JP5185006B2 - Toner for electrostatic image development - Google Patents

Description

  The present invention relates to an electrostatic charge image developing toner and a method for producing a negative charge image developing toner.

As a method for producing an electrostatic image developing toner having a uniform particle size and excellent image quality, an emulsion aggregation method in which the particle size and shape are intentionally controlled has been proposed (Patent Document 1). In addition, it has been conventionally known that a polyester resin is used as a binder for the purpose of improving the low-temperature fixing performance of an electrostatic image developing toner. It has been proposed to use polyester (Patent Document 2, etc.).
Japanese Patent Laid-Open No. 63-282275 JP 2005-77930 A

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

As a result of intensive studies to solve the above problems, the present inventors have reached the present invention.
That is, the present invention is an electrostatic charge image developing toner comprising toner particles containing a polyester resin (I) and a colorant, wherein the toner particles contain at least resin particles having a volume average particle diameter of 1 μm or less in water. A volume average particle diameter formed from a step including a step of dispersing and a step of aggregating the resin particles is a particle having a volume average particle size of 3 to 10 μm, and the polyester resin (I) is composed of a linear polyester (A) and a non-linear polyester (B). A polycondensation polyester resin of a carboxylic acid component and an alcohol component containing at least 40 mol% of one or more selected from aliphatic polycarboxylic acids having 9 to 30 carbon atoms and ester-forming derivatives thereof, JP SP value from 9.0 to 10.5 and (cal / cm ^{3) 1/2} in which crystalline polyester (A1), in that it contains 5% by weight or more in (a) And a method for producing a toner for developing an electrostatic image comprising toner particles containing a polyester resin (I) and a colorant, wherein at least a volume average particle diameter of the resin particles is 1 μm or less. A step of dispersing the resin particles in water, a step of aggregating the resin particles, and a step of fusing the agglomerated resin particles to obtain toner particles having a volume average particle size of 3 to 10 μm, wherein the polyester resin (I) is a linear polyester ( A carboxylic acid component composed of A) and a non-linear polyester (B), containing at least 40 mol% of an aliphatic polycarboxylic acid having 9 to 30 carbon atoms and an ester-forming derivative thereof, and an alcohol component; a polycondensation polyester resin, SP value from 9.0 to 10.5 and (cal / cm ^{3) 1/2} in which crystalline polyester (A1), of (a) A; method for producing a toner for developing electrostatic images which is characterized in that it contains 5% by weight or more.

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 and excellent in low-temperature fixability and blocking resistance.
Further, when a crystalline polyester having a peak top molecular weight of 5,000 to 150,000 in gel permeation chromatography of THF-soluble matter is used, the low-temperature fixability and hot offset resistance when used as a toner are improved in a well-balanced manner. When a crystalline polyester having a molecular weight of less than 5000 is used, the low-temperature fixability of the toner is greatly improved.

The present invention is described in detail below.
The electrostatic image developing toner of the present invention is obtained by dispersing a resin used for forming resin particles containing a polyester resin (I) and a colorant in water at 1 μm or less, and aggregating the water-dispersed resin. It is obtained by adjusting the particle size of the aggregated particles, melting and coalescing the aggregated particles to form particles.
The volume average particle size is determined by laser type particle size distribution measuring apparatus LA-920 (manufactured by Horiba, Ltd.), Multisizer III (manufactured by Coulter), ELS-800 (manufactured by Otsuka Electronics Co., Ltd.) using a laser Doppler method as an optical system, and the like. Can be measured. If there is a difference in the measured value of the particle diameter between the measuring devices, the measured value by ELS-800 is adopted.

The polyester resin (I) in the present invention is obtained, for example, by polycondensing one or more kinds of alcohol components (x) and one or more kinds of carboxylic acid components (y).
Examples of the alcohol component (x) include a diol (x1) and / or a polyol (x2) having 3 to 8 or more valences. Further, if necessary, monool (x3) of preferably 60 mol% or less, more preferably 50 mol% or less, particularly preferably 40 mol% or less may be used.
Examples of the carboxylic acid component (y) include a dicarboxylic acid (y1) and / or a polycarboxylic acid (y2) having 3 to 6 or more valences. If necessary, the monocarboxylic acid (y3) of preferably 60 mol% or less, more preferably 50 mol% or less, particularly preferably 40 mol% or less may be used.

Examples of the diol (x1) include alkylene glycols having 2 to 36 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol. , 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, etc.); C4-C36 alkylene ether glycol (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol) And polytetramethylene ether glycol); alicyclic diols having 6 to 36 carbon atoms (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); (poly) oxyalkylenes of the above alicyclic diols (Alkylene group having 2 to 4 carbon atoms, the same applies to the following polyoxyalkylene groups) Ether [oxyalkylene units (hereinafter abbreviated as AO units) 1 to 30]; and dihydric phenol [monocyclic dihydric phenol (for example, Hydroquinone), and polyoxyalkylene ethers of bisphenols (such as bisphenol A, bisphenol F and bisphenol S)] (number of AO units 2 to 30); and the like.
Among these (x1), preferred are alkylene glycols having 2 to 12 carbon atoms, polyoxyalkylene ethers of bisphenols (2 to 30 AO units), and combinations thereof. More preferred are polyoxyalkylene ethers of bisphenols (particularly bisphenol A) (2 and / or 3 carbon atoms of the alkylene group, 2 to 8 AO units), alkylene glycols of 2 to 12 carbon atoms (particularly ethylene glycol). , 1,2-propylene glycol), and combinations thereof.

Examples of the trivalent to octavalent or higher polyol (x2) include trihydric to octavalent or higher aliphatic polyhydric alcohols having 3 to 36 carbon atoms (alkane polyol and intramolecular or intermolecular dehydrates such as Glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, polyglycerin, and dipentaerythritol; sugars and derivatives thereof such as sucrose and methylglucoside); (poly) oxyalkylenes of the above aliphatic polyhydric alcohols Ether (number of AO units 1-30); polyoxyalkylene ether of trisphenols (trisphenol PA, etc.) (number of AO units 2-30); novolak resin (phenol novolak, cresol novolac, etc.) average degree of polymerization 3 60) Etc. (the number 2 to 30 of AO units) polyoxyalkylene ether.
Among these (x2), preferred are 3 to 8 or higher aliphatic polyhydric alcohols and polyoxyalkylene ethers of novolac resins (2 to 30 AO units), and particularly preferred are novolak resins. Of polyoxyalkylene ether (number of AO units 2 to 30).

As monool (x3), C1-C30 (preferably 1-24) alkanol (methanol, ethanol, isopropanol, dodecyl alcohol, stearyl alcohol, etc.), C3-C30 (preferably 3-24) are used. Examples include alkenols (allyl alcohol, propenyl alcohol, oleyl alcohol, etc.), aromatic alcohols having 7 to 36 carbon atoms (benzyl alcohol, etc.) and the like.
Among these (x3), preferred are alkanols having 1 to 30 carbon atoms, and more preferred are dodecyl alcohol and stearyl alcohol.

Examples of the dicarboxylic acid (y1) include alkane dicarboxylic acids having 4 to 36 carbon atoms (for example, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, 1,10-decanedicarboxylic acid, 1,12-dodecanedioic acid, And 1,18-octadecane dicarboxylic acid); alicyclic dicarboxylic acid having 6 to 40 carbon atoms [for example, dimer acid (dimerized linoleic acid)]; alkene dicarboxylic acid having 4 to 36 carbon atoms (for example, alkenyl succinic acid such as dodecenyl succinic acid) Acid, maleic acid, fumaric acid, citraconic acid, and mesaconic acid); aromatic dicarboxylic acids having 8 to 36 carbon atoms (such as phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid); and ester-forming derivatives thereof And the like.
Examples of the ester-forming derivatives include acid anhydrides, alkyl (C1-C24: methyl, ethyl, butyl, stearyl, etc.) esters, and partial alkyl (same as above) esters. The same applies to the following ester-forming derivatives.
Among these (y1), preferred are alkane dicarboxylic acids having 4 to 36 carbon atoms, alkene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms, and ester-forming derivatives thereof. .

Examples of the tricarboxylic acid having a valence of 3 to 6 or more (y2) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid), and aliphatics having 6 to 36 carbon atoms (fatty oils). Examples thereof include polycarboxylic acids (including cyclic) (hexanetricarboxylic acid, decanetricarboxylic acid and the like), and ester-forming derivatives thereof.
Among these (y2), trimellitic acid, pyromellitic acid, and ester-forming derivatives thereof are preferable.

Among monocarboxylic acids (y3), aliphatic (including alicyclic) monocarboxylic acids include alkane monocarboxylic acids (formic acid, acetic acid, propionic acid, butane) having 1 to 30 (preferably 1 to 24) carbon atoms. Acid, isobutanoic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, serotic acid, monitoring acid, melicic acid, etc.), C3-30 (preferably 3-24) Alkene monocarboxylic acids (acrylic acid, methacrylic acid, oleic acid, linoleic acid, etc.). Examples of the aromatic monocarboxylic acid in (y3) include aromatic monocarboxylic acids having 7 to 36 carbon atoms (benzoic acid, methylbenzoic acid, phenylpropionic acid, naphthoic acid, and the like).
Among these (y3), preferred are alkane monocarboxylic acids having 1 to 30 carbon atoms, and more preferred are lauric acid, palmitic acid, stearic acid, and behenic acid.

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

  The polyester resin (I) in the toner for developing an electrostatic charge image of the present invention is composed of a linear polyester (A) and a non-linear polyester (B) from the viewpoint of achieving both low-temperature fixability and offset resistance.

Furthermore, the linear polyester (A) is a polycondensation polyester resin of a carboxylic acid component and an alcohol component from the viewpoint of achieving both blocking resistance and low-temperature fixability, and has 9 to 30 carbon atoms (preferably 9 to 22 carbon atoms). 1 or more (y *) selected from aliphatic polycarboxylic acids and ester-forming derivatives thereof in the carboxylic acid component and having an SP value of 9.0 to 10.5 [(cal / cm ³ ) ^1/2 , the same shall apply hereinafter) and 5% or more of the crystalline polyester (A1). The content of (A1) in (A) is preferably 10% or more, and more preferably 20 to 95%.
In the above and the following, “%” means “% by weight” unless otherwise specified.
In the present invention, “crystalline polyester” refers to a polyester having a melting point [Tmp] of 25 ° C. or higher. Tmp is measured by the method described later.

