JP7274274B2 - Binder resin for toner - Google Patents

Description

The present invention relates to a binder resin for toner used for developing latent images formed by electrophotography, electrostatic recording, electrostatic printing, and the like, electrophotographic toner, and a method for producing electrophotographic toner. .

In the field of electrophotography, with the development of electrophotographic systems, there is a demand for the development of electrophotographic toners capable of achieving higher image quality and higher speed.

Patent Document 1 discloses a toner resin soluble in an organic solvent, which is made of an oligomer having a polyhydroxycarboxylic acid skeleton obtained from a diol having an aromatic ring and a hydroxycarboxylic acid, and a soft segment, and an elongating agent. A toner resin is described which is characterized by being elongation-reacted using Further, the soft segment is composed of an aliphatic ester, an aliphatic ether, an aliphatic silicone, or an aliphatic linear diol having 5 or more carbon atoms, and the soft segment is polycaprolactone, poly(tetra Methylene oxide)glycol or a carbinol-modified silicone at both ends is disclosed as a toner resin. It is described that the toner ensures heat-resistant storage stability, is excellent in low-temperature fixability, and has good charging stability during long-term stirring and charging stability against changes in usage environment such as temperature and humidity.

JP 2012-242448 A

With the development of electrophotographic systems, the toner of Patent Document 1 is required to have better low-temperature fixability.
However, when the low-temperature fixability of this toner is enhanced, the hot offset resistance is sometimes lowered. Furthermore, by increasing the low-temperature fixability of the toner, the durability of the toner is lowered, and the toner sometimes adheres to the photoreceptor.
One embodiment of the present invention relates to a binder resin for toner excellent in low-temperature fixability, hot offset resistance and durability, an electrophotographic toner, a method for producing an electrophotographic toner, and the like.

One embodiment of the present invention relates to the following [1] to [3].
[1] A reaction product of an alcohol component containing an α,ω-aliphatic diol having 2 to 14 carbon atoms, a carboxylic acid component containing an aliphatic dicarboxylic acid compound having 4 to 14 carbon atoms, and silicone,
The binder resin for toner, wherein the silicone is a silicone having at least one selected from an amino group, a carboxy group, an epoxy group, and a carbinol group.
[2] An electrophotographic toner containing the binder resin for toner described in [1] above.
[3] Step 1: A step of melt-kneading the toner raw material containing the binder resin described in [1] above; and Step 2: A step of pulverizing and classifying the melt-kneaded product obtained in Step 1 to obtain toner particles. A method of making an electrophotographic toner, comprising:

According to one embodiment of the present invention, it is possible to provide a binder resin for toner excellent in low temperature fixability, hot offset resistance and durability, an electrophotographic toner, and a method for producing an electrophotographic toner.

[Binder resin for toner]
A binder resin for toner according to one embodiment of the present invention (hereinafter also simply referred to as “resin (C)”) comprises an alcohol component containing an α,ω-aliphatic diol having 2 to 14 carbon atoms, It is a reaction product of a carboxylic acid component containing 14 or less aliphatic dicarboxylic acid compounds above and silicone.
The silicone is a silicone having at least one selected from an amino group, a carboxy group, an epoxy group, and a carbinol group. It is possible to provide a binder resin for toner excellent in durability, an electrophotographic toner, and a method for producing an electrophotographic toner.

Although the reason why such an effect is obtained is not clear, it is considered as follows.
By using a binder resin that is a reaction product of an alcohol component containing a predetermined α,ω-aliphatic diol, a carboxylic acid component containing a predetermined aliphatic dicarboxylic acid compound, and silicone, a mold release is achieved during fixing of an image. It is considered to be effective. This improves low-temperature fixability and hot offset resistance.
Further, since the alcohol component and the carboxylic acid component contained in the binder resin are hydrophobic, the reactivity with silicone is better than that of other binder resins contained in the toner. And the entire binder resin becomes more hydrophobic. This causes phase separation from other binder resins contained in the toner, and the binder resin of the present invention tends to exist on the surface. In general, the presence of a binder resin on the surface basically adversely affects toner evaluations such as durability.

Definitions of various terms used in this specification are shown below.
Whether a resin is crystalline or amorphous is determined by the crystallinity index. The crystallinity index is defined as the ratio of the softening point of the resin to the maximum endothermic peak temperature (softening point (°C)/maximum endothermic peak temperature (°C)) in the measurement method described in the Examples below. A crystalline resin is a resin having a crystallinity index of 0.6 or more and less than 1.4, preferably 0.7 or more, more preferably 0.9 or more, and preferably 1.2 or less. An amorphous resin is a resin having a crystallinity index of 1.4 or more and less than 0.6, preferably 1.5 or more and 0.5 or less, more preferably 1.6 or more and 0.5 or less. is. The crystallinity index 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. The maximum endothermic peak temperature refers to the temperature of the highest endothermic peak among the observed endothermic peaks. The crystallinity index can be calculated from values obtained by measuring the softening point of the resin and the maximum endothermic peak temperature described in Examples.
In the specification, the carboxylic acid compound includes not only the carboxylic acid, but also an anhydride that decomposes to produce an acid during the reaction, and an alkyl ester of each carboxylic acid (the number of carbon atoms in the alkyl group is 1 or more and 3 or less). It means that
Bisphenol A is 2,2-bis(4-hydroxyphenyl)propane.
In the specification, the term "binder resin" simply means a resin component contained in the toner including resin (A), resin (B) and resin (C).

<Resin (C)>
The reactant in the resin (C) is an alcohol component containing an α,ω-aliphatic diol having 2 to 14 carbon atoms from the viewpoint of obtaining an electrophotographic toner excellent in low temperature fixability, hot offset resistance and durability. and a carboxylic acid component containing an aliphatic dicarboxylic acid compound having 4 to 14 carbon atoms, and a predetermined silicone.
The predetermined silicone is silicone having at least one selected from an amino group, a carboxy group, an epoxy group, and a carbinol group.
Resin (C) is preferably crystalline.
Each component of the resin (C) will be described below.

[Alcohol component]
The alcohol component includes an α,ω-aliphatic diol having 2 to 14 carbon atoms.
The α,ω-aliphatic diol is preferably an α,ω-linear 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. Yes, and more preferably 10.
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, 1,6-hexanediol, or 1,10-decanediol is preferred, and 1,10-decanediol 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 100 mol % or less, more preferably 100 mol %.

The alcohol component may contain other alcohol components different from the α,ω-aliphatic diol. Examples of other alcohol components include aliphatic diols other than α,ω-aliphatic diols such as 1,2-propylene glycol and neopentyl glycol; aromatic diols such as alkylene oxide adducts of bisphenol A; trihydric or higher alcohols such as erythritol and trimethylolpropane; One or more of these alcohol components may be used.

[Carboxylic acid component]
The carboxylic acid component contains an aliphatic dicarboxylic acid compound having 4 to 14 carbon atoms.
The aliphatic dicarboxylic acid compound is preferably a linear aliphatic dicarboxylic acid compound.
The number of carbon atoms in the aliphatic dicarboxylic acid compound is preferably 4 or more, more preferably 8 or more, still more preferably 10 or more, and preferably 14 or less, more preferably 12 or less.
Examples of aliphatic dicarboxylic acid compounds include fumaric acid, sebacic acid, dodecanedioic acid, and tetradecanedioic acid. Among these, sebacic acid, dodecanedioic acid, or tetradecanedioic acid is preferred, and sebacic acid is more preferred. One or more of these carboxylic acid components may be used.

The amount of the aliphatic dicarboxylic acid compound in the carboxylic acid 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 100 mol % or less, more preferably 100 mol %.

The carboxylic acid component may contain other carboxylic acid components different from the aliphatic dicarboxylic acid compound. Other carboxylic acid components include, for example, aromatic dicarboxylic acid compounds such as terephthalic acid and isophthalic acid; trivalent or higher polyvalent carboxylic acid compounds. These carboxylic acid components may be used singly or in combination of two or more.

