JP2020020866A - Binder resin composition for toner - Google Patents

Abstract

To provide a binder resin composition for toner that exhibits excellent toner storage stability and excellent pigment dispersibility, a toner for electrostatic charge image development containing the binder resin composition, a method for manufacturing the binder resin composition, and a method for manufacturing the toner.SOLUTION: (1) A binder resin composition for toner containing a resin composition (A-P) obtained by condensing an amorphous polyester resin (A) having an acid radical and polyalkylene imine. (2) A toner for electrostatic charge image development containing the binder resin composition according to (1) and a coloring agent. (3) A method for manufacturing the binder resin composition for toner including a step 1 of condensing an amorphous polyester resin (A) having an acid radical and polyalkylene imine to obtain the resin composition (A-P). (4) A method for manufacturing the toner for electrostatic charge image development including a step A of fusing and kneading a toner raw material containing the resin composition (A-P) obtained by the method for manufacturing the resin composition according to (3) and a coloring agent.SELECTED DRAWING: None

Description

  The present invention relates to a binder resin composition for toner used for developing a latent image formed in an electrophotographic method, an electrostatic recording method, an electrostatic printing method, and the like, and an electrostatic image containing the binder resin composition. The present invention relates to a developing toner, a method for producing the binder resin composition, a method for producing the toner, and the like.

In the field of electrophotography, in order to reduce the environmental load, it is required to reduce the amount of toner that is melted by heat and fixed to paper, that is, to reduce the amount of toner attached. The problem of reducing the amount of adhesion is that it is difficult to obtain a high image density. In addition, if the pigment dispersion is insufficient, high coloring power cannot be obtained, and even if the amount of the pigment is increased, aggregation is more likely to occur, and the coloring power is limited. Therefore, it is known to use a pigment dispersant to improve the coloring power of the toner.
For example, Patent Document 1 discloses a metal phthalocyanine or a metal phthalocyanine derivative in which a central metal can have a five-coordinate structure or a six-coordinate structure, and n capable of coordinating with the central metal of the metal phthalocyanine or the metal phthalocyanine derivative. A pigment dispersant characterized by containing at least an electron-donating compound. It is described that the pigment dispersant can easily finely disperse a pigment in a dispersion medium.
In addition, Patent Document 2 discloses a polyallylamine derivative having a specific structure as providing a fine particle powder dispersible compound having excellent compatibility with a wide range of resins and excellent pigment dispersibility. Patent Document 3 discloses a polyallylamine derivative as a pigment dispersant.

JP-A-2003-277643 JP-A-9-169821 JP 2017-203143 A

The dispersant described in Patent Literature 1 is said to be capable of finely dispersing a phthalocyanine-based pigment in toner particles. However, the dispersant is not suitable for pigments other than phthalocyanine-based pigments (for example, quinacridone-based and naphthol-based pigments). The pigment dispersibility was insufficient. Patent Documents 2 and 3 also state that carbon black and phthalocyanine pigments can be finely dispersed in a binder resin. However, since the toner obtained by adding the dispersant is plasticized, there arises a problem that the storage stability under high temperature and high humidity is deteriorated.
The present invention relates to a binder resin composition for a toner, which exhibits excellent storage stability and excellent pigment dispersibility of a toner, a toner for developing an electrostatic image containing the binder resin composition, and the binder resin composition. And a method for producing the toner.

  The present inventors have proposed a binder resin composition for toner containing a resin composition (AP) obtained by condensing an amorphous polyester resin (A) having an acid group with a polyalkyleneimine, It has been found that the above-mentioned problems of storage stability and pigment dispersibility can be solved.

That is, the present invention relates to the following embodiments [1] to [4].
[1] A binder resin composition for a toner, comprising a resin composition (AP) obtained by condensing an amorphous polyester resin (A) having an acid group with a polyalkyleneimine.
[2] A toner for developing an electrostatic image, comprising the binder resin composition according to [1] and a colorant.
[3] Step 1: A binder resin composition for a toner, comprising a step of condensing an amorphous polyester resin (A) having an acid group with a polyalkyleneimine to obtain a resin composition (AP). Production method.
[4] Step A: a step of melting and kneading the resin composition (AP) obtained by the method for producing a resin composition according to [3] and a toner material containing a colorant, A method for producing an image developing toner.

  According to the present invention, a binder resin composition for toner, which exhibits excellent storage stability and excellent pigment dispersibility of a toner, a toner for developing an electrostatic image containing the binder resin composition, and the binder resin A method for producing the composition, a method for producing the toner, and the like can be provided.

[Binder resin composition for toner]
The binder resin composition for toner of the present invention (hereinafter, also simply referred to as “binder resin composition”) is an amorphous polyester resin (A) having an acid group (hereinafter, also simply referred to as “resin (A)”). ) And polyalkyleneimine are condensed to obtain a resin composition (AP) (hereinafter, also simply referred to as “resin composition (AP)”).
According to the binder resin composition, a toner having excellent storage stability is obtained, and further, excellent pigment dispersibility is exhibited.

The reason why the effects of the present invention can be obtained is not clear, but is considered as follows.
The resin composition (AP) contains a portion derived from polyalkylenimine in its structure, and acts as a dispersant for the colorant, whereby the colorant is finely dispersed in the binder resin composition. It is considered that In addition, since the colorant is dispersed by the resin composition (AP), plasticization due to the addition of the dispersant does not progress, high storage stability is obtained, and compatibility with the above-described high dispersibility can be achieved.

The crystallinity of the resin is represented by the ratio between the softening point and the maximum endothermic peak temperature measured by a differential scanning calorimeter (DSC), that is, the crystallinity index defined by “softening point / maximum endothermic peak temperature”. Generally, when the crystallinity index exceeds 1.4, the resin is amorphous, and when the crystallinity index is less than 0.6, the resin has low crystallinity and many amorphous portions. In the present invention, the “crystalline resin” has a crystallinity index of 0.6 or more, preferably 0.7 or more, more preferably 0.9 or more, and 1.4 or less, preferably 1.2 or less. The following resins are referred to, and “amorphous resin” refers to a resin having a crystallinity index of more than 1.4 or less than 0.6.
The above “endothermic maximum peak temperature” refers to the temperature of the peak having the largest peak area among the endothermic peaks observed under the conditions of the measurement method described in Examples.
The crystallinity of the resin can be adjusted by the type and ratio of the raw material monomers, production conditions (eg, reaction temperature, reaction time, cooling rate) and the like.
The “polyester resin” may include a modified polyester resin to such an extent that its properties are not substantially impaired. Examples of the modified polyester resin include a urethane-modified polyester resin in which a polyester resin is modified by a urethane bond, an epoxy-modified polyester resin in which a polyester resin is modified by an epoxy bond, and a composite having a polyester component and an addition polymerization resin component. Resins.
"Bisphenol A" means 2,2-bis (4-hydroxyphenyl) propane.
Examples of the “carboxylic acid compound” include carboxylic acids, anhydrides thereof, and alkyl esters having 1 to 3 carbon atoms.

<Resin composition (AP)>
The resin composition (AP) used in the present invention is obtained by condensing an amorphous polyester resin (A) having an acid group with a polyalkyleneimine. As described above, in the resin composition (AP), for example, a reaction product of the resin (A) and the polyalkylenimine, a by-product derived from the polyalkylenimine, and the unreacted resin (A) and the unreacted resin (A). The polyalkyleneimine remaining in the reaction is included. Then, it is considered that a reaction product of the resin (A) and the polyalkylenimine and a by-product derived from the polyalkylenimine functions as a dispersant for the colorant in the resin composition (AP).