  Furthermore, when it is desired to improve the low-temperature fixability and hot offset resistance in a well-balanced manner, as (A1), a crystalline polyester having a peak top molecular weight of gel permeation chromatography (hereinafter referred to as Mp) of 5000 to 150,000 ( A11) is preferably used. On the other hand, when it is desired to greatly improve the low-temperature fixability, it is preferable to use a crystalline polyester (A12) having an Mp of 1000 or more and less than 5000 as (A1).

The crystalline polyester (A1) contains 40 mol% or more of the alcohol component (x), one or more selected from aliphatic polycarboxylic acids having 9 to 30 carbon atoms and ester-forming derivatives thereof (y *). It can be obtained by polycondensation with the carboxylic acid component (y).
Specific examples of the diol (x1) in the alcohol component (x) constituting (A1) include those described above. (X1) is preferably ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decane. Diol and 1,12-dodecanediol, more preferably 1,4-butanediol, 1,6-hexanediol, and 1,9-nonanediol, 1,10-decanediol and 1,12-dodecanediol It is.
Specific examples of the trivalent to octavalent or higher polyol (x2) include those described above. Of these (x2), glycerin and trimethylolpropane are preferred.
Specific examples of the monool (x3) include those described above. Among (x3), C1-C30 (especially 1-24) alkanol is preferable, and dodecyl alcohol and stearyl alcohol are more preferable.

Specific examples of the carboxylic acid component (y) constituting (A1) include the dicarboxylic acid (y1), the trivalent to hexavalent or higher polycarboxylic acid (y2), and the monocarboxylic acid (y3). Can be mentioned.
One or more (y *) selected from aliphatic polycarboxylic acids having 9 to 30 carbon atoms (preferably 9 to 22 carbon atoms) and ester-forming derivatives thereof as essential constituents in (y) Among the alkanedicarboxylic acids having 4 to 36 carbon atoms and the alicyclic dicarboxylic acids having 6 to 40 carbon atoms and ester-forming derivatives thereof having the above-mentioned (y2), Among these aliphatic (including alicyclic) polycarboxylic acids having 6 to 36 carbon atoms, those having 9 to 30 carbon atoms and ester-forming derivatives thereof are exemplified.
Of these, preferred are alkane dicarboxylic acids having 9 to 22 carbon atoms and ester-forming derivatives thereof, and more preferred are azelaic acid, zebacic acid, 1,12-dodecanedioic acid, 1,18-octadecanedicarboxylic acid, And their ester-forming derivatives, particularly preferably zebacic acid and 1,12-dodecanedioic acid.

  As (y) that constitutes (A1), in addition to (y *), trimellitic acid, pyromellitic acid, and their anhydrides in (y2), and the number of carbons in (y3) 1-30 (especially 1-24) alkane monocarboxylic acid is mentioned.

  The crystalline polyester (A1) contains at least 40 mol% of one or more (y *) selected from aliphatic polycarboxylic acids having 9 to 30 carbon atoms and ester-forming derivatives thereof in the carboxylic acid component (y). To do. Preferably it is 50 mol% or more, More preferably, it is 60 mol% or more. When (A1) is crystalline polyester (A11), it is particularly preferably at least 70 mol%, most preferably at least 80 mol%. When the aliphatic polycarboxylic acid having 9 to 30 carbon atoms (y *) is less than 40 mol%, the rate and rate of crystallization are low, and the blocking resistance becomes insufficient.

In the present invention, in addition to (y *), in addition to (y *), a monocarboxylic acid having 1 to 30 carbon atoms (y31) in the carboxylic acid component (y) and / or the alcohol component (x) constituting the crystalline polyester (A1). ) And one or more selected from C1-C30 monools (x31) are preferable because the blocking resistance is further improved.
As C1-C30 monocarboxylic acid (y31) and C1-C30 monool (x31), it is C1-C30 among said monocarboxylic acid (y3) and said monool (x3). Things. Among these, an alkane monocarboxylic acid having 1 to 30 carbon atoms and an alkanol having 1 to 30 carbon atoms are preferable, and an alkane monocarboxylic acid having 1 to 30 carbon atoms is more preferable. In (A1), the constituent monomer of the crystalline polyester (A12) is preferably an alkane monocarboxylic acid having 10 to 30 carbon atoms and an alkanol having 10 to 30 carbon atoms, and more preferably a carbon number. 10-30 alkane monocarboxylic acids.
The polycondensation conditions of (A1) in the case of containing (y31) or (x31) as a structural unit are carried out in the same manner as in the production method of the polyester resin (I), but (y31) and / or (x31) A method of reacting (y31) and / or (x31) with the molecular terminal of the obtained polyester after preparing a crystalline polyester in advance with the carboxylic acid component (y) and the alcohol component (x) other than ()) is preferred.

  When the crystalline polyester (A11) is used as (A1), the content of the diol (x1) in the alcohol component (x) constituting (A11) is preferably 60 to 100 mol%, more preferably 80 to 100 mol%, particularly preferably 90 to 100 mol%, most preferably 100 mol%. Further, (x1) is preferably one kind of diol.

  The content of the dicarboxylic acid (y1) in the carboxylic acid component (y) constituting (A11) is preferably 40 to 100 mol%, more preferably 50 to 100 mol%, particularly preferably 60 to 99 mol. %. Further, the dicarboxylic acid (y1) is preferably one kind of dicarboxylic acid.

  The ratio of (y31) and (x31) in (A11) is such that the total of (y31) and (x31) is 40 mol% or less with respect to the total number of moles of the carboxylic acid component and alcohol component constituting (A11). It is preferable that it is 1-20 mol%.

When the crystalline polyester (A12) is used as (A1), (A12) is one or more selected from the alcohol component (x), an aliphatic polycarboxylic acid having 9 to 30 carbon atoms, and an ester-forming derivative thereof. An alcohol component (x) and a carboxylic acid component (y *) and at least one selected from a monocarboxylic acid having 10 to 30 carbon atoms (y311) and a monool having 10 to 30 carbon atoms (x311) Those obtained by polycondensation with y) are preferred. By containing a monocarboxylic acid (y311) having 10 to 30 carbon atoms and / or a monool (x311) having 10 to 30 carbon atoms, it has a low molecular weight but has a blocking resistance, a high crystallinity and a high crystallization speed. It is possible to achieve both.
(A12) is a monocarboxylic acid having 10 to 30 carbon atoms (y311) and / or a monool having 10 to 30 carbon atoms (x311), and is composed of 5 to 40 of all constituent monomers (total of carboxylic acid component and alcohol component). It is preferable to contain mol% (especially 10-30 mol%) from a viewpoint of crystallization speed and blocking resistance.

The equivalent ratio (OH group / COOH group) of the carboxylic acid component (y) and the alcohol component (x) constituting the crystalline polyester (A11) is preferably 0.85 to 1.18 from the viewpoint of storage stability, More preferably, it is 0.90 to 1.16, and particularly preferably 0.93 to 1.14.
The equivalent ratio (OH group / COOH group) of the carboxylic acid component (y) and the alcohol component (x) constituting the crystalline polyester (A12) is preferably 1.40 to 2.00 from the viewpoint of molecular weight. More preferably, it is 1.45 to 1.95, and particularly preferably 1.50 to 1.90.

The acid value of the crystalline polyester (A1) is preferably 0 to 100 (mg KOH / g, the same shall apply hereinafter), more preferably 0 to 80, and particularly preferably 0 to 60. When the acid value is 100 or less, the water-dispersed resin is easily agglomerated, and the charging characteristics when the toner is formed do not deteriorate.
The hydroxyl value of (A1) is preferably 0 to 100 (mg KOH / g, the same shall apply hereinafter), more preferably 0 to 80, particularly preferably 0 to 50. When the hydroxyl value is 100 or less, the hot offset resistance at the time of toner formation becomes better.

In the present invention, the acid value and hydroxyl value of the polyester resin are measured by the method defined in JIS K0070 (1992 edition).
When the sample has a solvent-insoluble component accompanying crosslinking, the sample after melt-kneading is used as a sample by the following method.
Kneading device: Labo plast mill MODEL4M150 manufactured by Toyo Seiki Co., Ltd.
Kneading conditions: 130 ° C., 70 rpm, 30 minutes

The SP value (solubility parameter) of the crystalline polyester (A1) is usually 9.0 to 10.5, preferably 9.1 to 10.2, more preferably 9.2 to 10.1, particularly preferably 9. .3 to 10.0.
If the SP value is less than 9.0, the compatibility with the non-linear polyester (B) is insufficient and the durability is insufficient, and if it exceeds 10.5, the glass transition temperature [Tg] is lowered and the blocking resistance is deteriorated. To do.
The SP value in the present invention is calculated by the method described in the following document proposed by Fedors et al.
"POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1974, Vol. 14, No. 2, ROBERT F. FEDORS. (Pp. 147-154)"

The number average molecular weight (hereinafter referred to as Mn) of the tetrahydrofuran (THF) soluble part of the crystalline polyester (A11) is preferably 2,000 to 15,000, more preferably 3,000 to 10,000, particularly preferably. 4,000 to 9,000.
On the other hand, the Mn of the crystalline polyester (A12) is preferably 500 to 5000, more preferably 1000 to 4500, and particularly preferably 1000 to 4000.
Mp of the THF soluble part of (A11) is usually 5000 to 150,000, preferably 8000 to 100,000, more preferably 10,000 to 90,000.
On the other hand, Mp of (A12) is usually 1000 or more and less than 5000, preferably 1200 to 4900, more preferably 1500 to 4500, and particularly preferably 2000 to 4400.

