JP7129038B2 - Binder resin composition for toner - Google Patents

Description

The present invention relates to a binder resin composition for toner, which is used for developing a latent image formed by an electrophotography method, an electrostatic recording method, an electrostatic printing method, or the like, and an electrostatic charge 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, there is a demand for reducing the adhesion amount of toner that is melted by heat and fixed on paper, that is, reducing the adhesion amount of toner. A problem with reducing the adhesion amount 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 pigment is increased, aggregation is likely to occur, and the coloring strength is limited. Therefore, it is known to use a pigment dispersant to improve the coloring power of the toner.
For example, Patent Document 1 describes a metal phthalocyanine or a metal phthalocyanine derivative in which the central metal can have a pentacoordinated structure or a hexacoordinated structure, and an n - a pigment dispersant characterized by containing at least an electron-donating compound; It is described that the pigment dispersant can easily finely disperse the pigment in the dispersion medium.
In addition, Patent Document 2 describes 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. Further, Patent Document 3 describes a polyallylamine derivative as a pigment dispersant.

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

The dispersant described in Patent Document 1 is said to be able to finely disperse the phthalocyanine pigment in the toner particles. Pigment dispersibility was insufficient. Also, in Patent Documents 2 and 3, it is said 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 provides a binder resin composition for toner, a toner for electrostatic image development containing the binder resin composition, and the binder resin composition, which exhibit excellent toner storage stability and excellent pigment dispersibility. and a method for manufacturing the toner.

The present inventors found that a binder resin composition for a toner containing a resin composition (AP) obtained by condensing an amorphous polyester resin (A) having an acid group with a polyalkyleneimine is It has been found that the above 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 toner containing a resin composition (AP) obtained by condensing an amorphous polyester resin (A) having an acid group with a polyalkyleneimine.
[2] An electrostatic charge image developing toner containing the binder resin composition described in [1] above 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 raw material containing a colorant, A method for producing a toner for image development.

According to the present invention, a binder resin composition for toner, a toner for electrostatic charge image development containing the binder resin composition, and the binder resin exhibiting excellent toner storage stability and excellent pigment dispersibility. 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") comprises an amorphous polyester resin (A) having an acid group (hereinafter also simply referred to as "resin (A)"). ) and a polyalkyleneimine (hereinafter also simply referred to as “resin composition (AP)”).
According to the binder resin composition, a toner exhibiting excellent storage stability can be obtained, and further, excellent pigment dispersibility is exhibited.

Although the reason why the effect of the present invention is obtained is not clear, it is considered as follows.
The resin composition (AP) contains a polyalkyleneimine-derived portion in its structure and functions as a dispersant for the colorant, so that the colorant is finely dispersed in the binder resin composition. It is thought that In addition, since the resin composition (AP) disperses the colorant, the plasticization due to the addition of the dispersant does not proceed, and high storage stability can be obtained, which is compatible with the aforementioned high dispersibility.

The crystallinity of a resin is represented by the ratio of the softening point to the maximum endothermic peak temperature measured by a differential scanning calorimeter (DSC), that is, the crystallinity index defined as “softening point/maximum endothermic peak temperature”. In general, when the crystallinity index exceeds 1.4, the resin is amorphous, and when the crystallinity index is less than 0.6, the crystallinity is low and the amorphous portion is large. 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. The term "amorphous resin" refers to a resin having a crystallinity index of more than 1.4 or less than 0.6.
The above-mentioned "maximum endothermic peak temperature" refers to the temperature of the peak having the maximum peak area among the endothermic peaks observed under the conditions of the measurement method described in the Examples.
The crystallinity of the resin can be adjusted by the type and ratio of raw material monomers, production conditions (eg, reaction temperature, reaction time, cooling rate), and the like.
The "polyester-based resin" may contain a polyester resin that has been modified to such an extent that its properties are not substantially impaired. Examples of modified polyester resins include urethane-modified polyester resins in which polyester resins are modified with urethane bonds, epoxy-modified polyester resins in which polyester resins are modified with epoxy bonds, and composites containing polyester components and addition polymerization resin components. resin.
"Bisphenol A" means 2,2-bis(4-hydroxyphenyl)propane.
Examples of the "carboxylic acid compound" include carboxylic acids, their anhydrides, 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 the amorphous polyester resin (A) having an acid group with a polyalkyleneimine. As described above, the resin composition (AP) contains, for example, a reaction product of the resin (A) and the polyalkyleneimine, a by-product derived from the polyalkyleneimine, an unreacted resin (A) and an unreacted Remaining polyalkyleneimine from the reaction and the like are included. It is believed that the reaction product of the resin (A) with the polyalkyleneimine and the by-product derived from the polyalkyleneimine acts as a dispersant for the colorant in the resin composition (AP).

<Amorphous polyester resin (A)>
The amorphous polyester resin (A) has acid groups.
Examples of acid groups include carboxy groups and sulfo groups. Among these, a carboxy group is preferred.
Examples of the amorphous polyester resin (A) include amorphous polyester resins and amorphous composite resins having polyester resin segments and vinyl resin segments. Among these, amorphous polyester resins are preferred.
An amorphous polyester resin is a polycondensate of an alcohol component and a carboxylic acid component. The alcohol component and carboxylic acid component contained in the amorphous polyester resin are described below.

