JP5185005B2 - Toner for electrostatic image development - Google Patents

Description

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

The present inventors arrived at the present invention after earnestly studying to solve these problems.
That is, the present invention is an electrostatic charge image developing toner including toner particles containing a toner resin and a colorant, wherein the toner particles disperse at least resin particles having a volume average particle diameter of 1 μm or less in water. A particle having a volume average particle diameter of 3 to 10 μm formed from a process including a process and a process of aggregating the resin particles, the polyester resin (A) is contained in the toner resin, and (A) is an acid Polyester resin (a) having a valence of 6 mgKOH / g or less and a hydroxyl value of 10 to 70 mgKOH / g, aliphatic carboxylic acid, aromatic carboxylic acid, acid anhydride and lower alkyl (1 to 4 carbon atoms) ester thereof It is a polyester resin obtained by reacting with one or more carboxylic acids (b) selected from the group consisting of: (A) THF-insoluble matter of 1 to 36% by weight, THF soluble An electrostatic charge having a peak top molecular weight of 4500 to 20000, a softening point of 120 to 180 ° C., and (A) satisfying the following formulas (1) and (2): An image developing toner; and a method for producing an electrostatic image developing toner comprising toner particles containing a toner resin and a colorant, the method comprising dispersing at least resin particles having a volume average particle diameter of 1 μm or less in water; A step of agglomerating the resin particles, and a step of fusing the agglomerated resin particles to obtain toner particles having a volume average particle diameter of 3 to 10 μm, the polyester resin (A) being contained in the toner resin; A) is a polyester resin (a) having an acid value of 6 mgKOH / g or less and a hydroxyl value of 10 to 70 mgKOH / g, an aliphatic carboxylic acid, an aromatic carboxylic acid, And a polyester resin obtained by reacting one or more carboxylic acids (b) selected from the group consisting of acid anhydrides and lower alkyl (C1-4) esters, and insoluble in THF in (A) The gel top permeation chromatography has a peak top molecular weight of 4500 to 20000, a softening point of 120 to 180 ° C., and (A) is represented by the following formulas (1) and (1): 2) A method for producing a toner for developing an electrostatic image characterized by satisfying the above.
Acid value / hydroxyl value ≧ 1 (however, acid value = 15-80 mg KOH / g) Formula (1)
THF insoluble matter (% by weight) / softening point (° C.) ≦ 0.2 (2)

   By using the toner for developing an electrostatic charge image of the present invention obtained by the production method of the present invention, it is possible to obtain a toner having a uniform particle size, excellent low-temperature fixability and blocking resistance, and good hot offset resistance. It is.

The present invention is described in detail below.
The toner for developing an electrostatic charge image of the present invention comprises a polyester resin (a) having a specific acid value and a specific hydroxyl value, an aliphatic carboxylic acid, an aromatic carboxylic acid, an acid anhydride thereof and a lower alkyl (1 carbon number). -4) A polyester resin (A) obtained by reacting with one or more carboxylic acids (b) selected from the group consisting of esters, a colorant, and, if necessary, a polyester resin containing no THF-insoluble matter ( The resin used for forming the resin particles containing B) is dispersed in water at 1 μm or less, and the water-dispersed resin is aggregated to adjust the particle size of the aggregated particles, 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 toner resin in the electrostatic image developing toner of the present invention includes a polyester resin (a) having a specific acid value and a specific hydroxyl value, an aliphatic carboxylic acid, an aromatic carboxylic acid, and their acid anhydrides and lower The polyester resin (A) obtained by making 1 or more types of carboxylic acid (b) chosen from the group which consists of alkyl (C1-C4) ester react is contained.
The polyester resin (a) is preferably one obtained by polycondensation of one or more polyol components and one or more polycarboxylic acid components.

  Among the polyol components of the raw material of the polyester resin (a), the dihydric alcohol (diol) includes an aliphatic diol having 2 to 36 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1 , 4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2,3-pentanediol, 1,6-hexanediol, 2,3-hexanediol, 3,4-hexanediol, neopentyl Glycols, 1,7-heptanediol, and alkanediols such as dodecanediol); polyalkylene ether glycols having 4 to 36 carbon atoms (such as diethylene glycol, dipropylene glycol, polyethylene glycol, and polypropylene glycol); The aliphatic diol C2-C4 alkylene oxide (hereinafter abbreviated as AO) [ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), butylene oxide, etc.] adduct (added mole number: 2 to 30); C6-C36 alicyclic diol (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); C2-C4 AO adduct (added mole number 2-30) of the alicyclic diol; Examples thereof include AO adducts having 2 to 4 carbon atoms (2 to 30 addition moles) of bisphenols (such as bisphenol A, bisphenol F, and bisphenol S), and two or more types may be used in combination.

Among the polyol components, the polyol having 3 to 8 or more valences includes 3 to 8 or more aliphatic polyhydric alcohols having 3 to 36 carbon atoms (glycerin, triethylolethane, trimethylolpropane, pentaerythritol and sorbitol). AO adduct having 2 to 4 carbon atoms of the above aliphatic polyhydric alcohol (addition mole number 2 to 30); AO adduct having 2 to 4 carbon atoms (addition moles) of trisphenols (trisphenol PA and the like); 2-30); novolak resins (phenol novolak, cresol novolak, etc .: average degree of polymerization 3-60) carbon number 2-4 AO adduct (added mole number 2-30), and the like. You may use together.
Among these polyol components, preferably, a polyalkylene ether glycol having 2 to 6 carbon atoms, an alicyclic diol having 6 to 36 carbon atoms, or an alicyclic diol having 6 to 36 carbon atoms having 2 to 4 carbon atoms. AO adducts, AO adducts having 2 to 4 carbon atoms of bisphenols, and AO adducts of 2 to 4 carbon atoms of novolak resins, more preferably AO (EO and EO and C2) of bisphenols. And / or PO) adducts, and AO (EO and / or PO) adducts having 2 to 3 carbon atoms of novolak resins.

Among the polycarboxylic acid components of the raw material of the polyester resin (a), as the aliphatic (including alicyclic) dicarboxylic acid, an alkanedicarboxylic acid having 2 to 50 carbon atoms (oxalic acid, malonic acid, succinic acid, adipic acid, Rephenic acid and sebacic acid), alkenedicarboxylic acids having 4 to 50 carbon atoms (alkenyl succinic acid such as dodecenyl succinic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and glutaconic acid), etc. Can be mentioned.
Examples of the aromatic dicarboxylic acid include aromatic dicarboxylic acids having 8 to 36 carbon atoms (such as phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid).

Among the polycarboxylic acid components, trivalent to hexavalent or higher aliphatic (including alicyclic) polycarboxylic acids include aliphatic tricarboxylic acids having 6 to 36 carbon atoms (such as hexanetricarboxylic acid) and unsaturated carboxylic acids. Examples include acid vinyl polymers [number average molecular weight (hereinafter referred to as Mn, according to gel permeation chromatography (GPC)): 450 to 10,000] (α-olefin / maleic acid copolymer and the like).
Among the polycarboxylic acid components, trivalent to hexavalent or higher aromatic polycarboxylic acids include aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, gel and pyromellitic acid, etc.), unsaturated Examples thereof include vinyl polymers of carboxylic acids [Mn: 450 to 10,000] (styrene / maleic acid copolymers, styrene / acrylic acid copolymers, styrene / fumaric acid copolymers, and the like).
As the polycarboxylic acid component, anhydrides and lower alkyl (carbon number 1 to 4) esters (methyl ester, ethyl ester, isopropyl ester, etc.) of these polycarboxylic acids may be used.

