mentioned.
[1] A resin precursor (monomer, oligomer, etc.) containing the polyester resin (A) or an organic solvent solution thereof is dispersed in water in the presence of a suitable dispersant if necessary, and then heated or cured. A method of producing an aqueous dispersion of resin particles by adding an agent and curing.
[2] A suitable emulsifier is dissolved in a precursor (monomer, oligomer, etc.) of a resin containing the polyester resin (A) or an organic solvent solution thereof (preferably a liquid, which may be liquefied by heating). Then, water is added to perform phase inversion emulsification, and a curing agent is added or the like to cure, thereby producing an aqueous dispersion of resin particles.
[3] A resin containing the polyester resin (A) is pulverized using a mechanical pulverizer such as a mechanical rotary type or a jet type, and then classified to obtain resin particles, and then in the presence of a suitable dispersant. To disperse in water.
[4] After resin particles are obtained by spraying a resin solution in which a resin containing the polyester resin (A) is dissolved in an organic solvent, the resin particles are dispersed in water in the presence of an appropriate dispersant. Method.
[5] Add a poor solvent to a resin solution obtained by dissolving a resin containing the polyester resin (A) in an organic solvent, or cool a resin solution previously dissolved in an organic solvent to precipitate resin particles, A method of removing the organic solvent to obtain resin particles and then dispersing the resin particles in water in the presence of a suitable dispersant.
[6] A method in which a resin solution in which a resin containing the polyester resin (A) is dissolved in an organic solvent is dispersed in water in the presence of a suitable dispersant, and the organic solvent is removed by heating or decompression.
[7] A method in which a suitable emulsifier is dissolved in a resin solution obtained by dissolving a resin containing the polyester resin (A) in an organic solvent, and then water is added to perform phase inversion emulsification.
Also for the ester group-containing additive (B), resin particles having a volume average particle diameter of 1 μm or less containing (B) can be dispersed in water by the same method as described above. Moreover, the resin particle containing both (A) and (B) can also be disperse | distributed.

In the above methods [1] to [7], as the emulsifier or dispersant used in combination, a known surfactant (s), water-soluble polymer (t) and the like can be used. Moreover, an organic solvent (u), a plasticizer (v), etc. can be used together as an auxiliary agent for emulsification or dispersion.
A dispersion device can be used for emulsification or dispersion. In order to easily make the volume average particle diameter 1 μm or less, it is preferable to disperse by applying a shearing force using a dispersing device.
The dispersion apparatus used in the present invention is not particularly limited as long as it is generally commercially available as an emulsifier or a disperser. For example, a homogenizer (manufactured by IKA), polytron (manufactured by Kinematica), TK auto homomixer ( Batch type emulsifiers such as Special Machine Industries Co., Ltd., Ebara Milder (Ebara Manufacturing Co., Ltd.), TK Fill Mix, TK Pipeline Homo Mixer (Special Machine Industries Co., Ltd.), Colloid Mill (Shinko Pantech Co., Ltd.) ), Continuous emulsifiers such as slasher, trigonal wet pulverizer (made by Mitsui Miike Chemical Co., Ltd.), Captron (made by Eurotech), fine flow mill (made by Taiheiyo Kiko Co., Ltd.), microfluidizer (made by Mizuho Industrial Co., Ltd.) ), Nanomizer (manufactured by Nanomizer), high pressure emulsifier such as APV Gaurin (manufactured by Gaurin), membrane emulsifier (manufactured by Chilling Industries) Membrane emulsifier, Vibro Mixer (Hiyaka Kogyo) vibrating emulsifier such as, ultrasonic emulsifier such as an ultrasonic homogenizer (manufactured by Branson Co., Ltd.). Among these, APV Gaurin, homogenizer, TK auto homomixer, Ebara milder, TK fill mix, and TK pipeline homomixer are preferable from the viewpoint of uniform particle size.

  Examples of the surfactant (s) include an anionic surfactant (s-1), a cationic surfactant (s-2), an amphoteric surfactant (s-3), and a nonionic surfactant (s-4). Etc. The surfactant (s) may be a combination of two or more surfactants. Specific examples of (s) include those described below and JP-A-2002-284881.

  As the anionic surfactant (s-1), a carboxylic acid or a salt thereof, a sulfate ester salt, a salt of a carboxymethylated product, a sulfonate salt, a phosphate ester salt, or the like is used.

As the carboxylic acid or a salt thereof, a saturated or unsaturated fatty acid having 8 to 22 carbon atoms or a salt thereof can be used. For example, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, olein Examples thereof include mixtures of acids, linoleic acid and ricinoleic acid, and higher fatty acids obtained by saponifying coconut oil, palm kernel oil, rice bran oil, beef tallow and the like.
Examples of the salt include salts such as sodium salt, potassium salt, amine salt, ammonium salt, quaternary ammonium salt, and alkanolamine salt (monoethanolamine salt, diethanolamine salt, triethanolamine salt, etc.).

The sulfate ester salts include higher alcohol sulfate esters (sulfate esters of aliphatic alcohols having 8 to 18 carbon atoms), higher alkyl ether sulfate esters salts (EO or PO 1 to 10 moles of aliphatic alcohols having 8 to 18 carbon atoms). Sulfates of adducts), sulfated oils (natural unsaturated fats or oils having a carbon number of 12 to 50, or neutralized by neutralization), sulfated fatty acid esters (unsaturated fatty acids (carbon number) 6-40) lower alcohols (one having 1 to 8 carbon atoms) sulfated and neutralized) and sulfated olefins (one having 12 to 18 carbon atoms sulfated and neutralized) can be used.
Examples of the salt include sodium salt, potassium salt, amine salt, ammonium salt, quaternary ammonium salt, alkanolamine salt (monoethanolamine salt, diethanolamine salt, triethanolamine salt, etc.) and the like.

  Examples of the higher alcohol sulfate ester salt include octyl alcohol sulfate ester salt, decyl alcohol sulfate ester salt, lauryl alcohol sulfate ester salt, stearyl alcohol sulfate ester salt, alcohol synthesized using a Ziegler catalyst (for example, trade name: ALFOL). 1214: manufactured by CONDEA) and alcohol synthesized by the oxo method (for example, trade names: Dovanol 23, 25, 45, Diadol 115-L, 115H, 135: manufactured by Mitsubishi Chemical Corporation, trade name: Tridecanol) : Manufactured by Kyowa Hakko, trade names: Oxocol 1213, 1215, 1415: manufactured by Nissan Chemical Co., Ltd.) and the like.

Examples of the higher alkyl ether sulfate ester salt include lauryl alcohol EO 2 mol adduct sulfate ester salt and octyl alcohol EO 3 mol adduct sulfate ester salt.
Examples of sulfated oils include sulfate salts such as castor oil, peanut oil, olive oil, rapeseed oil, beef tallow, and sheep fat.
Examples of sulfated fatty acid esters include sulfate salts such as butyl oleate and butyl ricinoleate.
Examples of the sulfated olefin include trade name: TEPOL (manufactured by Shell).

  Examples of the carboxymethylated salt include carboxymethylated salts of aliphatic alcohols having 8 to 16 carbon atoms and EO or carboxymethylated salts of 1 to 10 mol adducts of aliphatic alcohols having 8 to 16 carbon atoms. Can be used.

  Examples of the salt of a carboxymethylated product of an aliphatic alcohol include octyl alcohol carboxymethylated sodium salt, lauryl alcohol carboxymethylated sodium salt, dovanol 23 carboxymethylated sodium salt, tridecanol carboxymethylated sodium salt, and the like. It is done.

  Examples of carboxymethylated salts of EO 1 to 10 mol adducts of aliphatic alcohols include, for example, octyl alcohol EO3 mol adduct carboxymethylated sodium salt, lauryl alcohol EO4 mol adduct carboxymethylated sodium salt, and tridecanol EO5 mol addition. Carboxymethylated sodium salt and the like.

As sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, sulfosuccinic acid diester salts, α-olefin sulfonates, sulfonates of Igepon T-type and other aromatic ring-containing compounds can be used.
Examples of the alkylbenzene sulfonate include sodium dodecylbenzenesulfonate.

Examples of the alkyl naphthalene sulfonate include sodium dodecyl naphthalene sulfonate and the like.
Examples of the sulfosuccinic acid diester salt include sulfosuccinic acid di-2-ethylhexyl ester sodium salt.
Examples of the sulfonate of the aromatic ring-containing compound include mono- or disulfonate of alkylated diphenyl ether and styrenated phenol sulfonate.

As the phosphate ester salt, a higher alcohol phosphate ester salt, a higher alcohol EO adduct phosphate ester salt and the like can be used.
Examples of the higher alcohol phosphate salt include lauryl alcohol phosphate monoester disodium salt and lauryl alcohol phosphate diester sodium salt.
Examples of the higher alcohol EO adduct phosphate ester salt include oleyl alcohol EO 5 mol adduct phosphate monoester disodium salt.

As the cationic surfactant (s-2), a quaternary ammonium salt type surfactant, an amine salt type surfactant and the like can be used.
Examples of the quaternary ammonium salt type surfactant include tertiary amines having 3 to 40 carbon atoms and quaternizing agents (for example, alkylating agents such as methyl chloride, methyl bromide, ethyl chloride, benzyl chloride and dimethyl sulfate, and EO). For example, lauryltrimethylammonium chloride, didecyldimethylammonium chloride, dioctyldimethylammonium bromide, stearyltrimethylammonium bromide, lauryldimethylbenzylammonium chloride (benzalkonium chloride), cetylpyridinium chloride, poly Examples thereof include oxyethylene trimethyl ammonium chloride and stearamide ethyl diethyl methyl ammonium methosulfate.

As the amine salt type surfactant, a primary to tertiary amine is selected from inorganic acids (eg hydrochloric acid, nitric acid, sulfuric acid, hydroiodic acid, phosphoric acid and perchloric acid) or organic acids (acetic acid, formic acid, oxalic acid, lactic acid). , Gluconic acid, adipic acid, alkylphosphoric acid having 2 to 24 carbon atoms, malic acid, citric acid and the like).
Examples of the primary amine salt type surfactant include inorganic acid salts of aliphatic higher amines having 8 to 40 carbon atoms (for example, higher amines such as laurylamine, stearylamine, cetylamine, hardened tallow amine, and rosinamine). Alternatively, organic acid salts and higher fatty acid (carbon number 8 to 40, stearic acid, oleic acid, etc.) salts of lower amines (2 to 6 carbon atoms) and the like can be mentioned.

Examples of the secondary amine salt type surfactant include inorganic acid salts or organic acid salts such as EO adducts of aliphatic amines having 4 to 40 carbon atoms.
Examples of the tertiary amine salt type surfactant include aliphatic amines having 4 to 40 carbon atoms (for example, triethylamine, ethyldimethylamine, N, N, N ′, N′-tetramethylethylenediamine, etc.), EO (2 mol or more) adduct of aliphatic amine (2 to 40 carbon atoms), alicyclic amine having 6 to 40 carbon atoms (for example, N-methylpyrrolidine, N-methylpiperidine, N-methylhexamethyleneimine, N-methylmorpholine and 1,8-diazabicyclo (5,4,0) -7-undecene), nitrogen-containing heterocyclic aromatic amines having 5 to 30 carbon atoms (for example, 4-dimethylaminopyridine, N-methylimidazole) And 4,4'-dipyridyl, etc.) inorganic or organic acid salts and triethanolamine monostearate, stearamide ethyl diethyl Such as tertiary mineral or organic acid salts of amines such as chill ethanolamine.

  Examples of the amphoteric surfactant (s-3) include a carboxylate type amphoteric surfactant, a sulfate ester type amphoteric surfactant, a sulfonate type amphoteric surfactant, and a phosphate ester type amphoteric surfactant. Can be used.

  As the carboxylate type amphoteric surfactant, an amino acid type amphoteric surfactant, a betaine type amphoteric surfactant, an imidazoline type amphoteric surfactant and the like are used. The amino acid type amphoteric surfactant is an amphoteric surfactant having an amino group and a carboxyl group in the molecule, and examples thereof include a compound represented by the general formula (1).

[R—NH— (CH ₂ ) n —COO] mM (1)
[Wherein R is a monovalent hydrocarbon group; n is 1 or 2; m is 1 or 2; M is a hydrogen ion, an alkali metal ion, an alkaline earth metal ion, an ammonium cation, an amine cation, an alkanolamine cation, etc. It is. ]

  Examples of the double-sided active agent represented by the general formula (1) include alkyl (carbon number 6 to 40) aminopropionic acid type amphoteric surfactants (sodium stearylaminopropionate, sodium laurylaminopropionate, etc.); alkyl ( Examples thereof include C4-C24) aminoacetic acid type amphoteric surfactants (such as sodium laurylaminoacetate).

  The betaine-type amphoteric surfactant is an amphoteric surfactant having a quaternary ammonium salt-type cation moiety and a carboxylic acid-type anion moiety in the molecule, for example, alkyl (having 6 to 40 carbon atoms) dimethyl betaine. (Stearyldimethylaminoacetic acid betaine, lauryldimethylaminoacetic acid betaine, etc.), C6-C40 amide betaines (coconut oil fatty acid amidopropyl betaine, etc.), alkyls (C6-C40) dihydroxyalkyls (C6-C40) Examples include betaine (such as lauryl dihydroxyethyl betaine).

  The imidazoline type amphoteric surfactant is an amphoteric surfactant having a cation part having an imidazoline ring and a carboxylic acid type anion part. For example, 2-undecyl-N-carboxymethyl-N-hydroxyethyl imidazoli Examples include nitrobetaine.

  Other amphoteric surfactants include, for example, glycine-type amphoteric surfactants such as sodium lauroyl glycine, sodium lauryl diaminoethyl glycine, lauryl diaminoethyl glycine hydrochloride, dioctyl diaminoethyl glycine hydrochloride; sulfobetaines such as pentadecyl sulfotaurine Examples include amphoteric surfactants, sulfonate amphoteric surfactants, and phosphate ester type amphoteric surfactants.

As the nonionic surfactant (s-4), alkylene oxide (hereinafter referred to as AO) addition type nonionic surfactant, polyhydric alcohol type nonionic surfactant and the like can be used.
The AO addition type nonionic surfactant directly adds AO (2 to 20 carbon atoms) to a higher alcohol having 8 to 40 carbon atoms, a higher fatty acid having 8 to 40 carbon atoms or an alkylamine having 8 to 40 carbon atoms. Or, a higher fatty acid or the like is reacted with a polyalkylene glycol obtained by adding AO to glycol, or AO is added to an esterified product obtained by reacting a higher fatty acid with a polyhydric alcohol, or a higher fatty acid amide is added. It is obtained by adding AO.

Examples of AO include EO, PO, and butylene oxide.
Of these, EO and random or block adducts of EO and PO are preferred.
The number of moles of AO added is preferably 10 to 50 moles, and 50 to 100% of the AO is preferably EO.