[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 formula (I):

〔式（Ｉ）中、ＯＲ^１１及びＲ^１２Ｏは、それぞれ独立に、炭素数１以上４以下のアルキレンオキシ基（好ましくはエチレンオキシ基又はプロピレンオキシ基）であり、ｘ及びｙは、アルキレンオキサイドの平均付加モル数であって、それぞれ独立に正の数であり、ｘ及びｙの和の平均値は、好ましくは１以上、より好ましくは１．５以上であり、そして、好ましくは１６以下、より好ましくは８以下、更に好ましくは４以下である。〕で表されるＢＰＡ－ＡＯが挙げられる。
ＢＰＡ－ＡＯは、好ましくはビスフェノールＡのプロピレンオキサイド付加物（以下、「ＢＰＡ－ＰＯ」ともいう。）、ビスフェノールＡのエチレンオキサイド付加物（以下、「ＢＰＡ－ＥＯ」ともいう。）、より好ましくはＢＰＡ－ＰＯである。これらのＢＰＡ－ＡＯは、１種又は２種以上を用いてもよい。
ＢＰＡ－ＡＯの量は、アルコール成分中、好ましくは８０モル％以上、より好ましくは９０モル％以上、更に好ましくは９５モル％以上、更に好ましくは９８モル％以上であり、そして、１００モル％以下であり、更に好ましくは１００モル％である。

[In 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 an alkylene oxide are each independently positive numbers, 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, still more preferably 4 or less. ] BPA-AO represented by.
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"), more preferably BPA-PO. One or more of these BPA-AO may be used.
The amount of BPA-AO in the alcohol component is preferably 80 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, still more preferably 98 mol% or more, and 100 mol% or less. and more preferably 100 mol %.

The alcohol component may contain other alcohol components different from BPA-AO. Other alcohol components include, for example, linear or branched aliphatic diols, alicyclic diols, and trihydric or higher polyhydric alcohols.

The number of carbon atoms in the linear or branched aliphatic diol is preferably 2 or more, and is preferably 18 or less, more preferably 14 or less, still more preferably 10 or less, still more preferably 6 or less.
Examples of linear or branched aliphatic diols 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 diols, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, and 1,14-tetradecanediol.
Examples of alicyclic diols include hydrogenated bisphenol A and adducts of hydrogenated bisphenol A with an alkylene oxide having 2 or more and 4 or less carbon atoms (average addition mole number of 2 or more and 12 or less).
Examples of trihydric or higher polyhydric alcohols 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 contain a monohydric alcohol.
One or more of these alcohol components may be used.

[Carboxylic acid component]
Examples of the carboxylic acid component include dicarboxylic acid compounds and polycarboxylic acid compounds having a valence of 3 or more.

Dicarboxylic acid compounds include, for example, aromatic dicarboxylic acid compounds, aliphatic dicarboxylic acid compounds, and alicyclic dicarboxylic acid compounds.
The carbon number of the dicarboxylic acid compound is preferably 2 or more, more preferably 3 or more, and preferably 30 or less, more preferably 20 or less.
Examples of aromatic dicarboxylic acids include phthalic acid, isophthalic acid, and terephthalic acid. Among these, isophthalic acid and terephthalic acid are preferred, and terephthalic acid is more preferred.
Examples of aliphatic dicarboxylic acids include 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, Examples include succinic acid substituted with an aliphatic hydrocarbon group having 1 to 20 carbon atoms. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 8 or more, more preferably 9 or more, and preferably 16 or less, more preferably 14 or less. The aliphatic hydrocarbon group may be either linear or branched, and may be either a saturated aliphatic hydrocarbon group or 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, 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 50 mol% or more, more preferably 60 mol% or more, still more preferably 65 mol% or more, still more preferably 70 mol% or more, and 100 mol% or less.

Examples of trivalent or higher polyvalent carboxylic acid compounds include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, and pyromellitic acid. Among these, trimellitic acid or its anhydride is preferably included.
The content of 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 contain a monovalent carboxylic acid as appropriate.
One or more of these carboxylic acid components may be used.

The equivalent ratio of the carboxy group (COOH group) of the carboxylic acid component to the hydroxy group (OH group) of the alcohol component [COOH group/OH group] 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 even more 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. is preferably 90° C. or lower, more preferably 80° C. or lower, and still more preferably 70° C. or lower, from the viewpoint of further improving the

The acid value of the resin (A) is preferably 2 mgKOH/g or more, from the viewpoint of making it easier to obtain a resin composition (AP) having excellent storage stability and pigment dispersibility, and from the viewpoint of interaction with the colorant. 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, still more preferably 25 mgKOH/g or less.

The hydroxyl value of the resin (A) is preferably 2 mgKOH/g or more, more preferably 10 mgKOH/g or more, still more preferably 30 mgKOH/g or more, and preferably 60 mgKOH/g or less, more preferably 50 mgKOH/g or less. , and 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, still more preferably 1,800 or more, and preferably 50,000 or less, more preferably 10,000. 8,000 or less, more preferably 8,000 or less.

The weight average molecular weight of resin (A) 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. 10,000 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 raw material monomers, and production conditions such as reaction temperature, reaction time, and cooling rate. It can be adjusted as appropriate. Those values are determined by the method described in Examples below. When two or more resins (A) are used in combination, it is preferable that the values of the physical properties obtained as a mixture thereof are within the ranges described above.

[Method for producing 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, an esterification catalyst such as di(2-ethylhexanoic acid)tin (II), dibutyltin oxide, titanium diisopropylate bistriethanolamine, etc., is added to the alcohol component and the carboxylic acid component in a total amount of 100, if necessary. 0.01 parts by mass or more and 5 parts by mass or less per part by mass; Esterification promoter such as gallic acid (same as 3,4,5-trihydroxybenzoic acid), total amount of alcohol component and carboxylic acid component is 100 mass 0.001 parts by mass or more and 0.5 parts by mass or less may be used for polycondensation.
Further, when a monomer having an unsaturated bond such as fumaric acid is used in the polycondensation reaction, it is preferably 0.001 part by mass with respect to 100 parts by mass as the total amount of the alcohol component and the carboxylic acid component, if necessary. More than 0.5 parts by mass or less of the radical polymerization inhibitor may be used. Examples of radical polymerization inhibitors include 4-tert-butylcatechol.
The temperature of the polycondensation reaction is preferably 120° C. or higher, more preferably 160° C. or higher, still more preferably 180° C. or higher, and preferably 260° C. or lower, more preferably 240° C. or lower. In addition, you may perform polycondensation in an inert gas atmosphere.

<Polyalkyleneimine>
The polyalkyleneimine is preferably a polyalkyleneimine in which the alkylene group has 1 or more and 5 or less carbon atoms. A polyalkyleneimine is a compound that undergoes a condensation reaction with an acid group of the resin (A) and can be incorporated into the molecular skeleton of the resin (A).
The polyalkyleneimine in which the alkylene group has 1 to 5 carbon atoms is preferably a polyalkyleneimine in which the alkylene group has 2 to 4 carbon atoms, 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 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, still more preferably 0.5 parts by mass or more, relative to 100 parts by mass of the resin (A), and , preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even 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 5,000 or more. 000 or less, more preferably 4,000 or less.
The molecular weight value is determined by the method described in Examples.

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

The content of the resin composition (AP) in the binder resin composition is preferably 20% by mass or more, more preferably 40% by mass or more, and still more preferably 50% by mass, relative to the total amount of the resin components. 100% by mass or less, preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less.
The content of the resin composition (AP) in the toner particles is preferably 20% by mass or more, more preferably 40% by mass or more, still more preferably 50% by mass or more, and preferably 90% by mass or less. , more preferably 80% by mass or less, and still more preferably 70% by mass or less.

<Amorphous polyester resin (A2)>
In addition to the resin composition (AP), the binder resin composition preferably includes an amorphous polyester resin (A2) (hereinafter referred to as , simply referred to as “resin (A2)”).
The amorphous polyester-based resin (A2) is preferably an amorphous polyester-based resin (AH) having a softening point higher than that of the resin (A) by 5°C or more.
Resin (A2) is preferably an amorphous polyester resin.
An 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 preferred as the alcohol component.
BPA-AO is preferably BPA-PO and BPA-EO.
The molar ratio of BPA-PO to BPA-EO [BPA-PO/BPA-EO] is preferably 10/90 or more, more preferably 20/80 or more, still more preferably 30/70 or more, and preferably is 90/10 or less, more preferably 80/20 or less, still more preferably 70/30 or less.
As the carboxylic acid component, an aromatic dicarboxylic acid compound, an aliphatic dicarboxylic acid compound, and a polyvalent carboxylic acid compound having a valence of 3 or more are preferable.
As the aromatic dicarboxylic acid compound, isophthalic acid and terephthalic acid are preferred, and terephthalic acid is more preferred.
The amount of the aromatic dicarboxylic acid compound in the carboxylic acid component is preferably 40 mol% or more, more preferably 50 mol% or more, still more preferably 60 mol% or more, and preferably 98 mol% or less, more preferably is 95 mol % or less, more preferably 90 mol % or less, still more preferably 80 mol % or less.
As the aliphatic dicarboxylic acid compound, succinic acid or anhydride thereof substituted with an aliphatic hydrocarbon group having 1 to 20 carbon atoms is preferable, and succinic acid or its anhydride 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 1 mol% or more, more preferably 2 mol% or more, still more preferably 3 mol% or more, and preferably 30 mol% or less, more preferably is 20 mol % or less, more preferably 10 mol % or less.
As the polyvalent carboxylic acid compound having a valence of 3 or more, trimellitic acid or its anhydride is preferable.
The amount of trivalent or higher polyvalent carboxylic acid compound is preferably 1 mol% or more, more preferably 10 mol% or more, still more preferably 20 mol% or more, and preferably 40 mol% in the carboxylic acid component. Below, more preferably 35 mol % or less, still more 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, still more preferably 100° C. or higher, still more preferably 110° C. or higher, and still more preferably 110° C. or higher, from the viewpoint of further improving the storage stability of the toner. It is 115° C. or higher, more preferably 120° C. or higher, and from the viewpoint of further improving the low-temperature fixability of the toner, it is preferably 170° C. or lower, more preferably 160° C. or lower, still more preferably 150° C. or lower, and even more preferably 150° C. or lower. It is 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, still more preferably 55° C. or higher, still more 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 even more 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. and more preferably 25 mgKOH/g or less.

The hydroxyl value of the resin (A2) is preferably 2 mgKOH/g or more, more preferably 10 mgKOH/g or more, still more preferably 30 mgKOH/g or more, and preferably 60 mgKOH/g or less, more preferably 50 mgKOH/g or less. , and 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 depending on the type and ratio of raw material monomers, and production conditions such as reaction temperature, reaction time, and cooling rate. Those values are determined by the method described in Examples below. When two or more resins (A2) are used in combination, it is preferable that the values of the physical properties obtained as a mixture thereof are within the ranges described above.

The content of the resin (A2) in the binder resin composition is preferably 10% by mass or more, more preferably 20% by mass or more, and still more preferably 30% by mass or more, relative to the total amount of the resin components, The content is preferably 60% by mass or less, more preferably 50% by mass or less, and even 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, still more preferably 30% by mass or more, and preferably 60% by mass or less, more preferably It is 50% by mass or less, more preferably 40% by mass or less.

<Crystalline polyester resin (C)>
The binder resin composition preferably contains a crystalline polyester-based 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, crystalline polyester is preferred.
A crystalline polyester resin is, for example, a polycondensate of an alcohol component and a carboxylic acid component.
The alcohol component and carboxylic acid component of the crystalline polyester resin are described below.

The alcohol component preferably comprises an α,ω-aliphatic diol.
The number of carbon atoms in 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, still more preferably 12 or less. be.
Examples of α,ω-aliphatic diols 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, and 1,14-tetradecanediol mentioned. 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 80 mol% or more, more preferably 85 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% or more, and It is 100 mol % or less, more preferably 100 mol %.

The alcohol component may contain other alcohol components different from the α,ω-aliphatic diol. Other alcohol components include, for example, aliphatic diols other than α,ω-aliphatic diols, 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 preferred.
The number of carbon atoms in the aliphatic dicarboxylic acid is preferably 2 or more, more preferably 4 or more, and preferably 14 or less, more preferably 10 or less, still more preferably 8 or less.
Examples of aliphatic dicarboxylic acids include oxalic acid, malonic acid, fumaric acid, maleic acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, and tetradecanedioic acid. mentioned. Among these, fumaric acid is preferred.

The content of the aliphatic dicarboxylic acid in the carboxylic acid component is preferably 85 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, and preferably 100 mol% or less. is 100 mol %.

The carboxylic acid component may contain an aromatic dicarboxylic acid, an alicyclic dicarboxylic acid, and a polyvalent carboxylic acid having a valence of 3 or more, in addition to the aliphatic dicarboxylic acid.
Examples of the aromatic dicarboxylic acid, the alicyclic dicarboxylic acid, and the polyvalent carboxylic acid having a valence of 3 or more are the same as those exemplified above.
From the viewpoint of adjusting the molecular weight and softening point of the crystalline polyester resin, the carboxylic acid component may contain a monovalent carboxylic acid as appropriate. These may be used alone or in combination of two or more.

The equivalent ratio of the carboxy group (COOH group) of the carboxylic acid component to the hydroxy group (OH group) of the alcohol component [COOH group/OH group] 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, and still more preferably 75° C. or higher, from the viewpoint of further improving the storage stability of the toner. The temperature is preferably 150° C. or lower, more preferably 130° C. or lower, and still more preferably 120° C. or lower, from the viewpoint of increasing the temperature.

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

The acid value of 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. and more preferably 20 mgKOH/g or less.

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

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

The weight average molecular weight of 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. 10,000 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 raw material monomers, and production conditions such as reaction temperature, reaction time, and cooling rate. can do. Those values are determined by the method described in Examples below. When two or more resins (C) are used in combination, the softening point, melting point, and acid value obtained as a mixture thereof are preferably within the above ranges.

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

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

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

[Method for producing binder resin composition for toner]
In the method for producing the binder resin composition for toner of the present invention, from the viewpoint of obtaining excellent toner storage stability and excellent pigment dispersibility,
Step 1: A step of condensing an amorphous polyester 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: a step of mixing the resin composition (AP) and the amorphous polyester resin (A2);
may contain
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 with respect to the binder resin composition. Since it is the same as that described above, the description is omitted.

The temperature during condensation in step 1 is preferably 50° C. or higher, more preferably 100° C. or higher, still more preferably 130° C. or higher, and preferably 235° C. or lower, more preferably 200° C. or lower, still more preferably 170° C. ℃ or less.

From the viewpoint of improving storage stability and pigment dispersibility, the amount of the polyalkyleneimine compounded in step 1 is preferably 0.05 parts by mass or more, more preferably 0 parts by mass, relative to 100 parts by mass of the resin (A). .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 even more preferably 3 parts by mass or less.

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

[Electrostatic charge image developing toner]
The toner contains the binder resin composition described above.
The binder resin composition is preferably used as a binder resin for electrostatic charge image developing toner.
The content of the binder resin composition 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 in the binder resin component of the toner.
The toner contains, for example, toner particles and an external additive.
The toner particles preferably contain a binder resin composition.
The toner particles may also contain, for example, colorants, colorant derivatives, release agents, charge control agents, and other additives. Among these, the toner particles preferably contain a colorant.

<Colorant>
Colorants may be either pigments or dyes.
Examples of pigments include azo pigments, phthalocyanine pigments, condensed polycyclic pigments, and lake pigments.
Examples of azo pigments include C.I. I. Pigment Red 3 and other insoluble azo pigments, C.I. I. Pigment Red 48:1 and other soluble azo pigments, C.I. I. and condensed azo pigments such as Pigment Red 144.
Examples of phthalocyanine pigments include C.I. I. Pigment Blue 15:3 and other copper phthalocyanine pigments, C.I. I. and polyhalogenated zinc phthalocyanine pigments such as Pigment Green 58.
Examples of condensed polycyclic pigments include C.I. I. Pigment Red 177 and other anthraquinone pigments, C.I. I. Pigment Red 123 and other perylene pigments, C.I. I. Pigment Orange 43 and other perinone pigments, C.I. I. Pigment Red 122 and other quinacridone pigments, C.I. I. Pigment Red 269 and other naphthol pigments, C.I. I. Pigment Violet 23 and other dioxazine pigments, C.I. I. Pigment Yellow 139 and other isoindolinone pigments, C.I. I. Pigment Orange 66 and other isoindoline pigments, C.I. I. Pigment Yellow 138 and other quinophthalone pigments, C.I. I. Pigment Yellow 150 and other nickel azo complex pigments, C.I. I. Pigment Red 88 and other indigo pigments, C.I. I. Pigment Green 8 and other metal complex pigments, C.I. I. Pigment Red 254, C.I. I. Pigment Red 255, C.I. I. Diketopyrrolopyrrole-based pigments such as Pigment Orange 71 are included.
Examples of lake pigments include C.I. I. Pigment Red 57:1.
Among these, phthalocyanine pigments, quinacridone pigments, naphthol pigments and lake pigments are preferred, and phthalocyanine pigments and quinacridone pigments are more preferred.

Examples of dyes include azine dyes, anthraquinone dyes, perinone dyes, and rhodamine dyes. As the dye, more specifically, for example, 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. , magenta, cyan, blue, red, orange, and green. These may be used alone or in combination of two or more.

From the viewpoint of improving the image density of the toner, the content of the colorant is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and even more preferably 5 parts by mass or more with respect to 100 parts by mass of the total amount of the binder resin. , 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 even more preferably 20 parts by mass or less.

<Colorant derivative>
Colorant derivatives include, for example, colorants into which an acidic group or basic group has been introduced, or salts 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 having a sulfo group or a salt thereof is preferable.
Salts include, for example, halide salts, amine salts, and quaternary ammonium salts.
As the colorant derivative, a sulfonated product of copper phthalocyanine or a salt thereof is preferable.

From the viewpoint of improving the image density of the toner, 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 with respect to 100 parts by mass of the colorant. Yes, and preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less.

<Release agent>
The toner may contain a release agent.
Release agents include, for example, polypropylene wax, polyethylene wax, polypropylene polyethylene copolymer wax; hydrocarbon waxes such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax, and Sasol wax; and oxides thereof; carnauba wax. , montan waxes or their deoxidized 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, still more preferably 75° C. or higher, and is preferably 150° C. or lower, more preferably 130° C. or lower, and still more preferably 100° C. or lower. is.

The content of the release agent is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and still more preferably 0.8 parts by mass or more with respect to 100 parts by mass of the total amount of the binder resin, The content is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and even 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 either a positive charge control agent or a negative charge control agent.
Examples of positive charge control agents include nigrosine dyes such as "Nigrosine Base EX", "Oil Black BS", "Oil Black SO", "Bontron (registered trademark) N-01", "Bontron (registered trademark) N- 04", "Bontron (registered trademark) N-07", "Bontron (registered trademark) N-09", "Bontron (registered trademark) N-11" (manufactured by Orient Chemical Industry Co., Ltd.), etc.; tertiary amines as a side chain, a quaternary ammonium salt compound, such as "Bontron (registered trademark) P-51" (manufactured by Orient Chemical Industry Co., Ltd.), cetyltrimethylammonium bromide, "COPY CHARGE PX VP435" ( Clariant Co., Ltd.), etc.; polyamine resins such as "AFP-B" (Orient Chemical Industry Co., Ltd.); imidazole derivatives such as "PLZ-2001" and "PLZ-8001" (manufactured by Shikoku Kasei Kogyo Co., Ltd.) etc.; styrene-acrylic resins such as "FCA-701PT" (manufactured by Fujikura Kasei Co., Ltd.).

Examples of negatively chargeable charge control agents include metallized 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” (manufactured by Orient Chemical Industry Co., Ltd.), “Izenspiron Black TRH”, “T-77” (Hodogaya Chemical Industry Co., Ltd. manufactured by), etc.; metal compounds of benzylic acid compounds, such as “LR-147” and “LR-297” (manufactured by Nihon Carlit Co., Ltd.), etc.; 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” (manufactured by Orient Chemical Industry Co., Ltd.), “TN-105” (maintenance copper phthalocyanine dyes; quaternary ammonium salts such as "COPY CHARGE PX VP434" (manufactured by Clariant), nitroimidazole derivatives and the like; 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 0.01 parts by mass or more, more preferably 0.2 parts by mass or more, and still more preferably 0.5 parts by mass or more with respect to 100 parts by mass of the total amount of the binder resin, The content 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 even more preferably 2 parts by mass or less.

<Other additives>
Toner particles may contain other additives such as magnetic powder, fluidity improvers, conductivity modifiers, reinforcing fillers such as fibrous substances, antioxidants, anti-aging agents, and cleaning improvers. It may be contained as appropriate.

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 is 100% by mass or less, preferably 99% by mass or less. .

The volume-median particle size ( _D50 ) 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, more preferably 15 μm or less, still more preferably 10 μm. It is below. In this specification, the volume-median particle size ( _D50 ) means a particle size at which the cumulative volume frequency calculated as a volume fraction is 50% from the smaller particle size.

<External Additives>
The toner may further contain an external additive in order to improve fluidity. Examples of external additives include fine particles of inorganic materials such as silica, alumina, titania, zirconia, tin oxide and zinc oxide, and organic fine particles such as resin particles such as melamine resin fine particles and polytetrafluoroethylene resin fine particles. be done. 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.

Hydrophobizing agents include, for example, hexamethyldisilazane (HMDS), dimethyldichlorosilane (DMDS), silicone oil, octyltriethoxysilane (OTES), and methyltriethoxysilane. Among these, hexamethyldisilazane is preferred.

When the toner particles are surface-treated using an external additive, the content of the external additive is preferably 0.05 with respect to 100 parts by mass of the toner particles, from the viewpoint of charging property and fluidity of the toner. Part by mass or more, more preferably 0.08 part by mass or more, still more preferably 0.1 part by mass or more, and preferably 5 parts by mass or less, more preferably 3 parts by mass or less, still more preferably 2 parts by mass or less is.

[Toner manufacturing method]
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, an emulsion aggregation method, etc. However, from the viewpoint of productivity and dispersibility of a colorant, the toner may be obtained by a melt kneading method, an emulsion phase inversion method, a polymerization method, an emulsion aggregation method, or the like. Pulverized toner by a kneading method is preferred.

In the case of a pulverized toner, the method for producing the toner includes, for example, step A: a step of melt-kneading a resin composition (AP) and a toner raw material containing a colorant, and step B: the molten mixture obtained in step A. are pulverized and classified to obtain toner particles.

In step A, the toner raw material may contain other additives such as a charge control agent and a colorant. These toner raw materials are preferably mixed in advance with a mixer such as a Henschel mixer or a ball mill, and then supplied to a kneader.
The melt-kneading temperature is preferably 80° C. or higher, more preferably 90° C. or higher, still more preferably 95° C. or higher, and preferably 160° C. or lower, more preferably 130° C. or lower.
Melt-kneading in step A can be performed using a known kneader such as a closed kneader, a single-screw extruder, a twin-screw extruder, and an open-roll type kneader. From the viewpoint of melt-mixing crystals, a twin-screw extruder that can be set to high temperature conditions is preferred.
The molten mixture obtained in step A is cooled to the extent that it can be pulverized, and then subjected to the following step B.

The pulverization in step B may be performed in multiple steps. For example, the resin kneaded product obtained by curing the molten mixture may be coarsely pulverized to 1 mm or more and 5 mm or less, and then further finely pulverized to a desired particle size.
Pulverizers suitable for coarse pulverization include, for example, a hammer mill, an atomizer, and a Rotoplex. Pulverizers suitably used for fine pulverization include, for example, fluidized bed jet mills, impingement plate jet mills, and rotary mechanical mills. 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.

Classifiers used for classification include, for example, rotor classifiers, air classifiers, inertial classifiers, and sieve classifiers. In the classification step, the pulverized material removed due to insufficient pulverization may be subjected to the pulverization step again, and the pulverization step and the classification step may be repeated as necessary.

From the viewpoint of obtaining high-quality images, 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. It is preferably 15 μm or less, more preferably 10 μm or less.

As described above, the toner preferably has a fluidizing agent or the like added to the surface of the toner particles as an external additive.

Toners are used for developing latent images formed in electrophotography, electrostatic recording, electrostatic printing, and the like. The toner can be used as a one-component developer or mixed with a carrier and used as a two-component developer.

Each property of raw materials, etc., was measured and evaluated by the following methods.

[measurement]
[Acid value and hydroxyl value of resin]
The acid value and hydroxyl value of the resin are measured according to JIS K0070:1992. However, only the measurement solvent is changed 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 amorphous polyester resin. In the case of polyester resin, change the solvent to chloroform.

[Number average molecular weight and weight average molecular weight of resin]
The molecular weight distribution is measured by the gel permeation chromatography (GPC) method obtained by the following method, and the number average molecular weight and weight average molecular weight are determined.
(1) Preparation of sample solution Dissolve the sample in tetrahydrofuran (for amorphous polyester resin) or chloroform (for 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) with a pore size of 0.2 μm to remove undissolved matter to obtain a sample solution.
(2) Molecular weight measurement Using the following measurement device and analysis column, tetrahydrofuran (amorphous polyester resin) or chloroform (crystalline polyester resin) is passed as an eluent at a flow rate of 1 mL per minute, and a constant temperature bath of 40 ° C. Stabilize the column in 100 μL of the sample solution is injected there and measured. The molecular weight of the sample is calculated based on a previously prepared calibration curve. At this time, the calibration curve includes several types of monodisperse polystyrene "A-500" (5.0 × 10 ² ), "A-1000" (1.01 × 10 ³ ), "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” (3.97×10 ⁴ ), “F-10” (9.64×10 ⁴ ), “F-20” (1.90×10 ⁵ ), “F-40” (4.27×10 ⁵ ), "F-80" (7.06×10 ⁵ ), and "F-128" (1.09×10 ⁶ ) (manufactured by Tosoh Corporation) as standard samples.
Measuring device: "HLC-8220CPC" (manufactured by Tosoh Corporation)
Analysis column: "GMHXL" + "G3000HXL" (manufactured by Tosoh Corporation)

[Resin softening point]
Using a flow tester "CFT-500D" (manufactured by Shimadzu Corporation), while heating a 1 g sample at a temperature increase rate of 6 ° C./min, a load of 1.96 MPa was applied with a plunger, and the diameter was 1 mm and the length was 1 mm. extruded from the nozzle of The amount of plunger depression of the flow tester was plotted against the temperature, and the softening point was defined as the temperature at which half of the sample flowed out.

[Maximum endothermic peak temperature]
Using a differential scanning calorimeter "Q-20" (manufactured by TA Instruments Japan Co., Ltd.), the sample was cooled from room temperature (20 ° C.) to 0 ° C. at a cooling rate of 10 ° C./min for 1 minute at that temperature. After that, the temperature is increased to 180°C at a temperature increase rate of 10°C/min, and the temperature is measured. The temperature of the largest endothermic peak among the observed endothermic peaks is taken 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 the sample is weighed in an aluminum pan, heated to 200 ° C., and Cool from the temperature to 0°C at a cooling rate of 10°C/min. Next, the sample is heated at a heating rate of 10 ° C./min, and the temperature at the intersection of the extension of the baseline below the maximum endothermic peak temperature and the tangent line showing the maximum slope from the rising portion of the peak to the top of the peak is measured. Let it be the 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 the sample is weighed in an aluminum pan, and the temperature is lowered from room temperature at a rate of 10 ° C./min. to −10° C. and hold the temperature for 1 minute. Next, the sample is heated to 200° C. at a heating rate of 10° C./min, and then cooled to −30° C. at a cooling rate of 10° C./min. Next, the temperature of the sample is increased at a temperature increase rate of 10° C./min, and among the observed endothermic peaks, the peak temperature on the highest temperature side is taken as the melting point.

[Number average molecular weight (Mn) of polyalkyleneimine]
The molecular weight distribution is measured by the gel permeation chromatography (GPC) method shown below to determine the number average molecular weight.
(1) Preparation of Sample Solution A polyalkyleneimine is dissolved in a solution of 0.15 mol/L Na ₂ SO ₄ dissolved in a 1 mass % acetic acid aqueous solution 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.) with a pore size of 0.2 μm to remove undissolved components to obtain a sample solution.
(2) Molecular weight measurement Using the following measuring apparatus and analytical column, a solution of 0.15 mol/L Na ₂ SO ₄ dissolved in a 1% by mass acetic acid aqueous solution was passed as an eluent at a flow rate of 1 mL per minute, Stabilize the column in a constant temperature bath at 40°C. Then, 100 μL of sample solution is injected and measured. The molecular weight of the sample is calculated based on a previously prepared calibration curve. The calibration curve at this time includes several types of standard pullulan "P-5" (5.9 × 10 ³ ), "P-50" (4.73 × 10 ⁴ ), "P-200" (2.12 × 10 ⁵ ), "P-200" (2.12×10 ⁵ ), and "P-800" (7.08×10 ⁵ ) (manufactured by Showa Denko KK) as standard samples.
Measuring 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 the sample was weighed into an aluminum pan, heated to 200 ° C., and then cooled at a rate of 10 from 200 ° C. Cool to 0°C at °C/min. Next, the temperature of the sample is increased at a temperature increase rate of 10° C./min, and the calorie is measured. The obtained maximum endothermic peak temperature is defined as the melting point.

[Volume Median Particle Diameter of Toner Particles ( _D50 )]
The volume median particle size ( _D50 ) of 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 solution: “Isoton (registered trademark) II” (manufactured by Beckman Coulter, Inc.)
・ Dispersion: "Emulgen (registered trademark) 109P" [polyoxyethylene lauryl ether, manufactured by Kao Corporation, HLB (Hydrophile-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 is added to 5 mL of the dispersion liquid, dispersed for 1 minute with an ultrasonic disperser, then 25 mL of the electrolytic solution is added, and further dispersed for 1 minute with an ultrasonic disperser, Prepare a sample dispersion.
・Measurement conditions: In a beaker, the sample dispersion is 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 are measured. Then, the 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 resins AL-1 and AL-2)
The alcohol component and terephthalic acid shown in Table 1, and the esterification catalyst and cocatalyst were added to a 10-liter four-necked flask equipped with a thermometer, stainless steel stirring rod, fractionation tower, dehydration tube, condenser tube, and nitrogen inlet tube. It was placed in a flask, heated to 235° C. in a nitrogen atmosphere in a mantle heater, and reacted at normal pressure for 7 hours. Thereafter, a reaction under reduced pressure was carried out at 235° C. and 8 kPa until the desired acid value and softening point were reached to obtain resins AL-1 and AL-2. Various physical properties were measured and shown in Table 1.

Production example AH1 (production of resin AH-1)
10 equipped with an alcohol component, terephthalic acid, dodecenyl succinic anhydride, an esterification catalyst and co-catalyst shown in Table 1, a thermometer, a stainless steel stirring rod, a fractionator, a dehydration tube, a condenser tube, and a nitrogen inlet tube. The mixture was placed in a liter four-necked flask, heated to 235° C. in a nitrogen atmosphere in a mantle heater, and reacted under normal pressure for 2.5 hours and then under reduced pressure at 8 kPa for 1 hour. Then, after cooling to 190° C. under normal pressure and adding trimellitic anhydride, the temperature was increased stepwise to 210° C. at a rate of 10° C./h. After that, the reaction was carried out at 8 kPa to the desired softening point to obtain Resin AH-1. Various physical properties were measured and shown in Table 1.