<Amorphous polyester resin (A)>
The amorphous polyester resin (A) has an acid group.
Examples of the acid group include a carboxy group and a sulfo group. Among these, a carboxy group is preferred.
Examples of the amorphous polyester resin (A) include an amorphous polyester resin, and an amorphous composite resin having a polyester resin segment and a vinyl resin segment. Among these, an amorphous polyester resin is preferred.
The amorphous polyester resin is a polycondensate of an alcohol component and a carboxylic acid component. Hereinafter, the alcohol component and the carboxylic acid component contained in the amorphous polyester resin will be described.

(Alcohol component)
The alcohol component preferably contains at least one selected from the group consisting of an alkylene oxide adduct of bisphenol A (hereinafter, also referred to as “BPA-AO”) and an aliphatic diol having 2 to 6 carbon atoms, More preferably, it contains BPA-AO. BPA-AO preferably has the formula (I):

[In the formula (I), OR ¹¹ and R ¹² O are each independently an alkyleneoxy group having 1 to 4 carbon atoms (preferably an ethyleneoxy group or a propyleneoxy group), and x and y are alkylene oxides. , Which are each independently a positive number, and the average value of the sum of x and y is preferably 1 or more, more preferably 1.5 or more, and preferably 16 or less, It is more preferably 8 or less, further preferably 4 or less. BPA-AO represented by the following formula:
BPA-AO is preferably a propylene oxide adduct of bisphenol A (hereinafter also referred to as “BPA-PO”), an ethylene oxide adduct of bisphenol A (hereinafter also referred to as “BPA-EO”), and more preferably. BPA-PO. One or more of these BPA-AOs may be used.
The amount of BPA-AO in the alcohol component is preferably at least 80 mol%, more preferably at least 90 mol%, further preferably at least 95 mol%, further preferably at least 98 mol%, and at most 100 mol%. And more preferably 100 mol%.

  The alcohol component may contain another alcohol component different from BPA-AO. Examples of other alcohol components include linear or branched aliphatic diols, alicyclic diols, and tri- or higher polyhydric alcohols.

The carbon number of the linear or branched aliphatic diol is preferably 2 or more, and is preferably 18 or less, more preferably 14 or less, further preferably 10 or less, and still more preferably 6 or less.
Examples of the linear or branched aliphatic diol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butanediol. , 2,3-butanediol, neopentyl glycol, 1,4-butenediol, 1,2-pentanediol, 1,4-pentanediol, 2,4-pentanediol, 1,5-pentanediol, 1,2 -Hexanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 3,3-dimethyl-1,2-butanediol, 1,7-heptanediol, 1,8-octane Diol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecandio Le, 1,13-tri-decanediol, 1,14-tetradecane diol.
Examples of the alicyclic diol include hydrogenated bisphenol A and alkylene oxide adducts of hydrogenated bisphenol A having 2 to 4 carbon atoms (average addition mole number of 2 to 12).
Examples of the trihydric or higher polyhydric alcohol include glycerin, pentaerythritol, trimethylolpropane, sorbitol, and sorbitan.
From the viewpoint of adjusting the molecular weight and softening point of the obtained polyester, the alcohol component may include a monohydric alcohol.
One or more of these alcohol components may be used.

(Carboxylic acid component)
Examples of the carboxylic acid component include a dicarboxylic acid compound and a trivalent or higher polyvalent carboxylic acid compound.

Examples of the dicarboxylic acid compound include an aromatic dicarboxylic acid compound, an aliphatic dicarboxylic acid compound, and an alicyclic dicarboxylic acid compound.
The carbon number of the dicarboxylic acid compound is preferably 2 or more, more preferably 3 or more, and is preferably 30 or less, more preferably 20 or less.
Examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, and terephthalic acid. Among these, isophthalic acid and terephthalic acid are preferable, and terephthalic acid is more preferable.
As the aliphatic dicarboxylic acid, for example, oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, pentanedioic acid, adipic acid, sebacic acid, dodecanedioic acid, azelaic acid, And succinic acid substituted with an aliphatic hydrocarbon group having 1 to 20 carbon atoms. The carbon number of the aliphatic hydrocarbon group is preferably 8 or more, more preferably 9 or more, and is preferably 16 or less, more preferably 14 or less. The aliphatic hydrocarbon group may be any of a straight chain and a branched chain, and may be any of a saturated aliphatic hydrocarbon group and an unsaturated aliphatic hydrocarbon group. Examples of the succinic acid substituted with an aliphatic hydrocarbon group having 1 to 20 carbon atoms include octenyl succinic acid, nonenyl succinic acid, decenyl succinic acid, undecenyl succinic acid, dodecyl succinic acid, dodecenyl succinic acid, and tridecenyl succinic acid. , Tetradecenyl succinic acid and tetrapropenyl succinic acid.

Among these dicarboxylic acid compounds, aromatic dicarboxylic acids are preferred, and terephthalic acid is more preferred.
The amount of the aromatic dicarboxylic acid compound in the carboxylic acid component is preferably at least 50 mol%, more preferably at least 60 mol%, further preferably at least 65 mol%, further preferably at least 70 mol%, and Mol% or less.

Examples of the trivalent or higher polyvalent carboxylic acid compound include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, and pyromellitic acid. Among these, it is preferable to contain trimellitic acid or its anhydride.
The content of the trivalent or higher polycarboxylic acid is preferably 10 mol% or less, more preferably 5 mol% or less, still more preferably 1 mol% or less, and 0 mol% in the carboxylic acid component. .
From the viewpoint of adjusting the molecular weight and softening point of the resin, the carboxylic acid component may appropriately contain a monovalent carboxylic acid.
One or more of these carboxylic acid components may be used.

  The equivalent ratio [COOH group / OH group] of the carboxy group (COOH group) of the carboxylic acid component to the hydroxy group (OH group) of the alcohol component is preferably 0.7 or more, more preferably 0.8 or more, and , Preferably 1.3 or less, more preferably 1.2 or less, and still more preferably 1.0 or less.

[Physical properties of resin (A)]
The softening point of the resin (A) is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, and still more preferably 100 ° C. or higher, from the viewpoint of further improving the storage stability of the toner. From the viewpoint of further improvement, the temperature is preferably 130 ° C. or lower, more preferably 120 ° C. or lower, and further preferably 110 ° C. or lower.

  The glass transition temperature of the resin (A) is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, and still more preferably 55 ° C. or higher, from the viewpoint of further improving the storage stability of the toner. From the viewpoint of further improving, the temperature is preferably 90 ° C or lower, more preferably 80 ° C or lower, and further preferably 70 ° C or lower.

  The acid value of the resin (A) is preferably 2 mgKOH / g or more from the viewpoint of easily obtaining a resin composition (AP) having excellent storage stability and pigment dispersibility, and from the viewpoint of interaction with a colorant. It is more preferably at least 5 mgKOH / g, further preferably at least 10 mgKOH / g, and preferably at most 40 mgKOH / g, more preferably at most 30 mgKOH / g, even more preferably at most 25 mgKOH / g.

  The hydroxyl value of the resin (A) is preferably at least 2 mgKOH / g, more preferably at least 10 mgKOH / g, still more preferably at least 30 mgKOH / g, and preferably at most 60 mgKOH / g, more preferably at most 50 mgKOH / g. , More preferably 45 mgKOH / g or less.

  The number average molecular weight of the resin (A) is preferably 1,000 or more, more preferably 1,500 or more, further preferably 1,800 or more, and preferably 50,000 or less, more preferably 10,000. Or less, more preferably 8,000 or less.

  The weight average molecular weight of the resin (A) is preferably at least 2,000, more preferably at least 3,000, even more preferably at least 4,000, and preferably at most 100,000, more preferably at 50,000. Or less, more preferably 10,000 or less.

  The softening point, glass transition temperature, acid value, hydroxyl value, number average molecular weight, and weight average molecular weight of the resin (A) depend on the type and ratio of the raw material monomers, and the production conditions such as the reaction temperature, reaction time, and cooling rate. It can be adjusted appropriately. Those values are obtained by the method described in the examples described later. When two or more resins (A) are used in combination, the values of the physical properties obtained as a mixture thereof are preferably within the above ranges.