In the present invention, the molecular weight [Mp, Mn, and weight average molecular weight (Mw)] of the polyester resin is measured using gel permeation chromatography (GPC) under the following conditions.
Device (example): HLC-8120 manufactured by Tosoh Corporation
Column (example): TSK GEL GMH6 2 [Tosoh Corp.]
Measurement temperature: 40 ° C
Sample solution: 0.25% THF (tetrahydrofuran) solution Injection amount: 100 μl
Detection apparatus: Refractive index detector Reference material: Tosoh standard polystyrene (TSK standard POLYSYRENE) 12 points (molecular weight 500 1050 2800 5970 9100 18100 37900 96400 190000 355000 1090000 2890000)
The molecular weight showing the maximum peak height on the obtained chromatogram is referred to as peak top molecular weight (Mp). The molecular weight is measured by dissolving a polyester resin in THF and filtering out the insoluble matter with a glass filter.

The melting point [Tmp] of the crystalline polyester (A1) is preferably from 50 to 120 ° C., more preferably from 55 to 110 ° C., particularly preferably from 60 to 90 ° C. from the viewpoints of fixability, storage stability and durability. . In the present invention, Tmp is measured by the following method.
<Melting point [Tmp]>
Using a differential scanning calorimeter {for example, DSC210, manufactured by Seiko Denshi Kogyo Co., Ltd.], the sample to be measured was heated to 200 ° C., cooled to 0 ° C. at a cooling rate of 10 ° C./min, and then heated to 10 ° C. The temperature is increased at a time per minute and the change in endothermic heat is measured. A graph of “endothermic heat generation” and “temperature” is drawn, and the temperature corresponding to the maximum peak of the endothermic heat generation is defined as the melting point [Tmp].

The flow softening point [Tm] of (A1) is preferably 50 to 150 ° C, more preferably 60 to 130 ° C, particularly preferably 65 to 110 ° C. Within this range, the low-temperature fixability and blocking resistance are further improved. In the present invention, Tm is measured by the following method.
<Flow softening point [Tm]>
Using a descending flow tester {for example, CFT-500D, manufactured by Shimadzu Corporation), a load of 1.96 MPa was applied by a plunger while heating a measurement sample of 1 g at a heating rate of 6 ° C./min. Extrude from a nozzle with a diameter of 1 mm and a length of 1 mm, draw a graph of “plunger descent amount (flow value)” and “temperature”, and graph the temperature corresponding to 1/2 of the maximum plunger descent amount The value (temperature when half of the measurement sample flows out) is taken as the flow softening point [Tm].

The crystalline polyester (A1) has a ratio {[Tm] / [Tmp]} of “flow softening point [Tm]” and “melting point [Tmp]” from the viewpoint of crystallization speed at the time of toner formation and blocking resistance. , Preferably 0.8 to 1.8.
When (A1) is (A11), {[Tm] / [Tmp]} is more preferably 1.0 to 1.8, and particularly preferably 1.0 to 1.4. When (A1) is (A12), {[Tm] / [Tmp]} is preferably 0.8 to 1.4.

The number average molecular weight (Mn), peak top molecular weight (Mp), melting point [Tmp], flow softening point [Tm], and ratio {[Tm] / [Tmp]} of the crystalline polyester (A1) are within the above ranges. Includes at least one selected from an equivalent ratio (OH group / COOH group) of the alcohol component (x) and the carboxylic acid component (y), an aliphatic polycarboxylic acid having 9 to 30 carbon atoms, and an ester-forming derivative thereof. It can be easily carried out by adjusting the content and type of (y *) or selecting reaction conditions.
That is, when the equivalent ratio (OH group / COOH group) approaches 1, Mn increases, Tm and Tmp both increase, and when away from 1, Mn decreases and both Tm and Tmp decrease. Further, when the number of carbon atoms in (y *) increases, both Tm and Tmp decrease, but Tmp decreases more greatly. Therefore, {[Tm] / [Tmp]} can be controlled by adjusting the carbon number and equivalent ratio (OH group / COOH group) of the carboxylic acid of (y *).

In the linear polyester (A), if necessary, an amorphous linear polyester (A2) other than the crystalline polyester (A1) may be contained.
The linear polyester (A2) can be obtained, for example, by polycondensation of the diol (x1) and the dicarboxylic acid (y1), and the molecular terminal is further converted to (y1) or (y2) of the carboxylic acid component (y). ) May be modified with an anhydride or the like. In these, what modified | denatured the molecular terminal with the anhydride of (y1) or (y2) is preferable. The reaction ratio between the alcohol component (x) and the carboxylic acid component (y) is preferably 3/1 to 1/3, more preferably 2.5 as the equivalent ratio [OH] / [COOH] of the hydroxyl group to the carboxyl group. /1-1/2.5, particularly preferably 2 / 1-1 / 2.

  The acid value of the linear polyester (A2) is preferably 5 to 100, more preferably 10 to 80, and particularly preferably 15 to 60. When the acid value is 5 or more, it is easy to disperse in water to 1 μm or less, and the low-temperature fixability when converted to toner is good, and when it is 100 or less, the water-dispersed resin can easily aggregate. In addition, the charging characteristics when the toner is formed do not deteriorate.

  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 linear polyester (A ) And the carboxyl group of the non-linear polyester (B) described later may be at least partially neutralized with a base. The neutralization rate of the carboxyl group is preferably 20 to 100 equivalent%, more preferably 40 to 100 equivalent%.

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

  The hydroxyl value of (A2) is preferably 10 to 125, more preferably 20 to 100. When the hydroxyl value is 10 or more, the compatibility with the non-linear polyester (B) is good, and the glossiness (gloss) after fixing at the time of toner formation is good. Further, when the hydroxyl value is 125 or less, the hot offset resistance at the time of toner formation becomes better.

The glass transition temperature [Tg] of (A2) is preferably 45 ° C to 75 ° C, more preferably 50 ° C to 70 ° C. When Tg is 75 ° C. or lower, the low-temperature fixability at the time of toner formation is improved. Further, when Tg is 45 ° C. or higher, the blocking resistance at the time of toner formation is good.
In this invention, glass transition temperature [Tg] is measured by the method (DSC method) prescribed | regulated to ASTM D3418-82 using Seiko Denshi Kogyo Co., Ltd. DSC20 and SSC / 580.

The Mn of the linear polyester (A2) is preferably 1000 to 10000, more preferably 1500 to 9000. When Mn is 1000 or more, the resin strength necessary for fixing is expressed, and when it is 10,000 or less, the low-temperature fixability at the time of toner formation is good.
The Mp of (A2) is preferably 2000 to 12000, more preferably 3000 to 10000, from the viewpoint of the balance between resin strength and low temperature fixability.

The THF insoluble content in the linear polyester (A2) is preferably 5% or less from the viewpoint of low-temperature fixability at the time of toner formation. More preferably, it is 4% or less, and particularly preferably 3% or less.
The THF-insoluble matter in the present invention is determined by the following method.
Add 50 ml of THF to 0.5 g of the sample and stir to reflux for 3 hours. After cooling, the insoluble content 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 nonlinear polyester (B) used in the present invention comprises a polyol (x2) having 3 to 8 or more valences and / or a polycarboxylic acid (y2) having 3 to 6 or more valences, an alcohol component (x) and A polycondensate obtained by reacting at least a part of the carboxylic acid component (y) is preferred.
(B) is more preferably a resin obtained by further reacting a polyester resin (a) which is a polycondensation reaction product of (x) and (y) with one or more carboxylic acids (b). .

  In the polyester resin (a), the reaction ratio between the alcohol component (x) and the carboxylic acid component (y) is preferably 1.4 / 1 to 1 as an equivalent ratio [OH] / [COOH] of the hydroxyl group to the carboxyl group. It is 1.01 / 1, more preferably 1.35 / 1 to 1.1 / 1, and 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) preferably has an acid value of 6 or less and a hydroxyl value of 10 to 70. 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 6 or less or the hydroxyl value is 70 or less, the polycondensation of the polyester resin (a) is sufficient, the low molecular weight component is small, and the storage stability is good. When the hydroxyl value is greater than 10, the reaction efficiency with the carboxylic acid (b) is good.
In order to set the acid value and the hydroxyl value of (a) within these ranges, it is effective to adjust the reaction ratio between the alcohol component (x) and the carboxylic acid component (y).

  As for the molecular weight of (a), it is preferable that Mp is 2000-10000, and it is further more preferable that Mp is 3000-8000.

  When the nonlinear polyester (B) is obtained by the reaction of (a) and (b), the polyester resin (a) and the carboxylic acid (b) are derived from the equivalent of the hydroxyl group derived from (a) from OHa and (b). When the equivalent of the carboxyl group to be converted is COOHb, one obtained by reacting at an equivalent ratio of OHa / COOHb = 0.1 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 and glossiness at the time of toner formation are improved.

As the carboxylic acid (b), any of a monocarboxylic acid and a polycarboxylic acid can be used, and specific examples thereof include the dicarboxylic acid (y1), the tri- or hexavalent or higher polycarboxylic acid (y2). And the same monocarboxylic acid (y3).
The ratio of monocarboxylic acid to polycarboxylic acid (2 to 6 or more) is derived from the carboxyl group derived from monocarboxylic acid and polycarboxylic acid when the equivalent of all carboxyl groups of carboxylic acid used in the reaction is 100 (0-50) / (50-100) is preferable, and (0-20) / (80-100) is more 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.

  (B) is preferably an aromatic polycarboxylic acid having a valence of 2 or more in (y), and an aromatic polycarboxylic acid having 9 to 20 carbon atoms in the carboxylic acid (y2) having a valence of 3 to 6 or more. Carboxylic acid is more preferable, and trimellitic acid and trimellitic anhydride are particularly preferable.

  The content of the aromatic polycarboxylic acid having 9 to 20 carbon atoms of 3 to 6 or more in the carboxylic acid component constituting the nonlinear polyester (B) is preferably 30 mol% or less, 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 acid value of (B) is preferably 15 to 80, more preferably 18 to 60. The hydroxyl value is preferably 40 or less, and more preferably 25 or less.
When the acid value is 15 or more, it is easy to disperse in water to 1 μm or less, and the fixing strength is sufficient when the toner is formed. Further, when the hydroxyl value is 40 or less or the acid value is 80 or less, the water-dispersed resin is easily aggregated, and when it is made into a toner, it is hardly affected by the environmental conditions and has good stability.
In the present invention, the acid value and hydroxyl value of (B) preferably satisfy the relationship of the following formula (1), and more preferably satisfy the relationship of the formula (1 ′).
Acid value / Hydroxyl value ≧ 1 Formula (1)
Acid value / Hydroxyl value ≧ 1.1 Formula (1 ′)
When (acid value / hydroxyl value) is 1 or more, the glossiness at the time of toner formation and the glossiness in the fixing temperature range are good. In addition, in order to manufacture polyester resin (I) which satisfy | fills Formula (1), it can achieve by adjusting the reaction ratio of polyester resin (a) and carboxylic acid (b).