  As the AO addition type nonionic surfactant, for example, oxyalkylene alkyl ether (alkylene having 2 to 24 carbon atoms, alkyl carbon number 8 to 40) (for example, octyl alcohol EO 20 mol adduct, lauryl alcohol EO 20 mol adduct) , Stearyl alcohol EO 10 mol adduct, oleyl alcohol EO 5 mol adduct, lauryl alcohol EO 10 mol PO 20 mol block adduct, etc.); polyoxyalkylene higher fatty acid ester (alkylene having 2 to 24 carbon atoms, higher fatty acid having 8 to 40 carbon atoms) ) (For example, stearyl acid EO 10 mol adduct, lauryl acid EO 10 mol adduct, etc.); polyoxyalkylene polyhydric alcohol higher fatty acid ester (alkylene having 2 to 24 carbon atoms, polyhydric alcohol having 3 to 40 carbon atoms, higher fatty acid) Carbon number -40) (for example, lauric acid diester of polyethylene glycol (polymerization degree 20), oleic acid diester of polyethylene glycol (polymerization degree 20), etc.); polyoxyalkylene alkylphenyl ether (alkylene having 2 to 24 carbon atoms, alkyl carbon) 8 to 40) (for example, nonylphenol EO 4 mol adduct, nonylphenol EO 8 mol PO 20 mol block adduct, octylphenol EO 10 mol adduct, bisphenol A · EO 10 mol adduct, styrenated phenol EO 20 mol adduct, etc.); polyoxyalkylene Alkylamino ethers (alkylene having 2 to 24 carbon atoms, alkyl having 8 to 40 carbon atoms) and (for example, laurylamine EO 10 mol adduct, stearylamine EO 10 mol adduct, etc.); polyoxy Lukylene alkanolamide (2-24 carbon atoms of alkylene, 8-24 carbon atoms of amide (acyl moiety)) (for example, EO 10 mol adduct of hydroxyethyl lauric acid amide, EO 20 mol adduct of hydroxypropyl oleic acid amide, etc. ).

  As the polyhydric alcohol type nonionic surfactant, polyhydric alcohol fatty acid ester, polyhydric alcohol fatty acid ester AO adduct, polyhydric alcohol alkyl ether, polyhydric alcohol alkyl ether AO adduct and the like can be used. The polyhydric alcohol has 3 to 24 carbon atoms, the fatty acid has 8 to 40 carbon atoms, and the AO has 2 to 24 carbon atoms.

  Examples of the polyhydric alcohol fatty acid ester include pentaerythritol monolaurate, pentaerythritol monooleate, sorbitan monolaurate, sorbitan monostearate, sorbitan monolaurate, sorbitan dilaurate, sorbitan dioleate, and sucrose monostearate. Can be mentioned.

  Examples of polyhydric alcohol fatty acid ester AO adducts include ethylene glycol monooleate EO 10 mol adduct, ethylene glycol monostearate EO 20 mol adduct, trimethylolpropane monostearate EO 20 mol PO 10 mol random adduct, sorbitan monolaurate. EO 10 mol adduct, sorbitan distearate EO 20 mol adduct, sorbitan dilaurate EO 12 mol PO 24 mol random adduct and the like.

  Examples of the polyhydric alcohol alkyl ether include pentaerythritol monobutyl ether, pentaerythritol monolauryl ether, sorbitan monomethyl ether, sorbitan monostearyl ether, methyl glycoside and lauryl glycoside.

  Examples of the polyhydric alcohol alkyl ether AO adduct include sorbitan monostearyl ether EO 10 mol adduct, methyl glycoside EO 20 mol PO 10 mol random adduct, lauryl glycoside EO 10 mol adduct and stearyl glycoside EO 20 mol PO 20 mol random adduct. Can be mentioned.

  Examples of the water-soluble polymer (t) include cellulose compounds (for example, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose and saponified products thereof), gelatin, starch, dextrin, gum arabic, chitin , Chitosan, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, polyethyleneimine, polyacrylamide, acrylic acid (salt) -containing polymer (sodium polyacrylate, potassium polyacrylate, ammonium polyacrylate, in the sodium hydroxide part of polyacrylic acid) Sodium hydroxide, acrylic acid ester copolymer), styrene-maleic anhydride copolymer sodium hydroxide Beam (partial) neutralization product, water-soluble polyurethane (polyethylene glycol, reaction products of polycaprolactone diol with polyisocyanate and the like) and the like.

The organic solvent (u) used in the present invention contains a resin containing the polyester resin (A) or the polyester resin (A) in the dispersion to be emulsified even if it is added to water as necessary during the emulsification dispersion. It may be added to the oil phase containing the resin precursor].
Specific examples of the organic solvent (u) include aromatic hydrocarbon organic solvents such as toluene, xylene, ethylbenzene and tetralin; aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, mineral spirit and cyclohexane. Organic solvents: halogenated organic solvents such as methyl chloride, methyl bromide, methyl iodide, methylene dichloride, carbon tetrachloride, trichloroethylene, perchloroethylene; ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve Ester or ester ether organic solvents such as acetate; ether organic solvents such as diethyl ether, tetrahydrofuran, dioxane, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether; acetone, methyl Ketone organic solvents such as ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, cyclohexanone; methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 2-ethylhexyl alcohol, benzyl alcohol, etc. Alcohol-based organic solvents; amide-based organic solvents such as dimethylformamide and dimethylacetamide; sulfoxide-based organic solvents such as dimethylsulfoxide; heterocyclic compound-based organic solvents such as N-methylpyrrolidone; and a mixture of two or more of these Can be mentioned.

As a plasticizer (v), it is not limited at all, The following are illustrated.
(V1) Phthalates [dibutyl phthalate, dioctyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, etc.];
(V2) Aliphatic dibasic acid ester [di-2-ethylhexyl adipate, 2-ethylhexyl sebacate, etc.];
(V3) trimellitic acid ester [tri-2-ethylhexyl trimellitic acid, trioctyl trimellitic acid, etc.];
(V4) Phosphate ester [triethyl phosphate, tri-2-ethylhexyl phosphate, tricresyl phosphate, etc.];
(V5) fatty acid ester [butyl oleate and the like];
(V6) and mixtures of two or more thereof.

The toner for developing an electrostatic charge image of the present invention is one or more obtained by dispersing resin particles containing (A) and / or (B) having a volume average particle size of 1 μm or less obtained by the above method in water. Two or more kinds of resin particle dispersions are mixed as necessary, and the resin particles in the resin particle dispersion are agglomerated (aggregation step), and further heated to a temperature equal to or higher than the Tg of the resin to fuse the aggregated particles. It is done.
In the agglomeration step, after the agglomerated particles are formed from a part of the resin particle dispersion, the remaining resin particle dispersion may be additionally mixed. According to this method, the resin particles in the additionally mixed dispersion can be present on the outermost surface of the aggregated particles.

  As a method for adding an additive such as a colorant, which will be described later, and a release agent and a charge control agent, as necessary, to the toner for developing an electrostatic charge image, the resin particles having a volume average particle diameter of 1 μm or less are used in advance. The colorant and the release agent may be dispersed, the colorant dispersion in which the colorant is dispersed in the aggregation step, the release agent dispersion in which the release agent is dispersed, and the charge control in which the charge control agent is dispersed. An agent dispersion or the like may be mixed.

The agglomerated particles are formed by heteroaggregation or the like, and for the purpose of stabilizing the agglomerated particles and controlling the particle size / particle size distribution, as an aggregating agent, an ionic surfactant having a polarity different from the agglomerated particles, a metal salt, or the like It is formed by adding a compound having a monovalent or bivalent charge. Moreover, the particle size of the aggregated particles can be adjusted by changing the pH.
As the flocculant, a compound having a monovalent or divalent charge is preferable. Specific examples of the compound having a monovalent or divalent charge include the above-mentioned ionic surfactants, nonionic surfactants, and the like. Water-soluble surfactants, acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, and oxalic acid, inorganic acid metals such as magnesium chloride, sodium chloride, aluminum sulfate, calcium sulfate, ammonium sulfate, aluminum nitrate, silver nitrate, copper sulfate, and sodium carbonate Salt, sodium acetate, potassium formate, sodium oxalate, sodium phthalate, potassium salicylate and other aliphatic acids, metal salts of aromatic acids, metal salts of phenols such as sodium phenolate, metal salts of amino acids, triethanolamine Examples thereof include inorganic acid salts of aliphatic and aromatic amines such as hydrochloride and aniline hydrochloride. More preferably, metal salts of inorganic acids such as magnesium chloride, sodium chloride, aluminum sulfate, calcium sulfate, ammonium sulfate, aluminum nitrate, silver nitrate, copper sulfate, sodium carbonate, sodium acetate, potassium formate, sodium oxalate, sodium phthalate, salicylic acid Inorganic and organic metal salts such as aliphatic acids such as potassium, most preferably polyvalent inorganic metal salts such as aluminum sulfate, aluminum nitrate, aluminum chloride, and magnesium chloride are used for the stability of aggregated particles, It can be suitably used in terms of stability against heat and aging, removal during washing, and the like.
The amount of these flocculants added varies depending on the valence of the charge, but they are all small and are about 3% or less for monovalent, about 1% or less for divalent, and 0 for trivalent. About 5% or less. Since a smaller amount of the flocculant is preferable, a compound having a higher valence is preferable.