The equivalent ratio of the carboxy group of the carboxylic acid component to the hydroxyl 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, or more. It is preferably 1.2 or less.

〔silicone〕
The silicone used for the resin (C) is at least one selected from an amino group, a carboxyl group, an epoxy group, and a carbinol group from the viewpoint of obtaining an electrophotographic toner excellent in low-temperature fixability, hot offset resistance and durability. It is a silicone with seeds.

〔式中、Ｒは、それぞれ独立に、炭素数１以上５以下の炭化水素基であり、Ｒ’はそれぞれ独立に、炭素数１以上５以下のアルキレン基であり、ａは１又は０であり、Ｘは、それぞれ独立に、アミノ基、カルボキシ基、エポキシ基、又はヒドロキシ基であり、＊は結合部位である。〕で表される繰り返し単位、及び、式（２）：

〔式中、Ｒは、それぞれ独立に、炭素数１以上５以下の炭化水素基であり、＊は結合部位である。〕で表される繰り返し単位を有する。 More specifically, the silicone preferably has the formula (1):

[In the formula, each R is independently a hydrocarbon group having 1 to 5 carbon atoms, each R′ is independently an alkylene group having 1 to 5 carbon atoms, and a is 1 or 0; , X are each independently an amino group, a carboxy group, an epoxy group, or a hydroxy group, and * is a binding site. ] and a repeating unit represented by formula (2):

[In the formula, each R is independently a hydrocarbon group having 1 to 5 carbon atoms, and * is a bonding site. ] has a repeating unit represented by

〔式中、Ｒ’’は、炭素数１以上１０以下の炭化水素基であり、＊は結合部位である。〕で表される基であってもよい。 Note that the end of the silicone is represented by the formula (3):

[In the formula, R'' is a hydrocarbon group having 1 or more and 10 or less carbon atoms, and * is a bonding site. ] may be a group represented by

The number of carbon atoms in the hydrocarbon group of R is 5 or less, preferably 4 or less, more preferably 3 or less, still more preferably 2 or less, and still more preferably 1.
Hydrocarbon groups for R include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group and pentyl group. Among these, a methyl group is preferred.
The number of carbon atoms in the alkylene group of R' is 10 or less, preferably 8 or less, more preferably 5 or less, still more preferably 4 or less, still more preferably 3 or less, still more preferably 2 or less, and still more preferably 1.
Examples of the alkylene group for R′ include methanediyl, ethane-1,2-diyl, ethane-1,1-diyl, n-propane-1,3-diyl, n-propane-1,2- diyl group, 2-methylethane-1,2-diyl group, 1,4-n-butyl group, 1,2-tert-butyl group and 1,5-pentyl group. Among these, a methanediyl group is preferred.
The number of carbon atoms in the hydrocarbon group of R'' is 10 or less, more preferably 8 or less, still more preferably 6 or less, still more preferably 4 or less, more preferably 3 or less, still more preferably 2 or less, still more preferably 1. be.
Examples of hydrocarbon groups for R″ include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl and benzyl groups.

The weight average molecular weight (Mw) of the silicone is preferably 600 or more, more preferably 800 or more, still more preferably 1,000 or more, and preferably 20,000 or less, more preferably 10,000 or less, and still more preferably is 7,000 or less, more preferably 6,000 or less, still more preferably 5,000 or less, still more preferably 4,000 or less.
The number average molecular weight (Mn) of the silicone is preferably 500 or more, more preferably 700 or more, still more preferably 800 or more, and preferably 10,000 or less, more preferably 8,000 or less, still more preferably 6 ,000 or less, more preferably 4,000 or less, and still more preferably 3,000 or less.

The kinematic viscosity of the silicone at 25° C. is preferably 10 mm ² /s or more, more preferably 100 mm ² /s or more, still more preferably 1,000 mm ² /s or more, and preferably 4,000 mm ² /s. Below, more preferably 3,000 mm ² /s or less, still more preferably 2,500 mm ² /s or less.
The kinematic viscosity of silicone is measured at 25° C. using a fully automatic micro-kinematic viscometer (manufactured by Viscotec Co., Ltd.).

The functional group equivalent weight of the silicone is preferably 300 g/mol or more, more preferably 500 g/mol or more, still more preferably 1,000 g/mol or more, still more preferably 2,000 g/mol or more, and preferably 6, 000 g/mol or less, more preferably 5,000 g/mol or less, and still more preferably 4,000 g/mol or less.
In addition, the functional group equivalent means the mass of silicone per 1 mol of functional groups.

Examples of the above-mentioned silicone include modified silicone having an amino group in the side chain (commercially available, for example, "KF-864" (manufactured by Shin-Etsu Chemical Co., Ltd.)), modified silicone having a carboxy group in the side chain ( Commercially available products include, for example, "X-22-162C", "X-22-3701E" (manufactured by Shin-Etsu Chemical Co., Ltd.), "BY16-880" (manufactured by Dow Corning Toray Co., Ltd.), and epoxy groups. Modified silicone having a side chain (as a commercial product, "X-22-343" (manufactured by Shin-Etsu Chemical Co., Ltd.)), modified silicone having a hydroxy group in a side chain (as a commercial product, "X-22-4039 ” (manufactured by Shin-Etsu Chemical Co., Ltd.).

The mass ratio of the silicone in the resin (C) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 1, based on the total amount of the alcohol component, the carboxylic acid component, and the silicone. % by mass or more, more preferably 2% by mass or more, more preferably 3% by mass or more, still more preferably 4% by mass or more, and preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably It is 15% by mass or less, more preferably 10% by mass or less, and more preferably 7% by mass or less.

〔式中、Ｒ、Ｒ’、ａ、及び＊は、前述の式（１）と同定義である。〕で表される繰り返し単位、及び、式（２）：

〔式中、Ｒ、及び＊は、前述の式（２）と同定義である。〕で表される繰り返し単位を有する。
式（１ａ）中、＊－（Ｒ’）_ａ―ＮＨ_２で表される基は、例えば、下記の置換基１ａ－1～１ａ－３が挙げられる。

From the viewpoint of obtaining an electrophotographic toner excellent in low-temperature fixability, hot offset resistance and durability, the silicone is preferably silicone (a) having an amino group in its side chain (hereinafter also simply referred to as "silicone (a)"). is called).
That is, silicone (a) preferably has the formula (1a):

[In the formula, R, R', a, and * have the same definitions as in formula (1) above. ] and a repeating unit represented by formula (2):

[In the formula, R and * have the same definitions as in the above formula (2). ] has a repeating unit represented by
In formula (1a), the group represented by *-(R') _a -NH ₂ includes, for example, the following substituents 1a-1 to 1a-3.

〔式中、Ｒ’’、及び＊は、前述の式（３）と同定義である。〕で表される基であってもよい。 The terminal of silicone (a) is represented by formula (3):

[In the formula, R'' and * have the same definition as in the above formula (3). ] may be a group represented by

Examples of the silicone (a) include modified silicones having amino groups on side chains (commercially available products include, for example, "KF-864" (manufactured by Shin-Etsu Chemical Co., Ltd.)).

The silicone used for the resin (C) contains at least one selected from a carboxy group, an epoxy group, and a carbinol group from the viewpoint of obtaining an electrophotographic toner excellent in low temperature fixability, hot offset resistance and durability. It is a silicone (b) having one end or both ends.