  The THF-insoluble content of the non-linear polyester (B) is preferably 1 to 36%, more preferably 2 to 33%. When the THF insoluble content is 1% or more, the hot offset resistance at the time of toner formation is good, and when it is 36% or less, the low-temperature fixability at the time of toner formation is good.

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

  The flow softening point [Tm] of (B) is preferably 120 to 180 ° C, more preferably 122 to 170 ° C. Within this range, the blocking resistance is further improved.

In the present invention, the THF-insoluble matter and the flow softening point of (B) preferably satisfy the relationship of the following formula (2), and more preferably satisfy the relationship of the formula (2 ′).
THF insoluble matter (%) / flow softening point (° C.) ≦ 0.2 Formula (2)
0.01 ≦ THF insoluble matter (%) / flow softening point (° C.) ≦ 0.19 Formula (2 ′)
When (THF insoluble matter / flow softening point) is 0.2 or less, (A) and (B) are easily mixed uniformly, so that the low-temperature fixability and hot offset resistance at the time of toner formation are good. In addition, the glossiness at the glossiness expression temperature and the fixing temperature range is good.
In order to produce the non-linear polyester (B) satisfying the formula (2), for example, after producing the polyester resin (a), (B) is reacted by reacting (a) with the carboxylic acid (b). This can be achieved by adjusting the hydroxyl value of (a) to 10 to 70 mg KOH / g and adjusting the reaction ratio of (a) and (b).

As for the molecular weight of nonlinear polyester (B), it is preferable that Mp is 5000-20000, and it is further more preferable that it is 5500-15000. The weight average molecular weight (hereinafter referred to as Mw) is preferably 30000-300000, 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 at the time of toner formation is good.

In the present invention, the non-linear polyester (B) preferably has a difference in flow softening point [Tm] before and after being melted by heating at 200 ° C., preferably 10 ° C. or less, and more preferably 5 ° C. or less.
The difference in Tm before and after being melted by heating at 200 ° C. is measured, for example, as follows.
A test tube containing 3 g of (B) is placed in a block bath adjusted to 200 ° C., heated and dissolved for about 10 minutes, and then dissolved (B) is put into ice water together with the test tube and cooled. The flow softening point [Tm] is measured for (I) that has been heat-melted and (B) before heat-melting, and the difference is determined.

In the present invention, the nonlinear polyester (B) preferably has a Mp change rate of a component soluble in THF before and after being melted by heating at 200 ° C. of 10% or less, and more preferably 9% or less.
Note that the method of heat-melting treatment at 200 ° C. is the same as the method described in the previous section.
As a method for reducing the difference in Tm before and after 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, after completion of the reaction of (a) and (b) The nonlinear polyester (B) can be cooled in a shorter time using a belt cooler, drum cooler or the like.

  The weight ratio [(A) / (B)] of the linear polyester (A) and the non-linear polyester (B) in the polyester resin (I) used in the present invention is a balance between hot offset resistance and low-temperature fixability at the time of toner formation. From this point, it is preferably 10/90 to 95/5, more preferably 12/88 to 90/10, and particularly preferably 15/85 to 80/20.

The polyester resin (I) containing the crystalline polyester (A11) contained in the toner for developing an electrostatic charge image of the present invention has a loss elastic modulus (G ″) of 30000 dyne / from the viewpoint of low-temperature fixability at the time of toner formation. The temperature at which cm ² is reached [T30000] is preferably 130 ° C. or lower, more preferably 125 ° C. or lower.
Further, from the viewpoint of achieving both low-temperature fixability and hot offset resistance at the time of toner production, the loss elastic modulus at 100 ° C. [G ″ 100] (dyn / cm ² ) and the loss elastic modulus at 150 ° C. [G ″ 150] (Dyn / cm ² ) preferably satisfies the following formula (3), and more preferably satisfies the formula (3 ′).
[G "100] / [G" 150] ≦ 50 Formula (3)
[G "100] / [G" 150] ≤45 (3 ')
When [G "100] and [G" 150] satisfy the formula (3), it is considered that the viscosity in the low temperature region is small and the viscosity does not become too low in the high temperature region. Is wide.
In order to adjust the loss elastic modulus (G ″) of (I), for example, the amount of crystalline polyester (A11), the molecular weight of the resin in (A), and the number of crosslinking points may be increased or decreased.

In the present invention, the loss elastic modulus (G ″) of the polyester resin is measured using the following viscoelasticity measuring apparatus.
Apparatus: ARES-24A (Rheometric)
Jig: 25mm parallel plate Frequency: 20Hz
Distortion rate: 5%
Temperature increase rate: 5 ° C / min

The polyester resin (I) containing the crystalline polyester (A12) contained in the toner for developing an electrostatic charge image of the present invention is obtained when DSC measurement is performed by the above method from the viewpoint of blocking resistance at the time of toner formation. The melting heat amount Q1 of the melting peak derived from the crystalline polyester (A12) at the first temperature rise and the melting heat amount Q2 of the melting peak derived from the crystalline polyester (A12) at the second temperature rising satisfy the following formula (4). It is preferable that the formula (4 ′) is satisfied.
0.6 ≦ [Q2] / [Q1] ≦ 1.0 Formula (4)
0.7 ≦ [Q2] / [Q1] ≦ 1.0 Formula (4 ′)
When [Q2] / [Q1] satisfies the formula (4), the crystallization speed and the degree of crystallization are high, and the blocking resistance when used as a toner is good.
In order to adjust [Q2] / [Q1] of (I), the SP value of the crystalline polyester (A12) may be increased or decreased. For example, to increase [Q2] / [Q1] (closer to 1), the SP value may be decreased. Conversely, to decrease [Q2] / [Q1], the SP value may be increased. . Moreover, as means for reducing the SP value, the amount of the monocarboxylic acid having 10 to 30 carbon atoms (y311) and the monool having 10 to 30 carbon atoms (x311) in (A12) is increased, or in (A12) Of the aliphatic polycarboxylic acids (y *) having 9 to 30 carbon atoms, those having a large carbon number may be used. Conversely, in order to increase the SP value, the amount of the monocarboxylic acid having 10 to 30 carbon atoms (y311) and the monool having 10 to 30 carbon atoms (x311) in (A12) is reduced, or in (A12) What is necessary is just to use what has a small carbon number in C9-C30 aliphatic polycarboxylic acid (y *).

  The toner for developing an electrostatic charge image of the present invention may contain, in addition to the polyester resin (I), other resins usually used as a binder resin for a toner as long as the characteristics thereof are not impaired. Examples of other resins include polyester resins other than (A) and (B) whose Mn is 1,000 to 1,000,000, styrene resins, resins having a structure in which a vinyl resin is grafted on a polyolefin resin, epoxy resins, and polyurethane resins. Can be mentioned. Other resins may be blended with (A) and (B) or may be partially reacted. The content of the other resin is preferably 10% or less, more preferably 5% or less, with respect to the total amount of the binder resin [(I) and the total amount of other resins].

In the method for producing a toner for developing an electrostatic charge image of the present invention, a resin having a volume average particle diameter of 1 μm or less containing polyester resin (I) in water (including a mixed solvent of water and a small amount of a water-soluble organic solvent). The method for dispersing the particles is not particularly limited, but the following [1] to [7] can be mentioned.
[1] A resin precursor (monomer, oligomer, etc.) containing the polyester resin (I) or an organic solvent solution thereof is dispersed in water in the presence of an appropriate 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 resin precursor (monomer, oligomer, etc.) containing the polyester resin (I) or an organic solvent solution thereof (preferably in a liquid form, 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] Resin containing polyester resin (I) is pulverized using a fine pulverizer such as a mechanical rotary type or jet type, and then classified to obtain resin particles, and then in the presence of a suitable dispersant. To disperse in water.
[4] After obtaining resin particles by spraying a resin solution in which a resin containing the polyester resin (I) is dissolved in an organic solvent in a mist, 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 polyester resin (I) 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 obtained by dissolving a resin containing the polyester resin (I) 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 (I) in an organic solvent, and then water is added to perform phase inversion emulsification.

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

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

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

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

Examples of sulfate salts include higher alcohol sulfate esters (sulfate esters of aliphatic alcohols having 8 to 18 carbon atoms), higher alkyl ether sulfate esters (ethylene oxides of aliphatic alcohols having 8 to 18 carbon atoms (hereinafter referred to as EO). Description) or propylene oxide (hereinafter referred to as PO) 1 to 10 mol adduct sulfate ester salt), sulfated oil (natural unsaturated oil or fat having 12 to 50 carbon atoms, or unsaturated wax is neutralized by sulfation as it is. ), Sulfated fatty acid esters (sulfurized and neutralized lower alcohol (carbon number 1-8) esters of unsaturated fatty acids (carbon numbers 6-40)) and sulfated olefins (having 12-18 carbon atoms) An olefin sulfated and neutralized) can be used.
Examples of the salt include sodium salt, potassium salt, amine salt, ammonium salt, quaternary ammonium salt, alkanolamine salt (monoethanolamine salt, diethanolamine salt, triethanolamine salt, etc.) and the like.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The toner for developing an electrostatic charge image of the present invention is a resin in a resin particle dispersion obtained by the above method, in which resin particles containing a polyester resin (I) having a volume average particle size of 1 μm or less are dispersed in water. It is obtained by aggregating the particles (aggregation step), further heating to a temperature equal to or higher than the Tg of the resin, and fusing the agglomerated particles.
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 or higher charge is preferable, and specific examples of the compound having a monovalent or divalent or higher charge as the flocculant include the above-mentioned ionic surfactants and nonionic surfactants. Water-soluble surfactants such as hydrochloric acid, acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid, magnesium chloride, sodium chloride, aluminum sulfate, calcium sulfate, ammonium sulfate, aluminum nitrate, silver nitrate, copper sulfate, sodium carbonate, etc. Inorganic acid metal salt, aliphatic acid such as sodium acetate, potassium formate, sodium oxalate, sodium phthalate, potassium salicylate, metal salt of aromatic acid, metal salt of phenol such as sodium phenolate, metal salt of amino acid Inorganic acid salts of aliphatic and aromatic amines such as triethanolamine hydrochloride and aniline hydrochloride It is. 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 An inorganic or organic metal salt such as an aliphatic acid such as potassium, most preferably a polyvalent inorganic metal salt such as aluminum sulfate, aluminum nitrate, aluminum chloride or magnesium chloride is used for the stability of the aggregated particles, the heat of the coagulant. And can be suitably used in terms of stability over time, removal during cleaning, and the like.
The amount of these flocculants added varies depending on the valence of the charge, but they are all small and are about 3% or less for monovalent, about 1% or less for divalent, and 0 for trivalent. About 5% or less. Since a smaller amount of the flocculant is preferable, a compound having a higher valence is preferable.

