JP2023034242A - Binder resin composition for toner - Google Patents

Abstract

To provide a binder resin composition for a toner which is excellent in low temperature fixability and enables formation of an image of high quality even at the time of high speed printing, and a toner for electrostatic charge image development containing the binder resin composition.SOLUTION: A binder resin composition for a toner contains a crystalline resin (A) and an amorphous resin (B), wherein the crystalline resin (A) is a reactant of an alcohol component containing aliphatic diol, a carboxylic acid component containing an aliphatic dicarboxylic acid compound, and modified silicone, the crystalline resin (A) has a crystalline polyester resin segment and a silicone segment, the modified silicone is modified silicone having at least one functional group selected from an amino group, a carboxy group, an epoxy group and a carbinol group, and an absolute value ΔSP((cal/cm3)1/2)=|SPB-SPA| of a difference between a solubility parameter (SPA((cal/cm3)1/2)) of the crystalline polyester resin segment of the crystalline resin (A) and the solubility parameter (SPB((cal/cm3)1/2)) of the amorphous resin (B) satisfies the following expression: 0≤ΔSP≤1.05.SELECTED DRAWING: None

Description

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

In recent years, there has been a demand for paper resource saving, and opportunities for double-sided printing have increased in electrophotographic printing. High-speed printing can be achieved by adding a crystalline resin to plasticize the toner and improve low-temperature fixability. However, the adverse effect of this is that excessive plasticization of the toner deteriorates the heat-resistant storage stability of the toner, the image storage stability of printed matter, and the hot-offset resistance. .

Patent Document 1 discloses 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, an amino group, and a carboxy group. , an epoxy group, and a carbinol group. By having the above configuration, it is possible to provide a binder resin for toner excellent in low-temperature fixability, hot offset resistance and durability, a toner for developing an electrostatic charge image, and a method for producing a toner for developing an electrostatic charge image. .

Patent Document 2 describes a toner characterized by having a binder resin containing a polyester having a polysiloxane skeleton and toner particles containing a crystalline polyester. According to the toner, excellent low-temperature fixability and image preservability can be obtained.

Japanese Patent Application Laid-Open No. 2020-63348 Japanese Patent Application Laid-Open No. 2021-60582

In the binder resin for toner described in Patent Document 1, the compatibility of the crystalline polyester segment in the toner is low, and phase separation occurs in the toner to form domains, resulting in insufficient low-temperature fixability. rice field. Further, the toner described in Patent Document 2 solves the problem of image preservability in an environment in which the toner is kept warm for a long time after paper discharge, but the image recovery speed during rapid cooling is slow. For this reason, when printing on the opposite side of the printed matter before it is sufficiently cooled during transportation, such as when performing double-sided printing at high speed, the image may be damaged in the process of peeling off the printed matter from the material during transportation, resulting in damage to the image. There was a problem with quality.

TECHNICAL FIELD The present invention relates to a binder resin composition for toner which is excellent in low-temperature fixability and provides high-quality images even during high-speed printing, and a toner for developing electrostatic images containing the binder resin composition.

One embodiment of the present invention relates to the following [1] or [2].
[1] A binder resin composition for toner containing a crystalline resin (A) and an amorphous resin (B),
The crystalline resin (A) is a reaction product of an alcohol component containing an aliphatic diol, a carboxylic acid component containing an aliphatic dicarboxylic acid compound, and a modified silicone,
The crystalline resin (A) has a crystalline polyester resin segment and a silicone segment,
The modified silicone is a modified silicone having at least one functional group selected from an amino group, a carboxy group, an epoxy group, and a carbinol group,
The solubility parameter (SP _A ((cal/cm ³ ) ^1/2 )) of the crystalline polyester resin segment of the crystalline resin (A) and the solubility parameter (SP _B ((cal ΔSP ((cal/cm ³ ) ^1/2 )=│SP _B −SP _A │, which is the absolute value of the difference between the cal/cm ³ ) ^1/2 )), satisfies the following formula (1). Resin composition.
0≦ΔSP≦1.05 (1)
[2] An electrostatic charge image developing toner containing a binder resin and a colorant, wherein the binder resin contains the binder resin composition for toner according to [1]. .

INDUSTRIAL APPLICABILITY According to the present invention, there are provided a binder resin composition for toner that is excellent in low-temperature fixability and can provide high-quality images even during high-speed printing, and a toner for electrostatic charge image development containing the binder resin composition. be.

[Binder resin composition for toner]
A binder resin for toner according to one embodiment of the present invention comprises a crystalline resin (A) and an amorphous resin (B), and the crystalline resin (A) comprises an alcohol component containing an aliphatic diol, an is a reaction product of a carboxylic acid component containing a group dicarboxylic acid compound and a modified silicone, the crystalline resin (A) has a crystalline polyester resin segment and a silicone segment, and the modified silicone contains an amino group, a carboxy is a modified silicone having at least one functional group selected from groups, epoxy groups, and carbinol groups, and the solubility parameter (SP _A ((cal/cm ³ ) ^1/2 )) and the solubility parameter (SP _B ((cal/cm ³ ) ^1/2 )) of the amorphous resin (B), ΔSP ((cal/cm ³ ) ^{1 /2} )=|SP _B −SP _A | satisfies the following formula (1).
0≦ΔSP≦1.05 (1)
According to the binder resin composition for toner having the above structure, the binder resin composition for toner and the binder resin exhibit good both low-temperature fixability and image quality during high-speed continuous printing. An electrostatic charge image developing toner containing the composition can be provided.

Although the reason why such an effect is obtained is not clear, it is considered as follows. By using a crystalline resin (A) and an amorphous resin (B) having a crystalline polyester resin segment having a predetermined ΔSP value relationship and increasing the compatibility, the toner softens at a low temperature. Fixability is improved. Normally, in compatibility control based on the ΔSP value, the toner tends to soften at a low temperature, and the recovery of hardness during cooling slows down, so it is difficult to achieve both of these. However, in the present invention, the crystalline resin (A) is composed of a crystalline polyester resin segment that is highly compatible with the amorphous resin (B) and a silicone segment that is basically incompatible with polyester. ing. The crystalline resin (A), which is a composite, is considered to exist in a microphase-separated state in the toner. As a result, the composite melts when heated above its melting point during fixation, and the crystalline polyester resin segment plasticizes the toner, resulting in excellent low-temperature fixability. In addition, the crystallization of the crystalline polyester resin segment in the microphase separation state makes it possible to crystallize much faster than the conventional design in which the compatible crystalline polyester is segregated and crystallized, It is believed that the recovery of the image strength was rapid even during high-speed printing, and high-quality images were obtained.

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 has a crystallinity index of 0.6 or more and 1.4 or less. Amorphous resins are those in which no endothermic peak is observed or, if observed, the crystallinity index is less than 0.6 or greater than 1.4. 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.
In the specification, the carboxylic acid component of the polyester resin includes not only the compound but also an anhydride that decomposes during the reaction to generate an acid, 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). is also included.
"Volume-median particle size ( _D50 )" is a particle size at which the cumulative volume frequency calculated as a volume fraction is 50%, calculated from the smaller particle size.
"Bisphenol A" is 2,2-bis(4-hydroxyphenyl)propane.

[Crystalline resin (A)]
The crystalline resin (A) (hereinafter also simply referred to as “resin A”) is a reaction product of an alcohol component containing an aliphatic diol, a carboxylic acid component containing an aliphatic dicarboxylic acid compound, and a modified silicone, and is crystallized. It has a flexible polyester resin segment and a silicone segment.