[Production method of resin (A)]
The resin (A) may be produced, for example, by a method including a step A of performing a polycondensation reaction with an alcohol component and a carboxylic acid component.
In step A, if necessary, an esterification catalyst such as tin (II) di (2-ethylhexanoate), dibutyltin oxide, or titanium diisopropylate bistriethanolaminate may be used in a total amount of 100 parts of an alcohol component and a carboxylic acid component. 0.01 parts by mass or more and 5 parts by mass or less with respect to parts by mass; an esterification promoter such as gallic acid (same as 3,4,5-trihydroxybenzoic acid) or the like in total of 100 parts by mass of an alcohol component and a carboxylic acid component. The polycondensation may be performed using 0.001 parts by mass or more and 0.5 parts by mass or less with respect to parts.
When a monomer having an unsaturated bond such as fumaric acid is used in the polycondensation reaction, preferably 0.001 part by mass relative to 100 parts by mass of the alcohol component and the carboxylic acid component as necessary. At least 0.5 part by mass of the radical polymerization inhibitor may be used. Examples of the radical polymerization inhibitor include 4-tert-butylcatechol.
The temperature of the polycondensation reaction is preferably 120 ° C. or higher, more preferably 160 ° C. or higher, further preferably 180 ° C. or higher, and preferably 260 ° C. or lower, more preferably 240 ° C. or lower. The polycondensation may be performed in an inert gas atmosphere.

<Polyalkyleneimine>
The polyalkyleneimine is preferably a polyalkyleneimine having 1 to 5 carbon atoms in the alkylene group. The polyalkyleneimine is a compound that can be taken into the molecular skeleton of the resin (A) by a condensation reaction with an acid group of the resin (A).
The polyalkyleneimine having 1 to 5 carbon atoms in the alkylene group is preferably a polyalkyleneimine having 2 to 4 carbon atoms in the alkylene group, more preferably polyethyleneimine or polypropyleneimine, and still more preferably polyethyleneimine. These may be used alone or in combination of two or more.

  The amount of the polyalkyleneimine is preferably at least 0.05 part by mass, more preferably at least 0.1 part by mass, still more preferably at least 0.5 part by mass, based on 100 parts by mass of the resin (A). , Preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and still more preferably 3 parts by mass or less.

The number average molecular weight of the polyalkyleneimine is preferably 150 or more, more preferably 500 or more, still more preferably 800 or more, still more preferably 1,000 or more, and preferably 10,000 or less, more preferably 5,5 or more. 000 or less, more preferably 4,000 or less.
The value of the molecular weight is determined by the method described in the examples.

As described above, the resin composition (AP) is obtained by condensing an amorphous polyester resin (A) having an acid group with a polyalkyleneimine.
The method for producing the resin composition (AP) is the same as the method for producing a binder resin composition for a toner described below, and thus the description thereof is omitted.

In the binder resin composition, the content of the resin composition (AP) is preferably 20% by mass or more, more preferably 40% by mass or more, and still more preferably 50% by mass, based on the total amount of the resin components. And at most 100% by mass, preferably at most 90% by mass, more preferably at most 80% by mass, even more preferably at most 70% by mass.
The content of the resin composition (AP) in the toner particles is preferably at least 20% by mass, more preferably at least 40% by mass, even more preferably at least 50% by mass, and preferably at most 90% by mass. , More preferably 80% by mass or less, further preferably 70% by mass or less.

<Amorphous polyester resin (A2)>
The binder resin composition is preferably an amorphous polyester resin (A2) (hereinafter referred to as “A2”) having a softening point different from that of the resin (A) by 5 ° C. or more in addition to the resin composition (AP). , Simply referred to as “resin (A2)”).
The amorphous polyester resin (A2) is preferably an amorphous polyester resin (AH) having a softening point higher by at least 5 ° C. than the softening point of the resin (A).
The resin (A2) is preferably an amorphous polyester resin.
The amorphous polyester resin is, for example, a polycondensate of an alcohol component and a carboxylic acid component.

Examples of the alcohol component and the carboxylic acid component are the same as the alcohol component and the carboxylic acid component of the resin (A) described above.
BPA-AO is preferable as the alcohol component.
BPA-AO is preferably BPA-PO and BPA-EO.
The molar ratio between BPA-PO and BPA-EO [BPA-PO / BPA-EO] is preferably at least 10/90, more preferably at least 20/80, even more preferably at least 30/70, and preferably at least 30/70. Is at most 90/10, more preferably at most 80/20, even more preferably at most 70/30.
As the carboxylic acid component, an aromatic dicarboxylic acid compound, an aliphatic dicarboxylic acid compound, and a trivalent or higher polycarboxylic acid compound are preferable.
As the aromatic dicarboxylic acid compound, isophthalic acid and terephthalic acid are preferable, and terephthalic acid is more preferable.
The amount of the aromatic dicarboxylic acid compound in the carboxylic acid component is preferably at least 40 mol%, more preferably at least 50 mol%, still more preferably at least 60 mol%, and preferably at most 98 mol%, more preferably Is at most 95 mol%, more preferably at most 90 mol%, further preferably at most 80 mol%.
As the aliphatic dicarboxylic acid compound, succinic acid or an anhydride thereof substituted with an aliphatic hydrocarbon group having 1 to 20 carbon atoms is preferable, and succinic acid or a succinic acid substituted with an aliphatic hydrocarbon group having 12 carbon atoms is preferable. Anhydrides are more preferred, and dodecenyl succinate or its anhydrides are even more preferred.
The amount of the aliphatic dicarboxylic acid compound in the carboxylic acid component is preferably at least 1 mol%, more preferably at least 2 mol%, still more preferably at least 3 mol%, and preferably at most 30 mol%, more preferably Is at most 20 mol%, more preferably at most 10 mol%.
As the trivalent or higher polycarboxylic acid compound, trimellitic acid or its anhydride is preferable.
The amount of the trivalent or higher polycarboxylic acid compound in the carboxylic acid component is preferably 1 mol% or more, more preferably 10 mol% or more, further preferably 20 mol% or more, and preferably 40 mol%. Or less, more preferably 35 mol% or less, further preferably 30 mol% or less.

[Physical properties of resin (A2)]
The softening point of the resin (A2) is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, further preferably 100 ° C. or higher, further preferably 110 ° C. or higher, and further preferably, from the viewpoint of further improving the storage stability of the toner. 115 ° C. or higher, more preferably 120 ° C. or higher, and from the viewpoint of further improving the low-temperature fixability of the toner, preferably 170 ° C. or lower, more preferably 160 ° C. or lower, still more preferably 150 ° C. or lower, further preferably 140 ° C. or lower, more preferably 130 ° C. or lower.

  The glass transition temperature of the resin (A2) is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, further preferably 55 ° C. or higher, and further preferably 63 ° C. or higher, from the viewpoint of further improving the storage stability of the toner. From the viewpoint of further improving the low-temperature fixability of the toner, the temperature is preferably 90 ° C. or lower, more preferably 80 ° C. or lower, and further preferably 70 ° C. or lower.

  The acid value of the resin (A2) is preferably 2 mgKOH / g or more, more preferably 5 mgKOH / g or more, still more preferably 10 mgKOH / g or more, and preferably 40 mgKOH / g or less, more preferably 30 mgKOH / g or less. , More preferably 25 mgKOH / g or less.

  The hydroxyl value of the resin (A2) is preferably at least 2 mgKOH / g, more preferably at least 10 mgKOH / g, even more preferably at least 30 mgKOH / g, and preferably at most 60 mgKOH / g, more preferably at most 50 mgKOH / g. , More preferably 45 mgKOH / g or less.