  The toner for developing an electrostatic charge image of the present invention is a resin selected from a resin containing a polyester resin (I) serving as a binder resin, a colorant, and, if necessary, a release agent, a charge control agent, a fluidizing agent, and the like. Contains the above additives.

  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 preferably 30 to 97%, more preferably 40 to 95%, particularly preferably a binder resin containing the polyester resin (I) based on the toner weight. 45 to 92%; Colorant is preferably 0.05 to 60%, more preferably 0.1 to 55%, particularly preferably 0.5 to 50%; Among additives, a release agent is preferably 0 to 30%, more preferably 0.5 to 20%, particularly preferably 1 to 10%; the charge control agent is preferably 0 to 20%, more preferably 0.1 to 10%, particularly preferably 0. 5 to 7.5%; The fluidizing agent is preferably 0 to 10%, more preferably 0 to 5%, and particularly preferably 0.1 to 4%. The total content of 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 image developing toner of the present invention is mixed with carrier particles such as iron powder, glass beads, nickel powder, ferrite, magnetite, and ferrite whose surface is coated with a 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 titanium-containing catalyst>
Place 1000 parts of ethyl acetate and 800 parts of terephthalic acid in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube capable of bubbling in liquid, and gradually raise the temperature to 60 ° C. while bubbling in liquid with nitrogen. While adding 600 parts of titanium tetraisopropoxide dropwise, the mixture was reacted at 60 ° C. for 4 hours to obtain a slurry-like reaction mixture. The reaction mixture was filtered off with a filter paper and dried at 40 ° C./20 kPa · s, so that a titanium-containing catalyst (t1) composed of a mixture of titanium triisopropoxyterephthalate and unreacted terephthalic acid (titanium triisopropoxyterephthalate concentration 65% )

Production Example 2 <Synthesis of Crystalline Polyester (A11) (1)>
In a reaction vessel equipped with a condenser, stirrer and nitrogen inlet tube, 132 parts (1.12 mol) of 1,6-hexanediol, 230 parts (1.0 mol) of 1,10-decanedicarboxylic acid, and condensation 3 parts of tetrabutoxy titanate was added as a catalyst, and the reaction was carried out at 210 ° C. for 5 hours while distilling off the water produced under normal pressure. Next, the reaction was continued under a reduced pressure of 5 to 20 mmHg, and taken out when the acid value became 2 or less. This is designated as crystalline polyester (A11-1).
Crystalline polyester (A11-1) had Tmp of 66 ° C., Tm of 73 ° C. (Tm / Tmp = 1.1), Mp of 13,500, acid value of 1, and SP value of 9.6.
The number of moles in parentheses means a relative molar ratio (the same applies hereinafter).

Production Example 3 <Synthesis of Crystalline Polyester (A11) (2)>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 121 parts (1.03 mol) of 1,6-hexanediol, 230 parts (1.0 mol) of 1,10-decanedicarboxylic acid, and condensation 3 parts of tetrabutoxy titanate was added as a catalyst, and the reaction was carried out at 210 ° C. for 5 hours while distilling off the water produced under normal pressure. Next, the reaction was continued under a reduced pressure of 5 to 20 mmHg, and taken out when the acid value became 2 or less. This is designated as crystalline polyester (A11-2).
Crystalline polyester (A11-2) had Tmp of 73 ° C., Tm of 93 ° C. (Tm / Tmp = 1.3), Mp of 90000, acid value of 1, and SP value of 9.6.

Production Example 4 <Synthesis of Crystalline Polyester (A11) (3)>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 132 parts (1.12 mol) of 1,6-hexanediol, 343 parts (1.0 mol) of 1,18-octadecanedicarboxylic acid, and condensation 3 parts of tetrabutoxy titanate was added as a catalyst, and the reaction was carried out at 210 ° C. for 5 hours while distilling off the water produced under normal pressure. Next, the reaction was continued under a reduced pressure of 5 to 20 mmHg, and taken out when the acid value became 2 or less. This is designated as crystalline polyester (A11-3).
Crystalline polyester (A11-3) had Tmp of 68 ° C., Tm of 95 ° C. (Tm / Tmp = 1.4), Mp of 20000, acid value of 1, and SP value of 9.3.

Production Example 5 <Synthesis of Crystalline Polyester (A11) (4)>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 69 parts (1.12 mol) of ethylene glycol, 230 parts (1.0 mol) of 1,10-decanedicarboxylic acid, and tetrabutoxy as a condensation catalyst. 3 parts of titanate was added and reacted at 200 ° C. for 5 hours while distilling off the water generated under normal pressure. Next, the reaction was continued under a reduced pressure of 5 to 20 mmHg, and taken out when the acid value became 2 or less. This is designated as crystalline polyester (A11-4).
Crystalline polyester (A11-4) had Tmp of 108 ° C., Tm of 110 ° C. (Tm / Tmp = 1.0), Mp of 10,500, acid value of 2, and SP value of 10.0.

Production Example 6 <Synthesis of Crystalline Polyester (A11) (5)>
In a reaction vessel equipped with a condenser, stirrer and nitrogen inlet tube, 132 parts (1.12 mol) of 1,6-hexanediol, 230 parts (1.0 mol) of 1,10-decanedicarboxylic acid, and condensation 1 part of the titanium-containing catalyst (t1) obtained in Production Example 1 was added as a catalyst and reacted for 5 hours at 210 ° C. while distilling off the water produced under normal pressure. Next, the reaction was continued under a reduced pressure of 5 to 20 mmHg, and the acid value was adjusted to 2 or less. Next, 355 parts (0.16 mol) of stearic acid was added and reacted for 5 hours while distilling off the water produced at 210 ° C. under normal pressure. Next, the reaction was continued under a reduced pressure of 5 to 20 mmHg, and taken out when the acid value became 2 or less. This is designated as crystalline polyester (A11-5).
Crystalline polyester (A11-5) had Tmp of 70 ° C., Tm of 75 ° C. (Tm / Tmp = 1.1), Mp of 11000, acid value of 2, and SP value of 9.6.

Production Example 7 <Synthesis of Crystalline Polyester (A12) (1)>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 477 parts (4.04 moles) of 1,6-hexanediol, 620 parts of 1,12-dodecanedioic acid (2.7 moles), and condensation 1 part of the titanium-containing catalyst (t1) obtained in Production Example 1 was added as a catalyst and reacted for 5 hours at 210 ° C. while distilling off the water produced under normal pressure. Next, the reaction was continued under a reduced pressure of 5 to 20 mmHg, and the acid value was adjusted to 2 or less. Next, 497 parts (1.74 mol) of stearic acid was added, and the reaction was allowed to proceed for 5 hours at 210 ° C. while distilling off the water produced under normal pressure. Next, the reaction was continued under a reduced pressure of 5 to 20 mmHg, and taken out when the acid value became 2 or less. This is designated as crystalline polyester (A12-1).
Crystalline polyester (A12-1) had Tmp of 66 ° C., Tm of 65 ° C. (Tm / Tmp = 1.0), Mp of 4400, acid value of 2, hydroxyl value of 1, and SP value of 9.5. It was.

Production Example 8 <Synthesis of Crystalline Polyester (A12) (2)>
In a reaction vessel equipped with a condenser, stirrer and nitrogen inlet tube, 547 parts (4.63 moles) of 1,6-hexanediol, 551 parts (2.73 moles) of 1,10-decanedicarboxylic acid, and condensation 1 part of the titanium-containing catalyst (t1) obtained in Production Example 1 was added as a catalyst and reacted for 5 hours at 210 ° C. while distilling off the water produced under normal pressure. Next, the reaction was continued under a reduced pressure of 5 to 20 mmHg, and the acid value was adjusted to 2 or less. Next, 488 parts (1.71 mol) of stearic acid was added and reacted for 5 hours while distilling off the water produced at 210 ° C. under normal pressure. Next, the reaction was continued under a reduced pressure of 5 to 20 mmHg, and taken out when the acid value became 2 or less. This is designated as crystalline polyester (A12-2).
Crystalline polyester (A12-2) had Tmp of 57 ° C., Tm of 52 ° C. (Tm / Tmp = 0.9), Mp of 2700, acid value of 1, hydroxyl value of 38, and SP value of 9.5. It was.

Production Example 9 <Synthesis of Crystalline Polyester (A12) (3)>
In a reaction vessel equipped with a condenser, stirrer and nitrogen inlet tube, 547 parts (4.63 moles) of 1,6-hexanediol, 551 parts (2.73 moles) of 1,10-decanedicarboxylic acid, and condensation 1 part of the titanium-containing catalyst (t1) obtained in Production Example 1 was added as a catalyst and reacted for 5 hours at 210 ° C. while distilling off the water produced under normal pressure. Next, the reaction was continued under a reduced pressure of 5 to 20 mmHg, and the acid value was adjusted to 2 or less. Next, 733 parts (2.57 mol) of stearic acid was added and reacted for 5 hours while distilling off the water produced at 210 ° C. under normal pressure. Next, the reaction was continued under a reduced pressure of 5 to 20 mmHg, and taken out when the acid value became 2 or less. This is designated as crystalline polyester (A12-3).
The crystalline polyester (A12-3) had a Tmp of 60 ° C., a Tm of 58 ° C. (Tm / Tmp = 1.0), an Mp of 2700, an acid value of 1, a hydroxyl value of 6, and an SP value of 9.4. It was.