<Alcohol component>
The alcohol component includes an aliphatic diol, and α,ω-aliphatic diol is preferable as the aliphatic diol.
The number of carbon atoms in the 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.
Examples of aliphatic diols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8- α,ω such as octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol -aliphatic diols other than α,ω-aliphatic diols such as 1,2-propanediol, neopentyl glycol and the like.
Among these, α,ω-aliphatic diols are preferred, and ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecane Diols are more preferred, ethylene glycol and 1,6-hexanediol are more preferred, and 1,6-hexanediol is even more preferred.

The amount of the 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 more preferably 100 mol% or less. 100 mol %.

The alcohol component may contain other alcohol components different from the aliphatic diol. Other alcohol components include, for example, alkylene oxide adducts of aromatic diols such as alkylene oxide adducts of bisphenol A; trihydric or higher alcohols such as glycerin, pentaerythritol and trimethylolpropane. One or more of these alcohol components may be used.

<Carboxylic acid component>
It contains an aliphatic dicarboxylic acid compound as a carboxylic acid component. A linear aliphatic dicarboxylic acid compound is preferable as the aliphatic dicarboxylic acid compound.
The number of carbon atoms in the aliphatic dicarboxylic acid compound is preferably 4 or more, and preferably 14 or less, more preferably 12 or less.
Preferred examples of aliphatic dicarboxylic acid compounds include fumaric acid, sebacic acid, dodecanedioic acid, and tetradecanedioic acid. Among these, fumaric acid and dodecanedioic acid are more preferred, and fumaric acid is even 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; and trivalent or higher polyvalent carboxylic acid compounds. 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 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.

<Modified silicone>
The modified silicone used for the crystalline resin (A) contains an amino group, a carbinol group, a carboxyl group, and an epoxy group from the viewpoint of obtaining a toner for electrostatic charge image development with excellent low-temperature fixability and image quality under high-speed printing. A modified silicone having at least one functional group selected from, more preferably an amino group, a carbinol group, and a modified silicone having at least one functional group selected from a carboxy group, still more preferably an amino group is a modified silicone having
The modified silicone may have these functional groups in the side chain, one end, or both ends. Among these, it is preferable to have it on one terminal or on a side chain, and it is more preferable to have it on a side chain. That is, the modified silicone is preferably one-terminal functional group-modified silicone or side chain functional group-modified silicone, more preferably side chain functional group-modified silicone.

More specifically, modified silicone is preferably represented by the following formula (1).

〔式中、Ｒは、それぞれ独立に、炭素数１以上６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１０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、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、エポキシ基、グリシジル基、グリシジルオキシ基、又は脂環式エポキシ基であり、Ｒ”は炭素数１以上１０以下の炭化水素基であり、ｓは０以上３以下の整数であり、ｔは０以上３以下の整数であり、ｍは５以上３００以下の整数であり、ｎは０以上４０以下の整数であり、ただし、ｓ、ｔ、及びｎの少なくともいずれかは１以上である。〕

[In the formula, each R is independently a hydrocarbon group having 1 to 6 carbon atoms, each R' is independently an alkylene group having 1 to 10 carbon atoms, and a is 1 or 0; , X are each independently an amino group, a hydroxy group, a hydroxyalkyloxy group, a carboxy group, a carboxyalkyloxy group, an epoxy group, a glycidyl group, a glycidyloxy group, or an alicyclic epoxy group; s is an integer of 0 or more and 3 or less, t is an integer of 0 or more and 3 or less, m is an integer of 5 or more and 300 or less, and n is 0 or more and 40 or less. an integer, provided that at least one of s, t, and n is 1 or greater.]

In formula (1), the n repeating units and the m repeating units may be random or block, and are not particularly limited.

In formula (1), the number of carbon atoms in the hydrocarbon group of R is 6 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, pentyl group and phenyl group. Among these, a methyl group is preferred.

In formula (1), 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, and preferably 1 or more. is.
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, methanediyl group, ethane-1,2-diyl group, n-propane-1,3-diyl group and n-propane-1,2-diyl group are 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, and still more preferably 1. .
The hydrocarbon group of R″ includes, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, pentyl group and benzyl group.

X is an amino group, hydroxy group, hydroxyalkyloxy group, carboxy group, carboxyalkyloxy group, epoxy group, glycidyl group, glycidyloxy group, or alicyclic epoxy group. A hydroxyalkyloxy group may have multiple hydroxy groups. A carboxyalkyloxy group may have multiple carboxy groups.

s is 3 or less, preferably 2 or less, more preferably 1 or less.
t is 3 or less, preferably 2 or less, more preferably 1 or less.
When the modified silicone is one-terminal functional group-modified silicone, it is preferable that s=1, t=0 and n=0 or s=0, t=1 and n=0.
Moreover, when the modified silicone is both terminal functional group-modified silicone, it is preferable that s=t=1 and n=0.
Furthermore, when the modified silicone is side chain functional group-modified silicone, it is preferable that s=t=0 and n=1.
Among these, as described above, the modified silicone is preferably one-terminal functional group-modified silicone or side chain functional group-modified silicone, more preferably side chain functional group-modified silicone, further preferably n = 1, that is, It is a monofunctional side chain functional group-modified silicone.
m is 300 or less, preferably 200 or less, more preferably 100 or less, still more preferably 50 or less, and 5 or more, preferably 8 or more, more preferably 10 or more.
Moreover, when the modified silicone is a side chain functional group-modified silicone, it is preferable that s=t=0 and n≧1. In this case, n is 40 or less, preferably 20 or less, more preferably 10 or less, still more preferably 5 or less.

The functional group equivalent weight of the modified 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 1,250 g/mol or more, and preferably 10 ,000 g/mol or less, more preferably 8,000 g/mol or less, and still more preferably 6,000 g/mol or less.
In addition, the functional group equivalent means the mass of the modified silicone per 1 mol of the functional group.

The dynamic viscosity of the modified silicone at 25° C. is preferably 10 mm ² /s or more, more preferably 20 mm ² /s or more, still more preferably 30 mm ² /s or more, and preferably 4,000 mm ² /s or less. , more preferably 3,000 mm ² /s or less, and still more preferably 2,000 mm ² /s or less.
The kinematic viscosity of the modified silicone is measured at 25° C. using a fully automatic micro-kinematic viscometer (manufactured by Viscotec Co., Ltd.).

Examples of the above-mentioned modified silicones include modified silicones having an amino group, modified silicones having an amino group in the side chain (commercially available products include, for example, "KF-864" and "KF-865" (Shin-Etsu Chemical Co., Ltd. Co., Ltd.)), modified silicones having amino groups at both ends (commercially available products include, for example, "KF-8012" (manufactured by Shin-Etsu Chemical Co., Ltd.)), and modified silicones having an amino group at one end. be.
Examples of modified silicones having a carboxyl group include modified silicones having a carboxyl group in the side chain (commercially available products include, for example, "X-22-3701E" (manufactured by Shin-Etsu Chemical Co., Ltd.), "BY16-880" (Toray Industries, Inc.). manufactured by Dow Corning)), a modified silicone having a carboxy group at both ends (commercially available, for example, "X-22-162C" (manufactured by Shin-Etsu Chemical Co., Ltd.)), a modified silicone having a carboxy group at one end (Commercially available products include, for example, “X-22-3710” (manufactured by Shin-Etsu Chemical Co., Ltd.)).
Examples of the modified silicone having an epoxy group include modified silicone having an epoxy group in the side chain ("X-22-343" (manufactured by Shin-Etsu Chemical Co., Ltd.) as a commercial product), and modified silicone having an epoxy group at both ends. (Commercially available products are "X-22-163B" and "X-22-169B" (manufactured by Shin-Etsu Chemical Co., Ltd.)), modified silicone having an epoxy group at one end (commercially available products are, for example, "X -22-173BX" (manufactured by Shin-Etsu Chemical Co., Ltd.)).
Examples of modified silicone having a carbinol group (hydroxy group) include modified silicone having a carbinol group in the side chain (commercially available: "X-22-4039" (manufactured by Shin-Etsu Chemical Co., Ltd.)), carbinol group. Modified silicone having at both ends ("KF-6003""KF-6002" (manufactured by Shin-Etsu Chemical Co., Ltd.) as commercially available products), modified silicone having a carbinol group at one end (commercially available as "X-22-170BX" and "X-22-170DX" (manufactured by Shin-Etsu Chemical Co., Ltd.)).