[Production of crystalline polyester resin]
Production Example C1 [Production of Resin C-1]
The alcohol component and carboxylic acid component shown in Table 2, as well as the esterification catalyst and polymerization inhibitor, were added to a 10-liter four-distiller equipped with a thermometer, a stainless steel stirring rod, a fractionator, a dehydration tube, a condenser tube, and a nitrogen inlet tube. It was placed in a one-necked flask, heated to 140° C. in a nitrogen atmosphere in a mantle heater, reacted for 5 hours, and then heated stepwise to 200° C. at a rate of 10° C./h. After that, the reaction was carried out at 8 kPa until the desired softening point, to obtain a resin C-1. Various physical properties were measured and 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, stainless steel stir bar, fractionation tower, dehydration tube, condenser tube, and nitrogen inlet tube, and placed in a nitrogen atmosphere. In a mantle heater, the temperature was raised to 150° C. and the reaction was carried out at normal pressure for 3 hours to obtain resin compositions AP-1, AP-2 and AP-3.

[Toner production]
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 negative charge control agent "Bontron E-81" (manufactured by Orient Chemical Industry Co., Ltd.), a colorant of the type and amount shown in Table 4, And 1 part by mass of paraffin wax "HNP-9" (manufactured by Nippon Seiro Co., Ltd., melting point: 80 ° C.) as a release agent is sufficiently mixed with a Henschel mixer, then the total length of the kneading part is 1560 mm, the screw diameter is 42 mm, and the barrel inner diameter is 43 mm. Using a co-rotating twin-screw extruder, the roll rotation speed was 200 r/min and the heating temperature in the rolls was 100° C. for melt-kneading. The feed rate of the mixture was 20 kg/h and the average residence time was about 18 seconds. The resulting melt-kneaded product was cooled, coarsely pulverized, pulverized with 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., hydrophobic treatment agent: HMDS, average particle diameter: about 30 nm) is added as an external additive. and mixed with a Henschel mixer to obtain toners 1 to 4 and 81 to 83.

Examples 5-8, Comparative Examples 4-5 [Toners 5-8, 84-85]
100 parts by mass of a binder resin having a compounding ratio shown in Table 4, 1 part by mass of a negative charge control agent "Bontron E-81" (manufactured by Orient Chemical Industry Co., Ltd.), and C.I. I. Pigment Blue 15:3 “Cyanine Blue 4927” (manufactured by Dainichiseika Kogyo Co., Ltd.) 15 parts by weight, “SOLSPERSE 5000s” (manufactured by Nippon Lubrizol Co., Ltd.) 1 part by weight as a coloring agent derivative, and paraffin wax as a release agent Toners 5 to 8 and 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. rice field.

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., Inc.) was added.

[Evaluation of Toner]
[Storage]
4 g of toner was placed in a 20 mL container (approximately 3 cm in diameter) and left for 48 hours under an environment of 55° C. and 60% relative humidity. The degree of toner aggregation was visually observed every 6 hours up to 72 hours. The longer the value of the time at which the occurrence of aggregation is observed, the better the storage stability under high temperature and high humidity. Table 4 shows the results. ">72" in Table 4 indicates that no aggregation was observed even after 72 hours.

[Pigment Dispersibility]
0.1 g of 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. After the container was sealed with a cap, the mixture was stirred and mixed with a test tube mixer (manufactured by AS ONE Co., Ltd.) to melt and disperse the toner in chloroform. The obtained sample was placed in 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 entering 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 addition, "≧1000" in Table 4 indicates that the pigment particle size was 1000 nm or more.

As shown in Table 4, the toner containing the binder resin composition for toner containing the resin composition (AP) obtained by condensing the amorphous resin (A) having an acid group with polyethyleneimine , excellent storage stability and pigment dispersibility.

Claims (8)

Step 1: 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 step of melt-kneading the resin composition (AP) and a toner raw material containing a colorant;
Step B: A method for producing a toner for electrostatic charge image development, comprising a step of pulverizing and classifying the molten mixture obtained in Step A to obtain toner particles . 2. The method for producing a toner for electrostatic charge image development 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 method for producing a toner for electrostatic charge image development according to claim 1, wherein the amorphous polyester resin (A) has a softening point of 80[deg.] C. or more and 120[deg.] C. or less. Step 2: The resin composition (AP) and an amorphous polyester resin (A2) having a softening point different from that of the amorphous polyester resin (A) by 5°C or more are mixed. 4. The method for producing a toner for electrostatic charge image development according to claim 3 , further comprising a step between step 1 and step A. 5. The method for producing a toner for electrostatic charge image development according to claim 4, wherein the amorphous polyester resin (A2) has a softening point of 110[deg.] C. or higher and 170[deg.] C. or lower. 6. The method for producing a toner for electrostatic charge image development according to claim 4 , wherein in the step 2, the crystalline polyester resin (C) is further mixed . 7. The method for producing a toner for electrostatic charge image development according to claim 1 , wherein the step A further comprises a coloring agent derivative. 8. The method for producing a toner for electrostatic charge image development according to claim 7 , wherein the colorant derivative is a sulfonated product of copper phthalocyanine or a salt thereof.