  The softening point, glass transition temperature, acid value, and hydroxyl value of the resin (A2) can be appropriately adjusted according to the type and ratio of the raw material monomers, and the production conditions such as the reaction temperature, reaction time, and cooling rate. Those values are obtained by the method described in the examples described later. When two or more resins (A2) are used in combination, the values of the physical properties obtained as a mixture thereof are preferably within the above ranges.

In the binder resin composition, the content of the resin (A2) is preferably 10% by mass or more, more preferably 20% by mass or more, and still more preferably 30% by mass or more, based on the total amount of the resin components. And it is preferably 60% by mass or less, more preferably 50% by mass or less, and still more preferably 40% by mass or less.
The content of the resin (A2) in the toner particles is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, and preferably 60% by mass or less, more preferably It is at most 50% by mass, more preferably at most 40% by mass.

<Crystalline polyester resin (C)>
The binder resin composition preferably contains a crystalline polyester resin (C) (hereinafter, also simply referred to as “resin (C)”) from the viewpoint of further improving low-temperature fixability.
The crystalline polyester resin (C) is preferably a crystalline polyester resin having an acid group.
As the crystalline polyester resin (C), a crystalline polyester resin, a crystalline composite resin having a polyester resin segment and a vinyl resin segment, which will be described later, is preferable. Among these, a crystalline polyester is preferable.
The crystalline polyester resin is, for example, a polycondensate of an alcohol component and a carboxylic acid component.
Hereinafter, the alcohol component and the carboxylic acid component of the crystalline polyester resin will be described.

The alcohol component preferably comprises an α, ω-aliphatic diol.
The carbon number of the α, ω-aliphatic diol is preferably 2 or more, more preferably 4 or more, still more preferably 6 or more, and preferably 16 or less, more preferably 14 or less, and still more preferably 12 or less. is there.
Examples of the α, ω-aliphatic diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol No. Among these, ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol and 1,12-dodecanediol are preferred, and 1,6-hexanediol is more preferred.

  The amount of the α, ω-aliphatic diol in the alcohol component is preferably at least 80 mol%, more preferably at least 85 mol%, still more preferably at least 90 mol%, even more preferably at least 95 mol%, and It is 100 mol% or less, more preferably 100 mol%.

  The alcohol component may contain another alcohol component different from the α, ω-aliphatic diol. Other alcohol components include, for example, aliphatic diols other than α, ω-aliphatic diol, aromatic diols, alicyclic diols, and trihydric or higher polyhydric alcohols.

The carboxylic acid component is preferably an aliphatic dicarboxylic acid. As the aliphatic dicarboxylic acid, a linear aliphatic dicarboxylic acid is preferable.
The carbon number of the aliphatic dicarboxylic acid is preferably 2 or more, more preferably 4 or more, and is preferably 14 or less, more preferably 10 or less, and still more preferably 8 or less.
Examples of the aliphatic dicarboxylic acid include oxalic acid, malonic acid, fumaric acid, maleic acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecandioic acid, and tetradecandioic acid. No. Among these, fumaric acid is preferred.

  The content of the aliphatic dicarboxylic acid in the carboxylic acid component is preferably at least 85 mol%, more preferably at least 90 mol%, still more preferably at least 95 mol%, and at most 100 mol%, and preferably at most 100 mol%. Is 100 mol%.

The carboxylic acid component may contain, in addition to the aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, an alicyclic dicarboxylic acid, and a trivalent or higher polyvalent carboxylic acid.
Examples of aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and trivalent or higher polycarboxylic acids are the same as those exemplified above.
From the viewpoint of adjusting the molecular weight and the softening point of the crystalline polyester resin, the carboxylic acid component may appropriately contain a monovalent carboxylic acid. These may be used alone or in combination of two or more.

  The equivalent ratio [COOH group / OH group] of the carboxy group (COOH group) of the carboxylic acid component to the hydroxy group (OH group) of the alcohol component is preferably 0.7 or more, more preferably 0.8 or more, and , Preferably 1.3 or less, more preferably 1.2 or less.

[Physical properties of resin (C)]
The softening point of the resin (C) is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, further preferably 75 ° C. or higher, from the viewpoint of further improving the storage stability of the toner, and further improves the low-temperature fixability. From the viewpoint of performing the heating, the temperature is preferably 150 ° C or less, more preferably 130 ° C or less, and further preferably 120 ° C or less.

  The melting point of the resin (C) is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, and still more preferably 65 ° C. or higher, from the viewpoint of further improving the storability of the toner. From the viewpoint of improvement, the temperature is preferably 130 ° C. or lower, more preferably 120 ° C. or lower, and further preferably 115 ° C. or lower.

  The acid value of the resin (C) is preferably 2 mgKOH / g or more, more preferably 5 mgKOH / g or more, still more preferably 10 mgKOH / g or more, and preferably 40 mgKOH / g or less, more preferably 30 mgKOH / g or less. , More preferably 20 mgKOH / g or less.

  The hydroxyl value of the resin (C) is preferably at least 2 mgKOH / g, more preferably at least 10 mgKOH / g, still more preferably at least 30 mgKOH / g, and preferably at most 60 mgKOH / g, more preferably at most 50 mgKOH / g. , More preferably 45 mgKOH / g or less.

  The number average molecular weight of the resin (C) is preferably 1,000 or more, more preferably 1,500 or more, further preferably 1,800 or more, and preferably 50,000 or less, more preferably 10,000. Or less, more preferably 8,000 or less.

  The weight average molecular weight of the resin (C) is preferably 2,000 or more, more preferably 3,000 or more, still more preferably 4,000 or more, and preferably 100,000 or less, more preferably 50,000. Or less, more preferably 10,000 or less.

  The softening point, melting point, acid value, hydroxyl value, number average molecular weight, and weight average molecular weight of the resin (C) are appropriately adjusted according to the type and ratio of the raw material monomers, and the production conditions such as the reaction temperature, reaction time, and cooling rate. can do. Those values are obtained by the method described in the examples described later. When two or more resins (C) are used in combination, the values of the softening point, melting point, and acid value obtained as a mixture thereof are preferably within the above ranges.

  The resin (C) is obtained, for example, by polycondensing an alcohol component and a carboxylic acid component. The conditions for the polycondensation are the same as the conditions exemplified for the resin (A) described above.

The ratio [(AP) / (A2)] of the resin composition (AP) to the resin (A2) is preferably 20/80 or more, more preferably 40/60 or more, and further preferably 50/50. And it is preferably at most 80/20, more preferably at most 75/25, even more preferably at most 70/30.
The ratio [(C) / [(AP) + (A2)]] of the resin (C) to the total amount of the resin composition (AP) and the resin (A2) is preferably at least 1/99. , More preferably at least 2/98, even more preferably at least 3/97, and preferably at most 30/70, more preferably at most 20/80, even more preferably at most 10/90.

  The total content of the resin composition (AP), the resin (A2), and the resin (C) in the binder resin composition is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably. It is 95% by mass or more and 100% by mass or less.

[Production Method of Binder Resin Composition for Toner]
The method for producing the binder resin composition for toner of the present invention has excellent storage stability of the toner, and from the viewpoint of obtaining excellent pigment dispersibility,
Step 1: a step of condensing an amorphous polyester-based resin (A) having an acid group with a polyalkyleneimine having an alkylene group to obtain a resin composition (AP);
including.
The method for producing the binder resin composition includes, for example,
Step 2: mixing the resin composition (AP) and the amorphous polyester resin (A2),
May be included.
In step 2, the crystalline polyester resin (C) may be further mixed.
Examples of the resin (A), the polyalkyleneimine, the resin composition (AP), the resin (A2), and the resin (C) used in the production method and their preferred embodiments are described below with respect to the binder resin composition. The description is omitted because it is similar to that described above.