The silicone is preferably a silicone having an amino group from the viewpoint of obtaining an electrostatic charge image developing toner excellent in low-temperature fixability and image quality under high-speed printing. a) (hereinafter also simply referred to as “silicone (a)”), and silicone (a′) having an amino group at one or both ends (hereinafter also simply referred to as “silicone (a′)”). . Among these, silicone (a) having an amino group in its side chain is preferred.
That is, silicone (a) is preferably represented by formula (1a) and silicone (a') is preferably represented by formula (1a').

〔式中、Ｒ、Ｒ’、Ｒ”、ｍ及びｎは、前述の式（１）と同定義であり、好ましい範囲も同様である。〕

[In the formula, R, R′, R″, m and n have the same definitions as in formula (1) above, and the preferred ranges are also the same.]

〔式中、Ｒ、Ｒ’、Ｒ”、ａ、ｍ、ｓ、及びｔは、前述の式（１）と同定義である。〕

[Wherein, R, R′, R″, a, m, s, and t have the same definitions as in formula (1) above.]

In formula (1a'), it is preferred that s=1 and t=0, or s=0 and t=0, or s=t=1.

In formulas (1a) and (1a'), the group represented by *-R'-NH ₂ includes, for example, the following substituents 1a-1 to 1a-3.

The modified silicone used for the crystalline resin (A) is selected from a carboxy group, an epoxy group, and a carbinol group from the viewpoint of obtaining a toner for electrostatic charge image development with excellent low-temperature fixability and image quality under high-speed printing. A silicone (b) having at least one at one end is also preferred.
Silicone (b) is, more specifically, preferably represented by formula (1b).

〔式中、Ｒ、Ｒ’、Ｒ”、ａ、ｍ及びｎは、前述の式（１）と同定義であり、Ｘ’はそれぞれ独立にヒドロキシ基、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、エポキシ基、グリシジル基、グリシジルオキシ基、又は脂環式エポキシ基である。〕

[Wherein, R, R′, R″, a, m and n have the same definitions as in the above formula (1), and X′ each independently represents a hydroxy group, a hydroxyalkyloxy group, a carboxy group, a carboxyalkyl an oxy group, an epoxy group, a glycidyl group, a glycidyloxy group, or an alicyclic epoxy group.]

When X' is a hydroxy group or a hydroxyalkyloxy group, the group represented by *-(R') _a -X' includes, for example, the following substituents 1b-1 to 1b-3. Among these, the substituent 1b-1 or the substituent 1b-2 is preferred, and the substituent 1b-1 is more preferred.

When X' is a glycidyl group, a glycidyloxy group, or an alicyclic epoxy group, the group represented by *-(R') _a -X' is, for example, the following substituents 1b-4 to 1b-6 is mentioned. Among these, substituent 1b-4 is preferred.

When X' is a carboxy group or a carboxyalkyloxy group, examples of the group represented by *-(R') _a -X' include substituents 1b-7 below.

The amount of the modified silicone in the raw material of the resin A is 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component, from the viewpoint of obtaining a toner for electrostatic charge image development excellent in low-temperature fixability and image quality under high-speed printing. Therefore, it is more than 0 parts by mass, preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, still more preferably 3 parts by mass or more, still more preferably 4 parts by mass or more, and preferably 30 parts by mass Below, more preferably 25 parts by mass or less, still more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less.

The above amount is calculated based on the alcohol component, the carboxylic acid component and the modified silicone, and the amount of dehydration due to condensation is not considered.
When the modified silicone has a hydroxyl group or a carboxyl group, it can be understood as an alcohol component or a carboxylic acid component, but when the compound having a hydroxyl group or a carboxyl group contains a silicone skeleton, it is defined as a modified silicone. For example, when calculating the total amount of the alcohol component and the carboxylic acid component, the modified silicone having a hydroxyl group or a carboxy group is not included in the total amount.

(Method for producing crystalline resin (A))
The crystalline resin (A) is produced, for example, by polycondensation of an alcohol component, a carboxylic acid component, and a modified silicone. The alcohol component, the carboxylic acid component, and the modified silicone may be reacted all at once, or the alcohol component and the carboxylic acid component may be reacted and then reacted with the modified silicone, without any particular limitation.
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.
Further, when a monomer having an unsaturated bond such as fumaric acid is used for polycondensation, it is preferably 0.001 part by mass or more with respect to 100 parts by mass as the total amount of the alcohol component and the carboxylic acid component, if necessary. A radical polymerization inhibitor of 0.5 parts by mass or less may be used. Examples of radical polymerization inhibitors include 4-tert-butylcatechol.
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.

(Physical properties of crystalline resin (A))
The softening point of the crystalline resin (A) is preferably 60° C. or higher, more preferably 70° C. or higher, and still more preferably 70° C. or higher, from the viewpoint of obtaining a toner for electrostatic image development having excellent low-temperature fixability and image quality under high-speed printing. is 80° C. or higher, and preferably 150° C. or lower, more preferably 135° C. or lower, and even more preferably 120° C. or lower.
The melting point of the crystalline resin (A) is preferably 50.degree. It is 80° C. or higher, more preferably 85° C. or higher, and preferably 150° C. or lower, more preferably 135° C. or lower, and still more preferably 120° C. or lower.

The solubility parameter (SP _A (cal/cm ³ ) ^1/2 ) of the crystalline polyester resin segment in the crystalline resin (A) determines the electrostatic charge image developing toner excellent in low-temperature fixability and image quality under high-speed printing. From the viewpoint of obtaining, it is preferable to satisfy the following formula (2).
9.8≦SP _A ≦11.2 (2)
SP _A (cal/cm ³ ) ^1/2 is preferably 9.8 (cal/cm ³ ) ^1/2 or more, more preferably 10.0 (cal/cm ³ ) ^1/2 or more, still more preferably 10 .2 (cal/cm ³ ) ^1/2 or more, more preferably 10.4 (cal/cm ³ ) ^1/2 or more, and preferably 11.2 (cal/cm ³ ) ^1/2 or less, It is more preferably 11.0 (cal/cm ³ ) ^1/2 or less, still more preferably 10.8 (cal/cm ³ ) ^1/2 or less.
The solubility parameter of the crystalline polyester resin segment is the solubility parameter according to the Fedors method.

The dissolution endothermic amount (Q _B ) of the crystalline resin (A) is preferably 10 J/g or more, more preferably 10 J/g or more, from the viewpoint of obtaining a toner for electrostatic image development having excellent image quality under low-temperature fixability and high-speed printing. It is 30 J/g or more, more preferably 35 J/g or more, and preferably 200 J/g or less, more preferably 150 J/g or less, still more preferably 120 J/g or less.
The dissolution endotherm (Q _B ) of the crystalline resin (A) is measured by the method described in Examples.

The softening point, melting point, and melting endotherm of the crystalline resin (A), and the solubility parameter of the crystalline polyester resin segment are determined by the type and amount of raw material monomers, and production conditions such as reaction temperature, reaction time, and cooling rate. can be appropriately adjusted by the method described in Examples below. When two or more crystalline resins (A) are used in combination, the softening point, melting point, and melting endotherm of the crystalline resin (A) obtained as a mixture thereof, and the crystalline polyester resin segment It is preferred that the solubility parameters are each within the above ranges.