  Among these polycarboxylic acid components, preferred are alkane dicarboxylic acids having 2 to 50 carbon atoms, alkene dicarboxylic acids having 4 to 50 carbon atoms, aromatic dicarboxylic acids having 8 to 20 carbon atoms, and 9 to 20 carbon atoms. An aromatic polycarboxylic acid, more preferably adipic acid, alkenyl succinic acid having 16 to 50 carbon atoms, terephthalic acid, isophthalic acid, maleic acid, fumaric acid, trimellitic acid, pyromellitic acid, and combinations thereof Particularly preferred are adipic acid, terephthalic acid, trimellitic acid, and combinations thereof. Likewise preferred are anhydrides and lower alkyl esters of these acids.

  Moreover, as a polycarboxylic acid component, what consists of aromatic polycarboxylic acid and aliphatic polycarboxylic acid as needed, and contains 60 mol% or more of aromatic polycarboxylic acid is preferable. The content of the aromatic polycarboxylic acid is more preferably 70 to 100 mol%, particularly preferably 80 to 100 mol%. By containing 60 mol% or more of aromatic polycarboxylic acid, the resin strength increases and the low-temperature fixability is further improved.

In the present invention, the polyester resin (a) 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 240 ° C. The reaction time is preferably 30 minutes or longer, particularly 2 to 40 hours from the viewpoint of reliably performing the polycondensation reaction.
At this time, an esterification catalyst may be used as necessary. Examples of esterification catalysts include tin-containing catalysts (eg, dibutyltin oxide), antimony trioxide, titanium-containing catalysts [eg, titanium alkoxide, potassium titanyl oxalate, titanium terephthalate, titanium terephthalate alkoxide, and titanium dihydroxybis (triethanol Aminates) and their intramolecular polycondensates], zirconium-containing catalysts (for example, zirconyl acetate), and zinc acetate. It is also effective to reduce the pressure in order to improve the reaction rate at the end of the reaction.
The reaction ratio between the polyol component and the polycarboxylic acid component is preferably 1.4 / 1 to 1/1, more preferably 1.35 / 1 to 1 as the equivalent ratio [OH] / [COOH] of the hydroxyl group to the carboxyl group. 1.1 / 1, particularly preferably 1.35 / 1 to 1.2 / 1. In addition, the said reaction ratio is a ratio which excluded the part, when there exists a component removed out of a system during reaction.

The polyester resin (a) has an acid value of 6 (mg KOH / g, the same for the following acid values) or less and a hydroxyl value of 10 to 70 (mg KOH / g, the same for the following hydroxyl values). The acid value is preferably 5 or less, more preferably 4 or less, and the hydroxyl value is preferably 15 to 65, more preferably 20 to 60. When the acid value is more than 6 or when the hydroxyl value is more than 70, it indicates that the polycondensation of the polyester resin (a) is insufficient and that there are many low molecular weight components. The storage stability of deteriorates. When the hydroxyl value is less than 10, the reaction efficiency with the carboxylic acid (b) is deteriorated.
In order to set the acid value and hydroxyl value of the polyester resin (a) within these ranges, it is effective to adjust the reaction ratio between the polyol component and the polycarboxylic acid component.

  In the above and the following, the acid value and hydroxyl value of the polyester resin are measured by the method specified in JIS K0070 (1992 version).

  The molecular weight of the polyester resin (a) is preferably a peak top molecular weight (hereinafter referred to as Mp) of 2000 to 10,000, and more preferably Mp of 3000 to 8000. Further, Mn is preferably 500 to 8000, and more preferably 1000 to 7000.

In the present invention, the molecular weight [Mp, Mn, and weight average molecular weight (hereinafter referred to as Mw)] of the polyester resin is measured using GPC under the following conditions.
Above and below, the molecular weight (Mp, Mn, and Mw) of the polyester resin is measured under the following conditions using GPC.
Device (example): HLC-8120 manufactured by Tosoh Corporation
Column (example): TSK GEL GMH6 2 [Tosoh Corporation]
Measurement temperature: 40 ° C
Sample solution: 0.25 wt% THF (tetrahydrofuran) solution Solution injection amount: 100 μl
Detection device: Refractive index detector Reference material: Tosoh standard polystyrene (TSK standard POLYSYRENE) 12 points (Molecular weight 1050 2800 5970 9100 18100 37900 96400 190000 355000 1090000 2890000 4480000)
The molecular weight showing the maximum peak height on the obtained chromatogram is referred to as peak top molecular weight (Mp). The molecular weight of the toner resin was measured by dissolving the polyester resin for toner in THF and filtering out the insoluble matter with a glass filter as a sample solution.

  The polyester resin (A) is one or more selected from the group consisting of a polyester resin (a), an aliphatic carboxylic acid, an aromatic carboxylic acid, and their acid anhydrides and lower alkyl (C1-4) esters. When the mixing ratio at the time of the reaction is such that the equivalent of the hydroxyl group derived from (a) is OHa and the equivalent of the carboxyl group derived from (b) is COOHb, OHa / COOHb = 0. What is obtained by reacting at an equivalent ratio of 1 to 1.0 is preferable. OHa / COOHb is more preferably 0.2 to 0.9, and particularly preferably 0.3 to 0.8. When OHa / COOHb is 0.1 or more, the molecular weight becomes sufficiently large, and the hot offset resistance at the time of toner formation is improved. When it is 1.0 or less, the fluidity of the resin becomes good, and the low-temperature fixability at the time of toner formation is improved.

As the carboxylic acid (b), either a monocarboxylic acid or a polycarboxylic acid can be used. The ratio of the monocarboxylic acid to the polycarboxylic acid is such that the equivalent of all carboxyl groups of the carboxylic acid used in the reaction is 100. The equivalent ratio of the carboxyl group derived from the monocarboxylic acid and the carboxyl group derived from the polycarboxylic acid is preferably (0-50) / (50-100), and (0-20) / (80-100) is more preferred. preferable. When the ratio of the carboxyl derived from the monocarboxylic acid is 50 or less, the crosslinking is not insufficient and the strength of the resin is sufficiently obtained. Moreover, it is easy to adjust the acid value of the reaction product within a predetermined range.
As (b), acid anhydrides and lower alkyl (C1-4) esters (methyl esters, ethyl esters, isopropyl esters, etc.) may be used.

Among the monocarboxylic acids used as the carboxylic acid (b), the aliphatic (including alicyclic) monocarboxylic acids include alkane monocarboxylic acids having 1 to 50 carbon atoms (formic acid, acetic acid, propionic acid, butanoic acid, isobutane). Acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, etc.), C3-C50 alkene monocarboxylic acid (acrylic acid, methacrylic acid, oleic acid, linoleic acid, etc.), etc. .
Examples of the aromatic monocarboxylic acid include aromatic monocarboxylic acids having 7 to 36 carbon atoms (such as benzoic acid, methylbenzoic acid, phenylpropionic acid, and naphthoic acid).