  The temperature at the time of condensation in the step 1 is preferably 50 ° C. or higher, more preferably 100 ° C. or higher, further preferably 130 ° C. or higher, and preferably 235 ° C. or lower, more preferably 200 ° C. or lower, and further preferably 170 ° C. or lower. It is below ° C.

  The amount of the polyalkyleneimine in the step 1 is preferably at least 0.05 part by mass, more preferably 0 part by mass, based on 100 parts by mass of the resin (A) from the viewpoint of improving the storage stability and the pigment dispersibility. 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and still more preferably 3 parts by mass or less.

Step 2 is a step of mixing the resin composition (AP) obtained in step 1 with the resin (A2).
In step 2, it is preferable to mix the resin composition (AP) and the resin (A) so that the mass ratio of the resin (A) falls within the range described for the binder resin composition.
In step 2, the resin (C) may be further mixed. It is preferable that the resin composition (A-P) and the resin (A) are mixed so that the mass ratio of the resin (C) and the resin (C) falls within the range described for the binder resin composition.
The method of mixing the resin composition (AP), the resin (A2) and, if necessary, the resin (C) is not particularly limited, and can be uniformly mixed using, for example, a Henschel mixer.
In addition, the various additives described in the section of the toner for developing an electrostatic image described below may be mixed before adding the additives, or may be mixed simultaneously with the various additives.
When mixing with various additives at the same time, the same method as the mixing method described in the method for producing a toner for developing an electrostatic image described below can be used.

[Electrostatic image developing toner]
The toner contains the above-mentioned binder resin composition.
The binder resin composition is preferably used as a binder resin for a toner for developing an electrostatic image.
The content of the binder resin composition in the binder resin component of the toner is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and 100% by mass or less.
The toner contains, for example, toner particles and an external additive.
The toner particles preferably include a binder resin composition.
The toner particles may include, for example, a colorant, a colorant derivative, a release agent, a charge control agent, and other additives. The toner particles preferably contain a colorant among these.

<Colorant>
The colorant may be either a pigment or a dye.
Examples of the pigment include an azo pigment, a phthalocyanine pigment, a condensed polycyclic pigment, and a lake pigment.
Examples of the azo pigment include C.I. I. Insoluble azo pigments such as C.I. Pigment Red 3, C.I. I. Soluble azo pigments such as C.I. Pigment Red 48: 1, C.I. I. Pigment Red 144 and the like.
Examples of the phthalocyanine pigment include C.I. I. Pigment phthalocyanine pigments such as CI Pigment Blue 15: 3; I. And polyhalogenated zinc phthalocyanine pigments such as CI Pigment Green 58.
Examples of the condensed polycyclic pigment include C.I. I. Anthraquinone pigments such as C.I. Pigment Red 177; I. Perylene pigments such as C.I. Pigment Red 123; I. Perinone pigments such as CI Pigment Orange 43; I. Quinacridone pigments such as C.I. Pigment Red 122; I. Naphthol pigments such as C.I. Pigment Red 269; I. Dioxazine pigments such as C.I. Pigment Violet 23; I. Isoindolinone pigments such as C.I. Pigment Yellow 139; I. Isoindoline pigments such as CI Pigment Orange 66; I. Quinophthalone pigments such as CI Pigment Yellow 138; I. Pigment Yellow 150 and other nickel azo complex pigments; I. Indigo pigments such as CI Pigment Red 88; I. Metal complex pigments such as C.I. Pigment Green 8; I. Pigment Red 254, C.I. I. Pigment Red 255, C.I. I. And diketopyrrolopyrrole-based pigments such as CI Pigment Orange 71.
Lake pigments include, for example, C.I. I. Pigment Red 57: 1.
Of these, phthalocyanine pigments, quinacridone pigments, naphthol pigments, and lake pigments are preferred, and phthalocyanine pigments and quinacridone pigments are more preferred.

Examples of the dye include an azine dye, an anthraquinone dye, a perinone dye, and a rhodamine dye. More specifically, examples of the dye include C.I. I. Solvent Black 5, C.I. I. Solvent Black 7, Spirit Black SB, Toluidine Blue, C.I. I. Solvent Blue 11, C.I. I. Solvent Blue 12, C.I. I. Solvent Blue 35, C.I. I. Solvent Blue 59, C.I. I. Solvent Blue 74, 1-aminoanthraquinone, 2-aminoanthraquinone, hydroxyethylaminoanthraquinone, C.I. I. Solvent Violet 47, Solvent Orange 60, Solvent Orange 78, Solvent Orange 90, Solvent Violet 29, Solvent Red 135, Solvent Red 162, Solvent Red 179, Rhodamine-B base. The hue of the colorant is not particularly limited, and is yellow. And chromatic pigments such as magenta, cyan, blue, red, orange and green. These may be used alone or in combination of two or more.

  The content of the colorant is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and still more preferably 5 parts by mass or more based on 100 parts by mass of the total amount of the binder resin from the viewpoint of improving the image density of the toner. And more preferably 8 parts by mass or more, and preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and still more preferably 20 parts by mass or less.

<Colorant derivative>
Examples of the colorant derivative include a colorant into which an acidic group or a basic group has been introduced or a salt thereof.
The coloring agent derivative is preferably a coloring agent into which a sulfo group has been introduced or a salt thereof.
As a coloring agent, C.I. I. As a combination when Pigment Blue 15: 3 is used, a copper phthalocyanine compound into which a sulfo group is introduced or a salt thereof is preferable.
Examples of the salt include a halide salt, an amine salt and a quaternary ammonium salt.
As the colorant derivative, a sulfonated product of copper phthalocyanine or a salt thereof is preferable.

  The content of the colorant derivative is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and still more preferably 5 parts by mass or more, based on 100 parts by mass of the colorant, from the viewpoint of improving the image density of the toner. And it is preferably at most 30 parts by mass, more preferably at most 20 parts by mass, even more preferably at most 10 parts by mass.

<Release agent>
The toner may contain a release agent.
Examples of the release agent include polypropylene wax, polyethylene wax, polypropylene-polyethylene copolymer wax; hydrocarbon waxes such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax and Sasol wax or oxides thereof; carnauba wax , Montan wax or their deoxidizing waxes, ester waxes such as fatty acid ester waxes; fatty acid amides, fatty acids, higher alcohols, and fatty acid metal salts. These may be used alone or in combination of two or more.
The melting point of the release agent is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, even more preferably 75 ° C. or higher, and preferably 150 ° C. or lower, more preferably 130 ° C. or lower, and still more preferably 100 ° C. or lower. It is.

  The content of the release agent is preferably at least 0.1 part by mass, more preferably at least 0.5 part by mass, further preferably at least 0.8 part by mass, based on 100 parts by mass of the total amount of the binder resin. And it is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, still more preferably 5 parts by mass or less.

<Charge control agent>
The toner may contain a charge control agent. The charge control agent may contain any of a positive charge control agent and a negative charge control agent.
Examples of positively chargeable charge control agents include nigrosine dyes such as "Nigrosine Base EX", "Oil Black BS", "Oil Black SO", "Bontron (registered trademark) N-01", and "Bontron (registered trademark) N-". 04 "," Bontron (registered trademark) N-07 "," Bontron (registered trademark) N-09 "," Bontron (registered trademark) N-11 "(all manufactured by Orient Chemical Co., Ltd.) and the like; tertiary amines , A quaternary ammonium salt compound such as "Bontron (registered trademark) P-51" (manufactured by Orient Chemical Co., Ltd.), cetyltrimethylammonium bromide, "COPY CHARGE PX VP435" ( Polyamine resin, for example, "AFP-B" (Orient Chemical Co., Ltd.) ) And the like; imidazole derivatives such as "PLZ-2001" and "PLZ-8001" (all manufactured by Shikoku Kasei Kogyo Co., Ltd.); styrene-acrylic resins such as "FCA-701PT" (manufactured by Fujikura Kasei Co., Ltd.) Is mentioned.