〔式中、Ｒ、及び＊は、前述の式（１）と同定義である。〕で表される繰り返し単位を有し、
片末端又は両末端に、式（４）：

〔式中、Ｒ’’’は、それぞれ独立に、炭素数１以上１０以下のアルキレン基であり、
Ｘ’は、ヒドロキシ基、ヒドロキシアルキルオキシ基、カルボキシ基、カルボキシアルキルオキシ基、グリシジル基、又はグリシジルオキシ基であり、
＊は結合部位である。〕で表される基を有する。 The silicone is more particularly preferably of formula (2):

[In the formula, R and * have the same definitions as in the above formula (1). ] has a repeating unit represented by
Formula (4) at one or both ends:

[Wherein, each R''' is independently an alkylene group having 1 to 10 carbon atoms,
X' is a hydroxy group, a hydroxyalkyloxy group, a carboxy group, a carboxyalkyloxy group, a glycidyl group, or a glycidyloxy group;
* is the binding site. ] has a group represented by

〔式中、Ｒ’’、及び＊は、前述の式（３）と同定義である。〕で表される基であってもよい。 When one end is a group represented by formula (4), the other end is represented by formula (3):

[In the formula, R'' and * have the same definition as in the above formula (3). ] may be a group represented by

The number of carbon atoms in the alkylene group of R''' is 10 or less, preferably 8 or less, more preferably 5 or less, still more preferably 4 or less, still more preferably 3 or less, still more preferably 2 or less, and still more preferably 1. .
Examples of the alkylene group for R''' include methanediyl, ethane-1,2-diyl, ethane-1,1-diyl, n-propane-1,3-diyl, n-propane-1, 2-diyl group, 2-methylethane-1,2-diyl group, 1,4-n-butyl group, 1,2-tert-butyl group and 1,5-pentyl group. Among these, a methanediyl group is preferred.

Examples of the group represented by formula (4) include the following substituents 4-1 to 4-3 when X' is a hydroxy group or a hydroxyalkyloxy group. Among these, the substituent 4-1 or the substituent 4-2 is preferable, and the substituent 4-1 is more preferable.

Examples of the group represented by formula (4) include substituents 4-10 to 4-12 below when X' is a glycidyl group or a glycidyloxy group. Among these, substituents 4-10 are preferred.

Examples of the group represented by formula (4) include the following substituents 4-20 when X' is a carboxy group or a carboxyalkyloxy group.

Examples of the silicone (b) include carbinol-modified silicones at both ends (commercially available products include "X-22-160AS", "KF-6000", "KF-6001", "KF-6002", "KF -6003" (manufactured by Shin-Etsu Chemical Co., Ltd.), one-end carbinol-modified silicone (commercially available products include, for example, "X-22-170BX", "X-22-170DX", and "X-22-176DX ”, “X-22-176GX-A” (manufactured by Shin-Etsu Chemical Co., Ltd.), epoxy-modified silicone at both ends (commercially available products are “KF-105”, “X-22-163A”, “X -22-163B", "X-22-163C", "X-22-169AS", "X-22-169B" (manufactured by Shin-Etsu Chemical Co., Ltd.)), one end epoxy-modified silicone (commercially available are "X-22-173BX", "X-22-173DX" (manufactured by Shin-Etsu Chemical Co., Ltd.), both terminal carboxy-modified silicones (commercially available, "X-22-162C" (Shin-Etsu Chemical manufactured by Kogyo Co., Ltd.)).

[Physical properties of resin (C)]
The acid value of resin (C) is preferably 1 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 1 mgKOH/g or more, more preferably 5 mgKOH/g or more, still more preferably 7 mgKOH/g or more, and preferably 60 mgKOH/g or less, more preferably 40 mgKOH/g or less. and more preferably 20 mgKOH/g or less.

The softening point of the resin (C) is preferably 60° C. or higher, more preferably 70° C. or higher, and even more preferably 80° C. or higher, from the viewpoint of further improving hot offset resistance and durability. is preferably 120° C. or lower, more preferably 110° C. or lower, even more preferably 100° C. or lower, and even more preferably 90° C. or lower, from the viewpoint of further improving the temperature.

The melting point of the resin (C) is preferably 50° C. or higher, more preferably 55° C. or higher, still more preferably 60° C. or higher, still more preferably 70° C. or higher, from the viewpoint of further improving hot offset resistance and durability. And, from the viewpoint of further improving the low-temperature fixability, the temperature is preferably 100° C. or less, more preferably 90° C. or less, and still more preferably 80° C. or less.

The number average molecular weight of the resin (C) is preferably 1,000 or more, more preferably 2,000 or more, still more preferably 3,000 or more, still more preferably 4,000 or more, from the viewpoint of excellent hot offset resistance. and, from the viewpoint of excellent low-temperature fixability, it is preferably 10,000 or less, more preferably 8,000 or less, even more preferably 6,000 or less, still more preferably 5,000 or less.

The acid value, softening point, glass transition temperature, and number average molecular weight of the resin (C) can be appropriately adjusted depending on the type and amount of raw material monomer used, and production conditions such as reaction temperature, reaction time, and cooling rate. , and their values are obtained by the method described in Examples.

[Method for producing resin (C)]
Resin (C) is obtained, for example, by reacting an alcohol component, a carboxylic acid component, and silicone. In the reaction, if necessary, an esterification catalyst such as di(2-ethylhexanoic acid) tin (II), dibutyltin oxide, titanium diisopropylate bistriethanolamine, etc. is added to the total amount of the alcohol component and the carboxylic acid component. 0.01 parts by mass or more and 5 parts by mass or less per 100 parts by mass; an esterification promoter such as gallic acid (same as 3,4,5-trihydroxybenzoic acid), total amount of alcohol component and carboxylic acid component 100 0.001 parts by mass or more and 0.5 parts by mass or less may be used for the reaction.
The reaction temperature is preferably 120° C. or higher, more preferably 160° C. or higher, still more preferably 180° C. or higher, and preferably 250° C. or lower, more preferably 240° C. or lower.
In addition, you may perform reaction in inert gas atmosphere.

[Electrophotographic toner]
The toner used in the present invention contains a resin (C) from the viewpoint of obtaining a toner excellent in low temperature fixability, hot offset resistance and durability.
A toner includes, for example, toner particles and an external additive.
[Toner particles]
The toner particles preferably contain resin (C).
From the viewpoint of further improving either low-temperature fixability or hot-offset resistance, the toner particles preferably include the resin (A) and the resin (B ).
Toner particles may also contain waxes, charge control agents, colorants, magnetic powders, fluidity improvers, conductivity modifiers, reinforcing fillers such as fibrous substances, antioxidants, anti-aging agents, cleaning improvers, etc. may contain additives.

The content of the resin (C) is preferably 1% by mass or more, more preferably 3% by mass or more, more preferably 3% by mass or more, in the binder resin of the toner, from the viewpoint of further improving the low-temperature fixability and hot offset resistance of the toner. is 5% by mass or more, more preferably 8% by mass or more, and is preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, and still more preferably 15% by mass or less. .

<Resin (A)>
The toner may contain resin (A).
Resin (A) is preferably an amorphous resin.
Resin (A) is, for example, a polyester resin that is a polycondensate of an alcohol component and a carboxylic acid component.
Each component of the resin (A) will be described below.

[Alcohol component]
The alcohol component includes dihydric or higher alcohol.
The content of dihydric or higher alcohol 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.
Dihydric or higher alcohols include, for example, aromatic diols, linear or branched aliphatic diols, alicyclic diols, and trihydric or higher polyhydric alcohols. Among these, aromatic diols or linear or branched aliphatic diols are preferable, and aromatic diols are more preferable.