Among the polycarboxylic acids used as (b), aliphatic (including alicyclic) dicarboxylic acids, aromatic dicarboxylic acids, trivalent to hexavalent or higher aliphatic (including alicyclic) polycarboxylic acids, and Examples of the trivalent to hexavalent or higher aromatic polycarboxylic acid include those similar to those used for the polyester resin (a).
Among these, divalent or higher aromatic carboxylic acids are preferable, trivalent to hexavalent or higher aromatic polycarboxylic acids are more preferable, and trimellitic acid and trimellitic anhydride are particularly preferable.

  The content of the trivalent to hexavalent or higher aromatic polycarboxylic acid in the carboxylic acid component constituting the polyester resin (A) is preferably 1 to 30 mol%, more preferably 1 to 20 mol%. When it is 30 mol% or less, the fluidity of the resin is good, and the low-temperature fixability at the time of toner formation is improved.

The polyester resin (A) can be obtained by the same production method as the polyester resin (a) except that the polyester resin (A) is adjusted to have an acid value and an acid value / hydroxyl value in the following range.
The acid value of (A) is 15-80, preferably 18-60. Moreover, although the hydroxyl value of (A) should just satisfy | fill following formula (1), Preferably it is 1-40, More preferably, it is 3-30, Most preferably, it is 9-25.
When the acid value is less than 15, it is not easy to disperse in water to 1 μm or less, and the fixing strength of the obtained toner is weakened. On the other hand, when the acid value exceeds 80, the water-dispersed resin is not easily aggregated, and the obtained toner is easily affected by environmental conditions, and the stability is deteriorated.
In the present invention, the acid value and hydroxyl value of (A) satisfy the relationship of the following formula (1).
Acid value / Hydroxyl value ≧ 1 (however, acid value = 15-80) Formula (1)
When the acid value / hydroxyl value is less than 1, the glossiness in the glossiness expression temperature and the fixing temperature range is lowered. The acid value / hydroxyl value is preferably 2 to 10. In addition, in order to manufacture the polyester resin (A) which satisfy | fills Formula (1), it can achieve by adjusting the reaction ratio of a polyester resin (a) and carboxylic acid (b), for example.

The acid value of the polyester resin is usually derived from a carboxyl group. In the method for producing an electrostatic charge image developing toner of the present invention, in order to facilitate dispersion of resin particles of 1 μm or less in water, a polyester resin (A ) And a carboxyl group of the polyester resin (B) described later may be at least partially neutralized with a base. As for the neutralization rate of a carboxyl group, 20-100 equivalent% is preferable.
Examples of the base that forms the neutralized salt include ammonia, monoamines having 1 to 30 carbon atoms (such as ethylamine, n-butylamine, trimethylamine, triethylamine, and lauryldimethylamine), quaternary ammonium (such as lauryltrimethylammonium), and alkali metals. (Sodium, potassium, etc.) and alkaline earth metals (calcium, magnesium, etc.).

  The THF insoluble content of the polyester resin (A) is 1 to 36% by weight, preferably 2 to 33% by weight, more preferably 3 to 28% by weight, and particularly preferably 4 to 25% by weight. If the THF-insoluble content is less than 1% by weight, the hot offset resistance is lowered, and if it exceeds 36% by weight, the low-temperature fixability is lowered.

In the above and the following, the THF-insoluble content of the polyester resin 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.

The softening point of the polyester resin (A) used in the present invention is 120 to 180 ° C, preferably 122 to 170 ° C, more preferably 123 to 155 ° C, from the viewpoint of hot offset resistance and low-temperature fixability.
In the present invention, the temperature was raised at a constant speed using a flow tester under the following conditions, and the temperature at which the outflow amount was halved was defined as the softening point.
Device: Shimadzu Corporation flow tester CFT-500
Load: 20kg
Die: 1mmΦ-1mm
Temperature increase rate: 6 ° C./min.

In the present invention, the THF insoluble matter and the softening point of (A) satisfy the relationship of the following formula (2).
THF insoluble matter (% by weight) / softening point (° C.) ≦ 0.2 (2)
If the THF insoluble content / softening point exceeds 0.2, it is difficult to achieve both low-temperature fixability and hot offset resistance, and the glossiness at the glossiness expression temperature and the fixing temperature range decreases. The THF insoluble matter / softening point is preferably 0.01 to 0.19.
In order to produce the polyester resin (A) satisfying the formula (2), for example, after producing the polyester resin (a), the polyester resin (A) is reacted with the carboxylic acid (b). This can be achieved by producing A), in which the hydroxyl value of (a) is 10 to 70 mg KOH / g, and the reaction rate of (a) and (b) is adjusted. Specifically, when the reaction rate of (a) and (b) is lowered [that is, the amount of unreacted hydroxyl group of (a) and carboxyl group of (b) is increased], THF insoluble matter / softening On the contrary, the reaction rate of (a) and (b) is increased (that is, the amount of unreacted (a) hydroxyl group and (b) carboxyl group is decreased) and THF insoluble matter / softening The point goes up.

As for the molecular weight of a polyester resin (A), Mp is 4500-20000, Preferably it is 5000-20000, More preferably, it is 5500-15000. Mw is preferably 30000-300000, and more preferably 40000-250,000. Further, the ratio of Mw and Mn (hereinafter referred to as Mw / Mn) showing the molecular weight distribution is preferably 15 to 100, and more preferably 20 to 90.
When Mp, Mw, and Mw / Mn are within the above ranges, the balance between hot offset resistance and low-temperature fixability is good.

In the present invention, the difference in softening point between the polyester resin (A) before and after being heated and melted at 200 ° C. is preferably 10 ° C. or less, and more preferably 5 ° C. or less. In addition, the softening point after heating and melting at 200 ° C is preferably 110 to 190 ° C, and more preferably 120 to 180 ° C.
In addition, the difference of the softening point before and behind heat-melting at 200 degreeC is measured as follows.
A test tube containing 3 g of (A) is placed in a block bath adjusted to 200 ° C., heated and dissolved for about 10 minutes, and then dissolved (A) is put into ice water together with the test tube and cooled. For the heated and melted (A) and the pre-heated and melted (A), the softening point is measured by the above method, and the difference is obtained.

In the present invention, the polyester resin (A) preferably has a change rate of Mp of a component soluble in THF before and after being melted at 200 ° C. of 10% or less, and more preferably 9% or less. In addition, Mp after heating and melting at 200 ° C. is preferably 4050 to 22000, and more preferably 4500 to 20000.
The method of heat-melting treatment at 200 ° C. is the same as the method described in the previous section, and Mp is the same as the Mp measurement method of the polyester resin described above.
As a method for reducing the difference in softening point before and after heating and melting at 200 ° C. and the difference in Mp of components soluble in THF before and after heating and melting at 200 ° C., for example, the reaction of (a) and (b) A method of cooling the polyester resin (A) after completion in a shorter time using an apparatus such as a belt cooler can be mentioned.