Production Example 10 <Synthesis of Crystalline Polyester (A12) (4)>
In a reaction vessel equipped with a condenser, stirrer and nitrogen inlet tube, 516 parts (4.37 moles) of 1,6-hexanediol, 589 parts (2.92 moles) of 1,10-decanedicarboxylic acid, and condensation 1 part of the titanium-containing catalyst (t1) obtained in Production Example 1 was added as a catalyst and reacted for 5 hours at 210 ° C. while distilling off the water produced under normal pressure. Next, the reaction was continued under a reduced pressure of 5 to 20 mmHg, and the acid value was adjusted to 2 or less. Next, 878 parts (2.57 mol) of behenic acid was added, and the reaction was allowed to proceed for 5 hours while distilling off the water produced at 210 ° C. under normal pressure. Next, the reaction was continued under a reduced pressure of 5 to 20 mmHg, and taken out when the acid value became 2 or less. This is designated as crystalline polyester (A12-4).
Crystalline polyester (A12-4) had Tmp of 66 ° C., Tm of 67 ° C. (Tm / Tmp = 1.0), Mp of 2800, acid value of 1, hydroxyl value of 7, and SP value of 9.4. It was.

Production Example 11 <Synthesis of Crystalline Polyester (A12) (5)>
238 parts (2.02 mol) 1,6-hexanediol, 903 parts (3.93 mol) 1,12-dodecanedioic acid, and condensation in a reactor equipped with a condenser, stirrer and nitrogen inlet 1 part of the titanium-containing catalyst (t1) obtained in Production Example 1 was added as a catalyst and reacted for 5 hours at 210 ° C. while distilling off the water produced under normal pressure. Subsequently, the reaction was continued under a reduced pressure of 5 to 20 mmHg, and the hydroxyl value was adjusted to 2 or less. Next, 516 parts (1.91 mol) of stearyl alcohol was added and reacted for 5 hours at 210 ° C. while distilling off the water produced under normal pressure. Subsequently, the reaction was continued under a reduced pressure of 5 to 20 mmHg, and taken out when the hydroxyl value became 2 or less. This is designated as crystalline polyester (A12-5).
The crystalline polyester (A12-5) had a Tmp of 59 ° C., a Tm of 62 ° C. (Tm / Tmp = 1.1), an Mp of 2500, an acid value of 42, a hydroxyl value of 1, and an SP value of 9.4. It was.

Production Example 12 <Synthesis of linear polyester (A2) other than (A1) (1)>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, 592 parts (3 mol) of 1,2-propylene glycol (hereinafter referred to as propylene glycol), 194 parts (1 mol) of dimethyl terephthalate, and 3 parts of tetrabutoxy titanate was added as a condensation catalyst, and the reaction was allowed to proceed for 8 hours at 180 ° C. while distilling off the methanol produced under a nitrogen stream. Next, while the temperature was gradually raised to 230 ° C., the reaction was carried out while distilling off propylene glycol produced under a nitrogen stream, and when Tm reached 78 ° C., the reaction was cooled to 180 ° C. and 68 parts of trimellitic anhydride (0. 36 mol) was added, and the mixture was taken out after reaction for 1 hour under normal pressure. The taken out resin was cooled to room temperature and then pulverized into particles. This is designated as linear polyester (A2-1).
The linear polyester (A12-1) had a Tg of 58 ° C., a Tm of 96 ° C., an Mp of 4000, an acid value of 40, a hydroxyl value of 55, and a THF-insoluble content of 0%.

Production Example 13 <Synthesis of linear polyester (A) (1) and preparation of resin particle dispersion>
Put 400 parts of (A2-1) and 600 parts of (A11-1) in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, raise the temperature to 180 ° C., perform melt blending for 1 hour, and take out. It was. This is designated as linear polyester (A-1).
To 100 parts of linear polyester (A-1), 100 parts of acetone was added and dissolved, and 2.5 parts of triethylamine was further added. While stirring with a homogenizer (10000 rpm), 300 parts of water was added to an acetone solution of polyester, and acetone was distilled off under reduced pressure at 40 ° C. and 100 mmHg to obtain [resin particle dispersion W1]. The volume average particle diameter of the [resin particle dispersion W1] measured with a laser particle size distribution analyzer LA-920 (manufactured by Horiba Seisakusho) was 0.09 μm.

Production Example 14 <Synthesis of Linear Polyester (A) (2) and Preparation of Resin Particle Dispersion>
Put 400 parts of (A2-1) and 600 parts of (A11-2) in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, raise the temperature to 180 ° C., perform melt blending for 1 hour, and take out. It was. This is designated as linear polyester (A-2).
To 100 parts of linear polyester (A-2), 100 parts of acetone was added and dissolved, and 2.5 parts of triethylamine was further added. While stirring with a homogenizer (10000 rpm), 300 parts of water was added to an acetone solution of polyester, and acetone was distilled off under reduced pressure at 40 ° C. and 100 mmHg to obtain [resin particle dispersion W2]. The volume average particle diameter of the [resin particle dispersion W2] measured by a laser particle size distribution analyzer LA-920 (manufactured by Horiba Seisakusho) was 0.09 μm.

Production Example 15 <Synthesis of linear polyester (A) (3) and preparation of resin particle dispersion>
Put 400 parts of (A2-1) and 600 parts of (A11-3) in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, raise the temperature to 180 ° C., perform melt blending for 1 hour, and take out. It was. This is designated as linear polyester (A-3).
To 100 parts of linear polyester (A-3), 100 parts of acetone was added and dissolved, and 2.5 parts of triethylamine was further added. While stirring with a homogenizer (10000 rpm), 300 parts of water was added to an acetone solution of polyester, and acetone was distilled off under reduced pressure at 40 ° C. and 100 mmHg to obtain [resin particle dispersion W3]. The volume average particle diameter of the [resin particle dispersion W3] measured by a laser particle size distribution analyzer LA-920 (manufactured by Horiba Seisakusho) was 0.09 μm.

Production Example 16 <Synthesis of linear polyester (A) (4) and preparation of resin particle dispersion>
Put 400 parts of (A2-1) and 600 parts of (A11-4) in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, raise the temperature to 180 ° C., perform melt blending for 1 hour, and take out. It was. This is designated as linear polyester (A-4).
To 100 parts of linear polyester (A-4), 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 W4]. The volume average particle diameter of the [resin particle dispersion W4] measured by a laser particle size distribution analyzer LA-920 (manufactured by Horiba Seisakusho) was 0.09 μm.

Production Example 17 <Synthesis of linear polyester (A) (5) and preparation of resin particle dispersion>
500 parts of (A2-1) and 500 parts of (A11-5) are placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, heated to 180 ° C. and melt blended for 1 hour, then taken out. It was. This is designated as linear polyester (A-5).
To 100 parts of linear polyester (A-5), 100 parts of acetone was added and dissolved, and 2.5 parts of triethylamine was further added. While stirring with a homogenizer (10000 rpm), 300 parts of water was added to an acetone solution of polyester, and acetone was distilled off under reduced pressure at 40 ° C. and 100 mmHg to obtain [resin particle dispersion W5]. The volume average particle diameter of the [resin particle dispersion W5] measured by a laser particle size distribution analyzer LA-920 (manufactured by Horiba Seisakusho) was 0.09 μm.

Production Example 18 <Synthesis of linear polyester (A) (6) and preparation of resin particle dispersion>
Place 800 parts of (A2-1) and 200 parts of (A12-1) in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, raise the temperature to 180 ° C., perform melt blending for 1 hour, and take out. It was. This is designated as linear polyester (A-6).
To 100 parts of linear polyester (A-6), 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 W6]. The volume average particle diameter of the [resin particle dispersion W6] measured by a laser particle size distribution analyzer LA-920 (manufactured by Horiba Seisakusho) was 0.09 μm.

Production Example 19 <Synthesis of linear polyester (A) (7) and preparation of resin particle dispersion>
Put 400 parts of (A2-1) and 600 parts of (A12-2) in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, raise the temperature to 180 ° C., perform melt blending for 1 hour, and take out. It was. This is designated as linear polyester (A-7).
To 100 parts of linear polyester (A-7), 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 W7]. The volume average particle diameter of the [resin particle dispersion W7] measured by a laser particle size distribution analyzer LA-920 (manufactured by Horiba Seisakusho) was 0.09 μm.

Production Example 20 <Synthesis of linear polyester (A) (8) and preparation of resin particle dispersion>
Place 900 parts of (A2-1) and 100 parts of (A12-3) in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, raise the temperature to 180 ° C., perform melt blending for 1 hour, and take out. It was. This is designated as linear polyester (A-8).
To 100 parts of linear polyester (A-8), 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 W8]. The volume average particle diameter of the [resin particle dispersion W8] measured by a laser particle size distribution analyzer LA-920 (manufactured by Horiba Seisakusho) was 0.09 μm.

Production Example 21 <Synthesis of linear polyester (A) (9) and preparation of resin particle dispersion>
Place 900 parts of (A2-1) and 100 parts of (A12-4) in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, raise the temperature to 180 ° C., perform melt blending for 1 hour, and take out. It was. This is designated as linear polyester (A-9).
To 100 parts of linear polyester (A-9), 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 W9]. The volume average particle diameter of the [resin particle dispersion W9] measured by a laser particle size distribution analyzer LA-920 (manufactured by Horiba, Ltd.) was 0.09 μm.

Production Example 22 <Synthesis of linear polyester (A) (10) and preparation of resin particle dispersion>
Place 900 parts of (A2-1) and 100 parts of (A12-5) in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, raise the temperature to 180 ° C., perform melt blending for 1 hour, and take out. It was. This is designated as linear polyester (A-10).
To 100 parts of linear polyester (A-10), 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 W10]. The volume average particle diameter of the [resin particle dispersion W10] measured by a laser particle size distribution analyzer LA-920 (manufactured by Horiba Seisakusho) was 0.09 μm.