（式中、ＯＲ^１及びＲ^２Ｏはオキシアルキレン基であり、Ｒ^１及びＲ^２はそれぞれ独立にエチレン基又はプロピレン基であり、ｘ及びｙはアルキレンオキサイドの平均付加モル数を示し、それぞれ正の数であり、ｘとｙの和の値は、１以上、好ましくは１．５以上であり、そして、１６以下、好ましくは８以下、より好ましくは４以下である）で表されるビスフェノールＡのアルキレンオキサイド付加物である。
ビスフェノールＡのアルキレンオキサイド付加物としては、例えば、ビスフェノールＡのプロピレンオキサイド付加物、ビスフェノールＡのエチレンオキサイド付加物が挙げられる。これらは、１種又は２種以上を用いてもよい。これらの中でも、ビスフェノールＡのプロピレンオキサイド付加物、及びビスフェノールＡのエチレンオキサイド付加物の組合せが好ましい。
ビスフェノールＡのプロピレンオキサイド付加物と、ビスフェノールＡのエチレンオキサイド付加物とのモル比（ビスフェノールＡのプロピレンオキサイド付加物／ビスフェノールＡのエチレンオキサイド付加物）は、好ましくは１０／９０以上、より好ましくは１５／８５以上、更に好ましくは２０／８０以上であり、そして、好ましくは９０／１０以下、より好ましくは７０／３０以下、更に好ましくは５０／５０以下である。
ビスフェノールＡのアルキレンオキサイド付加物の量は、アルコール成分中、好ましくは７０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。 The aromatic diol is preferably an alkylene oxide adduct of bisphenol A, more preferably of formula (I):

(Wherein, OR ¹ and R ² O are oxyalkylene groups, R ¹ and R ² are each independently an ethylene group or a propylene group, x and y represent the average number of added moles of alkylene oxide, each positive and the sum of x and y is 1 or more, preferably 1.5 or more, and 16 or less, preferably 8 or less, more preferably 4 or less). is an alkylene oxide adduct of
Examples of bisphenol A alkylene oxide adducts include bisphenol A propylene oxide adducts and bisphenol A ethylene oxide adducts. These may be used alone or in combination of two or more. Among these, a combination of a propylene oxide adduct of bisphenol A and an ethylene oxide adduct of bisphenol A is preferred.
The molar ratio of the propylene oxide adduct of bisphenol A to the ethylene oxide adduct of bisphenol A (propylene oxide adduct of bisphenol A/ethylene oxide adduct of bisphenol A) is preferably 10/90 or more, more preferably 15. /85 or more, more preferably 20/80 or more, and preferably 90/10 or less, more preferably 70/30 or less, and even more preferably 50/50 or less.
The amount of the alkylene oxide adduct of bisphenol A in the alcohol component is preferably 70 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, and 100 mol% or less, and further Preferably it is 100 mol %.

As linear or branched aliphatic diols, aliphatic diols having hydroxyl groups bonded to secondary carbon atoms are preferred.
The number of carbon atoms in the aliphatic diol having hydroxyl groups bonded to secondary carbon atoms is preferably 3 or more and 4 or less.
Aliphatic diols having hydroxyl groups bonded to secondary carbon atoms include, for example, 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, and 2,3-butanediol.
The amount of the aliphatic diol having a hydroxyl group bonded to a secondary carbon atom is preferably 70 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, in the alcohol component, and 100 mol % or less, more preferably 100 mol %.

Other linear or branched aliphatic diols include, for example, ethylene glycol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,8- octanediol, 1,9-nonanediol, 1,10-decanediol and 1,12-dodecanediol.

Examples of alicyclic diols include hydrogenated bisphenol A [2,2-bis(4-hydroxycyclohexyl)propane], alkylene oxide of hydrogenated bisphenol A having 2 to 4 carbon atoms (average added mole number 2 to 12 below) adducts.
Examples of trihydric or higher polyhydric alcohols include glycerin, pentaerythritol, trimethylolpropane, and sorbitol.
One or more of these alcohol components may be used.

[Carboxylic acid component]
The carboxylic acid component includes a divalent or higher carboxylic acid compound.
The content of the divalent or higher carboxylic acid compound 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.
Divalent or higher carboxylic acid compounds include, for example, aromatic dicarboxylic acid compounds, linear or branched aliphatic dicarboxylic acid compounds, alicyclic dicarboxylic acid compounds, and trivalent or higher polyvalent carboxylic acid compounds. Among these, aromatic dicarboxylic acid compounds are preferred.

Examples of aromatic dicarboxylic acids include phthalic acid, isophthalic acid, and terephthalic acid. Among these, isophthalic acid or terephthalic acid is preferred, and terephthalic acid is more preferred.
The amount of the aromatic dicarboxylic acid in the carboxylic acid component is preferably 30 mol% or more, more preferably 50 mol% or more, still more preferably 80 mol% or more, still more preferably 90 mol% or more, and 100 mol % or less.

The number of carbon atoms in the linear or branched aliphatic dicarboxylic acid is preferably 2 or more, more preferably 4 or more, still more preferably 8 or more, still more preferably 10 or more, and preferably 22 or less, more preferably 16. It is below.
Linear or branched aliphatic dicarboxylic acids include, for example, oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, acid, succinic acid substituted with an aliphatic hydrocarbon group having 1 to 20 carbon atoms, anhydrides thereof, or alkyl esters having 1 to 3 carbon atoms.
Examples of the succinic acid substituted with an aliphatic hydrocarbon group having 1 to 20 carbon atoms include dodecylsuccinic acid, dodecenylsuccinic acid, and octenylsuccinic acid. Among these, succinic acid substituted with an aliphatic hydrocarbon group having 1 to 20 carbon atoms or anhydrides thereof are preferable.
The amount of linear or branched aliphatic dicarboxylic acid in the carboxylic acid component is preferably 2 mol% or more, more preferably 3 mol% or more, still more preferably 5 mol% or more, and preferably 30 mol%. Below, more preferably 20 mol % or less, still more preferably 10 mol % or less.

The trivalent or higher polyvalent carboxylic acid is preferably a trivalent carboxylic acid, such as trimellitic acid or its anhydride. Among these, trimellitic acid or its anhydride is preferred.
When a trivalent or higher polycarboxylic acid is contained, the amount of the trivalent or higher polycarboxylic acid is preferably 1 mol% or more, more preferably 2 mol% or more, still more preferably 5 mol% in the carboxylic acid component. Above, it is more preferably 10 mol % or more, still more preferably 15 mol % or more, still more preferably 20 mol % or more, and preferably 35 mol % or less, more preferably 30 mol % or less.
One or more of these carboxylic acid components may be used.

The equivalent ratio of the carboxy group of the carboxylic acid component to the hydroxy 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, it is 1.2 or less.

[Physical properties of resin (A)]
The acid value of resin (A) is preferably 0.1 mgKOH/g or more, more preferably 0.5 mgKOH/g or more, still more preferably 1 mgKOH/g or more, and preferably 20 mgKOH/g or less, more preferably It is 10 mgKOH/g or less, more preferably 5 mgKOH/g or less.

The hydroxyl value of the resin (A) is preferably 1 mgKOH/g or more, more preferably 10 mgKOH/g or more, still more preferably 20 mgKOH/g or more, and preferably 60 mgKOH/g or less, more preferably 50 mgKOH/g or less. , more preferably 40 mgKOH/g or less, more preferably 35 mgKOH/g or less.

The softening point of the resin (A) is preferably 70° C. or higher, more preferably 90° C. or higher, and still more preferably 100° C. or higher. It is preferably 130° C. or lower, more preferably 120° C. or lower, still more preferably 115° C. or lower, still more preferably 110° C. or lower.

The glass transition temperature of the resin (A) is preferably 45° C. or higher, more preferably 48° C. or higher, still more preferably 50° C. or higher, still more preferably 55° C. or higher, from the viewpoint of further improving hot offset resistance and durability. From the viewpoint of further improving the low-temperature fixability, the temperature is preferably 80° C. or lower, more preferably 70° C. or lower, and even more preferably 63° C. or lower.