[Amorphous resin (B)]
The binder resin composition for toner of the present embodiment contains an amorphous resin (B).
The solubility parameter (SP _A ((cal/cm ³ ) ^1/2 )) of the crystalline polyester resin segment of the crystalline resin (A) and the solubility parameter (SP _B ((cal ΔSP ((cal/cm ³ ) ^1/2 )=│SP _B −SP _A │, which is the absolute value of the difference between the cal/cm ³ ) ^1/2 )), satisfies the following formula (1). SP _A and SP _B are solubility parameters according to the Fedors method.
0≦ΔSP≦1.05 (1)
ΔSP is 1.05 or less, preferably 0.90 or less, more preferably 0.75 or less, still more preferably 0.60 or less, still more preferably 0.40 or less, still more preferably 0.25 or less, still more preferably 0.15 or less.
Either of SP _A and SP _B may be larger, but from the viewpoint of molecular design, it is preferable that SP _B >SP _A.

In addition, the solubility parameter (SP _B ((cal/cm ³ ) ^1/2 )) of the amorphous resin (B) provides a toner for electrostatic charge image development with excellent low-temperature fixability and image quality under high-speed printing. ^{From the viewpoint of _ _ 2} or more, and preferably 12.50 (cal/cm ³ ) ^1/2 or less, more preferably 12.00 (cal/cm ³ ) ^1/2 or less, still more preferably 11.50 (cal/cm ³ ) ^1/2 or less.

The amorphous resin (B) (hereinafter also referred to as "resin B") is not particularly limited as long as it is a resin that satisfies the above range of ΔSP. It is preferably a flexible polyester-based resin.
The amorphous polyester-based resin is, for example, an amorphous polyester-based resin containing a polycondensate of an alcohol component and a carboxylic acid component.
Examples of amorphous polyester resins include polyester resins and modified polyester resins. Modified polyester resins include, for example, urethane-modified polyester resins, epoxy-modified polyester resins, and composite resins containing polyester resin segments and addition polymerized resin segments. Among these, addition polymerization of an amorphous polyester resin that is a polycondensate of an alcohol component and a carboxylic acid component, or a polyester resin segment that is a polycondensate of an alcohol component and a carboxylic acid component, and a raw material monomer containing a styrene compound. It is preferably an amorphous composite resin containing an addition polymerized resin segment that is a substance.

<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 in the alcohol component.
Dihydric or higher alcohols include, for example, alkylene oxide adducts of aromatic diols, linear or branched aliphatic diols, alicyclic diols, and trihydric or higher polyhydric alcohols. Among these, alkylene oxide adducts of aromatic diols or linear or branched aliphatic diols are preferred, and alkylene oxide adducts of aromatic diols are more preferred.

The alkylene oxide adduct of an aromatic diol is preferably an alkylene oxide adduct of bisphenol A, more preferably of formula (I):

（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はアルキレンオキシ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のアルキレンオキシド付加物である。
ビスフェノールＡのアルキレンオキシド付加物としては、例えば、ビスフェノールＡのプロピレンオキシド付加物、ビスフェノールＡのエチレンオキシド付加物が挙げられる。これらの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のプロピレンオキシド付加物、及びビスフェノールＡのプロピレンオキシド付加物とビスフェノールＡのエチレンオキシド付加物との組合せが好ましい。
ビスフェノールＡのアルキレンオキシド付加物を含む場合、その量は、アルコール成分中、好ましくは７０ｍｏｌ％以上、より好ましくは９０ｍｏｌ％以上、更に好ましくは９５ｍｏｌ％以上であり、そして、１００ｍｏｌ％以下であり、更に好ましくは１００ｍｏｌ％である。

(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 moles of alkylene oxide added, 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. You may use these 1 type(s) or 2 or more types. Among these, the propylene oxide adduct of bisphenol A and the combination of the propylene oxide adduct of bisphenol A and the ethylene oxide adduct of bisphenol A are preferred.
When an alkylene oxide adduct of bisphenol A is included, its amount 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.
When an aliphatic diol having a hydroxyl group bonded to a secondary carbon atom is used as the alcohol component, the amount thereof in the alcohol component is preferably 70 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more. and is 100 mol % or less, more preferably 100 mol %.

Other linear or branched aliphatic diols include, for example, ethylene glycol, 1,3-propanediol, 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 addition 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 carboxylic acid compound having a valence of 2 or more, and examples thereof include dicarboxylic acids and polycarboxylic acids having a valence of 3 or more.
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 100% by mass or less in the carboxylic acid component. .
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 acid compounds 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 compound is preferably 30 mol % or more, more preferably 40 mol % or more, still more preferably 50 mol % or more, and 100 mol % or less in the carboxylic acid component.

The number of carbon atoms in the linear or branched aliphatic dicarboxylic acid compound 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 or less.
Linear or branched aliphatic dicarboxylic acid compounds 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, tetradecane Examples include diacids, succinic acids substituted with aliphatic hydrocarbon groups having 1 to 20 carbon atoms, or their anhydrides 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.
When a linear or branched aliphatic dicarboxylic acid compound is included, the amount thereof in the carboxylic acid component is preferably 2 mol% or more, more preferably 5 mol% or more, still more preferably 10 mol% or more, and preferably 30 mol%. % or less, more preferably 20 mol % or less.

The trivalent or higher polyvalent carboxylic acid compound 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 polyvalent carboxylic acid compound is included, the amount of the trivalent or higher polyvalent carboxylic acid compound is preferably 1 mol% or more, more preferably 3 mol% or more, and still more preferably 5 mol% or more in the carboxylic acid component. and is preferably 35 mol % or less, more preferably 25 mol % or less, and still more preferably 20 mol % or less.
One or more of these carboxylic acid compounds may be used.

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

When the amorphous resin (B) has an addition polymerized resin segment, the addition polymerized segment is, for example, an addition polymer of a raw material monomer containing a styrene compound.
Styrenic compounds include, for example, unsubstituted or substituted styrene. Examples of the substituent with which styrene is substituted include an alkyl group having 1 to 5 carbon atoms, a halogen atom, an alkoxy group having 1 to 5 carbon atoms, a sulfonic acid group, or a salt thereof.
Styrenic compounds include, for example, styrene, methylstyrene, α-methylstyrene, β-methylstyrene, tert-butylstyrene, chlorostyrene, chloromethylstyrene, methoxystyrene, styrenesulfonic acid and salts thereof. Among these, styrene is preferred.
The content of the styrenic compound in the raw material monomers of the addition polymerized resin segment is preferably 50% by mass or more, more preferably 65% by mass or more, still more preferably 75% by mass or more, and 100% by mass or less. , preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less.

Examples of raw material monomers other than styrene compounds include (meth)acrylic acid esters such as alkyl (meth)acrylate, benzyl (meth)acrylate, and dimethylaminoethyl (meth)acrylate; olefins; halovinyls such as vinyl chloride; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as methyl vinyl ether; vinylidene halides such as vinylidene chloride; . Among these, (meth)acrylic acid esters are preferred, and alkyl (meth)acrylates are more preferred.
The number of carbon atoms in the alkyl group in the alkyl (meth)acrylate is preferably 1 or more, more preferably 4 or more, still more preferably 6 or more, and is preferably 24 or less, more preferably 22 or less, and still more preferably 20. It is below.
Examples of alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, (iso)propyl (meth)acrylate, (iso- or tertiary) butyl (meth)acrylate, (meth)acrylate, ) (iso)amyl acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (iso)octyl (meth)acrylate, (iso)decyl (meth)acrylate, (meth)acrylic acid ( iso) dodecyl, (iso) palmityl (meth) acrylate, (iso) stearyl (meth) acrylate, (iso) behenyl (meth) acrylate and the like, preferably 2-ethylhexyl (meth) acrylate or ( Meth)stearyl acrylate, more preferably 2-ethylhexyl acrylate, stearyl methacrylate, and still more preferably 2-ethylhexyl acrylate.
In addition, "(iso or tertiary)" and "(iso)" mean both when these prefixes exist and when they do not exist, and when these prefixes do not exist, normal is indicated. Moreover, "(meth)acrylic acid" indicates acrylic acid or methacrylic acid.