  Examples of the negatively chargeable charge control agent include metal-containing azo dyes such as “Varifast (registered trademark) Black 3804”, “Bontron (registered trademark) S-31”, “Bontron (registered trademark) S-32”, “Bontron” (Registered trademark) S-34 "," Bontron (registered trademark) S-36 "(all manufactured by Orient Chemical Industry Co., Ltd.)," Eizen Spiron Black TRH "," T-77 "(Hodogaya Chemical Industry Co., Ltd.) Metal compounds of benzylic acid compounds, such as "LR-147" and "LR-297" (all manufactured by Nippon Carlit Co., Ltd.); metal compounds of salicylic acid compounds, such as "Bontron (registered trademark) E" -81 "," Bontron (registered trademark) E-84 "," Bontron (registered trademark) E-88 "," Bontron E-304 " Co., Ltd.), "TN-105" (Hodogaya Chemical Industry Co., Ltd.), etc .; Copper phthalocyanine dye; Quaternary ammonium salts, such as "COPY CHARGE PX VP434" (Clariant), nitroimidazole derivatives, etc .; Organometallic compounds And the like. These charge control agents may be used alone or in combination of two or more.

  The content of the charge control agent is preferably at least 0.01 part by mass, more preferably at least 0.2 part by mass, further preferably at least 0.5 part by mass, based on 100 parts by mass of the total amount of the binder resin. And it is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 3 parts by mass or less, and still more preferably 2 parts by mass or less.

<Other additives>
The toner particles further include additives such as magnetic powder, a fluidity improver, a conductivity adjuster, a reinforcing filler such as a fibrous substance, an antioxidant, an antioxidant, and a cleanability improver as other additives. You may contain suitably.

  The content of the toner particles in the toner is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and 100% by mass or less, preferably 99% by mass or less. .

The volume median particle diameter (D ₅₀ ) of the toner particles is preferably 2 μm or more, more preferably 3 μm or more, and still more preferably 4 μm or more, and preferably 20 μm or less, more preferably 15 μm or less, and further preferably 10 μm or less. It is as follows. In this specification, the volume median particle size (D ₅₀ ) means a particle size at which the cumulative volume frequency calculated by the volume fraction becomes 50% as calculated from the smaller particle size.

<External additives>
The toner may further contain an external additive to improve the fluidity. Examples of the external additive include fine particles of an inorganic material such as silica, alumina, titania, zirconia, tin oxide, and zinc oxide, and organic fine particles such as melamine-based resin fine particles and resin particles such as polytetrafluoroethylene resin fine particles. Can be These may be used alone or in combination of two or more. Among these external additives, silica is preferred, and hydrophobic silica treated with a hydrophobizing agent is more preferred.

  Examples of the hydrophobizing agent include hexamethyldisilazane (HMDS), dimethyldichlorosilane (DMDS), silicone oil, octyltriethoxysilane (OTES), and methyltriethoxysilane. Of these, hexamethyldisilazane is preferred.

  When the surface treatment of the toner particles is performed using an external additive, the content of the external additive is preferably 0.05% based on 100 parts by mass of the toner particles from the viewpoint of the chargeability and fluidity of the toner. It is at least 0.08 parts by mass, more preferably at least 0.1 part by mass, and preferably at most 5 parts by mass, more preferably at most 3 parts by mass, even more preferably at most 2 parts by mass. It is.

[Method of Manufacturing Toner]
The toner may be a toner obtained by any known method such as a melt-kneading method, an emulsification phase inversion method, a polymerization method, and an emulsion aggregation method, but from the viewpoint of productivity and dispersibility of a colorant, Pulverized toner by a kneading method is preferred.

When the toner is a pulverized toner, the method for producing the toner includes, for example, step A: a step of melt-kneading a toner material containing a resin composition (AP) and a colorant, and step B: a melt mixture obtained in step A. To obtain toner particles.

In step A, the toner raw material may contain other additives such as a charge control agent and a colorant. It is preferable that these toner raw materials are previously mixed by a mixer such as a Henschel mixer or a ball mill and then supplied to a kneader.
The temperature of the melt kneading is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, even more preferably 95 ° C. or higher, and is preferably 160 ° C. or lower, more preferably 130 ° C. or lower.
The melt-kneading in the step A can be performed using a known kneader such as a closed kneader, a single-screw extruder, a twin-screw extruder, or an open-roll kneader. From the viewpoint of melting and mixing the crystals, a twin-screw extruder that can be set to a high temperature condition is preferable.
The molten mixture obtained in the step A is cooled to a degree that can be pulverized, and then supplied to the subsequent step B.

The pulverization in the step B may be performed in multiple stages. For example, the resin kneaded product obtained by curing the molten mixture may be roughly pulverized to 1 mm or more and 5 mm or less, and then finely pulverized to a desired particle size.
Pulverizers suitably used for coarse pulverization include, for example, a hammer mill, an atomizer, and a rotoplex. Examples of the pulverizer suitably used for the fine pulverization include a fluidized-bed jet mill, a collision plate jet mill, and a rotary mechanical mill. From the viewpoint of pulverization efficiency, it is preferable to use a fluidized bed jet mill and a collision plate jet mill, and it is more preferable to use a collision plate jet mill.

  Examples of the classifier used for classification include a rotor classifier, an airflow classifier, an inertial classifier, and a sieve classifier. In the classification step, the pulverized material that has been insufficiently pulverized and removed may be subjected to the pulverization step again, and the pulverization step and the classification step may be repeated as necessary.

The volume median particle diameter (D ₅₀ ) of the toner particles is preferably 2 μm or more, more preferably 3 μm or more, still more preferably 4 μm or more, and preferably 20 μm or less, from the viewpoint of obtaining a high-quality image. Preferably it is 15 μm or less, more preferably 10 μm or less.

  As described above, it is preferable that the toner is added to the surface of the toner particles using a fluidizing agent or the like as an external additive.

  The toner is used for developing a latent image formed in an electrophotographic method, an electrostatic recording method, an electrostatic printing method, or the like. The toner can be used as a one-component developer or as a two-component developer by mixing with a carrier.

  The properties of the raw materials and the like were measured and evaluated by the following methods.

[Measurement]
(Acid value and hydroxyl value of resin)
The acid value and the hydroxyl value of the resin are measured based on the method of JIS K0070: 1992. However, only the measurement solvent was converted from a mixed solvent of ethanol and ether specified in JIS K0070: 1992 to a mixed solvent of acetone and toluene [acetone: toluene = 1: 1 (volume ratio)] in the case of an amorphous polyester resin. In the case of a polyester resin, change to a solvent of chloroform.