The number average molecular weight of the resin (A) is preferably 1,000 or more, more preferably 1,500 or more, still more preferably 2,000 or more, still more preferably 2,500 or more, from the viewpoint of excellent hot offset resistance. and, from the viewpoint of excellent low-temperature fixability, it is preferably 10,000 or less, more preferably 8,000 or less, even more preferably 6,000 or less, still more preferably 4,000 or less, and still more preferably 3,000 or less. 500 or less.

The acid value, softening point, glass transition temperature, and number average molecular weight of the resin (A) can be appropriately adjusted depending on the type and amount of raw material monomer used, and production conditions such as reaction temperature, reaction time, and cooling rate. , and their values are obtained by the method described in Examples.
When two or more reactants are used in combination, the acid value, hydroxyl value, softening point, and glass transition temperature obtained as a mixture thereof are preferably within the ranges described above.

[Method for producing resin (A)]
Resin (A) is obtained, for example, by reacting an alcohol component and a carboxylic acid component. In the reaction, if necessary, an esterification catalyst such as di(2-ethylhexanoic acid) tin (II), dibutyltin oxide, titanium diisopropylate bistriethanolamine, etc. is added to the total amount of the alcohol component and the carboxylic acid component. 0.01 parts by mass or more and 5 parts by mass or less per 100 parts by mass; an esterification promoter such as gallic acid (same as 3,4,5-trihydroxybenzoic acid), total amount of alcohol component and carboxylic acid component 100 0.001 parts by mass or more and 0.5 parts by mass or less may be used for the reaction.
The reaction temperature is preferably 120° C. or higher, more preferably 160° C. or higher, still more preferably 180° C. or higher, and preferably 250° C. or lower, more preferably 240° C. or lower.
In addition, you may perform reaction in inert gas atmosphere.

The content of the resin (A) is preferably 10% by mass or more, more preferably 20% by mass or more, more preferably 20% by mass or more, in the binder resin of the toner, from the viewpoint of further improving the low-temperature fixability and hot offset resistance of the toner. is 30% by mass or more, more preferably 40% by mass or more, more preferably 50% by mass or more, and is 100% by mass or less, preferably 90% by mass or less, more preferably 80% by mass or less, further preferably 70% by mass. % by mass or less.

<Resin (B)>
The toner may contain a resin (B).
The resin (B) has a softening point different from that of the resin (A) by 5°C or more. The resin (B) preferably has a softening point higher than that of the resin (A) by 5°C or more, more preferably higher than that of the resin (A) by 10°C or more. Preferably, it has a softening point higher than that of resin (A) by 15°C or more.
Resin (B) is a polycondensate of an alcohol component and a carboxylic acid component.
Resin (B) is preferably amorphous.
The alcohol component and the carboxylic acid component are as exemplified for the resin (A) described above.

[Physical properties of resin (B)]
The acid value of the resin (B) is preferably 0.1 mgKOH/g or more, more preferably 5 mgKOH/g or more, still more preferably 10 mgKOH/g or more, still more preferably 15 mgKOH/g or more, and preferably 40 mgKOH/g. g or less, more preferably 35 mgKOH/g or less, still more preferably 30 mgKOH/g or less, still more preferably 23 mgKOH/g or less, still more preferably 20 mgKOH/g or less.

The hydroxyl value of the resin (B) is preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more, still more preferably 30 mgKOH/g or more, still more preferably 35 mgKOH/g or more, and preferably 60 mgKOH/g or less. , more preferably 50 mgKOH/g or less, still more preferably 40 mgKOH/g or less.

The softening point of the resin (B) is preferably 70° C. or higher, more preferably 90° C. or higher, still more preferably 100° C. or higher, still more preferably 110° C. or higher, from the viewpoint of further improving hot offset resistance and durability. From the viewpoint of further improving low-temperature fixability, the temperature is preferably 160° C. or lower, more preferably 150° C. or lower, still more preferably 140° C. or lower, and even more preferably 130° C. or lower.

The glass transition temperature of the resin (B) is preferably 50° C. or higher, more preferably 60° C. or higher, still more preferably 63° C. or higher, and preferably 80° C. or lower, more preferably 75° C. or lower, still more preferably 70°C or less.

The number average molecular weight of the resin (B) is preferably 1,000 or more, more preferably 2,000 or more, still more preferably 3,000 or more, still more preferably 3,500 or more, from the viewpoint of excellent hot offset resistance. and, from the viewpoint of excellent low-temperature fixability, it is preferably 10,000 or less, more preferably 8,000 or less, even more preferably 6,000 or less, still more preferably 4,000 or less.

The acid value, hydroxyl value, softening point, glass transition temperature, and number average molecular weight of the resin (B) are appropriately adjusted depending on the type and amount of raw material monomers used, and production conditions such as reaction temperature, reaction time, and cooling rate. and their values are determined by the method described in Examples.

Resin (B) is obtained, for example, by polycondensation of an alcohol component and a carboxylic acid component. For the polycondensation conditions, for example, the reaction conditions shown in the above-described method for producing the resin (A) can be applied.

When the resin (B) is contained, the mass ratio of the resin (A) to the resin (B) [resin (A)/resin (B)] is preferably 20/80 or more, more preferably 30/70 or more, still more preferably 40/60 or more, still more preferably 50/50 or more, and preferably 90/10 or less, more preferably 80/20 or less be.

When the resin (B) is contained, the content of the resin (B) in the binder resin of the toner is preferably 10% by mass or more, more preferably 10% by mass or more, from the viewpoint of improving low-temperature fixability and hot offset resistance. 20% by mass or more, more preferably 25% by mass or more, and preferably 90% by mass or less, more preferably 70% by mass or less, even more preferably 60% by mass or less, even more preferably 50% by mass or less, still more preferably is 40% by mass or less.

<Wax>
Waxes include, for example, hydrocarbon waxes, ester waxes, silicone waxes, and fatty acid amide waxes.
Hydrocarbon waxes include, for example, mineral or petroleum hydrocarbon waxes such as paraffin wax and Fischer-Tropsch wax; synthetic hydrocarbon waxes such as polyolefin waxes such as polyethylene wax, polypropylene wax and polybutene wax.
Examples of ester waxes include mineral or petroleum ester waxes such as montan wax; vegetable ester waxes such as carnauba wax, rice wax and candelilla wax; and animal ester waxes such as beeswax.
Fatty acid amide waxes include, for example, oleic acid amide and stearic acid amide. These may be used alone or in combination of two or more.
Among these, hydrocarbon waxes or ester waxes are preferred, ester waxes are more preferred, and carnauba waxes are even more preferred.

The melting point of the wax is preferably 60° C. or higher, more preferably 70° C. or higher, and preferably 160° C. or lower, more preferably 150° C. or lower, still more preferably 140° C. or lower.
When two or more waxes are used in combination, the melting point of each wax is preferably within the above range.
The content of the wax is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, still more preferably 5 parts by mass or less, still more preferably 3 parts by mass or less, with respect to 100 parts by mass of the binder resin in the toner. More preferably 1 part by mass or less, more preferably 0.5 parts by mass or less, still more preferably 0.1 parts by mass or less, and preferably 0 or more.

<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 N-01", "Bontron N-04", and "Bontron N-07."","BontronN-09","BontronN-11" (manufactured by Orient Chemical Industry Co., Ltd.), etc.; triphenylmethane dyes containing tertiary amines as side chains, quaternary ammonium salt compounds, such as " Bontron P-51" (manufactured by Orient Chemical Industry Co., Ltd.), cetyltrimethylammonium bromide, "COPY CHARGE PX VP435" (manufactured by Clariant Co., Ltd.), etc.; polyamine resins, such as "AFP-B" (manufactured by Orient Chemical Industry Co., Ltd.) ; imidazole derivatives such as "PLZ-2001" and "PLZ-8001" (manufactured by Shikoku Kasei Co., Ltd.); styrene-acrylic resins such as "FCA-701PT" (manufactured by Fujikura Kasei Co., Ltd.) and the like. be done.