Production Example 23 <Synthesis of Nonlinear Polyester (B) (1) and Preparation of Resin Particle Dispersion>
Propylene oxide of 41 parts (0.13 mole) of bisphenol A / ethylene oxide 2 mole adduct, 457 parts (1.14 mole) of bisphenol A / propylene oxide 3 mole adduct, phenol novolak (average functional group number: 5.6) 9 parts (0.01 mole) of 6 mole adduct, 166 parts (1.0 mole) of terephthalic acid, 93 parts (0.8 mole) of fumaric 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 reduced pressure of 5 to 20 mmHg. When the acid value became 2 or less, the mixture was cooled to 180 ° C., and 41 parts (0.21 mol) of trimellitic anhydride was added. The reaction was further carried out at 230 ° C. under a reduced pressure of 5 to 20 mmHg, and the mixture was taken out when Tm reached 132 ° C. The taken out resin was cooled to room temperature and then pulverized into particles. This is designated as nonlinear polyester (B-1).
Nonlinear polyester (B-1) has a Tg of 58 ° C., Tm of 135 ° C., Mp of 11,300, an acid value of 20, a hydroxyl value of 5 (acid value / hydroxyl value = 4), and a THF insoluble content of 6% (THF Insoluble matter / flow softening point = 0.04).
To 100 parts of linear polyester (B-1), 100 parts of acetone was added and dissolved, and 2.5 parts of triethylamine was further added. While stirring with a homogenizer (10000 rpm), 300 parts of water was added to an acetone solution of polyester, and acetone was distilled off under reduced pressure at 40 ° C. and 100 mmHg to obtain [resin particle dispersion W14]. The volume average particle diameter of the [resin particle dispersion W14] measured with a laser particle size distribution analyzer LA-920 (manufactured by Horiba Seisakusho) was 0.09 μm.

Production Example 24 <Synthesis of Nonlinear Polyester (B) (2) and Preparation of Resin Particle Dispersion>
486 parts (1.21 mol) of bisphenol A / propylene oxide 3 mol adduct, 23 parts (0.29 mol) of propylene oxide 6 mol adduct of phenol novolak (average functional group number: 5.6), 166 parts of terephthalic acid ( 1.0 mol), and 3 parts of tetrabutoxytitanate as a condensation catalyst were added and reacted at 230 ° C. in a nitrogen stream for 5 hours while distilling off the generated water. 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. , 230 ° C., 5 to 20 mmHg under reduced pressure, and taken out when Tm reached 140 ° C. The taken out resin was cooled to room temperature and then pulverized into particles. This is designated as nonlinear polyester (B-2).
The nonlinear polyester (B-2) has a Tg of 57 ° C., Tm of 145 ° C., Mp of 8300, an acid value of 20, a hydroxyl value of 18 (acid value / hydroxyl value = 1.1), and a THF-insoluble content of 28%. (THF insoluble matter / flow softening point = 0.19).
To 100 parts of linear polyester (B-2), 100 parts of acetone was added and dissolved, and 2.5 parts of triethylamine was further added. While stirring with a homogenizer (10000 rpm), 300 parts of water was added to an acetone solution of polyester, and acetone was distilled off under reduced pressure at 40 ° C. and 100 mmHg to obtain [resin particle dispersion W15]. The volume average particle diameter of the [resin particle dispersion W15] measured by a laser particle size distribution analyzer LA-920 (manufactured by Horiba, Ltd.) was 0.09 μm.

Comparative Production Example 1 <Synthesis of Comparative Crystalline Polyester (1)>
1,4-butanediol 117 parts (1.3 mol), fumaric acid 116 parts (1.0 mol), and tetrabutoxy titanate as a condensation catalyst in a reactor equipped with a condenser, stirrer and nitrogen inlet tube 3 parts were added and reacted at 200 ° C. for 5 hours while distilling off the water produced under normal pressure. Subsequently, the reaction was continued under a reduced pressure of 5 to 20 mmHg, and after 5 hours, the water was removed when it was no longer distilled off. This is designated as crystalline polyester (A11′-6).
Crystalline polyester (A11′-6) had Tmp of 123 ° C., Tm of 82 ° C. (Tm / Tmp = 0.7), and SP value of 10.7. Mp and acid value could not be measured because they were insoluble in the measurement solvent.

Comparative production example 2 <Synthesis of linear polyester for comparison (1) and preparation of resin particle dispersion>
The linear polyester (A2-1) obtained in Production Example 12 is used as a comparative linear polyester (A′-11) as it is.
To 100 parts of linear polyester (A′-11), 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 W′11]. The volume average particle diameter of the [resin particle dispersion W′11] measured with a laser particle size distribution analyzer LA-920 (manufactured by Horiba Seisakusho) was 0.09 μm.

Comparative Production Example 3 <Synthesis of linear polyester for comparison (2) and preparation of resin particle dispersion>
After placing 400 parts of (A2-1) and 600 parts of (A11′-6) in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, the temperature was raised to 180 ° C. and melt blending was conducted for 1 hour. I took it out. This is designated as comparative linear polyester (A′-12).
To 100 parts of linear polyester (A′-12), 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 W′12]. The volume average particle diameter of the [resin particle dispersion W′12] measured by a laser particle size distribution analyzer LA-920 (manufactured by Horiba Seisakusho) was 0.09 μm.

Comparative Production Example 4 <Synthesis of linear polyester for comparison (3) and preparation of resin particle dispersion>
970 parts of (A2-1) and 30 parts of (A11-1) are placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, heated to 180 ° C. and melt blended for 1 hour, then taken out. It was. This is designated as comparative linear polyester (A′-13).
To 100 parts of linear polyester (A′-13), 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 W′13]. The volume average particle diameter of the [resin particle dispersion W′13] measured with a laser particle size distribution analyzer LA-920 (manufactured by Horiba Seisakusho) was 0.09 μm.

Production Example 25 <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 26 <Preparation of Release Agent Dispersion>
80 parts of paraffin wax (melting point 73 ° C.), 1 part of an anionic surfactant (manufactured by Sanyo Chemical Industries: Eleminol MON-7) and 120 parts of ion-exchanged water are mixed and dissolved at 95 ° C., and then with a TK homomixer. Dispersion was carried out to obtain [Releasing Agent Dispersion Liquid 1].

Example 1 <Production of toner particles for developing an electrostatic image>
In a stainless steel beaker, 60 parts of [resin particle dispersion W1], 100 parts of [resin particle dispersion W14], 15 parts of [colorant dispersion 1], 15 parts of [release agent dispersion 1], 600 parts of ion-exchanged water 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 diameter of the agglomerated particles became around 5.0 μm, 40 parts of [Resin Particle Dispersion Liquid W14] was added while maintaining the pH constant 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 (C-1).

Example 2 <Preparation of toner particles for developing electrostatic image>
Toner particles (C-2) were obtained in the same manner as in Example 1 except that 60 parts of [resin particle dispersion W1] was changed to 60 parts of [resin particle dispersion W2].

Example 3 <Preparation of toner particles for developing electrostatic image>
[Resin Particle Dispersion Liquid W1] 60 parts, [Resin Particle Dispersion Liquid W3] 60 parts, [Resin Particle Dispersion Liquid W14] 100 parts (first time) and [Resin Particle Dispersion Liquid W14] 40 parts (second time) [Resin particle dispersion W14] was changed to 70 parts (140 parts in total), and toner particles (C-3) were obtained in the same manner as in Example 1.

Example 4 <Preparation of toner particles for developing electrostatic image>
[Resin particle dispersion W1] 60 parts, [Resin particle dispersion W14] 140 parts, [Colorant dispersion 1] 15 parts, [Releasing agent dispersion 1] 15 parts, Ion exchange water 600 parts, Magnesium sulfate 1 After adding a part and making it disperse | distribute using TK type | mold homomixer, it heated up, stirring to 60 degreeC after adjusting to pH7.0. When hydrochloric acid (0.1 mol / L) was added until the volume average particle diameter of the aggregated particles became around 5.0 μm, the mixture was stirred at 60 ° C. for 1 hour while keeping the pH constant, and further heated and stirred at 80 ° C. It went for 2 hours. Thereafter, the mixture was filtered, washed with 500 parts of ion exchange water four times, and dried at 40 ° C. for 18 hours to obtain toner particles (C-4).

Example 5 <Preparation of toner particles for electrostatic image development>
[Resin particle dispersion W1] 60 parts in [Resin particle dispersion W5] 30 parts, [Resin particle dispersion W14] 140 parts in [Resin particle dispersion W14] 170 parts, except that it is changed to 170 parts Thus, toner particles (C-5) were obtained.

Example 6 <Preparation of toner particles for electrostatic image development>
[Resin particle dispersion W14] 100 parts (first time) and [Resin particle dispersion W14] 40 parts (second time) are both changed to [Resin particle dispersion W15] 70 parts (total 140 parts). In the same manner as in Example 1, toner particles (C-6) were obtained.

Example 7 <Preparation of toner particles for developing electrostatic image>
[Resin particle dispersion W1] 60 parts to [Resin particle dispersion W5] 160 parts, [Resin particle dispersion W14] 100 parts (first time) and [Resin particle dispersion W14] 40 parts (second time) [Resin particle dispersion W14] was changed to 20 parts (total 40 parts), and toner particles (C-7) were obtained in the same manner as in Example 1.

Example 8 <Preparation of toner particles for developing electrostatic image>
60 parts of [resin particle dispersion W1] are replaced with 60 parts of [resin particle dispersion W6], 100 parts (first time) of [resin particle dispersion W14] and 40 parts (second time) of [resin particle dispersion W14] [Resin particle dispersion W14] was changed to 70 parts (140 parts in total), and toner particles (C-8) were obtained in the same manner as in Example 1.

Example 9 <Preparation of toner particles for electrostatic image development>
60 parts of [resin particle dispersion W1] are added to 60 parts of [resin particle dispersion W7], 100 parts (first time) of [resin particle dispersion W14] and 40 parts (second time) of [resin particle dispersion W14] [Resin particle dispersion W14] was changed to 70 parts (140 parts in total), and toner particles (C-9) were obtained in the same manner as in Example 1.

Example 10 <Preparation of toner particles for developing electrostatic image>
60 parts of [resin particle dispersion W1] are replaced with 60 parts of [resin particle dispersion W8], 100 parts (first time) of [resin particle dispersion W14] and 40 parts (second time) of [resin particle dispersion W14] [Resin particle dispersion W14] was changed to 70 parts (140 parts in total), and toner particles (C-10) were obtained in the same manner as in Example 1.

Example 11 <Preparation of toner particles for electrostatic image development>
[Resin Particle Dispersion Liquid W1] Same as Example 4 except that 60 parts of [Resin Particle Dispersion Liquid W9] are changed to 30 parts, and [Resin Particle Dispersion Liquid W14] 140 parts are changed to [Resin Particle Dispersion Liquid W14] 170 parts. Thus, toner particles (C-11) were obtained.

Example 12 <Preparation of toner particles for developing electrostatic image>
60 parts of [resin particle dispersion W1] are added to 60 parts of [resin particle dispersion W9], 100 parts (first time) of [resin particle dispersion W14] and 40 parts (second time) of [resin particle dispersion W14] [Resin particle dispersion W15] was changed to 70 parts (total 140 parts), and toner particles (C-12) were obtained in the same manner as in Example 1.

Example 13 <Preparation of toner particles for developing electrostatic image>
60 parts of [resin particle dispersion W1] are added to 60 parts of [resin particle dispersion W10], 100 parts (first time) of [resin particle dispersion W14] and 40 parts (second time) of [resin particle dispersion W14] [Resin particle dispersion W14] was changed to 70 parts (140 parts in total), and toner particles (C-13) were obtained in the same manner as in Example 1.

Example 14 <Preparation of toner particles for electrostatic image development>
[Resin particle dispersion W1] 60 parts to [Resin particle dispersion W10] 160 parts, [Resin particle dispersion W14] 100 parts (first time) and [Resin particle dispersion W14] 40 parts (second time) And [resin particle dispersion W14], toner particles (C-14) were obtained in the same manner as in Example 1 except that the amount was changed to 20 parts (total 40 parts).

Comparative Example 1 <Preparation of electrostatic charge image developing toner particles>
Example 4 except that 60 parts of [resin particle dispersion W1] are changed to 60 parts of [resin particle dispersion W′11] and 140 parts of [resin particle dispersion W14] are changed to 140 parts of [resin particle dispersion W15]. In the same manner as above, toner particles (C′-1) were obtained.

Comparative Example 2 <Preparation of electrostatic charge image developing toner particles>
[Resin particle dispersion W1] 60 parts, [Resin particle dispersion W′12] 60 parts, [Resin particle dispersion W14] 100 parts (first time) and [Resin particle dispersion W14] 40 parts (second time) The toner particles (C′-2) were changed in the same manner as in Example 1 except that [resin particle dispersion W15] was changed to 100 parts (first time) and [resin particle dispersion W15] was changed to 40 parts (second time). Obtained.

Comparative Example 3 <Preparation of electrostatic charge image developing toner particles>
[Resin particle dispersion W1] 60 parts, [Resin particle dispersion W′13] 60 parts, [Resin particle dispersion W14] 100 parts (first time) and [Resin particle dispersion W14] 40 parts (second time) Were changed to [Resin Particle Dispersion Liquid W15] 70 parts (total 140 parts) in the same manner as in Example 1 to obtain toner particles (C′-3).

Examples [1] to [14] and Comparative Examples [1] to [3]
Colloidal with respect to 100 parts of each of toner particles (C-1) to (C-14) obtained by the production method of the present invention and comparative toner particles (C′-1) to (C′-3) Silica (Aerosil R972: made by Nippon Aerosil) 0.5 parts was mixed in a sample mill, and the toners (T1) to (T14) of the present invention and comparative toners (T′1) to (T′3) were mixed. Obtained.
The evaluation results evaluated by the following evaluation methods are shown in Table 1.

[Evaluation method]
[1] Physical Properties of Toner Resin The linear polyester to be used and the non-linear polyester were mixed at a ratio contained in the toner, and melt-mixed with a continuous kneader at a jacket temperature of 130 ° C. and a residence time of 3 minutes. After the molten resin is cooled to room temperature, it is pulverized by a pulverizer and formed into particles, and [T30000], [G "100] / [G" 150], and [Q2] / [Q1] of the toner resin of the present invention. Was measured by the method described above.
[2] Minimum fixing temperature (MFT)
Using the toner of the present invention and the comparative toner (the following evaluation method is the same), an unfixed image developed using a commercially available copying machine (AR5030; manufactured by Sharp) is transferred to a commercially available copying machine (AR5030; manufactured by Sharp). Evaluation was performed using a fixing machine. 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.
[3] 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.
[4] Blocking resistance 10.0 g of the sample was placed in a 200 ml polycup and left to stand in a circulating dryer at 40 ° C. After 5 days, the sample was taken out from the dryer, and the fluidity of the sample was confirmed.
(Judgment)
A: Flows when the cup is tilted.
○: It flows when the cup is tilted and patted with a spatula.
Δ: Flows when the cup is tilted and pucked strongly with a spatula.
X: The cup does not flow even when tilted and spatula strongly.
A judgment of ◯ or more is judged to have good blocking resistance.
[5] Average particle size and particle size distribution Volume average particle size and number average particle size were measured with Multisizer III (manufactured by Coulter).

  As described above, the electrostatic charge image developing toners of the present invention (Examples [1] to [14]) all showed significantly better results than the comparative charge image development toners.

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

Claims (8)

An electrostatic charge image developing toner comprising toner particles containing a polyester resin (I) and a colorant, wherein the toner particles include a step of dispersing resin particles having a volume average particle size of 1 μm or less in water and the resin. Particles having a volume average particle diameter of 3 to 10 μm formed from a process including a process of aggregating the particles, the polyester resin (I) is composed of a linear polyester (A) and a non-linear polyester (B), and has a carbon number A polycondensation polyester resin of a carboxylic acid component and an alcohol component containing at least 40 mol% of one or more selected from 9-30 aliphatic polycarboxylic acids and ester-forming derivatives thereof, and having an SP value of 9.0 ~10.5 (cal / cm ^{3) 1/2} a crystal polyester (A1), an electrostatic image, characterized in that it contains 5% by weight or more in (a) developing A toner, the crystalline polyester (A1) is a crystalline polyester peak top molecular weight by gel permeation chromatography of the THF-soluble matter is 5,000 to 150,000 (A11), the loss elastic polyester resin (I) The temperature [T30000] at which the rate (G ″) becomes 30000 (dyn / cm ² ) is 130 ° C. or less, the loss elastic modulus [G ″ 100] (dyn / cm ² ) at 100 ° C., and the loss elasticity at 150 ° C. An electrostatic charge image developing toner having a rate [G "150] (dyn / cm ² ) satisfying the following formula (3):
[G "100] / [G" 150] ≦ 50 Formula (3)   The carboxylic acid component and / or the alcohol component constituting the crystalline polyester (A1) further contains one or more selected from monocarboxylic acids having 1 to 30 carbon atoms and monools having 1 to 30 carbon atoms. Item 2. The toner for developing an electrostatic charge image according to Item 1.   The crystalline polyester (A1) has a melting point [Tmp] of 50 to 120 ° C., a flow softening point [Tm] of 50 to 150 ° C., and [Tm] / [Tmp] of 0.8 to 1.8. The toner for developing an electrostatic image according to claim 1 or 2. Non-linear polyester (B) has a THF-insoluble content of 1 to 36% by weight, a THF-soluble content of gel permeation chromatography having a peak top molecular weight of 5,000 to 20,000, a flow softening point of 120 to 180 ° C., The electrostatic image developing toner according to claim 1, wherein the toner has an acid value of 15 to 80 and (B) satisfies the following formulas (1) and (2).
Acid value / Hydroxyl value ≧ 1 Formula (1)
THF insoluble matter (% by weight) / flow softening point (° C.) ≦ 0.2 (2)   The electrostatic charge image according to any one of claims 1 to 4, wherein the crystalline polyester (A1) is a crystalline polyester (A12) having a peak top molecular weight of 1000 or more and less than 5000 in gel permeation chromatography of a THF-soluble component. Development toner. 6. The electrostatic charge image developing according to claim 5 , wherein 5 to 40 mol% of all constituent monomers of the crystalline polyester (A12) is a monocarboxylic acid having 10 to 30 carbon atoms and / or a monool having 10 to 30 carbon atoms. toner. The amount of heat of fusion Q1 of the melting peak derived from the crystalline polyester (A12) at the first temperature increase and the melting peak derived from the crystalline polyester (A12) at the second temperature increase when the linear polyester (A) was subjected to DSC measurement. The toner for electrostatic image development according to claim 5 or 6 , wherein the heat of fusion Q2 satisfies the following formula (4).
0.6 ≦ [Q2] / [Q1] ≦ 1.0 Formula (4) A method for producing a toner for developing an electrostatic charge image comprising toner particles containing a polyester resin (I) and a colorant, wherein the resin particles having at least a volume average particle size of 1 μm or less are dispersed in water, A process of agglomerating, and a step of fusing the agglomerated resin particles to obtain toner particles having a volume average particle diameter of 3 to 10 μm, wherein the polyester resin (I) is composed of linear polyester (A) and nonlinear polyester (B) A polycondensation polyester resin of a carboxylic acid component and an alcohol component containing at least 40 mol% of one or more selected from aliphatic polycarboxylic acids having 9 to 30 carbon atoms and ester-forming derivatives thereof, having an SP value the but 9.0~10.5 (cal / cm ^{3) 1/2} in which crystalline polyester (A1), and characterized in that it contains 5% by weight or more in (a) That a method for producing a toner for developing electrostatic images, the crystalline polyester (A1) is a crystalline polyester peak top molecular weight by gel permeation chromatography of the THF-soluble portion is from 5000 to 150,000 (A11), The temperature [T30000] at which the loss elastic modulus (G ″) of the polyester resin (I) reaches 30000 (dyn / cm ² ) is 130 ° C. or less, and the loss elastic modulus [G ″ 100] (dyn / cm ² ) at 100 ° C. And a loss elastic modulus [G "150] (dyn / cm ² ) at 150 ° C. satisfying the following formula (3):
[G "100] / [G" 150] ≦ 50 Formula (3)