(Number average molecular weight and weight average molecular weight of resin)
The molecular weight distribution is measured by gel permeation chromatography (GPC) obtained by the following method, and the number average molecular weight and weight average molecular weight are determined.
(1) Preparation of sample solution The sample is dissolved in tetrahydrofuran (for an amorphous polyester resin) or chloroform (for a crystalline polyester resin) at 25 ° C so that the concentration becomes 0.5 g / 100 mL. . Next, this solution is filtered using a fluororesin filter “DISMIC-25JP” (manufactured by ADVANTEC) having a pore size of 0.2 μm to remove insoluble components, thereby obtaining a sample solution.
(2) Measurement of molecular weight Using the following measuring apparatus and analytical column, tetrahydrofuran (amorphous polyester resin) or chloroform (crystalline polyester resin) was flowed at a flow rate of 1 mL per minute as an eluent, and the temperature was kept at 40 ° C. Stabilize the column in. 100 μL of the sample solution is injected therein and the measurement is performed. The molecular weight of the sample is calculated based on a calibration curve created in advance. The calibration curve at this time includes several types of monodisperse polystyrene “A-500” (5.0 × 10 ² ), “A-1000” (1.01 × 10 ³ ), and “A-2500” (2.63). × 10 ³ ), “A-5000” (5.97 × 10 ³ ), “F-1” (1.02 × 10 ³ ), “F-2” (1.81 × 10 ⁴ ), “F- 4 "(3.97 x 10 ⁴ )," F-10 "(9.64 x 10 ⁴ )," F-20 "(1.90 x 10 ⁵ )," F-40 "(4.27 x 10 ⁴ ) ⁵ ) A standard sample of “F-80” (7.06 × 10 ⁵ ) and “F-128” (1.09 × 10 ⁶ ) (all manufactured by Tosoh Corporation) is used.
Measurement device: "HLC-8220CPC" (manufactured by Tosoh Corporation)
Analysis column: "GMHXL" + "G3000HXL" (manufactured by Tosoh Corporation)

(Softening point of resin)
Using a flow tester “CFT-500D” (manufactured by Shimadzu Corporation), while heating 1 g of the sample at a heating rate of 6 ° C./min, a load of 1.96 MPa was given by a plunger, and the diameter was 1 mm and the length was 1 mm. Extruded from the nozzle. The plunger depression amount of the flow tester was plotted against the temperature, and the temperature at which half of the sample flowed out was taken as the softening point.

[Maximum endothermic peak temperature]
Using a differential scanning calorimeter “Q-20” (manufactured by TA Instruments Japan Co., Ltd.), the sample cooled from room temperature (20 ° C.) to 0 ° C. at a rate of 10 ° C./min. Then, the temperature is measured while increasing the temperature to 180 ° C. at a rate of 10 ° C./min. The temperature of the largest peak among the observed endothermic peaks is defined as the maximum endothermic peak temperature.

(Glass transition temperature of amorphous polyester resin and toner)
Using a differential scanning calorimeter “Q-20” (manufactured by TA Instruments Japan Co., Ltd.), 0.01 to 0.02 g of a sample was weighed in an aluminum pan, and the temperature was raised to 200 ° C. Cool from temperature to 0 ° C. at a rate of 10 ° C./min. Next, the sample was heated at a heating rate of 10 ° C./min, and the temperature at the intersection of the extended line of the base line below the maximum endothermic peak temperature and the tangent line indicating the maximum slope from the rising portion of the peak to the top of the peak was determined. Glass transition temperature.

(Melting point of crystalline polyester resin)
Using a differential scanning calorimeter “Q-100” (manufactured by TA Instruments Japan Co., Ltd.), 0.01 to 0.02 g of a sample is weighed in an aluminum pan, and the temperature is decreased from room temperature at a rate of 10 ° C./min. And keep the temperature for 1 minute. Next, the temperature of the sample is raised to 200 ° C. at a rate of 10 ° C./min, and then cooled to −30 ° C. at a rate of 10 ° C./min. Next, the sample is heated at a heating rate of 10 ° C./min, and the peak temperature on the highest temperature side among the observed endothermic peaks is defined as the melting point.

[Number average molecular weight (Mn) of polyalkyleneimine]
The molecular weight distribution is measured by gel permeation chromatography (GPC) shown below, and the number average molecular weight is determined.
(1) Preparation of sample solution Polyalkylenimine is dissolved in a solution in which Na ₂ SO ₄ is dissolved in a 1% by mass aqueous acetic acid solution at 0.15 mol / L so that the concentration becomes 0.2 g / 100 mL. Next, this solution is filtered using a fluororesin filter “FP-200” (manufactured by Sumitomo Electric Industries, Ltd.) having a pore size of 0.2 μm to remove insoluble components to obtain a sample solution.
(2) Measurement of molecular weight Using a measuring apparatus and an analytical column described below, a solution in which Na ₂ SO ₄ was dissolved in a 1% by mass aqueous acetic acid solution at 0.15 mol / L as an eluent was flowed at a flow rate of 1 mL per minute. Stabilize the column in a constant temperature bath at 40 ° C. Then, 100 μL of the sample solution is injected and measurement is performed. The molecular weight of the sample is calculated based on a calibration curve created in advance. The calibration curve at this time includes several types of standard pullulan “P-5” (5.9 × 10 ³ ), “P-50” (4.73 × 10 ⁴ ), and “P-200” (2.12 × 10 ⁵ ), “P-200” (2.12 × 10 ⁵ ), and “P-800” (7.08 × 10 ⁵ ) (all manufactured by Showa Denko KK) are used as standard samples.
Measurement device: "HLC-8320GPC" (manufactured by Tosoh Corporation)
Analysis column: α + α-M + α-M (manufactured by Tosoh Corporation)

(Melting point of release agent)
Using a differential scanning calorimeter “Q100” (manufactured by TA Instruments Japan Co., Ltd.), 0.02 g of a sample was weighed in an aluminum pan, heated to 200 ° C., and then cooled from 200 ° C. at a cooling rate of 10 ° C. Cool to 0 ° C at ° C / min. Next, the sample is heated at a heating rate of 10 ° C./min, and the calorific value is measured. The maximum peak temperature of the obtained endotherm is defined as the melting point.

[Volume median particle diameter (D ₅₀ ) of toner particles]
The volume median particle size (D ₅₀ ) of the toner particles is measured as follows.
-Measuring device: "Coulter Multisizer (registered trademark) III" (manufactured by Beckman Coulter, Inc.)
・ Aperture diameter: 50 μm
・ Analysis software: “Coulter Multisizer (registered trademark) III version 3.51” (manufactured by Beckman Coulter, Inc.)
・ Electrolyte: “ISOTON (registered trademark) II” (manufactured by Beckman Coulter, Inc.)
-Dispersion: "Emulgen (registered trademark) 109P" [polyoxyethylene lauryl ether, manufactured by Kao Corporation, HLB (Hydrophil-Lipophile Balance, Griffin method) = 13.6] is dissolved in the electrolytic solution, and the concentration is 5 mass. % Dispersion is obtained.
Dispersion conditions: 10 mg of the measurement sample was added to 5 mL of the dispersion, dispersed for 1 minute by an ultrasonic disperser, 25 mL of the electrolytic solution was added, and further dispersed for 1 minute by an ultrasonic disperser, Prepare a sample dispersion.
Measurement conditions: In a beaker, the sample dispersion was added to 100 mL of the electrolytic solution to adjust the particle size of 30,000 particles to a concentration that can be measured in 20 seconds, and then 30,000 particles were measured. Then, a volume median particle size (D ₅₀ ) is determined from the obtained particle size distribution.

[Production of amorphous polyester resin]
Production Examples AL1, AL2 (Production of Resin AL-1, AL-2)
The alcohol component, terephthalic acid, and the esterification catalyst and cocatalyst shown in Table 1 were treated with a thermometer, a stainless steel stirrer, a fractionation tower, a dehydration tube, a cooling tube, and a nitrogen inlet tube equipped with a four-liter four-necked nozzle. The mixture was placed in a flask, heated to 235 ° C. in a mantle heater under a nitrogen atmosphere, and reacted at normal pressure for 7 hours. Thereafter, a reduced pressure reaction was performed at 235 ° C. and 8 kPa to a desired acid value and a softening point to obtain resins AL-1 and AL-2. Various physical properties were measured and are shown in Table 1.