The (meth)acrylic acid ester content in the raw material monomers of the addition polymerized resin segment is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and preferably 50% by mass or more. % by mass or less, more preferably 35% by mass or less, and even more preferably 25% by mass or less.
The total amount of the styrenic compound and the (meth)acrylic acid ester in the raw material monomers of the addition polymerized resin segment is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and even more preferably. is 100% by mass.

Resin B preferably has structural units derived from bi-reactive monomers that are covalently bonded to polyester resin segments and addition polymerized resin segments.
The “structural unit derived from a bireactive monomer” means a unit obtained by reacting a functional group and an addition polymerizable group of a bireactive monomer.
Examples of addition polymerizable groups include carbon-carbon unsaturated bonds (ethylenically unsaturated bonds).
The bi-reactive monomers include, for example, addition polymerizable monomers having at least one functional group selected from a hydroxyl group, a carboxyl group, an epoxy group, a primary amino group and a secondary amino group in the molecule. . Among these, addition polymerizable monomers having at least one functional group selected from a hydroxyl group and a carboxy group are preferred, and addition polymerizable monomers having a carboxy group are more preferred, from the viewpoint of reactivity.
Addition-polymerizable monomers having a carboxy group include, for example, acrylic acid, methacrylic acid, fumaric acid, and maleic acid. Among these, acrylic acid and methacrylic acid are preferred, and acrylic acid is more preferred, from the viewpoint of reactivity in both polycondensation reaction and addition polymerization reaction.
When the bireactive monomer is an addition-polymerizable monomer having a carboxy group, the amount of the structural unit derived from the bireactive monomer is preferably 1 mol part or more per 100 mol parts of the alcohol component of the polyester resin segment of resin B, It is more preferably 2 mol parts or more, still more preferably 3 mol parts or more, and preferably 30 mol parts or less, more preferably 20 mol parts or less, still more preferably 10 mol parts or less.

When the resin B is a composite resin, the content of the polyester resin segment in the composite resin is preferably 35% by mass or more, more preferably 50% by mass or more, based on the total amount of the polyester resin segment and the addition polymerized resin segment. , more preferably 70% by mass or more, and preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less. In addition, the structural unit derived from the bi-reactive monomer is included in the polyester resin segment in the calculation.

When the resin B is a composite resin, the content of the addition polymerized resin segment in the composite resin is preferably 5% by mass or more, more preferably 10% by mass, based on the total amount of the polyester resin segment and the addition polymerized resin segment. Above, more preferably 15% by mass or more, preferably 65% by mass or less, more preferably 50% by mass or less, and even more preferably 30% by mass or less. In addition, the structural unit derived from the bi-reactive monomer is included in the polyester resin segment in the calculation.

The above amount is calculated based on the ratio of the amounts of the polyester resin segment, the raw material monomer of the addition polymerization resin segment, the bi-reactive monomer, and the radical polymerization initiator, and the mass excluding the dehydration amount due to polycondensation in the polyester resin segment Standard. When a radical polymerization initiator is used, the mass of the radical polymerization initiator is included in the addition polymerization resin segment in the calculation.

The amorphous resin (B) may be produced, for example, in step A of polycondensing an alcohol component and a carboxylic acid component. It may be produced by a method including A and a step B of addition-polymerizing the raw material monomer of the addition-polymerized resin segment and the bi-reactive monomer.
Process B may be performed after process A, process A may be performed after process B, or process A and process B may be performed simultaneously.
In step A, a part of the carboxylic acid component is subjected to a polycondensation reaction, and then step B is carried out. A method of further advancing the polycondensation reaction with the carboxy group of the constituent site derived from the reactive monomer is preferred.

In step A, if necessary, an esterification catalyst such as di(2-ethylhexanoic acid) tin (II), dibutyltin oxide, titanium diisopropoxybis(triethanolamine) is added to the alcohol component and the carboxylic acid component. 0.01 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the total amount of; Polycondensation may be carried out using 0.001 parts by mass or more and 0.5 parts by mass or less per 100 parts by mass of the total amount.
Further, when a monomer having an unsaturated bond such as fumaric acid is used for polycondensation, it is preferably 0.001 part by mass or more with respect to 100 parts by mass as the total amount of the alcohol component and the carboxylic acid component, if necessary. A radical polymerization inhibitor of 0.5 parts by mass or less 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 250° C. or lower, more preferably 240° C. or lower. In addition, you may perform polycondensation in an inert gas atmosphere.

Examples of the radical polymerization initiator for addition polymerization in step B include peroxides such as dibutyl peroxide, persulfates such as sodium persulfate, and 2,2′-azobis(2,4-dimethylvaleronitrile) such as azo compounds.
The amount of the radical polymerization initiator to be used is preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the raw material monomer for the addition polymerization resin segment.
The addition polymerization temperature is preferably 110° C. or higher, more preferably 130° C. or higher, and preferably 230° C. or lower, more preferably 220° C. or lower, still more preferably 210° C. or lower.

(Physical properties of resin B)
The softening point of Resin B is preferably 70° C. or higher, more preferably 90° C. or higher, and still more preferably 100° C. or higher, and from the viewpoint of further improving low-temperature fixability, it is preferably 160° C. or lower, more preferably 160° C. or lower. It is 150° C. or less, more preferably 145° C. or less.
The glass transition temperature of Resin B is preferably 40° C. or higher, more preferably 50° C. or higher, and still more preferably 55° C. or higher. is 70° C. or lower, more preferably 65° C. or lower.

Resin B is an amorphous resin BL having a low softening point and a temperature of 5° C. or higher than the amorphous resin BL, from the viewpoint of obtaining a toner for electrostatic image development having excellent low-temperature fixability and image quality under high-speed printing. It is preferable to use together an amorphous resin BH having a high softening point.
The difference in softening point between the amorphous resin BL and the amorphous resin BH is preferably 10° C. or more, more It is preferably 20° C. or higher, more preferably 30° C. or higher, and preferably 80° C. or lower, more preferably 60° C. or lower, and still more preferably 50° C. or lower.
When the amorphous resin BL and the amorphous resin BH are used together, the mass ratio BL/BH of the amorphous resin BL and the amorphous resin BH is excellent in low-temperature fixability and image quality under high-speed printing. From the viewpoint of obtaining a toner for electrostatic charge image development, it is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.4 or more, and preferably 10 or less, more preferably 5 or less, and furthermore It is preferably 2.5 or less, more preferably 1 or less.

The softening point, glass transition temperature, and solubility parameters of Resin B 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. , is determined by the method described in the Examples.
When two or more resins B are used in combination, the softening point, glass transition temperature and solubility parameter values obtained as a mixture thereof are preferably within the ranges described above.

In the binder resin composition of the present embodiment, the mass ratio of the crystalline resin (A) to the amorphous resin (B) (crystalline resin (A)/amorphous resin (B)) , and preferably 1/99 or more, more preferably 3/97 or more, still more preferably 5/95 or more, still more preferably 8/92, from the viewpoint of obtaining a toner for developing an electrostatic charge image excellent in image quality under high-speed printing. and preferably 50/50 or less, more preferably 30/70 or less, even more preferably 20/80 or less, and even more preferably 15/85 or less.

[Electrostatic charge image developing toner]
The electrostatic image developing toner of the present invention (hereinafter also simply referred to as "toner") is an electrostatic image developing toner containing a binder resin and a colorant, wherein the binder resin is the above-described toner of the present embodiment. It contains a binder resin composition for toner.
According to the present invention, it is possible to provide a toner for electrostatic image development that is excellent in low-temperature fixability and image quality under high-speed printing.
The electrostatic charge image developing toner contains at least a binder resin and a colorant, and may contain other components such as a release agent and a charge control agent. Further, the toner for developing an electrostatic charge image preferably contains toner base particles and an external additive externally added to the toner base particles (hereinafter also referred to as "toner particles").

<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 0.3 parts by mass or more, more preferably 1 part by mass or more with respect to 100 parts by mass of the total amount of the binder resin, and It is preferably 20 parts by mass or less, more preferably 10 parts by mass or less.
In addition, from the viewpoint of improving the image density of the toner, the content of the colorant is preferably 0.3% by mass or more, more preferably 1% by mass or more, and preferably 20% by mass with respect to the toner particles. % or less, more preferably 10 mass % or less.

<Release agent>
Examples of release agents include hydrocarbon waxes, ester waxes, silicone waxes, and fatty acid amide waxes.

The melting point of the releasing agent is preferably 60° C. or higher, more preferably 70° C. or higher, and preferably 160° C. or lower, more preferably 150° C. or lower, and still more preferably 140° C. or lower.
When two or more release agents are used in combination, the melting point of each release agent is preferably within the above range.
In the present invention, since the silicone segment of the crystalline resin (A) contributes to releasability, the toner may not contain a release agent.
The content of the release agent is preferably 1 part by mass or less, more preferably 0.5 parts by mass or less, and still more preferably 0.1 part by mass or less with respect to 100 parts by mass as the total amount of the binder resin, and , preferably 0 parts by mass 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." ”, “Bontron N-09”, “Bontron N-11”, “Bontron N-79” (manufactured by Orient Chemical Industry Co., Ltd.), etc.; ammonium salt compounds such as "Bontron P-51" (manufactured by Orient Chemical Industry Co., Ltd.), cetyltrimethylammonium bromide, "COPY CHARGE PX VP435" (manufactured by Clariant), etc.; polyamine resins such as "AFP-B" (Orient Kagaku Kogyo Co., Ltd.), etc.; imidazole derivatives, such as “PLZ-2001” and “PLZ-8001” (manufactured by Shikoku Kasei Kogyo Co., Ltd.), etc.; styrene-acrylic resins, such as “FCA-701PT” (Fujikura Kasei Co., Ltd.) and the like.

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;
The charge control agent to be used may be appropriately selected according to the characteristics of the printer using the toner, the type of colorant, and the like.

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, still more preferably 1 part by mass or more, relative to 100 parts by mass of the total amount of the binder resin, 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.

[Toner manufacturing method]
The toner may be a toner obtained by any known method such as a melt-kneading method, an emulsion phase inversion method, a polymerization method, or an emulsion aggregation method. is preferred.
In the case of the pulverized toner by the melt-kneading method, raw materials such as a crystalline resin (A), an amorphous resin (B), a colorant, and a charge control agent are uniformly mixed with a mixer such as a Henschel mixer, and then It can be produced by melt-kneading with a closed-type kneader, single-screw or twin-screw extruder, open-roll type kneader, or the like, followed by cooling, pulverization, and classification.
The method for producing the toner preferably includes a step of melt-kneading a mixture containing the crystalline resin (A), the amorphous resin (B) and the like at a temperature in the range of 80°C or higher and 200°C or lower. The melt-kneading temperature is preferably 80° C. or higher, more preferably 90° C. or higher, and preferably 200° C. or lower, more preferably 180° C. or lower.
The method for producing the toner preferably includes a step of pulverizing and classifying the mixture obtained by melt-kneading to obtain toner particles. The pulverization and classification can be performed by known methods.

The volume-median particle size (D ₅₀ ) of the toner particles is preferably 2 μm or more, more preferably 3 μm or more, and further preferably 3 μm or more, from the viewpoint of obtaining a toner for electrostatic charge image development with excellent low-temperature fixability and image quality under high-speed printing. The thickness is preferably 4 μm or more, and from the viewpoint of hot offset resistance, it is 8 μm or less, preferably 7 μm or less, and more preferably 6.8 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 fine particles, alumina fine particles, cerium oxide fine particles, 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, preferably 5 parts by mass or less, and more preferably 4 parts by mass, with respect to 100 parts by mass of the toner particles. 3 parts by mass or less, more preferably 3 parts by mass or less.

The storage elastic modulus G′ (Pa) at 120° C. when the temperature of the toner is raised at 5° C./min is preferable from the viewpoint of obtaining a toner for electrostatic charge image development excellent in image quality under low-temperature fixability and high-speed printing. is 5.0×10 ³ Pa or more, more preferably 7.0×10 ³ Pa or more, still more preferably 8.0×10 ³ or more, still more preferably 8.3×10 ³ or more, and preferably It is 2.0×10 ⁴ or less, more preferably 1.5×10 ⁴ or less, still more preferably 1.2×10 ⁴ or less.
In addition, the storage elastic modulus G′ (Pa) at 80° C. when the toner is rapidly cooled at 20° C./min after being heated to 200° C. is an electrostatic image developing toner having excellent low-temperature fixability and image quality under high-speed printing. From the viewpoint of obtaining a toner, the pressure is preferably 4.0×10 ⁵ Pa or more, more preferably 4.5×10 ⁵ Pa or more, still more preferably 4.8×10 ⁵ Pa or more, and 10×10 ⁵ Pa or more. Below, more preferably 9.0×10 ⁵ Pa or less, still more preferably 8.0×10 ⁵ Pa or less.
The storage modulus G' is measured by the method described in Examples.

The crystal recovery rate (%) of the crystalline resin in the toner is preferably 5% or more, more preferably 10%, from the viewpoint of obtaining a toner for electrostatic charge image development with excellent low-temperature fixability and image quality under high-speed printing. As mentioned above, it is more preferably 15% or more, and although the upper limit is not particularly limited, it is preferably 80% or less, more preferably 70% or less from the viewpoint of ease of production.
The crystal recovery rate (%) represents the extent to which the crystalline resin expresses the crystallization ability in the toner, and is the endothermic peak area derived from the crystalline resin observed in the measurement of the dissolution endotherm of the toner. is the dissolution endothermic quantity Q _A (J/g), and the endothermic peak area of the crystalline resin (A) before being formed into a toner is the dissolution endothermic quantity Q _B (J/g).
Crystal recovery rate (%) = (Q _A /Q _B ) x 100
Specifically, it is measured and calculated by the method described in Examples.

Toners are used, for example, 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.
In the descriptions such as "alkylene oxide (X)", the numerical value X in parentheses means the average number of added moles of the alkylene oxide.

[Measuring method]
[Kinematic viscosity of modified silicone]
The catalog value of each product was adopted as the kinematic viscosity of the modified silicone.

[Functional group equivalent of modified silicone]
The catalog value of each product was adopted for the functional group equivalent of the modified silicone.

[Resin softening point, crystallinity index, melting point and glass transition temperature]
(1) 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 It was extruded through a 1 mm, 1 mm long nozzle. 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.
(2) Crystallinity index Using a differential scanning calorimeter "Q100" (manufactured by TA Instrument Japan Co., Ltd.), 0.02 g of the sample was weighed into an aluminum pan and cooled to 0 ° C. at a cooling rate of 10 ° C./min. bottom. Next, the sample was allowed to stand still for 1 minute, then heated to 180°C at a heating rate of 10°C/min, and the calorific value was measured. Among the observed endothermic peaks, the temperature of the peak with the maximum peak area is defined as the maximum endothermic peak temperature (1), and (softening point (°C)) / (maximum endothermic peak temperature (1) (°C)) A crystallinity index was determined.
(3) Melting point and glass transition temperature 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 the temperature It was cooled to 0°C at a cooling rate of 10°C/min. Then, the temperature of the sample was increased at a temperature increase rate of 10°C/min, and the calorie was measured. Among the observed endothermic peaks, the temperature of the peak with the maximum peak area was defined as the maximum endothermic peak temperature (2). In the case of a crystalline resin, the peak temperature was 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 was defined as the glass transition temperature.

[Dissolution endotherm]
Using a differential scanning calorimeter "Q-100" (manufactured by TA Instruments Japan Co., Ltd.), each sample was heated from room temperature (20 ° C.) to 180 ° C. at a heating rate of 10 ° C./min, and observed. The endothermic peak area derived from the crystalline resin (A) was defined as the dissolution endotherm. Table 1 shows the amount of heat absorbed by dissolution of the resin before being formed into a toner as the amount of heat absorbed by dissolution Q _B (J/g).

[Toner storage elastic modulus (G′)]
Using a viscoelasticity measuring device (rheometer) "MCR-302" (manufactured by Anton Paar), the measurement was performed at a shear strain of 0.05% and a frequency of 1 Hz.
A parallel plate with a diameter of 25 mm is heated to 100 ° C. and left to stand, and a pellet with a diameter of 20 mm and a thickness of 5 mm obtained by pressing 2.0 g of the sample at 30 MPa is placed on the parallel plate at 100 ° C. and lifted with a parallel plate of 8 mm. After sandwiching from , the temperature was lowered to 40°C and then raised to 200°C at a rate of 5°C/min to determine the storage modulus [G' (T = 120°C)] at 120°C. Further, the temperature was lowered from 200°C to 40°C at a rate of 20°C/min, and the storage elastic modulus [G' (T = 80°C)] at 80°C was determined.

[Crystal recovery rate (%) of crystalline resin in toner]
The crystal recovery rate (%) of the crystalline resin in the toner was defined by the following method as to how much the crystalline resin in the toner expresses its inherent crystallization ability.
Each toner was measured according to the above-described method for measuring the endothermic amount of dissolution, and the observed endothermic peak area derived from the crystalline resin was taken as the endothermic amount of dissolution Q _A (J/g). The dissolution endotherm _QA was obtained by dividing by the amount of the crystalline resin (A) in the toner. On the other hand, the temperature of the crystalline resin (A) before toner production was also raised under the same conditions, and the observed endothermic peak area derived from the crystalline resin (A) was defined as the dissolution endothermic amount _QB . The crystal recoverability was defined by the following formula using the dissolution endotherm _QA and the dissolution endotherm _QB .
Crystal recovery rate (%) = (Q _A /Q _B ) x 100
The crystal recovery rate is represented by a numerical value of 100 to 0, and a larger numerical value indicates that the crystallization of the crystalline polyester resin in the toner is accelerated. Table 3 shows the results.

Test Example 1 [low-temperature fixability]
A printer "HL-2040" (manufactured by Brother Industries, 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 rotation speed of the fixing roll of 100 mm/sec. Meanwhile, the unfixed image was fixed at each temperature to obtain a fixed image. After attaching a mending tape (manufactured by Sumitomo 3M Co., Ltd.) to the image obtained at each fixing temperature, the tape was sufficiently attached to the fixed image by placing a 500 g cylindrical weight on the tape. After that, the mending tape was slowly peeled off from the fixed image. The image density before and after peeling was measured using an image density measuring device "GRETAG SPM50" (manufactured by GRETAG), and the image density ratio before and after rubbing ([image density after rubbing/image density before rubbing] x 100) was the first. A temperature exceeding 90% was defined as the minimum fixing temperature, and was used as an index of low-temperature fixability. The smaller the value, the better the low-temperature fixability.

Test Example 2 [Image quality in high-speed printing]
The printer, the external fixing device, and the unfixed image were used in the same manner as in Test Example 1, except that the printing speed was set to 200 mm/sec. rice field. The quality of the obtained fixed image was evaluated according to the criteria shown below.
Evaluation A: No visible scratches or streaks are observed on the fixed image.
Evaluation B: Scratches and defects are observed only at the edges of the fixed image.
Evaluation C: Visually visible scratches and streaks are observed on the fixed image.

[Resin production]
Production Example 1 (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 4,790 g of 1,6-hexanediol, 4,710 g of fumaric acid, and silicone "X -22-170BX" (manufactured by Shin-Etsu Chemical Co., Ltd.) 425 g and a polymerization inhibitor (tertiary butyl catechol) 5 g were 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./h, and after reaching 200° C., 28 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 softening point was reached to obtain a crystalline resin A-1. Physical properties are shown in Table 1.

Production Examples 2 to 7, Comparative Production Examples 1 and 2 (Resins A-2 to A-7, A-9, A-10)
Crystalline resins A-2 to A-7, A-9, and A-10 were obtained in the same manner as in Production Example 1, except that the raw material composition was changed as shown in the table. Physical properties are shown in Table 1.

Production Example 8 (Resin A-8)
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 2,190 g of ethylene glycol, 7,310 g of dodecanedioic acid, and silicone "KF-864" were added. (manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and the temperature was raised to 140° C. with stirring under a nitrogen atmosphere and held for 1 hour. Thereafter, the temperature was raised at a rate of 10° C./h, and after reaching 200° C., 28 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 softening point was reached to obtain a crystalline resin A-8. Physical properties are shown in Table 1.

The modified silicone and unmodified silicone used in Production Examples 1 to 8 and Comparative Production Example 2 are as follows.
・X-22-170BX: Modified silicone oil “X-22-170BX” (silicone having a carbinol group (hydroxy group) at one end, kinematic viscosity (25° C.) = 40 mm ² /s, functional group equivalent weight 2,800 g / mol, manufactured by Shin-Etsu Chemical Co., Ltd.)
・X-22-170DX: Modified silicone oil “X-22-170DX” (silicone having a carbinol group (hydroxy group) at one end, kinematic viscosity (25° C.) = 65 mm ² /s, functional group equivalent weight 4,670 g / mol, manufactured by Shin-Etsu Chemical Co., Ltd.)
・KF-865: Modified silicone oil “KF-865” (silicone having a monoamino group in its side chain, kinematic viscosity (25°C) = 110 mm ² /s, functional group equivalent = 5,000 g/mol, Shin-Etsu Chemical Co., Ltd. made)
・KF-8012: Modified silicone oil “KF-8012” (silicone having amino groups at both ends, kinematic viscosity (25°C) = 90 mm ² /s, functional group equivalent = 2,200 g/mol, Shin-Etsu Chemical Co., Ltd. made)
・X-22-3710: Modified silicone oil “X-22-3710” (silicone having a carboxyl group at one end on average, kinematic viscosity (25°C) = 60 mm ² /s, functional group equivalent weight 1,450 g/mol , manufactured by Shin-Etsu Chemical Co., Ltd.)
・KF-864: modified silicone “KF-864” (silicone having a monoamino group in the side chain, kinematic viscosity (25 ° C.) = 1,700 mm ² / s, functional group equivalent = 3,800 g / mol, Shin-Etsu Chemical Co., Ltd. manufactured by the company)
・ KF96-50cs: Unmodified silicone oil “KF96-50cs” (silicone oil (dimethyl silicone oil), kinematic viscosity (25° C.) 50 mm ² / s, manufactured by Shin-Etsu Chemical Co., Ltd.)

Production Example 9 (Resin B-1)
The inside of a 10 L four-necked flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 7,250 g of the propylene oxide (2.2) adduct of bisphenol A and 2 of terephthalic acid were added. , 750 g, and 50 g of di(2-ethylhexanoic acid) tin (II) are added, heated to 235° C. while stirring under a nitrogen atmosphere, maintained at 235° C. for 6 hours, and then the pressure in the flask is reduced. Amorphous resin B-1 was obtained by carrying out the reaction to the desired softening point at 8 kPa. Physical properties are shown in Table 2.

Production Example 10 (Resin B-2)
The interior 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 raw material monomers and esterification of polyester resins other than trimellitic anhydride shown in Table 2 were performed. A catalyst was added, and the temperature was raised to 160° C. under a nitrogen atmosphere while stirring, and a mixed solution of a raw material monomer for an addition polymerization resin, a bireactive monomer, and a radical polymerization initiator shown in Table 2 was added dropwise over 1 hour. . After that, the temperature was maintained at 160° C. for 30 minutes for addition polymerization, then the temperature was raised to 200° C. over 1 hour, and the reaction was further carried out under a reduced pressure of 8 kPa for 1 hour. After that, the temperature was raised to 235° C. over 30 minutes, and after polycondensation at 235° C. for 5 hours, the reaction was carried out under a reduced pressure of 8 kPa for 1 hour. After that, the mixture was cooled to 220° C., trimellitic anhydride shown in Table 2 was added and allowed to react for 1 hour, and then a crosslinking reaction was performed at 8 kPa until a predetermined softening point was reached to obtain amorphous resin B-2. rice field. Physical properties are shown in Table 2.

Production Example 11 (Resin B-3)
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 4,860 g of propylene oxide (2.2) adduct of bisphenol A and 4,860 g of bisphenol A were added. Add 1,935 g of ethylene oxide (2.2) adduct, 1,515 g of terephthalic acid, 1,120 g of dodecenyl succinic anhydride (DDSA-C), and 50 g of di(2-ethylhexanoic acid) tin (II), and place in a nitrogen atmosphere. , while stirring, the temperature was raised to 235° C., and 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 570 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. to obtain an amorphous resin B-3. Physical properties are shown in Table 2.

Comparative Production Examples 3 and 4 (Resins B-4 and B-5)
Amorphous resins B-4 and B-5 were obtained in the same manner as in Production Example 9, except that the raw material compositions were changed as shown in Table 2. Physical properties are shown in Table 2.
KF-6000 used in Comparative Production Example 3 is as follows.
・KF-6000: Modified silicone oil “KF-6000” (silicone having carbinol groups (hydroxy groups) at both ends, kinematic viscosity (25 ° C.) = 35 mm ² / s, functional group equivalent weight 470 g / mol, Shin-Etsu Chemical Co., Ltd. Co., Ltd.)

Comparative Production Example 5 (Resin B-6)
An amorphous resin B-6 was obtained in the same manner as in Production Example 11, except that the raw material composition was changed as shown in Table 2. Physical properties are shown in Table 2.

Examples 1-8 and Comparative Examples 1-3
100 parts by mass of the binder resin shown in Table 3, 2.0 parts by mass of the positive charge control agent "Bontron N-79" (manufactured by Orient Chemical Industry Co., Ltd.), and the colorant "Regal 330R" (manufactured by Cabot Corporation, carbon Black) 6.0 parts by mass was added and sufficiently premixed with a Henschel mixer, then using a co-rotating twin-screw extruder, a roll rotation speed of 200 r / min (peripheral speed of 0.3 m / min), the inside of the roll Melt-kneading was carried out at a heating temperature of 100°C. The resulting melt-kneaded product was cooled and coarsely pulverized, and then melt-kneaded using a co-rotating twin-screw extruder having a kneading portion with a total length of 1,560 mm, a screw diameter of 42 mm, and a barrel inner diameter of 43 mm. The rotation speed of the screw was 200 r/min (peripheral speed 0.3 m/min), the heating setting temperature in the rolls was 100°C, the temperature of the kneaded product was 160°C, the supply rate of the kneaded product was 10 kg/h, and the average retention rate was 10 kg/h. The time was approximately 18 seconds.

After cooling the kneaded product, it was coarsely pulverized to about 1 mm using a hammer mill (manufactured by Hosokawa Micron Corporation). The obtained coarsely pulverized material is finely pulverized with a collision plate type jet mill pulverizer IDS-2 type (manufactured by Nippon Pneumatic Industry Co., Ltd.) at a supply rate of 4.0 kg / h to obtain the desired volume median particle size. (D ₅₀ ) was set to 6.5 μm and the pulverization pressure was adjusted to obtain toner particles.

To 100 parts by mass of the obtained toner particles, 1.0 parts by mass of hydrophobic silica "NAX-50" (manufactured by Nippon Aerosil Co., Ltd., hydrophobizing agent: HMDS, average particle diameter: 30 nm) is added, and the mixture is mixed with a Henschel mixer. A toner was obtained by mixing.

From the results of Examples and Comparative Examples, the toner for electrostatic charge image development containing the binder resin composition for toner of the present invention was excellent in low-temperature fixability, and high-quality images were obtained even during high-speed printing.
On the other hand, in Comparative Example 1 in which the amorphous polyester resin was modified with silicone and Comparative Example 2 in which unmodified silicone was used, image defects occurred during high-speed printing, and high-quality images could not be obtained.
Comparative Example 3, in which ΔSP was 1.11 (cal/cm ³ ) ^1/2 and exceeded 1.05 (cal/cm ³ ) ^1/2 , was inferior in low-temperature fixability. This is probably because the compatibility between the crystalline resin (A) and the amorphous resin (B) was insufficient.

Claims (8)

A binder resin composition for toner containing a crystalline resin (A) and an amorphous resin (B),
The crystalline resin (A) is a reaction product of an alcohol component containing an aliphatic diol, a carboxylic acid component containing an aliphatic dicarboxylic acid compound, and a modified silicone,
The crystalline resin (A) has a crystalline polyester resin segment and a silicone segment,
The modified silicone is a modified silicone having at least one functional group selected from an amino group, a carboxy group, an epoxy group, and a carbinol group,
The solubility parameter (SP _A ((cal/cm ³ ) ^1/2 )) of the crystalline polyester resin segment of the crystalline resin (A) and the solubility parameter (SP _B ((cal ΔSP ((cal/cm ³ ) ^1/2 )=│SP _B −SP _A │, which is the absolute value of the difference between the cal/cm ³ ) ^1/2 )), satisfies the following formula (1). Resin composition.
0≦ΔSP≦1.05 (1) 2. The binder resin composition for toner according to claim 1, wherein said modified silicone has at least one of an amino group, a carbinol group and a carboxy group as a functional group. 3. The binder resin composition for toner according to claim 1, wherein the modified silicone is one-terminal functional group-modified silicone or side chain functional group-modified silicone. Claims 1 to 3, wherein the amount of the modified silicone compounded in the crystalline resin (A) is more than 0 parts by mass and 30 parts by mass or less with respect to 100 parts by mass as the total amount of the alcohol component and the carboxylic acid component. 3. The binder resin composition for toner according to any one of . The solubility parameter (SP _A ((cal/cm ³ ) ^1/2 )) of the crystalline polyester resin segment in the crystalline resin (A) satisfies the following formula (2), according to any one of claims 1 to 4. binder resin composition for toner.
9.8≦SP _A ≦11.2 (2) 6. The binder resin composition for toner according to claim 1, wherein the amorphous resin (B) is an amorphous polyester resin. The mass ratio of the crystalline resin (A) to the amorphous resin (B) (crystalline resin (A)/amorphous resin (B)) is 1/99 or more and 50/50 or less. The binder resin composition for toner according to any one of claims 1 to 6. A toner for electrostatic charge image development containing a binder resin and a colorant, wherein the binder resin contains the binder resin composition for toner according to any one of claims 1 to 7. toner for.