The toner resin used in the toner for developing an electrostatic charge image of the present invention may contain a polyester resin (B) not containing a THF-insoluble component together with the polyester resin (A). The electrostatic charge image developing toner of the present invention exhibits excellent fixability even when only the polyester resin (A) is used as the toner resin. However, the use of the polyester resin (B) together with the polyester resin (A) Excellent fixability can be obtained.
The polyester resin (B) is usually obtained by polycondensation of one or more polyol components and one or more polycarboxylic acid components, and the composition is not particularly limited.

  Among the polyol components used as the raw material of (B), as the diol, the aliphatic diol having 2 to 36 carbon atoms, the polyalkylene ether glycol having 4 to 36 carbon atoms, and the carbon number 2 of the aliphatic diol having 2 to 36 carbon atoms. -4 AO adduct (addition mole number 2-30), alicyclic diol having 6-36 carbon atoms, AO adduct having 2-4 carbon atoms of alicyclic diol having 6-36 carbon atoms (addition mole number) 2 to 30), and AO adducts having 2 to 4 carbon atoms (2 to 30 addition moles) of bisphenols, and the like may be used in combination. Specific examples thereof are the same as those used for the polyester resin (a).

  Among the polyol components, the alcohol having 3 to 8 or more valences includes 3 to 8 or more aliphatic polyhydric alcohols having 3 to 36 carbon atoms, or AO having 2 to 4 carbon atoms of the aliphatic polyhydric alcohols. Adduct (addition mole number 2 to 30), trisphenol A2 adduct having 2 to 4 carbon atoms (addition mole number 2 to 30), novolak resin 2 to 4 carbon atoms AO adduct (addition mole number 2) ~ 30) and the like, and two or more of them may be used in combination. Specific examples thereof are the same as those used for the polyester resin (a).

  Among these polyol components, preferred are aliphatic diols having 2 to 6 carbon atoms, polyalkylene ether glycols having 4 to 36 carbon atoms, alicyclic diols having 6 to 36 carbon atoms, and alicyclic diols having 6 to 36 carbon atoms. AO adduct having 2 to 4 carbon atoms, an AO adduct having 2 to 4 carbon atoms of bisphenols, and an AO adduct having 2 to 4 carbon atoms of novolak resin, more preferably 2 to 6 carbon atoms. An aliphatic diol, an AO (EO and PO) adduct having 2 to 3 carbon atoms of bisphenols, and an AO (EO and PO) adduct having 2 to 3 carbon atoms of a novolak resin.

Among the polycarboxylic acid components, aliphatic (including alicyclic) dicarboxylic acid, aromatic dicarboxylic acid, 3 to 6 or more aliphatic (including alicyclic) polycarboxylic acid, and 3 to 6 valent Examples of the aromatic polycarboxylic acid higher than that include those used for the polyester resin (a).
As the polycarboxylic acid component, anhydrides and lower alkyl (C1 to C4) esters of these polycarboxylic acids may be used.
Among these polycarboxylic acid components, preferred are the same polycarboxylic acids used for the polyester resin (a).

The acid value of the polyester resin (B) is preferably 5 to 80, more preferably 8 to 50, and particularly preferably 10 to 30.
The hydroxyl value is preferably 60 or less, more preferably 50 or less, and particularly preferably 5 to 45.

  As for the molecular weight of a polyester resin (B), it is preferable that Mp is 3000-10000, and it is more preferable that Mp is 3500-9000.

In the present invention, the polyester resin (B) can be produced in the same manner as in an ordinary polyester production method. For example, the method similar to the manufacturing method of the above-mentioned polyester resin (a) is mentioned.
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 weight ratio of the polyester resin (A) to the polyester resin (B) in the toner resin used in the toner for developing an electrostatic charge image of the present invention is (5-5) when the total of (A) and (B) is 100. 100) / (95-0) is preferable, (8-95) / (92-5) is more preferable, and (10-80) / (90-20) is particularly preferable.

The toner resin used for the electrostatic image developing toner of the present invention preferably contains only the polyester resin (A) or only the polyester resin (A) and the polyester resin (B). In addition to these, other commonly used resins may be contained within a range that does not impair the characteristics. Other resins include polyester resins other than (A) and (B), vinyl resins [copolymers of styrene and alkyl (meth) acrylate, copolymers of styrene and diene monomers, etc.], epoxy resins ( Bisphenol A diglycidyl ether ring-opening polymer), urethane resin (diol and / or polyaddition product of tri- or higher valent polyol and diisocyanate, etc.). When two or more kinds of polyester resins are used in combination, and when at least one kind of polyester resin and another resin are used, powder mixing, melt mixing, or partial reaction may be performed. Further, it may be dispersed separately in water at the time of toner formation.
The Mn of other resins is preferably 1000 to 100,000. The content of the other resin is preferably 10% by weight or less, more preferably 8% by weight or less with respect to the total amount of the resin for toner [the total amount of (A), (B) and other resin]. is there.

In the method for producing a toner for developing an electrostatic charge image of the present invention, a volume containing a polyester resin (A) and, if necessary, a polyester resin (B) in water (including a mixed solvent of water and a small amount of a water-soluble organic solvent). The method for dispersing the resin particles having an average particle diameter of 1 μm or less is not particularly limited, but the following [1] to [7] are 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 polyester resin (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 methods [1] to [7], a known surfactant (s), water-soluble polymer (t) and the like can be used as the emulsifier or dispersant used in combination. 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), an AO addition type nonionic surfactant and a polyhydric alcohol type nonionic surfactant 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% by weight 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.

In the toner for developing an electrostatic charge image of the present invention, the resin particles containing the polyester resin (A) having a volume average particle diameter of 1 μm or less and, if necessary, the polyester resin (B) obtained by the above method are dispersed in water. 1 type or 2 or more types 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 glass transition temperature of the resin. It is obtained by fusing.
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% by weight for divalent, or about 3% for trivalent. It is about 0.5% by weight 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 polyester resin (A) serving as a binder resin and, if necessary, a toner resin containing a polyester resin (B), a colorant, and, if necessary, a release agent and a charge control agent. And at least one toner additive selected from fluidizing agents and the like.

  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 charge image of the present invention is based on the toner weight [% in this item is% by weight. ], A resin for toner containing the polyester resin (A) and, if necessary, the polyester resin (B) is preferably 30 to 97%, more preferably 40 to 95%, particularly preferably 45 to 92%; Preferably 0.05 to 60%, more preferably 0.1 to 55%, particularly preferably 0.5 to 50%; among toner additives, a release agent is preferably 0 to 30%, and more preferably 0.5 to 20%, particularly preferably 1 to 10%; 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.

Production Example 1 <Synthesis of polyester (A) and preparation of resin particle dispersion>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 41 parts (0.13 mole) of bisphenol A / EO 2 mole adduct, 457 parts (1.14 mole) of bisphenol A / PO3 mole adduct, phenol 9 parts (0.01 mol) of PO6 mol adduct of novolak (average functional group number 5.6), 166 parts (1.0 mol) of terephthalic acid, and 3 parts of tetrabutoxytitanate as a condensation catalyst were added at 230 ° C. with nitrogen. The reaction was carried out for 5 hours while distilling off the water produced under an air stream. Next, the reaction was carried out under a reduced pressure of 5 to 20 mmHg, and when the acid value became 2 or less, it was taken out, cooled to room temperature, pulverized and granulated. This is designated as polyester resin (a1).
The acid value of the polyester resin (a1) was 1.8, the hydroxyl value was 46, Mn was 2500, and Mp was 5500.