Production Example AH1 (Production of Resin AH-1)
The alcohol component shown in Table 1, terephthalic acid and dodecenyl succinic anhydride, and the esterification catalyst and cocatalyst were equipped with a thermometer, a stainless steel stirring rod, a fractionation tower, a dehydration tube, a cooling tube, and a nitrogen introduction tube. The mixture was placed in a liter four-necked flask, heated to 235 ° C. in a mantle heater in a nitrogen atmosphere, reacted at normal pressure for 2.5 hours, and then reacted at 8 kPa for 1 hour under reduced pressure. Thereafter, the mixture was cooled to 190 ° C. under normal pressure, trimellitic anhydride was added, and the temperature was increased stepwise to 210 ° C. at a rate of 10 ° C./h. Thereafter, the reaction was performed at 8 kPa to a desired softening point to obtain a resin AH-1. Various physical properties were measured and are shown in Table 1.

[Production of crystalline polyester resin]
Production Example C1 [Production of Resin C-1]
An alcohol component, a carboxylic acid component, an esterification catalyst and a polymerization inhibitor shown in Table 2 were added to a 10-liter four-liter liter equipped with a thermometer, a stainless steel stirring rod, a fractionating tower, a dehydrating tube, a cooling tube, and a nitrogen introducing tube. The mixture was placed in a one-necked flask, heated to 140 ° C. in a mantle heater in a nitrogen atmosphere, and reacted for 5 hours. Thereafter, the temperature was raised stepwise to 200 ° C. at a rate of 10 ° C./h. Thereafter, the reaction was carried out at 8 kPa to a desired softening point to obtain a resin C-1. Various physical properties were measured and are shown in Table 2.

[Production of resin composition (AP)]
Production Examples AP1, AP2, AP3 [Production of Resin Compositions AP-1, AP-2, AP-3]
The resin and polyalkyleneimine shown in Table 3 were placed in a 10-liter four-necked flask equipped with a thermometer, a stainless steel stirrer, a fractionating tower, a dehydrating tube, a cooling tube, and a nitrogen introducing tube. The temperature was raised to 150 ° C. in a mantle heater, and the reaction was carried out at normal pressure for 3 hours to obtain resin compositions AP-1, AP-2 and AP-3.

[Manufacture of toner]
Examples 1 to 4, Comparative Examples 1 to 3 [Toners 1 to 4, 81 to 83]
100 parts by mass of a binder resin having a compounding ratio shown in Table 4, 1 part by mass of a negatively chargeable charge control agent "Bontron E-81" (manufactured by Orient Chemical Co., Ltd.), coloring agents of the kind and amount shown in Table 4, After thoroughly mixing 1 part by mass of a paraffin wax “HNP-9” (manufactured by Nippon Seiro Co., Ltd., melting point: 80 ° C.) as a mold release agent with a Henschel mixer, the total length of the kneading portion is 1560 mm, the screw diameter is 42 mm, and the barrel inner diameter is 43 mm. , And melt-kneaded at a roll rotation speed of 200 r / min and a heating temperature of 100 ° C. in the roll. The feed rate of the mixture was 20 kg / h and the average residence time was about 18 seconds. The obtained melt-kneaded product was cooled, coarsely pulverized, then pulverized by a jet mill and classified to obtain toner particles having a volume median particle size (D ₅₀ ) of 8 μm.
To 100 parts by mass of the obtained toner particles, 1.0 part by mass of hydrophobic silica “AEROSIL NAX 50” (manufactured by Nippon Aerosil Co., Ltd., hydrophobizing agent: HMDS, average particle size: about 30 nm) is added as an external additive. Then, toners 1 to 4, 81 to 83 were obtained by mixing with a Henschel mixer.

Examples 5 to 8, Comparative Examples 4 to 5 [Toners 5 to 8, 84 to 85]
100 parts by mass of the binder resin having the compounding ratio shown in Table 4, 1 part by mass of the negatively chargeable charge control agent "Bontron E-81" (manufactured by Orient Chemical Industries, Ltd.), and C.I. I. Pigment Blue 15: 3 15 parts by mass of “Cyanine Blue 4927” (manufactured by Dainichi Seika Kogyo Co., Ltd.), 1 part by mass of “SOLSPERSE 5000s” (manufactured by Nippon Lubrisol Co., Ltd.) as a colorant derivative, and paraffin wax as a release agent Toners 5 to 8, 84 to 85 were obtained in the same manner as in Example 1, except that 1 part by mass of “HNP-9” (manufactured by Nippon Seiro Co., Ltd., melting point: 80 ° C.) was sufficiently mixed with a Henschel mixer. Was.

Comparative Examples 6 and 7 (Toners 86 and 87)
Toners 86 and 87 were obtained in the same manner as in Comparative Example 4 except that a dispersant “AJISPER PB821” (manufactured by Ajinomoto Fine Techno Co., Ltd.) was added.

[Evaluation of Toner]
[Preservability]
4 g of the toner was placed in a 20 mL container (about 3 cm in diameter), and left for 48 hours in an environment at a temperature of 55 ° C. and a relative humidity of 60%. The occurrence of toner aggregation was visually observed every 6 hours up to 72 hours. The larger the value of the time when the occurrence of agglomeration was observed, the better the preservability under high temperature and high humidity. Table 4 shows the results. In Table 4, “> 72” indicates that no aggregation was observed even after 72 hours.

(Pigment dispersibility)
0.1 g of the toner was weighed into a 20 mL container (about 3 cm in diameter) so that the toner concentration was 1% by mass, and diluted with chloroform to a total of 10 g. Next, after the container was closed with a cap, the mixture was stirred and mixed with a test tube mixer (manufactured by AS ONE Corporation) to melt and disperse the toner in chloroform. The obtained sample was put into a quartz cuvette cell (four-sided transmission) up to 10 mm or more from the bottom of the cell, and set in a nanoparticle analyzer “SZ-100” (manufactured by Horiba, Ltd.). After inputting the refractive index of the sample and the refractive index and viscosity of the dispersion medium, select the measurement mode (standard mode), calculation conditions (standard) and distribution form (polydispersion, standard), and measure the pigment particle size at 25 ° C. did. Table 4 shows the results. In Table 4, “≧ 1000” indicates that the pigment particle size was 1000 nm or more.

  As shown in Table 4, a toner containing a binder resin composition for a toner containing a resin composition (AP) obtained by condensing an amorphous resin (A) having an acid group with polyethyleneimine is: It can be seen that they have excellent storage stability and pigment dispersibility.

Claims (12)

  A binder resin composition for toner, comprising a resin composition (AP) obtained by condensing an amorphous polyester resin (A) having an acid group with a polyalkylenimine.   The binder resin composition for a toner according to claim 1, wherein the amorphous polyester resin (A) is a polycondensate of an alcohol component containing an alkylene oxide adduct of bisphenol A and a carboxylic acid component.   3. The binder resin composition for a toner according to claim 1, wherein the amorphous polyester resin (A) has a softening point of 80 ° C. or more and 120 ° C. or less. 4.   4. The binder resin composition for a toner according to claim 3, comprising an amorphous polyester resin (A2) having a softening point different from the softening point of the amorphous polyester resin (A) by 5 ° C. or more. 5.   The binder resin composition for a toner according to claim 4, wherein the amorphous polyester resin (A2) has a softening point of 110C or more and 170C or less.   The binder resin composition for a toner according to claim 1, further comprising a crystalline polyester resin (C).   A toner for developing an electrostatic image, comprising the binder resin composition according to claim 1 and a colorant.   The electrostatic image developing toner according to claim 7, further comprising a colorant derivative.   9. The toner for developing an electrostatic image according to claim 8, wherein the colorant derivative is a sulfonated product of copper phthalocyanine or a salt thereof.   Step 1: A method for producing a binder resin composition for toner, comprising a step of condensing an amorphous polyester resin (A) having an acid group with a polyalkyleneimine to obtain a resin composition (AP).   Step A: a process for melting and kneading the resin composition (AP) obtained by the method for producing a resin composition according to claim 10 and a toner material containing a colorant, the method comprising: Manufacturing method of toner.   The method for producing a toner for developing an electrostatic image according to claim 11, wherein the toner raw material further includes a colorant derivative.