Examples of negatively chargeable charge control agents include metallized azo dyes such as "Barifast Black 3804", "Bontron S-31", "Bontron S-32", "Bontron S-34", and "Bontron S-36" ( (manufactured by Orient Chemical Industry Co., Ltd.), "Eizen Spiron Black TRH", "T-77" (manufactured by Hodogaya Chemical Industry Co., Ltd.), etc.; LR-297" (manufactured by Nippon Carlit Co., Ltd.), etc.; metal compounds of salicylic acid compounds, such as "Bontron E-81", "Bontron E-84", "Bontron E-88", and "Bontron E-304" (manufactured by Orient Chemical Industry Co., Ltd.), "TN-105" (manufactured by Hodogaya Chemical Industry Co., Ltd.), etc.; copper phthalocyanine dye; imidazole derivatives and the like; organometallic compounds and the like;
Among charge control agents, negative charge control agents are preferred, and metal compounds such as benzilic acid compounds are more preferred.

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 preferably 10 parts by mass or less with respect to 100 parts by mass of the binder resin in the toner. , more preferably 5 parts by mass or less, still more preferably 3 parts by mass or less, still more preferably 2 parts by mass or less.

<Colorant>
As the colorant, all dyes, pigments, etc. used as colorants for toners can be used, including carbon black, phthalocyanine blue, permanent brown FG, brilliant first scarlet, pigment green B, rhodamine-B base, Solvent Red 49, Solvent Red 146, Solvent Blue 35, quinacridone, carmine 6B, disazo yellow, etc. can be used, and the toner of the present invention may be either black toner or other color toner.

From the viewpoint of improving the image density of the toner, the content of the colorant is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more with respect to 100 parts by mass of the binder resin. 40 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less.

[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 the pulverized toner by the melt-kneading method, the method for producing the toner preferably comprises: Step 1: Melt-kneading the toner raw material containing the resin (C); It includes a step of classifying to obtain toner particles.
In step 1, for example, raw materials such as resin (C), resin (A), resin (B), wax, charge control agent, colorant, etc. are uniformly mixed with a mixer such as a Henschel mixer, and then a closed kneader, Melt-kneading can be performed using a single-screw or twin-screw extruder, an open-roll type kneader, or the like.
In step 1, preferably, the mixture containing the above toner raw materials may be melt-kneaded at a temperature within the range of 80° C. or higher and 160° C. or lower. The melt-kneading temperature is preferably 90° C. or higher, more preferably 100° C. or higher, and preferably 160° C. or lower, more preferably 150° C. or lower.
In step 1, the melt-kneaded product after melt-kneading may be cooled and subjected to the next step.

Step 2 preferably includes a step of pulverizing and classifying the melt-kneaded product obtained by melt-kneading to obtain toner particles. The pulverization and classification can be performed by known methods.

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 10 μm or less. It is preferably 9 μm or less, more preferably 8 μm or less.

The toner is preferably added to the surface of the toner particles with a fluidizing agent or the like as an external additive.
Examples of external additives include inorganic material fine particles such as hydrophobic silica, titanium oxide, alumina, cerium oxide, and carbon black, and polymer fine particles such as polycarbonate, polymethyl methacrylate, and silicone resin. Among these, hydrophobic silica is preferred.
When an external additive is used, the amount of the external additive added is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and preferably 5 parts by mass with respect to 100 parts by mass of the toner particles. Below, more preferably 4 parts by mass or less, still more preferably 3 parts by mass or less.

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.

EXAMPLES The present invention will be specifically described below with reference to Examples, but the present invention is not limited to these Examples. Physical properties such as resins were measured by the following methods.

[Measuring method]
[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 is applied with a plunger, and the diameter is 1 mm and the length is 1 mm. extruded from the nozzle of Plot the amount of plunger descent of the flow tester against the temperature, and let the softening point be the temperature at which half of the sample flows out.

[Melting point and glass transition temperature of resin]
Using a differential scanning calorimeter "Q100" (manufactured by TA Instruments Japan Co., Ltd.), 0.02 g of the sample was weighed in an aluminum pan, heated to 200 ° C., and cooled from that temperature at a cooling rate of 10 ° C./min. Cool to 0°C. Next, the temperature of the sample is increased at a temperature increase rate of 10° C./min, and the calorie is measured. Among the observed endothermic peaks, the temperature of the peak having the maximum peak area is defined as the maximum endothermic peak temperature. In the case of a crystalline resin, the peak temperature is taken as the melting point.
In the case of an amorphous resin, when a peak is observed, the temperature of the peak is measured. The temperature at the point of intersection with the extended line of the baseline on the low temperature side is defined as the glass transition temperature.

[Acid value and hydroxyl value of resin]
The acid value and hydroxyl value of the resin are measured according to the neutralization titration method described in JIS K 0070:1992.
However, the acid value was measured using chloroform as the measurement solvent. Tetrahydrofuran is used to measure the hydroxyl value.

[Number average molecular weight of resin]
The molecular weight distribution is measured by gel permeation chromatography (GPC) and the number average molecular weight is obtained by the following method.
(1) Preparation of sample solution A sample is dissolved in tetrahydrofuran 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 Toyo Co., Ltd.) with a pore size of 0.2 μm to remove insoluble components to obtain a sample solution.
(2) Molecular weight measurement Using the following measuring apparatus and analytical column, tetrahydrofuran is passed as an eluent at a flow rate of 1 mL per minute, and the column is stabilized in a constant temperature bath at 40°C. 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. The calibration curve at this time includes several kinds of monodisperse polystyrenes "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 ⁴ ), "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-8220GPC" (manufactured by Tosoh Corporation)
Analysis column: "GMHXL + G3000HXL" (manufactured by Tosoh Corporation)

[Average particle size of external additive]
The average particle size refers to the number average particle size, which is the number average value of the particle sizes of 500 particles measured from a scanning electron microscope (SEM) photograph of the external additive. If there is a major axis and a minor axis, the particle size of the particles refers to the major axis.

[Volume Median Particle Diameter of Toner Particles]
The volume-median particle diameter ( _D50 ) of toner particles is measured under the following conditions.
Measuring machine: "Coulter Multisizer II" (manufactured by Beckman Coulter, Inc.)
Aperture diameter: 50 μm
Analysis software: "Coulter Multisizer AccuComp Version 1.19" (manufactured by Beckman Coulter, Inc.)
Electrolyte: "Isoton II" (manufactured by Beckman Coulter, Inc.)
Dispersion liquid: A surfactant "Emulgen 109P" (manufactured by Kao Corporation, polyoxyethylene lauryl ether, HLB (griffin): 13.6) dissolved in an electrolytic solution and adjusted to 5% by mass Dispersion conditions: the dispersion Add 10 mg of the measurement sample to 5 mL of the liquid and disperse it for 1 minute with an ultrasonic disperser, then add 25 mL of the electrolytic solution and further disperse it with an ultrasonic disperser for 1 minute to prepare a sample dispersion. do.
Measurement conditions: To 100 mL of the electrolytic solution, the sample dispersion is added so that the particle size of 30,000 particles can be measured in 20 seconds, 30,000 particles are measured, and the volume is determined from the particle size distribution. Determine the median particle size ( _D50 ).