622 parts of polyester resin (a1), 41 parts (0.21 mol) of trimellitic anhydride and 3 parts of tetrabutoxy titanate as a catalyst are placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe. After replacing the gas phase inside with nitrogen, after reacting at 180 ° C. for 2 hours under sealed at normal pressure, react at 220 ° C. under reduced pressure of 500 to 700 mmHg, and when the softening point becomes 135 ° C., it is taken out through a belt cooler. And pulverized into particles. It was OHa / COOHb = 0.77 at the time of reaction. This is designated as polyester resin (A1).
The polyester resin (A1) has an acid value of 20, a hydroxyl value of 10, Mw of 120,000, Mp of 11,000, a softening point of 135 ° C., and a THF-insoluble content of 6% by weight, that is, the left side of the formula (1) is 2. 0, the left side of the formula (2) was 0.04. The softening point when (A1) is heated and melted at 200 ° C. and then cooled with ice water is 133 ° C. (difference in softening point before and after heating and melting: −2 ° C.), and Mp is 11500 (Mp before and after heating and melting). Change rate: + 5%).

  To 100 parts of the polyester resin (A1), 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]. The volume average particle size of [Resin Particle Dispersion WA1] measured by a laser particle size distribution analyzer LA-920 (manufactured by Horiba Seisakusho) was 0.09 μm.

Production Example 2 <Synthesis of polyester (B) and preparation of resin particle dispersion>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 379 parts (1.2 moles) of bisphenol A · EO 2 mole adduct, 447 parts (1.3 moles) of bisphenol A · PO2 mole adduct, terephthalate 332 parts (2.0 moles) of acid and 3 parts of tetrabutoxy titanate as a condensation catalyst were added and reacted at 230 ° C. for 5 hours while distilling off the water produced under a nitrogen stream. 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 40 parts (0.21 mol) of trimellitic anhydride, and reacted for 2 hours under sealed at atmospheric pressure. After taking out and cooling to room temperature, it was pulverized into particles. This is designated as polyester resin (B1).
The acid value of the polyester resin (B1) was 21, the hydroxyl value was 37, Mn was 2000, Mp was 4200, and the THF insoluble content was 0% by weight.

  To 100 parts of the polyester resin (B1), 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 WB1]. The volume average particle diameter of the [resin particle dispersion WB1] measured by a laser particle size distribution measuring apparatus LA-920 (manufactured by Horiba Seisakusho) was 0.09 μm.

Production Example 3 <Synthesis of Polyester (A) and Preparation of Resin Particle Dispersion>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 37 parts (0.11 mole) of bisphenol A · EO 2 mole adduct, 407 parts (1.01 mole) of bisphenol A · PO3 mole adduct, phenol Add 22 parts (0.03 mole) of PO6 mole adduct of novolak (average functional group number 5.6), 22 parts (0.03 mole), 166 parts (1.0 mole) terephthalic acid, and 3 parts of tetrabutoxy titanate as a condensation catalyst. The reaction was carried out for 5 hours while distilling off the water produced under a nitrogen stream. Next, the reaction was carried out under a reduced pressure of 5 to 20 mmHg, and when the acid value became 2 or less, it was taken out, cooled to room temperature, pulverized and granulated. This is designated as polyester resin (a2).
The acid value of the polyester resin (a2) was 2.1, the hydroxyl value was 38, Mn was 3000, and Mp was 5800.

In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, 596 parts of polyester resin (a2), 31 parts (0.1 mol) of trimellitic anhydride, and 3 parts of tetrabutoxy titanate as a catalyst were added. After replacing the gas phase inside with nitrogen, after reacting at 180 ° C. for 2 hours under sealed at normal pressure, react at 220 ° C. under reduced pressure of 500 to 700 mmHg, and when the softening point becomes 130 ° C., it is taken out through a belt cooler. And pulverized into particles. It was OHa / COOHb = 0.51 at the time of reaction. This is designated as polyester resin (A2).
The polyester resin (A2) has an acid value of 30, a hydroxyl value of 12, Mw of 70000, Mp of 7600, a softening point of 130 ° C., and a THF-insoluble content of 20% by weight, that is, the left side of the formula (1) is 2. 5. The left side of the formula (2) was 0.15. The softening point when (A2) is heated and melted at 200 ° C. and then cooled with ice water is 132 ° C. (difference in softening point before and after heating and melting: + 2 ° C.), and Mp is 7300 (rate of change of Mp before and after heat melting) : -4%).

  To 100 parts of the polyester resin (A2), 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]. The volume average particle diameter of the [resin particle dispersion WA2] measured by a laser particle size distribution analyzer LA-920 (manufactured by Horiba Seisakusho) was 0.09 μm.

Production Example 4 <Synthesis of Polyester (A) and Preparation of Resin Particle Dispersion>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 3 parts (0.01 mol) of bisphenol A · EO 2 mol adduct, 486 parts (1.21 mol) of bisphenol A · PO 3 mol adduct, phenol As novolak (average functional group number 5.6) PO6 mol adduct 23 parts 23 parts (0.03 mol), terephthalic acid 159 parts (0.96 mol), adipic acid 6 parts (0.04 mol) and a condensation catalyst Tetrabutoxy titanate (3 parts) was added and reacted at 230 ° C. for 5 hours while distilling off water produced under a nitrogen stream. Next, the reaction was carried out under a reduced pressure of 5 to 20 mmHg, and when the acid value became 2 or less, it was taken out, cooled to room temperature, pulverized and granulated. This is designated as polyester resin (a3).
The acid value of the polyester resin (a3) was 1.6, the hydroxyl value was 53, Mn was 2000, and Mp was 4800.

650 parts of polyester resin (a3), 56 parts (0.29 mol) of trimellitic anhydride, and 3 parts of tetrabutoxy titanate as a catalyst are placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe. After replacing the gas phase inside with nitrogen, after reacting at 180 ° C. for 2 hours under sealed at normal pressure, react at 220 ° C. under reduced pressure of 500 to 700 mmHg, and when the softening point becomes 135 ° C., it is taken out through a belt cooler. And pulverized into particles. It was OHa / COOHb = 0.31 at the time of reaction. This is designated as polyester resin (A3).
The acid value of the polyester resin (A3) is 40, the hydroxyl value is 9, Mw is 60000, Mp is 6800, the softening point is 135 ° C., and the THF-insoluble content is 25% by weight, that is, the left side of the formula (1) is 4. 8. The left side of Formula (2) was 0.19. The softening point when (A3) is heated and melted at 200 ° C. and then cooled with ice water is 140 ° C. (difference in softening point before and after heating and melting: + 5 ° C.), and Mp is 7300 (rate of change of Mp before and after heating and melting) : + 7%).

  To 100 parts of the polyester resin (A3), 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 WA3]. The volume average particle diameter of the [resin particle dispersion WA3] measured by a laser particle size distribution analyzer LA-920 (manufactured by Horiba Seisakusho) was 0.09 μm.

Production Example 5 <Synthesis of Polyester (A) and Preparation of Resin Particle Dispersion>
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 228 parts (3.0 mol) of 1,2-propylene glycol (hereinafter referred to as propylene glycol), 171 parts of dimethyl terephthalate (0.88 mol) ), 18 parts (0.12 mol) of adipic acid, and 3 parts of tetrabutoxy titanate as a condensation catalyst were allowed to react at 180 ° C. for 8 hours while distilling off the produced methanol. Next, while gradually raising the temperature to 230 ° C., the reaction is carried out for 4 hours while distilling off the propylene glycol and water produced in a nitrogen stream, and further the reaction is carried out under a reduced pressure of 5 to 20 mmHg, and the softening point becomes 100 ° C. It was taken out at the time. The taken out resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (a4). The acid value of the polyester resin (a4) was 2, the hydroxyl value was 29, Mn was 2000, and Mp was 3500.

207 parts of polyester resin (a4), 9 parts (0.05 mol) of trimellitic anhydride and 3 parts of tetrabutoxy titanate as a catalyst were placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe. After replacing the gas phase inside with nitrogen, react at 180 ° C for 2 hours under sealed at normal pressure, then react at 220 ° C under reduced pressure of 5-20mmHg, and when the softening point reaches 160 ° C, take out through the belt cooler And pulverized into particles. It was OHa / COOHb = 0.41 at the time of reaction. This is designated as polyester resin (A4).
The polyester resin (A4) has an acid value of 22, a hydroxyl value of 1, Mw of 200000, Mp of 9400, a softening point of 160 ° C., and a THF-insoluble content of 5% by weight, that is, the left side of the formula (1) is 4. 9. The left side of Equation (2) was 0.03.
Met. The softening point when (A4) is heated and melted at 200 ° C. and then cooled with ice water is 163 ° C. (difference in softening point before and after heating and melting: + 3 ° C.), and Mp is 10200 (rate of change of Mp before and after heat melting) : + 9%).

  To 100 parts of the polyester resin (A4), 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 WA4]. The volume average particle diameter of the [resin particle dispersion WA4] measured by a laser particle size distribution measuring apparatus LA-920 (manufactured by Horiba Seisakusho) was 0.09 μm.

Production Example 6 <Synthesis of Polyester (A) and Preparation of Resin Particle Dispersion>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 3 parts (0.01 mol) of bisphenol A · EO 2 mol adduct, 98 parts (0.28 mol) of bisphenol A · PO 2 mol adduct, bisphenol A. PO 3 mol adduct 339 parts (0.84 mol), phenol novolak (average functional group number 5.6) PO 6 mol adduct 22 parts (0.03 mol), terephthalic acid 141 parts (0.85 mol), 9 parts (0.08 mol) of fumaric acid, 9 parts (0.05 mol) of trimellitic anhydride and 3 parts of tetrabutoxy titanate as a condensation catalyst were added while distilling off the water produced at 230 ° C. under a nitrogen stream. The reaction was allowed for 5 hours. Next, the reaction was carried out under a reduced pressure of 5 to 20 mmHg, and when the acid value became 2 or less, it was taken out, cooled to room temperature, pulverized and granulated. This is designated as polyester resin (a5).
The acid value of the polyester resin (a5) was 1.3, the hydroxyl value was 39, Mn was 1600, and Mp was 3300.

In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 583 parts of polyester resin (a5), 28 parts (0.15 mol) of trimellitic anhydride, and 1 part of tetrabutoxy titanate as a catalyst were added. After the gas phase inside was replaced with nitrogen, the reaction was carried out at 180 ° C. for 2 hours under sealed at normal pressure, and then at 200 ° C. under reduced pressure (10-50 mmHg) and under normal pressure (760 mmHg), the softening point reached 142 ° C. At that time, it was taken out through a belt cooler and pulverized into particles. OHa / COOHb at the time of reaction was 0.94. This is designated as polyester resin (A5).
The acid value of the polyester resin (A5) is 24, the hydroxyl value is 23, the Mw is 53000, the Mp is 5000, the softening point is 142 ° C., the THF-insoluble matter is 28% by weight, that is, the left side of the formula (1) is 1. 0, the left side of the formula (2) was 0.20. The softening point when (A5) was heated and melted at 200 ° C. and then cooled with ice water was 150 ° C. (difference in softening point before and after heating and melting: + 8 ° C.), and Mp was 4800 (rate of change of Mp before and after heating and melting). : -4%).

  To 100 parts of the polyester resin (A5), 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 WA5]. The volume average particle diameter of [Resin Particle Dispersion WA5] measured by a laser particle size distribution analyzer LA-920 (manufactured by Horiba Seisakusho) was 0.09 μm.

Production Example 7 <Synthesis of polyester (A) and preparation of resin particle dispersion>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 3 parts (0.01 mol) of bisphenol A · EO 2 mol adduct, 572 parts (1.42 mol) of bisphenol A · PO 3 mol adduct, phenol Add 22 parts (0.03 mol) of PO6 mol adduct of novolak (average functional group number 5.6), 166 parts (1.00 mol) of terephthalic acid, and 3 parts of tetrabutoxy titanate as a condensation catalyst, and add nitrogen at 230 ° C. The reaction was carried out for 5 hours while distilling off the water produced under an air stream. Subsequently, it was made to react under the reduced pressure of 5-20 mmHg, and it pick_out | removed when the acid value became 10 or less, and it grind | pulverized and granulated after cooling to room temperature. This is designated as polyester resin (a6).
The acid value of the polyester resin (a6) was 7.6, the hydroxyl value was 84, Mn was 900, and Mp was 2100.

In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 724 parts of polyester resin (a6), 132 parts (0.69 mol) of trimellitic anhydride, and 1 part of tetrabutoxy titanate as a catalyst were added. After the inside gas phase was replaced with nitrogen, after reacting at 180 ° C. for 2 hours under sealed at normal pressure, it was reacted at 200 ° C. under reduced pressure (50 to 100 mmHg) and passed through a belt cooler when the softening point reached 123 ° C. It was taken out and pulverized into particles. It was OHa / COOHb = 0.36 at the time of reaction. This is designated as polyester resin (A6).
The acid value of the polyester resin (A6) is 55, the hydroxyl value is 4.1, the Mw is 111000, the Mp is 5500, the softening point is 123 ° C., the THF-insoluble content is 9% by weight, that is, the left side of the formula (1) is 13.4, the left side of Equation (2) was 0.07. The softening point when (A6) is heated and melted at 200 ° C. and then cooled with ice water is 120 ° C. (difference in softening point before and after heating and melting: −3 ° C.), and Mp is 5800 (change in Mp before and after heating and melting). Rate: + 5%).

  To 100 parts of the polyester resin (A6), 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 WA6]. The volume average particle size of [Resin Particle Dispersion WA6] measured with a laser particle size distribution analyzer LA-920 (manufactured by Horiba Seisakusho) was 0.09 μm.