  The toner for developing an electrostatic charge image of the present invention includes a resin composition for a toner containing a polyester resin (A) serving as a binder resin and an ester group-containing additive (B), a colorant, and, if necessary, a release agent, 1 or more types of toner additives chosen from a charge control agent, a fluidizing agent, etc. are contained.

  As the colorant, all of dyes and pigments used as toner colorants can be used. Specifically, carbon black, iron black, Sudan Black SM, First Yellow G, Benzidine Yellow, Pigment Yellow, Indian First Orange, Irgasin Red, Paranitroaniline Red, Toluidine Red, Carmine FB, Pigment Orange R, Lake Red 2G, Rhodamine FB, Rhodamine B Lake, Methyl Violet B Lake, Phthalocyanine Blue, Pigment Blue, Brilliant Green, Phthalocyanine Green, Oil Yellow GG, Kayaset YG, Orazol Brown B and Oil Pink OP, etc. Or 2 or more types can be mixed and used. Further, if necessary, magnetic powder (a powder of a ferromagnetic metal such as iron, cobalt, nickel, or a compound such as magnetite, hematite, ferrite) can also be included as a colorant.

The release agent preferably has a softening point of 50 to 170 ° C., and examples thereof include polyolefin wax, natural wax, aliphatic alcohol having 30 to 50 carbon atoms, fatty acid having 30 to 50 carbon atoms, and a mixture thereof.
Polyolefin waxes include (co) polymers [obtained by (co) polymerization] of olefins (for example, ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-dodecene, 1-octadecene, and mixtures thereof). And olefin (co) polymer oxides with oxygen and / or ozone, maleic acid modifications of olefin (co) polymers [eg maleic acid and its derivatives (maleic anhydride, Modified products such as monomethyl maleate, monobutyl maleate and dimethyl maleate), olefins and unsaturated carboxylic acids [such as (meth) acrylic acid, itaconic acid and maleic anhydride] and / or unsaturated carboxylic acid alkyl esters [(meta ) Alkyl acrylate (alkyl 1 to 1 carbon atoms) 8) esters and maleic acid alkyl (C1-18 alkyl) copolymers of an ester, etc.] or the like, and Sasol wax.
Examples of natural waxes include carnauba wax, montan wax, paraffin wax, and rice wax. Examples of the aliphatic alcohol having 30 to 50 carbon atoms include triacontanol. Examples of the fatty acid having 30 to 50 carbon atoms include triacontane carboxylic acid.

  As charge control agents, nigrosine dyes, triphenylmethane dyes containing tertiary amines as side chains, quaternary ammonium salts, polyamine resins, imidazole derivatives, quaternary ammonium base-containing polymers, metal-containing azo dyes, copper phthalocyanine dyes , Salicylic acid metal salts, boron complexes of benzylic acid, sulfonic acid group-containing polymers, fluorine-containing polymers, halogen-substituted aromatic ring-containing polymers, and the like.

Examples of the fluidizing agent include colloidal silica, alumina powder, titanium oxide powder, and calcium carbonate powder.
The fluidizing agent is preferably added after the toner particles are formed.

  The composition ratio in the toner for developing an electrostatic image of the present invention is preferably 30 to 97%, preferably 30 to 97%, based on the toner weight, the resin composition containing the polyester resin (A) and the ester group-containing additive (B). Preferably 40 to 95%, particularly preferably 45 to 92%; the colorant is preferably 0.05 to 60%, more preferably 0.1 to 55%, particularly preferably 0.5 to 50%; Of the additives, the release agent is preferably 0 to 30%, more preferably 0.5 to 20%, particularly preferably 1 to 10%; the charge control agent is preferably 0 to 20%, more preferably 0.1 to 10%, particularly preferably 0.5 to 7.5%; the fluidizing agent is preferably 0 to 10%, more preferably 0 to 5%, particularly preferably 0.1 to 4%. . The total content of the toner additives is preferably 3 to 70%, more preferably 4 to 58%, and particularly preferably 5 to 50%. When the composition ratio of the toner is in the above range, a toner having good chargeability can be easily obtained.

The toner for developing an electrostatic charge image of the present invention has a volume average particle diameter of usually 3 to 10 μm, preferably 4 to 8 μm from the viewpoint of image resolution.
The volume average particle size / number average particle size is preferably 1.0 to 1.2, more preferably 1.0 to 1.15, from the viewpoint of particle size uniformity.

  The electrostatic charge image developing toner of the present invention is mixed with carrier particles such as ferrite whose surface is coated with iron powder, glass beads, nickel powder, ferrite, magnetite and resin (acrylic resin, silicone resin, etc.) as necessary. And used as a developer of an electric latent image. The weight ratio of toner to carrier particles is usually 1/99 to 100/0. In addition, instead of carrier particles, it can be rubbed with a member such as a charging blade to form an electrical latent image.

  The toner for developing an electrostatic charge image of the present invention is fixed on a support (paper, polyester film, etc.) by a copying machine, a printer or the like to form a recording material. As a method for fixing to the support, a known hot roll fixing method, flash fixing method, or the like can be applied.

  EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. Hereinafter, a part shows a weight part.

A method for measuring the properties of the resin obtained in the production example is shown below. Measurement methods other than the following are based on the above methods.
1. Glass transition temperature [Tg]
The method defined in ASTM D3418-82 (DSC method).
Apparatus: Seiko Electronics Co., Ltd. DSC20, SSC / 580
2. Tetrahydrofuran (THF) insoluble matter 50 ml of THF is added to 0.5 g of a sample, and the mixture is stirred and refluxed for 3 hours. After cooling from the reflux temperature to 20 ° C., the insoluble matter is filtered off with a glass filter and dried under reduced pressure at 80 ° C. for 3 hours. The insoluble content was calculated from the weight of the resin content on the glass filter and the weight ratio of the sample.
3. Flow softening point [Tm]
Using a flow tester, the temperature was raised at a constant speed under the following conditions, and the temperature at which the outflow amount was halved was defined as the softening point.
Apparatus: Flow tester CFT-500D manufactured by Shimadzu Corporation
Load: 20kg
Die: 1mmΦ-1mm
Temperature increase rate: 6 ° C./min.

Production Example 1 <Synthesis of ester group-containing additive and preparation of resin particle dispersion>
Into a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 6445 parts (18.5 mol) of a bisphenol A / PO2 mole adduct was gradually heated to 130 ° C. and reached 130 ° C. Then, 3555 parts (18.5 mol) of trimellitic anhydride was charged, held at 130 ° C. for 1 hour, and then taken out. The extracted compound was cooled to room temperature and then pulverized into particles. This is designated as an ester group-containing additive (B-1).
The Tg of the ester group-containing additive (B-1) is 62 ° C., Tm is 94 ° C. (Tm-Tg: 32 ° C.), Mn is 900, the acid value is 196, the hydroxyl value is 89, and the THF insoluble content is 0%. Met.
The number of moles in () means a relative molar ratio. (The same applies hereinafter)
To 100 parts of the polyester group-containing additive (B-1), 100 parts of acetone was added and dissolved, and 2.5 parts of triethylamine was further added. While stirring with a homogenizer (10000 rpm), 300 parts of water was added to an acetone solution of polyester, and acetone was distilled off under reduced pressure at 40 ° C. and 100 mmHg to obtain [resin particle dispersion WB-1]. The volume average particle diameter of [Resin Particle Dispersion WB-1] measured by a laser particle size distribution analyzer LA-920 (manufactured by Horiba Seisakusho) was 0.09 μm.

Production Example 2 <Synthesis of ester group-containing additive and preparation of resin particle dispersion>
Into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, 1652 parts (21.7 mol) of 1,2-propylene glycol (hereinafter simply referred to as propylene glycol) was placed, and the temperature was gradually raised to 130 ° C. When heated to 130 ° C., 8348 parts of trimellitic anhydride (4
3.5 mol) was added, held at 130 ° C. for 1 hour, and then taken out. The extracted compound was cooled to room temperature and then pulverized into particles. This is designated as an ester group-containing additive (B-2).
The ester group-containing additive (B-2) has a Tg of 45 ° C., a Tm of 78 ° C. (Tm-Tg: 33 ° C.), an Mn of 440, an acid value of 897, a hydroxyl value of 392, and a THF-insoluble content of 0%. Met.
To 100 parts of the polyester group-containing additive (B-2), 100 parts of acetone was added and dissolved, and 2.5 parts of triethylamine was further added. Under stirring with a homogenizer (10000 rpm), 300 parts of water was added to an acetone solution of polyester, and acetone was distilled off under reduced pressure at 40 ° C. and 100 mmHg to obtain [resin particle dispersion WB-2]. The volume average particle diameter of the [resin particle dispersion WB-2] measured by a laser particle size distribution analyzer LA-920 (manufactured by Horiba Seisakusho) was 0.09 μm.

Production Example 3 <Synthesis of ester group-containing additive and preparation of resin particle dispersion>
When 5743 parts (11.1 moles) of bisphenol A / PO 5 mole adduct is placed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, the temperature is gradually raised to 130 ° C. and reaches 130 ° C. Then, 4257 parts (22.2 mol) of trimellitic anhydride was charged, held at 130 ° C. for 1 hour, and then taken out. The extracted compound was cooled to room temperature and then pulverized into particles. This is designated as an ester group-containing additive (B-3).
The ester group-containing additive (B-3) has a Tg of 49 ° C., a Tm of 82 ° C. (Tm-Tg: 33 ° C.), an Mn of 800, an acid value of 260, a hydroxyl value of 8, and a THF insoluble content of 0%. Met.
To 100 parts of the polyester group-containing additive (B-3), 100 parts of acetone was added and dissolved, and 2.5 parts of triethylamine was further added. While stirring with a homogenizer (10000 rpm), 300 parts of water was added to an acetone solution of polyester, and acetone was distilled off under reduced pressure at 40 ° C. and 100 mmHg to obtain [resin particle dispersion WB-3]. The volume average particle diameter of [Resin Particle Dispersion WB-3] measured by a laser particle size distribution analyzer LA-920 (manufactured by Horiba Seisakusho) was 0.09 μm.

Production Example 4 <Synthesis of ester group-containing additive and preparation of resin particle dispersion>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 2441 parts (39.4 moles) of ethylene glycol were placed, gradually heated to 130 ° C, and when the temperature reached 130 ° C, anhydrous trimellit 7559 parts (39.4 moles) of acid was charged, held at 130 ° C. for 1 hour, and then taken out. The extracted compound was cooled to room temperature and then pulverized into particles. This is designated as ester group-containing additive (B-4).
The ester group-containing additive (B-4) has a Tg of 41 ° C., a Tm of 73 ° C. (Tm-Tg: 32 ° C.), an Mn of 220, an acid value of 450, a hydroxyl value of 200, and a THF insoluble content of 0%. Met.
To 100 parts of the polyester group-containing additive (B-4), 100 parts of acetone was added and dissolved, and 2.5 parts of triethylamine was further added. While stirring with a homogenizer (10000 rpm), 300 parts of water was added to an acetone solution of polyester, and acetone was distilled off under reduced pressure at 40 ° C. and 100 mmHg to obtain [resin particle dispersion WB-4]. The volume average particle diameter of [Resin Particle Dispersion WB-4] measured by a laser particle size distribution analyzer LA-920 (manufactured by Horiba Seisakusho) was 0.09 μm.

Production Example 5 <Synthesis of ester group-containing additive and preparation of resin particle dispersion>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, 5323 parts (15.7 mol) of bisphenol A diglycidyl ether was gradually heated to 150 ° C, and when the temperature reached 150 ° C, 4678 parts (28.2 moles) of terephthalic acid were charged, kept at 150 ° C. for 2 hours, and then taken out. The extracted compound was cooled to room temperature and then pulverized into particles. This is designated as an ester group-containing additive (B-5).
The ester group-containing additive (B-5) has a Tg of 55 ° C., a Tm of 92 ° C. (Tm-Tg: 37 ° C.), an Mn of 930, an acid value of 110, a hydroxyl value of 100, and a THF insoluble content of 0%. Met.
To 100 parts of the polyester group-containing additive (B-5), 100 parts of acetone was added and dissolved, and 2.5 parts of triethylamine was further added. While stirring with a homogenizer (10000 rpm), 300 parts of water was added to an acetone solution of polyester, and acetone was distilled off under reduced pressure at 40 ° C. and 100 mmHg to obtain [resin particle dispersion WB-5]. The volume average particle diameter of the [resin particle dispersion WB-5] measured by a laser particle size distribution analyzer LA-920 (manufactured by Horiba Seisakusho) was 0.09 μm.

Production Example 6 <Synthesis of Nonlinear Polyester and Preparation of Resin Particle Dispersion>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 2280 parts (30 moles) of propylene glycol, 1649 parts (8.5 moles) of dimethyl terephthalate, 219 parts (1.5 moles) of adipic acid and 3 parts of tetrabutoxy titanate was added as a condensation catalyst, and the reaction was allowed to proceed for 8 hours at 180 ° C. while distilling off the methanol produced under a nitrogen stream. Next, while gradually raising the temperature up to 230 ° C., propylene glycol produced in a nitrogen stream and water were allowed to react for 4 hours while distilling off water, and the reaction was further carried out under reduced pressure of 5 to 20 mmHg, and the softening point was 90 ° C. At that time, it was cooled to 180 ° C., 115 parts (0.6 mol) of trimellitic anhydride was added, and the reaction was conducted for 2 hours under sealed at atmospheric pressure, followed by reaction under reduced pressure of 220 ° C. and 5-20 mmHg, and the softening point was 155 ° C. When it became, it took out. The taken out resin was cooled to room temperature and then pulverized into particles. This is designated as nonlinear polyester (A1-1).
The nonlinear polyester (A1-1) had a Tg of 60 ° C., a Tm of 155 ° C., an Mp of 9000, an Mn of 7000, an acid value of 23, a hydroxyl value of 2, and a THF insoluble content of 20%.
To 100 parts of nonlinear polyester (A1-1), 100 parts of acetone was added and dissolved, and 2.5 parts of triethylamine was further added. While stirring with a homogenizer (10000 rpm), 300 parts of water was added to an acetone solution of polyester, and acetone was distilled off under reduced pressure at 40 ° C. and 100 mmHg to obtain [resin particle dispersion WA1-1]. The volume average particle diameter of the [resin particle dispersion WA1-1] measured by a laser particle size distribution analyzer LA-920 (manufactured by Horiba Seisakusho) was 0.09 μm.

Production Example 7 <Synthesis of Nonlinear Polyester and Preparation of Resin Particle Dispersion>
2543 parts (11.3 moles) of bisphenol A · PO3 mole adduct, 1527 parts (9.2 moles) of terephthalic acid, 93 parts (0.8 moles) of fumaric acid and 3 parts of tetrabutoxytitanate as a condensation catalyst The reaction was carried out for 5 hours while distilling off the water produced under nitrogen flow at ℃. Next, the reaction was carried out under reduced pressure of 5 to 20 mmHg. When the acid value became 2 or less, the mixture was cooled to 180 ° C., added with 250 parts (1.3 mol) of trimellitic anhydride, and reacted for 2 hours under sealed atmosphere. The reaction was carried out under reduced pressure of 230 ° C. and 5-20 mmHg, and the sample was taken out when the softening point reached 140 ° C. The taken out resin was cooled to room temperature and then pulverized into particles. This is designated as nonlinear polyester (A1-2).
The nonlinear polyester (A1-2) had a Tg of 57 ° C., a Tm of 145 ° C., an Mp of 8300, an Mn of 6200, an acid value of 16, a hydroxyl value of 24, and a THF insoluble content of 30%.
To 100 parts of nonlinear polyester (A1-2), 100 parts of acetone was added and dissolved, and 2.5 parts of triethylamine was further added. While stirring with a homogenizer (10000 rpm), 300 parts of water was added to an acetone solution of polyester, and acetone was distilled off under reduced pressure at 40 ° C. and 100 mmHg to obtain [resin particle dispersion WA1-2]. The volume average particle diameter of the [resin particle dispersion WA1-2] measured by a laser particle size distribution analyzer LA-920 (manufactured by Horiba Seisakusho) was 0.09 μm.

Production Example 8 <Synthesis of Linear Polyester and Preparation of Resin Particle Dispersion>
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 2280 parts (30 moles) of propylene glycol, 1940 parts (10 moles) of dimethyl terephthalate and 3 parts of tetrabutoxy titanate as a condensation catalyst were added. The reaction was carried out for 8 hours while distilling off the methanol produced under a nitrogen stream. Next, while the temperature was gradually raised to 230 ° C., the reaction was carried out while distilling off propylene glycol produced under a nitrogen stream, and cooling was performed when the softening point reached 45 ° C. When the temperature reached 180 ° C., 787 parts (4.1 mol) of trimellitic anhydride was charged, held at 180 ° C. for 1 hour, and then taken out. The taken out resin was cooled to room temperature and then pulverized into particles. This is designated as linear polyester (A2-1).
Tg of linear polyester (A2-1) is 54 ° C., Tm is 85 ° C. (Tm-Tg: 31 ° C.), Mp is 2000, Mn is 1100, acid value is 140, hydroxyl value is 81, and THF insoluble matter is 0. %Met.
To 100 parts of linear polyester (A2-1), 100 parts of acetone was added and dissolved, and 2.5 parts of triethylamine was further added. Under stirring with a homogenizer (10000 rpm), 300 parts of water was added to an acetone solution of polyester, and acetone was distilled off under reduced pressure at 40 ° C. and 100 mmHg to obtain [resin particle dispersion WA2-1]. The volume average particle diameter of the [resin particle dispersion WA2-1] measured by a laser particle size distribution analyzer LA-920 (manufactured by Horiba Seisakusho) was 0.09 μm.

Production Example 9 <Synthesis of Linear Polyester and Preparation of Resin Particle Dispersion>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 2990 parts (18.0 moles) of terephthalic acid, 7660 parts (23.4 moles) of bisphenol A · EO 2 mole adduct, and tetrabutoxy as a condensation catalyst 3 parts of titanate was added and reacted at 230 ° C. under a nitrogen stream for 5 hours while distilling off generated water. Next, the reaction was carried out under reduced pressure of 5 to 20 mmHg. When the softening point reached 94 ° C., the produced polymer was taken out, cooled to room temperature, pulverized and granulated. This is designated as linear polyester (A2-2). Tg of linear polyester (A2-2) is 60 ° C., Tm is 94 ° C. (Tm-Tg: 34 ° C.), Mp is 3500, Mn is 1800, acid value is 2, hydroxyl value is 55, THF insoluble matter is 0 %Met.
To 100 parts of linear polyester (A2-2), 100 parts of acetone was added and dissolved, and 2.5 parts of triethylamine was further added. While stirring with a homogenizer (10000 rpm), 300 parts of water was added to an acetone solution of polyester, and acetone was distilled off under reduced pressure at 40 ° C. and 100 mmHg to obtain [resin particle dispersion WA2-2]. The volume average particle diameter of the [resin particle dispersion WA2-2] measured by a laser particle size distribution analyzer LA-920 (manufactured by Horiba Seisakusho) was 0.09 μm.

Production Example 10 <Synthesis of linear polyester and preparation of resin particle dispersion>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 2300 parts (18.0 moles) of terephthalic acid, 8198 parts (23.4 moles) of bisphenol A.PO2 mole adduct, and tetrabutoxy as a condensation catalyst 3 parts of titanate was added and reacted at 230 ° C. under a nitrogen stream for 5 hours while distilling off generated water. Next, the reaction was carried out under reduced pressure of 5 to 20 mmHg, and when the acid value became 2 or less, after cooling to 180, 1283 parts of trimellitic anhydride was charged, and kept at 180 ° C. for 1 hour, and then taken out. The taken out resin was cooled to room temperature and then pulverized into particles. This is designated as linear polyester (A2-3). The linear polyester (A2-3) has a Tg of 61 ° C., a Tm of 93 ° C. (Tm-Tg: 32 ° C.), an Mp of 2000, an Mn of 1400, an acid value of 58, a hydroxyl value of 73, and a THF insoluble content of 0. %Met.
To 100 parts of linear polyester (A2-3), 100 parts of acetone was added and dissolved, and 2.5 parts of triethylamine was further added. While stirring with a homogenizer (10000 rpm), 300 parts of water was added to an acetone solution of polyester, and acetone was distilled off under reduced pressure at 40 ° C. and 100 mmHg to obtain [resin particle dispersion WA2-3]. The volume average particle diameter of [resin particle dispersion WA2-3] measured by a laser particle size distribution measuring apparatus LA-920 (manufactured by Horiba, Ltd.) was 0.09 μm.

Production Example 11 <Preparation of resin particle dispersion of linear polyester / ester group-containing additive>
To 50 parts of linear polyester (A2-1) and 50 parts of polyester group-containing additive (B-1), 100 parts of acetone was added and dissolved, and 2.5 parts of triethylamine was further added. While stirring with a homogenizer (10000 rpm), 300 parts of water was added to an acetone solution of polyester, and acetone was distilled off under reduced pressure at 40 ° C. and 100 mmHg to obtain [resin particle dispersion WC-1]. The volume average particle diameter of the [resin particle dispersion WC-1] measured by a laser particle size distribution measuring apparatus LA-920 (manufactured by Horiba Seisakusho) was 0.09 μm.

Production Example 12 <Preparation of resin particle dispersion of linear polyester / ester group-containing additive>
To 50 parts of linear polyester (A2-2) and 50 parts of polyester group-containing additive (B-1), 100 parts of acetone was added and dissolved, and 2.5 parts of triethylamine was further added. While stirring with a homogenizer (10000 rpm), 300 parts of water was added to an acetone solution of polyester, and acetone was distilled off under reduced pressure at 40 ° C. and 100 mmHg to obtain [resin particle dispersion WC-2]. The volume average particle diameter of the [resin particle dispersion WC-2] measured by a laser particle size distribution analyzer LA-920 (manufactured by Horiba Seisakusho) was 0.09 μm.

Production Example 13 <Preparation of resin particle dispersion of linear polyester / ester group-containing additive>
To 50 parts of linear polyester (A2-3) and 50 parts of polyester group-containing additive (B-1), 100 parts of acetone was added and dissolved, and 2.5 parts of triethylamine was further added. Under stirring with a homogenizer (10000 rpm), 300 parts of water was added to an acetone solution of polyester, and acetone was distilled off under reduced pressure at 40 ° C. and 100 mmHg to obtain [resin particle dispersion WC-3]. The volume average particle diameter of [Resin Particle Dispersion WC-3] measured by a laser particle size distribution analyzer LA-920 (manufactured by Horiba Seisakusho) was 0.09 μm.

Comparative Production Example 1 <Synthesis of ester group-containing additive for comparison and preparation of resin particle dispersion>
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 2836 parts (37.3 moles) of propylene glycol was put, and the temperature was gradually raised to 130 ° C. 7164 parts (37.3 moles) of acid was charged, held at 130 ° C. for 1 hour, and then taken out. The extracted compound was cooled to room temperature and then pulverized into particles. This is designated as an ester group-containing additive (B′-1).
The ester group-containing additive (B′-1) has a Tg of 39 ° C., a Tm of 79 ° C. (Tm-Tg: 40 ° C.), an Mn of 350, an acid value of 444, a hydroxyl value of 206, and a THF insoluble content of 0. %Met.
To 100 parts of the polyester group-containing additive (B′-1), 100 parts of acetone was added and dissolved, and 2.5 parts of triethylamine was further added. Under stirring with a homogenizer (10000 rpm), 300 parts of water was added to an acetone solution of polyester, and acetone was distilled off under reduced pressure at 40 ° C. and 100 mmHg to obtain [resin particle dispersion WB′-1]. The volume average particle diameter of the [resin particle dispersion WB′-1] measured by a laser particle size distribution analyzer LA-920 (manufactured by Horiba Seisakusho) was 0.09 μm.

Comparative Production Example 2 <Synthesis of ester group-containing additive for comparison and preparation of resin particle dispersion>
6301 parts (19.3 moles) of bisphenol A · EO2 mole adduct was placed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, and the temperature was gradually raised to 130 ° C. and reached 130 ° C. Then, 3699 parts (19.3 moles) of trimellitic anhydride was charged, held at 130 ° C. for 1 hour, and then taken out. The extracted compound was cooled to room temperature and then pulverized into particles. This is designated as an ester group-containing additive (B′-2).
The ester group-containing additive (B′-2) has a Tg of 87 ° C., a Tm of 152 ° C. (Tm-Tg: 66 ° C.), an Mn of 1800, an acid value of 126, a hydroxyl value of 12, and a THF insoluble content of 0. %Met.
To 100 parts of the polyester group-containing additive (B′-2), 100 parts of acetone was added and dissolved, and 2.5 parts of triethylamine was further added. Under stirring with a homogenizer (10000 rpm), 300 parts of water was added to an acetone solution of polyester, and acetone was distilled off under reduced pressure at 40 ° C. and 100 mmHg to obtain [resin particle dispersion WB′-2]. The volume average particle diameter of the [resin particle dispersion WB′-2] measured by a laser particle size distribution analyzer LA-920 (manufactured by Horiba, Ltd.) was 0.09 μm.

Comparative Production Example 3 <Synthesis of ester group-containing additive for comparison and preparation of resin particle dispersion>
When 5194 parts (12.5 moles) of bisphenol A / EO 4 mole adduct is placed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, the temperature is gradually raised to 130 ° C. and reaches 130 ° C. Then, 4806 parts (25.0 moles) of trimellitic anhydride was charged, held at 130 ° C. for 1 hour, and then taken out. The extracted compound was cooled to room temperature and then pulverized into particles. This is designated as an ester group-containing additive (B′-3).
The ester group-containing additive (B′-3) has a Tg of 73 ° C., a Tm of 110 ° C. (Tm-Tg: 37 ° C.), an Mn of 2300, an acid value of 250, a hydroxyl value of 5, and a THF insoluble content of 0. %Met.
To 100 parts of the polyester group-containing additive (B′-3), 100 parts of acetone was added and dissolved, and 2.5 parts of triethylamine was further added. While stirring with a homogenizer (10000 rpm), 300 parts of water was added to an acetone solution of polyester, and acetone was distilled off under reduced pressure at 40 ° C. and 100 mmHg to obtain [resin particle dispersion WB′-3]. The volume average particle diameter of the [resin particle dispersion WB′-3] measured by a laser particle size distribution analyzer LA-920 (manufactured by Horiba Seisakusho) was 0.09 μm.

Production Example 14 <Preparation of Colorant Dispersion>
100 parts of a phthalocyanine pigment (manufactured by Sanyo Dye: Cyanine Blue KRO), 2 parts of an anionic surfactant (manufactured by Sanyo Chemical Industries: Eleminol MON-7) and 250 parts of ion-exchanged water are mixed and dispersed with a TK homomixer [ Colorant dispersion 1] was obtained.

Production Example 15 <Preparation of Release Agent Dispersion>
80 parts of paraffin wax (melting point 73 ° C.), 1 part of an anionic surfactant (manufactured by Sanyo Chemical Industries: Eleminol MON-7) and 120 parts of ion-exchanged water are mixed and dissolved at 95 ° C., and then with a TK homomixer. Dispersion was carried out to obtain [Releasing Agent Dispersion Liquid 1].

Example 1 <Production of toner particles for developing an electrostatic image>
In a stainless steel beaker, 20 parts of [resin dispersion WA1-1], 160 parts of [resin dispersion WB-1], 15 parts of [colorant dispersion 1], 15 parts of [release agent dispersion 1], ion-exchanged water 600 parts and 1 part of magnesium sulfate were added and dispersed using a TK homomixer. After adjusting the pH to 7.0, the temperature was raised to 60 ° C. with stirring. When hydrochloric acid (0.1 mol / L) was added until the volume average particle diameter of the agglomerated particles became around 5.0 μm, 20 parts of [resin particle dispersion WA1-1] was added while maintaining the pH constant, and 60 parts After stirring at 0 ° C. for 1 hour, the mixture was further heated and stirred at 80 ° C. for 2 hours. Thereafter, the mixture was filtered, washed 4 times with 500 parts of ion exchange water, and dried at 40 ° C. for 18 hours to obtain toner particles (D-1).

Example 2 <Preparation of toner particles for developing electrostatic image>
Toner particles (D-2) were obtained in the same manner as in Example 1 except that 160 parts of [Resin dispersion WB-1] was changed to 160 parts of [Resin dispersion WB-2].

Example 3 <Preparation of toner particles for developing electrostatic image>
Toner particles (D-3) were obtained in the same manner as in Example 1 except that 160 parts of [Resin dispersion WB-1] was changed to 160 parts of [Resin dispersion WB-3].

Example 4 <Preparation of toner particles for developing electrostatic image>
160 parts of [resin dispersion WB-1] is 120 parts of [resin dispersion WB-4], 20 parts of [resin dispersion WA1-1] (twice) is 40 parts of [resin dispersion WA1-1] (2 Times) (80 parts in total), except that the toner particles (D-4) were obtained in the same manner as in Example 1.

Example 5 <Preparation of toner particles for electrostatic image development>
160 parts of [Resin dispersion WB-1] are 100 parts of [Resin dispersion WB-5], 20 parts of [Resin dispersion WA1-1] (twice) are 50 parts of [Resin dispersion WA1-1] (2 Times) (100 parts in total), except that the toner particles (D-5) were obtained in the same manner as in Example 1.

Example 6 <Preparation of toner particles for electrostatic image development>
Toner particles (D-6) were prepared in the same manner as in Example 1 except that 20 parts (2 times) of [Resin dispersion WA1-1] were changed to 20 parts (2 times) of [Resin dispersion WA1-2]. Obtained.

Example 7 <Preparation of toner particles for developing electrostatic image>
In a stainless steel beaker, 20 parts of [resin dispersion WA1-1], 80 parts of [resin dispersion WA2-1], 80 parts of [resin dispersion WB-1], 15 parts of [colorant dispersion 1], [release] Agent dispersion 1] 15 parts, 600 parts of ion-exchanged water, and 1 part of magnesium sulfate were added and dispersed using a TK homomixer. After adjusting the pH to 7.0, the temperature was raised to 60 ° C. with stirring. . When hydrochloric acid (0.1 mol / L) was added until the volume average particle size of the aggregated particles became around 5.0 μm, 20 parts of [resin particle dispersion WA1-1] was added while keeping the pH constant, After stirring at 60 ° C. for 1 hour, heating and stirring were further performed at 80 ° C. for 2 hours. Thereafter, the mixture was separated by filtration, washed four times with 500 parts of ion exchange water, and dried at 40 ° C. for 18 hours to obtain toner particles (D-7).

Example 8 <Preparation of toner particles for developing electrostatic image>
Except for changing 80 parts of [resin dispersion WA2-1] to 120 parts of [resin dispersion WA2-2] and 80 parts of [resin dispersion WB-1] to 40 parts of [resin dispersion WB-1] In the same manner as in Example 7, toner particles (D-8) were obtained.

Example 9 <Preparation of toner particles for electrostatic image development>
Except for changing 80 parts of [resin dispersion WA2-1] to 40 parts of [resin dispersion WA2-3] and 80 parts of [resin dispersion WB-1] to 120 parts of [resin dispersion WB-1]. In the same manner as in Example 7, toner particles (D-9) were obtained.

Example 10 <Preparation of toner particles for developing electrostatic image>
Toner particles (D-10) were obtained in the same manner as in Example 1 except that 160 parts of [Resin dispersion WB-1] was changed to 160 parts of [Resin dispersion WC-1].

Example 11 <Preparation of toner particles for electrostatic image development>
Toner particles (D-11) were obtained in the same manner as in Example 1 except that 160 parts of [Resin dispersion WB-1] was changed to 160 parts of [Resin dispersion WC-2].

Example 12 <Preparation of toner particles for developing electrostatic image>
[Resin dispersion WB-1] 160 parts [Resin dispersion WC-3] 120 parts, [Resin dispersion WA1-1] 20 parts (twice) [Resin dispersion WA1-1] 40 parts (2 Times) (80 parts in total), except that the toner particles (D-12) were obtained in the same manner as in Example 1.

Comparative Example 1 <Preparation of electrostatic charge image developing toner particles>
Comparative toner particles (D′-1) were obtained in the same manner as in Example 1 except that 160 parts of [Resin dispersion WB-1] was changed to 160 parts of [Resin dispersion WB′-1].

Comparative Example 2 <Preparation of electrostatic charge image developing toner particles>
Comparative toner particles (D′-2) were obtained in the same manner as in Example 1 except that 160 parts of [Resin dispersion WB-1] was changed to 160 parts of [Resin dispersion WB′-2].

Comparative Example 3 <Preparation of electrostatic charge image developing toner particles>
Comparative toner particles (D′-3) were obtained in the same manner as in Example 1 except that 160 parts of [Resin dispersion WB-1] was changed to 160 parts of [Resin dispersion WB′-3].

Examples 13 to 24 and Comparative Examples 4 to 6
Colloidal with respect to 100 parts of each of toner particles (D-1) to (D-12) obtained by the production method of the present invention and comparative toner particles (D′-1) to (D′-3) 0.5 parts of silica (Aerosil R972: manufactured by Nippon Aerosil Co., Ltd.) is mixed in a sample mill, and the electrostatic image developing toners (T-1) to (T-12) of the present invention and comparative electrostatic image development. Toners (T′-1) to (T′-3) were obtained.
The evaluation results evaluated by the following evaluation methods are shown in Table 1.

[Evaluation method]
[Volume average particle diameter / number average particle diameter]
Volume average particle diameter and number average particle diameter were measured with Multisizer III (manufactured by Coulter Inc.).

(Low temperature fixability)
After adding 1.0% Aerosil R972 (manufactured by Nippon Aerosil Co., Ltd.) to the resin particles and mixing well, the powder is uniformly placed on the paper surface so as to be 0.6 mg / cm ² (at this time As a method for placing the body on the paper surface, a printer from which the heat fixing machine is removed is used (other methods may be used as long as the powder can be placed uniformly at the above-mentioned weight density). The temperature at which cold offset was generated when passing through a roller under conditions of a fixing speed (heating roller peripheral speed) of 213 mm / sec and a fixing pressure (pressure roller pressure) of 10 kg / cm ² was measured.

[Blocking resistance]
20 g of a sample was put in a 200 ml polycup and allowed to stand in a circulating dryer at 40 ° C. After 5 days, the sample was taken out from the dryer, and the fluidity of the sample was confirmed.
(Judgment)
A: Flows when the cup is tilted.
○: It flows when the cup is tilted and patted with a spatula.
Δ: Flows when the cup is tilted and pucked strongly with a spatula.
X: The cup does not flow even when tilted and spatula strongly.
A judgment of ◯ or more is judged to have good blocking resistance.

  The electrostatic image developing toner of the present invention has a uniform particle size, excellent low-temperature fixability and blocking resistance, and is particularly useful for color.

Claims (10)

  An electrostatic charge image developing toner comprising toner particles containing at least a resin composition for a toner and a colorant, wherein the toner particles are dispersed in water at least with resin particles having a volume average particle size of 1 μm or less; A particle having a volume average particle diameter of 3 to 10 μm formed from a process including a process of aggregating resin particles, and the resin composition for toner contains a non-linear polyester (A1) and, if necessary, a linear polyester (A2). The polyester resin (A) and the ester group-containing additive (B) are contained, the number average molecular weight of the tetrahydrofuran (THF) soluble component of (B) is 1000 or less, and the glass transition temperature [Tg] (B) ( C.) and a flow softening point [Tm] (° C.) satisfy a relationship of [Tm] − [Tg] ≦ 38 (° C.).   The toner for developing an electrostatic charge image according to claim 1, wherein the glass transition temperature [Tg] (° C) of (B) is 40 to 75 (° C) and the acid value is 100 to 1000 (mgKOH / g).   3. The electrostatic image developing toner according to claim 1, wherein (B) is a reaction product of a polyol and a polycarboxylic acid, or a reaction product of an epoxy group-containing compound and a polycarboxylic acid.   The toner for developing an electrostatic charge image according to claim 1, wherein the THF-insoluble matter in (A1) is 3 to 50% by weight.   (A) contains (A2), the acid value of (A2) is 2 to 200 (mg KOH / g), the glass transition temperature [Tg] (° C.) and the flow softening point [Tm] of (A2) ( The toner for developing an electrostatic charge image according to claim 1, wherein [° C.] satisfies a relationship of [Tm] − [Tg] ≦ 38 (° C.).   6. The electrostatic image developing toner according to claim 5, wherein the glass transition temperature [Tg] (° C.) of (A2) is 40 to 75 (° C.) and the hydroxyl value is 25 to 125 (mg KOH / g).   The toner for developing an electrostatic charge image according to claim 1, wherein a weight ratio of (A1) to (A2) is 100/0 to 20/80.   The toner for developing an electrostatic charge image according to claim 1, wherein the weight ratio of (A) to (B) is 50/50 to 99/1.   The toner for developing an electrostatic charge image according to claim 1, further comprising one or more additives selected from a release agent, a charge control agent, and a fluidizing agent.   A method for producing a toner for developing an electrostatic image comprising toner particles containing at least a resin composition for a toner and a colorant, wherein the resin particles have a step of dispersing resin particles having a volume average particle size of 1 μm or less in water, And a step of fusing the agglomerated resin particles to obtain toner particles having a volume average particle diameter of 3 to 10 μm. In the toner resin composition, the nonlinear polyester (A1) and, if necessary, the linear polyester (A2) ) -Containing polyester resin (A) and an ester group-containing additive (B), the tetrahydrofuran (THF) -soluble number average molecular weight of (B) is 1000 or less, and the glass transition temperature of (B) An electrostatic charge image developing toner characterized in that [Tg] (° C.) and flow softening point [Tm] (° C.) satisfy a relationship of [Tm] − [Tg] ≦ 38 (° C.) Production method.