[Evaluation method]
[Low temperature fixability and hot offset resistance]
A printer "Microline (registered trademark) 5400" (manufactured by Oki Data Co., Ltd.) modified to print an unfixed image was filled with toner, and an unfixed solid image of 2 cm square was printed. Using an external fixing device modified from "OKI MICROLINE 3010" (manufactured by Oki Data Co., Ltd.), the temperature of the fixing roll was increased from 100° C. to 230° C. by 5° C. at a fixing roll rotation speed of 180 mm/sec. Meanwhile, the unfixed image was fixed at each temperature to obtain a fixed image.
Images obtained at each fixing temperature were visually observed to confirm the presence or absence of hot offset. A temperature 5° C. lower than the lowest fixing temperature at which hot offset occurs was used as an index of hot offset resistance. The higher the value, the better the hot offset resistance.
The image obtained at each fixing temperature is rubbed 5 times with a sand eraser "ER-502R" (manufactured by Lion Office Co., Ltd.) with a load of 400g, and the image density before and after rubbing is measured with an image density measuring device "Gretag SPM50". (manufactured by Gretag Macbeth), and the temperature at which the image density ratio before and after rubbing ([image density after rubbing/image density before rubbing]×100) first exceeds 90% is defined as the lowest fixing temperature. It was used as an index of fixability. The smaller the value, the better the low-temperature fixability.

〔durability〕
Modified copy machine "AR-505" (manufactured by Sharp Corporation) (printing speed: 120 ppm, resolution: 600 dpi, development system: 1 magnet roll, organic photoreceptor, reversal development, contact development method, fixing temperature: 170 ° C. ), and a print pattern with a halftone dot area ratio of 20% was continuously printed on 500,000 sheets of cut paper of A4 size (210 mm×297 mm). Note that the same developer as the one initially mounted was used for replenishment of the developer in continuous printing. Durability was measured according to the following method.
In continuous printing, as a result of filming of the toner on the photoreceptor, the number of sheets in which white spots appeared in the printed solid portion was defined as the number of sheets with filming occurrence, and the durability was evaluated.

[Resin production]
Production Example A1 (Resin A-1)
The inside of a four-necked flask with an internal volume of 10 L equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 1413 g of propylene oxide (2.2) adduct of bisphenol A and ethylene oxide of bisphenol A were added. (2.2) 4156 g of the adduct, 2430 g of terephthalic acid, and 40 g of di(2-ethylhexanoic acid)tin (II) are added, heated to 235°C under a nitrogen atmosphere with stirring, and held at 235°C for 6 hours. After that, the pressure in the flask was lowered, and the reaction was carried out to the desired softening point at 8 kPa to obtain an amorphous resin A-1. Physical properties are shown in Table 1.

Production Example A2 (Resin A-2)
The inside of a four-necked flask with an internal volume of 10 L equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 2758 g of 1,2-propanediol, 5242 g of terephthalic acid, and di(2-ethylhexanoic acid) were replaced with nitrogen. ) 40 g of tin (II) was added, and the temperature was gradually increased from 180°C to 220°C over 6 hours while stirring in a nitrogen atmosphere. After that, reaction was carried out at 8.0 kPa to a desired softening point to obtain amorphous resin A-2. Physical properties are shown in Table 1.

Production Example B1 (Resin B-1)
The inside of a four-necked flask with an internal volume of 10 L equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 2890 g of propylene oxide (2.2) adduct of bisphenol A and ethylene oxide of bisphenol A were added. (2.2) 2684 g of the adduct, 1563 g of terephthalic acid, 210 g of dodecenyl succinic anhydride, and 24 g of tin (II) di(2-ethylhexanoate) were added, and the temperature was raised to 235°C under a nitrogen atmosphere while stirring. After holding at 235° C. for 6 hours, the pressure in the flask was lowered and held at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, cool to 220 ° C., add 653 g of trimellitic anhydride, react at 220 ° C. for 0.5 hours, then reduce the pressure in the flask and set the desired softening point at 20 kPa. Amorphous resin B-1 was obtained by reacting up to . Physical properties are shown in Table 1.

Production Example A81 [Resin A-81]
The inside of a four-necked flask with an internal volume of 10 L equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 70 parts by mass (5091 g) of L-lactide and 10 parts by mass (2182 g) of D-lactide were added. , and 10 parts by mass (727 g) of bis(2-hydroxypropyl) terephthalate (BHPT) were added, and the internal temperature was gradually raised to perform dehydration treatment under reduced pressure conditions. Then, the temperature was further raised under N ₂ purging, and after visually confirming that the system was homogenized, 24 g of di(2-ethylhexanoate) tin (II) was introduced into the system to carry out a polymerization reaction. At this time, the internal temperature of the system was controlled so as not to exceed 190°C. After 2 hours of reaction time, the system was switched to the outflow line again, unreacted lactide was removed under reduced pressure conditions, the polymerization reaction was completed, and a resin oligomer was obtained. After that, 100 parts by mass (5882 g) of resin oligomer and 10 parts by mass (588 g) of silicone "X22-160AS" (manufactured by Shin-Etsu Chemical Co., Ltd.) were added to the flask, and the internal temperature was gradually increased. After confirming the homogenization of the system, dehydration treatment was performed under reduced pressure. Next, the temperature was further raised, and 24 g of di(2-ethylhexanoic acid) tin (II) was added to the system at 170°C, and then 9 parts by mass (529 g) of an elongation agent [isophorone diisocyanate (IPDI)] was gradually added to elongate. A reaction was carried out to obtain Resin A-81. Physical properties are shown in Table 1.

Various silicones used in the table are as follows.
X-22-160AS: Polyalkylsiloxane "X-22-160AS" (manufactured by Shin-Etsu Chemical Co., Ltd., silicone having a carbinol group at its end, viscosity (25 ° C.): 35 mm ² / s, functional group equivalent: 470 g / mol)

Production Example C1 (Resin C-1)
The inside of a four-necked flask with an internal volume of 10 L equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 3702 g of 1,10-decanediol, 4298 g of sebacic acid, and silicone "KF-864" ( Shin-Etsu Chemical Co., Ltd.) 362 g was added, and the temperature was raised to 140° C. with stirring under a nitrogen atmosphere, and the temperature was maintained for 1 hour. Thereafter, the temperature was raised at a rate of 10° C./hour, and after reaching 200° C., 24 g of di(2-ethylhexanoate)tin (II) was added and the temperature was maintained for 1 hour. After holding, the pressure in the flask was lowered, and the reaction was carried out at 8 kPa until the desired acid value was reached to obtain a crystalline resin C-1. Physical properties are shown in the table.

Production Examples C2-C3, C11-C13, C81 (Resins C-2-C-3, C-11-C-13, C-81)
Crystalline resins C-2 to C-3, C-11 to C-13, and C-81 were obtained in the same manner as in Production Example C1, except that the raw material composition was changed as shown in the table. Physical properties are shown in the table.

Production Example C4 (Resin C-4)
The inside of a four-necked flask with an internal volume of 10 L equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 3702 g of 1,10-decanediol, 4298 g of sebacic acid, silicone "X-22-162C (manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and the temperature was raised to 140° C. with stirring under a nitrogen atmosphere and maintained for 1 hour. Thereafter, the temperature was raised at a rate of 10° C./hour, and after reaching 200° C., 24 g of di(2-ethylhexanoate)tin (II) was added and the temperature was maintained for 1 hour. After holding, the pressure in the flask was lowered, and the reaction was carried out at 8 kPa until the desired acid value was reached to obtain a crystalline resin C-4. Physical properties are shown in the table.

Production Examples C5 to C10, C82 (Resins C-5 to C-10, C-82)
Crystalline resins C-5 to C-10 and C-82 were obtained in the same manner as in Production Example C4, except that the raw material composition was changed as shown in the table. Physical properties are shown in the table.