Production Example 8 <Synthesis of polyester (A) and preparation of resin particle dispersion>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 40 parts (0.13 mole) of bisphenol A · EO 2 mole adduct, 444 parts (1.14 mole) of bisphenol A · PO3 mole adduct, phenol 9 parts (0.01 mol) of PO6 mol adduct of novolak (average number of functional groups: 5.6), 161 parts (0.97 mol) of terephthalic acid, and 3 parts of tetrabutoxy titanate as a condensation catalyst were added at 230 ° C. with nitrogen. The reaction was carried out for 5 hours while distilling off the water produced under an air stream. Next, the reaction was carried out under a reduced pressure of 5 to 20 mmHg. When the acid value became 2 or less, the reduced pressure was stopped and the mixture was cooled to 180 ° C. The acid value of the polyester resin at this time was 2, the hydroxyl value was 46, Mn was 2600, and Mp was 5600.

Thereafter, 132 parts (0.69 mol) of trimellitic anhydride and 1 part of tetrabutoxytitanate as a catalyst were further added, and after replacing the gas phase in the system with nitrogen, the reaction was performed at 180 ° C. for 2 hours under atmospheric pressure sealing. The mixture was reacted at 200 ° C. under reduced pressure (50 to 100 mmHg), and when the softening point reached 123 ° C., it was taken out through a belt cooler and pulverized into particles. It was OHa / COOHb = 0.36 at the time of reaction. This is designated as polyester resin (A7).
The polyester resin (A7) has an acid value of 20, a hydroxyl value of 10, Mw of 123000, Mp of 11100, a softening point of 135 ° C., and a THF-insoluble content of 6% by weight, that is, the left side of the formula (1) is 2. 0, the left side of the formula (2) was 0.04. Moreover, after (A7) was heat-melted at 200 ° C. and cooled with ice water, the softening point was 133 ° C. (difference in softening point before and after heat-melting: −2 ° C.), and Mp was 11600 (change in Mp before and after heat-melting) Rate: + 5%).

  To 100 parts of the polyester resin (A7), 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 WA7]. The volume average particle diameter of [Resin Particle Dispersion WA7] measured with a laser particle size distribution analyzer LA-920 (manufactured by Horiba Seisakusho) was 0.09 μm.

Comparative Production Example 1 <Synthesis of polyester (A ') and preparation of resin particle dispersion>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 572 parts (1.4 moles) of bisphenol A / PO3 mole adduct, 22 parts of PO6 mole adduct of phenol novolac (average functional group number 5.6) (0.03 mol), 166 parts (1.0 mol) of terephthalic acid, and 3 parts of tetrabutoxytitanate as a condensation catalyst were allowed to react for 5 hours while distilling off the water produced at 230 ° C. under a nitrogen stream. . Next, the reaction was carried out under a reduced pressure of 5 to 20 mmHg, and when the acid value became 2 or less, it was taken out, cooled to room temperature, pulverized and granulated. This is designated as polyester resin (a′1).
The acid value of the polyester resin (a′1) was 1.9, the hydroxyl value was 76, Mn was 1000, and Mp was 2500.

In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 724 parts of polyester resin (a′1), 83 parts (0.43 mol) of trimellitic anhydride and 3 parts of tetrabutoxy titanate as a catalyst were placed. Then, after replacing the gas phase in the system with nitrogen, after reacting at 180 ° C. for 2 hours under sealed at atmospheric pressure, react at 220 ° C. under reduced pressure of 10 to 50 mmHg, and when the softening point becomes 125 ° C., After cooling to room temperature, it was pulverized into particles. OHa / COOHb at the time of reaction was 0.79. This is designated as polyester resin (A′1).
The acid value of the polyester resin (A′1) is 25, the hydroxyl value is 23, the Mw is 15000, the Mp is 5000, the softening point is 135 ° C., and the THF insoluble matter is 35% by weight, that is, the left side of the formula (1) is 1.1, the left side of the formula (2) was 0.26.
The softening point when (A′1) was heated and melted at 200 ° C. and then cooled with ice water was 123 ° C. (difference in softening point before and after heating and melting: −12 ° C.), and Mp was 4000 (Mp before and after heating and melting). Change rate: -20%).

  To 100 parts of the polyester resin (A′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 WA′1]. The volume average particle diameter of the [resin particle dispersion WA′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 Polyester (A ′) and Preparation of Resin Particle Dispersion>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 480 parts (1.2 moles) of bisphenol A / PO3 mole adduct, 22 parts of PO6 mole adduct of phenol novolac (average functional group number 5.6) (0.03 mol), 166 parts (1.0 mol) of terephthalic acid, and 3 parts of tetrabutoxytitanate as a condensation catalyst were allowed to react for 5 hours while distilling off the water produced at 230 ° C. under a nitrogen stream. . Next, the reaction was carried out under a reduced pressure of 5 to 20 mmHg, and when the acid value became 2 or less, it was taken out, cooled to room temperature, pulverized and granulated. This is designated as polyester resin (a′2).
The acid value of the polyester resin (a′2) was 2.0, the hydroxyl value was 46, Mn was 2600, and Mp was 5600.

In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 716 parts of a polyester resin (a′2), 50 parts (0.26 mol) of trimellitic anhydride, and 3 parts of tetrabutoxy titanate as a catalyst are placed. Then, after replacing the gas phase in the system with nitrogen, after reacting at 180 ° C. under sealed at atmospheric pressure for 2 hours, react at 220 ° C. under reduced pressure of 500 to 700 mmHg, and when the softening point becomes 130 ° C., Cooled to room temperature and pulverized into particles. OHa / COOHb at the time of reaction was 3.37. This is designated as polyester resin (A′2).
The acid value of the polyester resin (A′2) is 17, the hydroxyl value is 37, the Mw is 25500, the Mp is 5700, the softening point is 142 ° C., the THF insoluble matter is 19% by weight, that is, the left side of the formula (1) is 0.5 and the left side of the formula (2) was 0.13.
The softening point when (A′2) was heated and melted at 200 ° C. and then cooled with ice water was 131 ° C. (difference in softening point before and after heating and melting: −11 ° C.), and Mp was 4200 (Mp before and after heating and melting). Change rate: -26%).

  To 100 parts of the polyester resin (A′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 WA′2]. The volume average particle diameter of the [resin particle dispersion WA′2] measured by a laser particle size distribution analyzer LA-920 (manufactured by Horiba, Ltd.) was 0.09 μm.

Production Example 9 <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 10 <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>
30 parts of [resin particle dispersion WA1], 140 parts of [resin particle dispersion WB1], 15 parts of [colorant dispersion 1], 15 parts of [release agent dispersion 1], 600 parts of ion-exchanged water in a stainless steel beaker Then, 1 part of magnesium sulfate was 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 agglomerated particles was around 5.0 μm, 30 parts of [resin particle dispersion WA1] was added while maintaining the pH constant, and at 60 ° C. After stirring for 1 hour, heating and stirring were further performed 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>
[Resin particle dispersion WA1] 30 parts (twice) are all changed to [Resin particle dispersion WA2] 20 parts (total 40 parts) and [Resin particle dispersion WB1] 140 parts to 160 parts In the same manner as in Example 1, toner particles (D-2) were obtained.

Example 3 <Preparation of toner particles for developing electrostatic image>
[Resin particle dispersion WA1] 30 parts (twice) are all changed to [Resin particle dispersion WA3] 10 parts (total 20 parts) and [Resin particle dispersion WB1] 140 parts to 180 parts In the same manner as in Example 1, toner particles (D-3) were obtained.

Example 4 <Preparation of toner particles for developing electrostatic image>
Toner particles (D-4) are the same as in Example 1 except that 30 parts (two times) of [resin particle dispersion WA1] are changed to 30 parts (total of 60 parts) of [resin particle dispersion WA4]. Got.

Example 5 <Preparation of toner particles for electrostatic image development>
[Resin particle dispersion WA1] 30 parts (twice) were all changed to [Resin particle dispersion WA5] 20 parts (total 40 parts) and [Resin particle dispersion WB1] 140 parts to 160 parts In the same manner as in Example 1, toner particles (D-5) were obtained.

Example 6 <Preparation of toner particles for electrostatic image development>
[Resin Particle Dispersion WA1] 30 parts (twice) were changed to [Resin Particle Dispersion WA6] 50 parts (100 parts in total) and [Resin Particle Dispersion Liquid WB1] 140 parts were changed to 100 parts. In the same manner as in Example 1, toner particles (D-6) were obtained.

Example 7 <Preparation of toner particles for developing electrostatic image>
[Resin particle dispersion WA1] 30 parts (twice) are all changed to [Resin particle dispersion WA7] 20 parts (total 40 parts) and [Resin particle dispersion WB1] 140 parts to 160 parts In the same manner as in Example 1, toner particles (D-7) were obtained.

Comparative Example 1 <Preparation of electrostatic charge image developing toner particles>
[Resin particle dispersion WA1] 30 parts (twice) are all changed to [Resin particle dispersion WA′1] 20 parts (total 40 parts) and [Resin particle dispersion WB1] 140 parts to 160 parts Was similar to Example 1 to obtain toner particles (D′-1).
Comparative Example 2 <Preparation of electrostatic charge image developing toner particles>
[Resin particle dispersion WA1] 30 parts (twice) are all changed to [Resin particle dispersion WA′2] 20 parts (total 40 parts) and [Resin particle dispersion WB1] 140 parts to 160 parts Was the same as in Example 1 to obtain a comparative toner particle (D′-2).

Examples 8-14 and Comparative Examples 3-4
Colloidal with respect to 100 parts of each of toner particles (D-1) to (D-7) obtained by the production method of the present invention and comparative toner particles (D′-1) to (D′-2) Silica (Aerosil R972: manufactured by Nippon Aerosil Co., Ltd.) 0.5 parts is mixed in a sample mill, and the electrostatic image developing toners (T-1) to (T-7) of the present invention and comparative electrostatic image development Toners (T′-1) to (T′-2) were obtained.
[Evaluation method]
[1] Minimum fixing temperature (MFT)
An unfixed image developed using a commercial copying machine (AR5030; manufactured by Sharp) was evaluated using a fixing machine of a commercial copying machine (AR5030; manufactured by Sharp). The fixing roll temperature at which the residual ratio of the image density after rubbing the fixed image with a pad becomes 70% or more was set as the minimum fixing temperature.
[2] Hot offset generation temperature (HOT)
The fixing was evaluated in the same manner as the MFT, and the presence or absence of hot offset on the fixed image was visually evaluated. The fixing roll temperature at which hot offset occurred was defined as the hot offset occurrence temperature.
[3] Blocking resistance 10.0 g of the sample was placed in a 200 ml polycup and left standing 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.
[4] Particle size Volume average particle size and number average particle size were measured with Multisizer III (manufactured by Coulter Inc.).

  The evaluation results evaluated by the following evaluation methods are shown in Table 1.

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

Claims (7)

An electrostatic charge image developing toner comprising a toner resin and toner particles containing a colorant, wherein the toner particles comprise at least a step of dispersing resin particles having a volume average particle size of 1 μm or less in water and the resin particles. Particles having a volume average particle diameter of 3 to 10 μm formed from a process including an aggregating process, containing a polyester resin (A) in the toner resin, and (A) having an acid value of 6 mgKOH / g or less And selected from the group consisting of a polyester resin (a) having a hydroxyl value of 10 to 70 mgKOH / g, an aliphatic carboxylic acid, an aromatic carboxylic acid, and their acid anhydrides and lower alkyl (C1 to C4) esters. It is a polyester resin obtained by reacting with one or more carboxylic acids (b), and (A) has a THF-insoluble content of 1 to 36% by weight, and a THF-soluble gel permeation. The peak top molecular weight of the chromatographic chromatography is 4500 to 20000, the softening point is 120 to 180 ° C., and the peak top molecular weight of the gel permeation chromatography of the THF soluble matter before and after (A) is heated and melted at 200 ° C. A toner for developing an electrostatic charge image , wherein the change rate is 10% or less and (A) satisfies the following formulas (1) and (2):
Acid value / hydroxyl value ≧ 1 (however, acid value = 15-80 mg KOH / g) Formula (1)
THF insoluble matter (% by weight) / softening point (° C.) ≦ 0.2 (2)   The electrostatic image developing toner according to claim 1, wherein the weight average molecular weight of (A) is 30,000 to 300,000.   The toner for developing an electrostatic charge image according to claim 1 or 2, wherein the difference in softening point between before and after (A) is heated and melted at 200 ° C is 10 ° C or less. In the toner resin, with polyester resin (A), the further claim 1 or an electrostatic image developing toner according to 3 containing a polyester resin (B) containing no THF-insoluble matter. The weight ratio [(A) / (B)] of (A) and (B) is (5-100) / (95-0), where the sum of (A) and (B) is 100. Item 5. The toner for developing an electrostatic charge image according to Item 4 . Furthermore a release agent, a charge control agent, and one or more of claims 1 to toner for electrostatic image development according to any one of 5 containing additive selected from fluidizing agents. A method for producing an electrostatic charge image developing toner comprising toner particles and toner particles containing a colorant, wherein the resin particles having a volume average particle size of 1 μm or less are dispersed in water, and the resin particles are agglomerated. And a step of fusing the agglomerated resin particles to obtain toner particles having a volume average particle size of 3 to 10 μm, the polyester resin (A) being contained in the toner resin, and (A) having an acid value Of polyester resin (a) having a hydroxyl value of 10 to 70 mgKOH / g, aliphatic carboxylic acids, aromatic carboxylic acids, and their acid anhydrides and lower alkyl (1 to 4 carbon atoms) esters. It is a polyester resin obtained by reacting at least one carboxylic acid (b) selected from the group consisting of 1 to 36% by weight of THF-insoluble matter in (A), and THF-soluble matter. The gel top permeation chromatography has a peak top molecular weight of 4500 to 20000 and a softening point of 120 to 180 ° C. The peak top molecular weight of the gel soluble permeation chromatography before and after (A) is heated and melted at 200 ° C. The change rate of the toner is 10% or less, and (A) satisfies the following formulas (1) and (2):
Acid value / hydroxyl value ≧ 1 (however, acid value = 15-80 mg KOH / g) Formula (1)
THF insoluble matter (% by weight) / softening point (° C.) ≦ 0.2 (2)