Various silicones used in the table are as follows.
KF-864: Modified silicone "KF-864" (manufactured by Shin-Etsu Chemical Co., Ltd., silicone having an amino group in the side chain [silicone (a) described above], viscosity (25 ° C.): 1,700 mm ² / s, functional Base equivalent: 3,800 g / mol)
X-22-162C: Modified silicone oil "X-22-162C" (silicone having carboxy groups at both ends [silicone (b) described above (one end is a group represented by formula (4), the group is a substituent 4-20)], kinematic viscosity (25° C.) 220 mm ² /s, number average molecular weight Mn 2,600, weight average molecular weight Mw 7,800, functional group equivalent 2,300 g/mol, manufactured by Shin-Etsu Chemical Co., Ltd. )
BY16-750: Modified silicone oil "BY16-750" (silicone having carboxy groups at both ends [silicone (b) described above (both ends are groups represented by formula (4), X' is a carboxy group Yes)], kinematic viscosity (25 ° C.) 170 mm ² / s, number average molecular weight Mn 1,400, weight average molecular weight Mw 2,200, functional group equivalent 750 g / mol, Dow Corning Toray Co., Ltd.)
KF-6000: modified silicone oil "KF-6000" (silicone having carbinol groups at both ends [silicone (b) described above (both ends are groups represented by formula (4), and the groups are substituted Group 4-1)], kinematic viscosity (25° C.) 35 mm ² /s, number average molecular weight Mn 1,000, weight average molecular weight Mw 1,400, functional group equivalent 467 g/mol, manufactured by Shin-Etsu Chemical Co., Ltd.)
X-22-173BX: modified silicone oil "X-22-173BX" (silicone having a glycidyl group at one end [silicone (b) described above (only one end is a group represented by formula (4), Substituent 4-10)], kinematic viscosity (25° C.) 30 mm ² /s, number average molecular weight Mn 1,900, weight average molecular weight Mw 3,300, functional group equivalent 2,500 g/mol, Shin-Etsu Chemical Co., Ltd. made)
X-22-3701E: Silicone “X-22-3701E” (manufactured by Shin-Etsu Chemical Co., Ltd., silicone having a carboxyl group in the side chain, viscosity (25° C.): 2,000 mm ² /s, functional group equivalent: 4, 000g/mol)
X-22-163C: Modified silicone oil "X-22-163C" (silicone having glycidyl groups at both ends [silicone (b) described above (both ends are groups represented by formula (4), is a substituent 4-10)], kinematic viscosity (25° C.) 120 mm ² / s, number average molecular weight Mn 2,700, weight average molecular weight Mw 6,800, functional group equivalent 2,700 g / mol, manufactured by Shin-Etsu Chemical Co., Ltd. )
X-22-170BX: modified silicone oil "X-22-170BX" (silicone having a carbinol group at one end [silicone (b) described above (one end is a group represented by formula (4), Substituent 4-1)], kinematic viscosity (25° C.) 40 mm ² /s, number average molecular weight Mn 1,900, weight average molecular weight Mw 3,500, functional group equivalent 20 g/mol, manufactured by Shin-Etsu Chemical Co., Ltd.)
KF96-100cs: silicone oil “KF96-100cs” (silicone oil, kinematic viscosity (25° C.) 100 mm ² /s, manufactured by Shin-Etsu Chemical Co., Ltd.)

[Toner production]
Example 1 [Toner 1]
60 parts by mass of amorphous resin A-1, 30 parts by mass of amorphous resin B-1, 10 parts by mass of crystalline resin C-1,
1 part by mass of a negative charge control agent "LR-147" (manufactured by Nippon Carlit Co., Ltd.) and 1 part by mass of a copper phthalocyanine pigment "ECB-301" (manufactured by Dainichiseika Kogyo Co., Ltd.) were mixed using a Henschel mixer. After mixing for 1 minute, the mixture was melt-kneaded under the following conditions.
The obtained raw material mixture was mixed with a twin-screw kneader “PCM-30” (manufactured by Ikegai Co., Ltd., shaft diameter 29 mm, shaft cross-sectional area 7.06 cm ² ), and a mixture supply rate of 8 kg / h and a barrel setting. Melt-kneading was performed under the conditions of a temperature of 100° C. and a rotation speed of 200 r/min (peripheral speed of 0.30 m/sec).
The resulting melt-kneaded product was subjected to a pulverization classifier "IDS-2/DS2 type" (manufactured by Nippon Pneumatic Industry Co., Ltd.) at a kneaded product supply rate of 2.5 kg / h, an upper damper of 30 °, a CC ring of 30 mm, Pulverization and classification were performed under the conditions of an OE ring of 20 mm, a louver of 1.5 mm, and a collision plate distance of 30 mm to obtain toner particles having a volume median particle diameter (D ₅₀ ) of 7.0 μm.
100 parts by mass of the obtained toner particles, 0.5 parts by mass of hydrophobic silica "R972" (manufactured by Nippon Aerosil Co., Ltd., hydrophobic treatment agent: DMDS, average particle diameter: 16 nm) as an external additive, and hydrophobic silica "RY-50" (manufactured by Nippon Aerosil Co., Ltd., hydrophobic treatment agent: silicone oil, average particle size: 40 nm) 1.0 part by mass of Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) at 3000 r / min (peripheral speed 32 m /sec) for 3 minutes to obtain Toner 1. Table 3 shows the results of various evaluations.

Examples 2-3, Reference Examples 4-6, Examples 7-8, Reference Example 9, Examples 10-14 , Comparative Examples 1-3 [Toners 2-14, 81-83]
Toners 2 to 14 and 81 to 83 were obtained in the same manner as in Example 1, except that the resin was changed as shown in Table 3. Table 3 shows the results of various evaluations.

From the results of Examples , Reference Examples, and Comparative Examples, it can be seen that the present invention can provide a toner excellent in low-temperature fixability, hot offset resistance, and durability.

Claims (6)

A reaction product of an alcohol component containing an α,ω-aliphatic diol having 2 to 14 carbon atoms, a carboxylic acid component containing an aliphatic dicarboxylic acid compound having 4 to 14 carbon atoms, and silicone,
The silicone has the formula (1):

[In the formula, each R is independently a hydrocarbon group having 1 to 5 carbon atoms, each R′ is independently an alkylene group having 1 to 5 carbon atoms, a is 1 , and X is an amino group, a carboxy group, an epoxy group, or a hydroxy group, and * is a binding site. ] and a repeating unit represented by formula (2):

[In the formula, each R is independently a hydrocarbon group having 1 to 5 carbon atoms, and * is a bonding site. ], and both ends of the silicone are represented by the formula (3):

[In the formula, R'' is a hydrocarbon group having 1 or more and 10 or less carbon atoms, and * is a bonding site. ] is a group represented by, or
The silicone has the formula (2):

[In the formula, each R is independently a hydrocarbon group having 1 to 5 carbon atoms, and * is a bonding site. ] has a repeating unit represented by
Formula (4) at one end:

[Wherein, each R''' is independently an alkylene group having 1 to 10 carbon atoms,
X' is a hydroxy group, a hydroxyalkyloxy group, a carboxy group, a carboxyalkyloxy group, a glycidyl group, or a glycidyloxy group;
* is the binding site. ] and the other end is a group represented by formula (3),
A binder resin for toner having a melting point of 50° C. or higher . The silicone has a repeating unit represented by formula (1) and a repeating unit represented by formula (2), both ends are groups represented by formula (3), and X is amino 2. The binder resin for toner according to claim 1, which is a group. The silicone has a repeating unit represented by formula (2), has a group represented by formula (4) at one end, and has a group represented by formula (3) at the other end. 2. The binder resin for toner according to claim 1, wherein X' is at least one selected from a carboxy group, an epoxy group and a carbinol group. 4. The toner according to any one of claims 1 to 3, wherein the mass ratio of the silicone is 0.1% by mass or more and 10% by mass or less with respect to the total amount of the alcohol component, the carboxylic acid component and the silicone. Binder resin for An electrophotographic toner containing the binder resin for toner according to any one of claims 1 to 4. Step 1: a step of melt-kneading a toner raw material containing the binder resin according to any one of claims 1 to 4; and Step 2: a step of pulverizing and classifying the melt-kneaded product obtained in step 1 to obtain toner particles. A method for producing an electrophotographic toner, comprising: