Toner binder resin composition

Abstract

The present invention relates to a binder resin composition for toner which is excellent in low-temperature fixing property and can obtain high-quality images even at high-speed printing, and an electrostatic charge image developing toner containing the binder resin composition. 【Solution means】 A binder resin composition for toner containing a crystalline resin (A) and an amorphous resin (B), wherein 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, and 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, and the solubility parameter (SP A ((cal / cm 3 )) of the crystalline polyester resin segment of the crystalline resin (A) and the solubility parameter (SP 1 / 2 )) of the amorphous resin (B), and the absolute value of the difference ΔSP ((cal / cm B )) is a binder resin composition for toner that satisfies the following formula (1). 3 ) 1 / 2 ) = │SP 3 - SP 1 / 2 │ satisfies the following formula (1). B - SP A │ satisfies the following formula (1): 0 ≦ ΔSP ≦ 1.05 (1) 0 ≦ ΔSP ≦ 1.05 (1)

Description

[Technical Field]

[0001] The present invention relates to a binder resin composition for toner used in developing latent images formed in electrophotography, electrostatic recording, electrostatic printing, etc., a toner for developing electrostatic images containing the binder resin composition, and a method for manufacturing the toner for developing electrostatic images. [Background technology]

[0002] In recent years, with the increasing demand for paper conservation, double-sided printing has become more common in electrophotographic printing. However, double-sided printing takes longer than single-sided printing, and this time difference becomes significant as the number of prints increases. High-speed printing can be achieved by adding crystalline resins to plasticize the toner and improve its low-temperature fixation. However, a drawback of this is that excessive plasticization of the toner can worsen the toner's heat resistance, image preservation of printed materials, and resistance to hot offset printing. Development efforts are underway to achieve a balance between these challenges.

[0003] Patent Document 1 describes a toner binder resin characterized by being 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 a silicone having at least one selected from an amino group, a carboxyl group, an epoxy group, and a carbinol group. With the above configuration, it is possible to provide a toner binder resin, a toner for electrostatic image development, and a method for manufacturing the toner for electrostatic image development that are excellent in low-temperature fixing properties, hot offset resistance, and durability.

[0004] 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. This toner provides excellent low-temperature fixation and image preservation properties. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2020-63348 [Patent Document 2] Japanese Patent Publication No. 2021-60582 [Overview of the project] [Problems that the invention aims to solve]

[0006] The toner binder resin described in Patent Document 1 has poor compatibility of its crystalline polyester segments with toner, leading to phase separation and domain formation within the toner, resulting in insufficient low-temperature fixation. Furthermore, while the toner described in Patent Document 2 solves the problem of image preservation in environments where the paper is kept warm for extended periods after ejection, the image recovery speed during rapid cooling is slow. Therefore, when performing high-speed double-sided printing, for example, if the printed material is not sufficiently cooled during transport before printing on the opposite side, the image can be damaged during the process of separating the material from the printed material during transport, resulting in issues with image quality.

[0007] The present invention relates to a binder resin composition for toner that exhibits excellent low-temperature fixation and can produce high-quality images even during high-speed printing, and toner for electrostatic image development containing the binder resin composition. [Means for solving the problem]

[0008] One embodiment of the present invention relates to either [1] or [2] below. [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 carboxyl group, an epoxy group, and a carbinol group. The solubility parameter (SP B , 3 , , , 1 / 2 , , A ,

[0010] , ((cal / cm 3 )) of the crystalline polyester resin segment of the crystalline resin (A), and the solubility parameter (SP )) of the amorphous resin (B), and the absolute value of the difference ΔSP ((cal / cm )) = │SP - SP │ satisfies the following formula (1), a binder resin composition for toner. 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〕.

Advantages of the Invention

[0009] According to the present invention, there is provided a binder resin composition for toner having excellent low-temperature fixing properties and capable of obtaining high-quality images even during high-speed printing, and an electrostatic charge image developing toner containing the binder resin composition.

Embodiments for Carrying Out the Invention

[0010] [Binder Resin Composition for Toner] The binder resin for toner according to an embodiment of the present invention includes 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 )) of the crystalline polyester resin segment of the crystalline resin (A), and the solubility parameter (SP )) of the amorphous resin (B), and the solubility parameter (SP B ​​​​​​​​​​​​​((cal / cm 3 ) 1 / 2 ΔSP((cal / cm)) is the absolute value of the difference 3 ) 1 / 2 )=│SP B - SP A │ satisfies the following equation (1). 0 ≤ ΔSP ≤ 1.05 (1) A toner binder resin composition having the above configuration provides a toner binder resin composition that exhibits good low-temperature fixation and good image quality during high-speed, continuous printing, as well as a toner for electrostatic image development containing the binder resin composition.

[0011] The reason for this effect is not entirely clear, but it is thought to be as follows: By using a crystalline resin (A) and an amorphous resin (B) having crystalline polyester resin segments with predetermined ΔSP values, the compatibility is increased, causing the toner to soften at low temperatures and improving low-temperature fixation. Normally, controlling compatibility using ΔSP values ​​makes it difficult to achieve both, as the toner becomes more flexible at low temperatures, but the recovery of hardness during cooling is also slower. However, in this invention, the crystalline resin (A) is a composite 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. The composite crystalline resin (A) is thought to exist in a microphase-separated state within the toner. As a result, when heated above its melting point during fixing, the composite melts, and the crystalline polyester resin segments plasticize the toner, resulting in excellent low-temperature fixing properties. On the other hand, when cooled below its melting point, the crystalline polyester resin segments, which are in a microphase-separated state, crystallize rapidly. This allows for crystallization significantly faster than conventional designs that segregate and crystallize miscible crystalline polyester, resulting in faster recovery of image intensity even during high-speed printing and the acquisition of high-quality images.

[0012] The definitions of various terms used in this specification are shown below. Whether a resin is crystalline or amorphous is determined by its 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 one in which the crystallinity index is 0.6 or higher and 1.4 or lower. An amorphous resin is one 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, as well as manufacturing conditions such as reaction temperature, reaction time, and cooling rate. In this specification, the carboxylic acid component of the polyester resin includes not only the compound itself, but also anhydrides that decompose during the reaction to produce acid, and alkyl esters of each carboxylic acid (alkyl group having 1 to 3 carbon atoms). "Volume-intermediate particle size (D 50 ")" refers to the particle size at which the cumulative volume frequency calculated using volume fractions accounts for 50% of the total volume frequency, starting from the smallest particle size. "Bisphenol A" is 2,2-bis(4-hydroxyphenyl)propane.

[0013] [Crystalline resin (A)] 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 has a crystalline polyester resin segment and a silicone segment.

[0014] <Alcohol content> The alcohol component includes an aliphatic diol, and an α,ω-aliphatic diol is preferred. The number of carbon atoms in the aliphatic diol is preferably 2 or more, more preferably 4 or more, even more preferably 6 or more, and preferably 16 or less, more preferably 14 or less, and even more preferably 12 or less. Examples of aliphatic diols include α,ω-aliphatic diols such as 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, as well as aliphatic diols other than α,ω-aliphatic diols such as 1,2-propanediol and neopentyl glycol. Among these, α,ω-aliphatic diols are preferred, ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, and 1,12-dodecanediol are more preferred, ethylene glycol and 1,6-hexanediol are even more preferred, and 1,6-hexanediol is even more preferred.

[0015] The amount of aliphatic diol is preferably 80 mol% or more, more preferably 85 mol% or more, even more preferably 90 mol% or more, even more preferably 95 mol% or more, and 100 mol% or less, and even more preferably 100 mol%, in the alcohol component.

[0016] The alcohol component may contain other alcohol components other than aliphatic diols. Examples of other alcohol components include alkylene oxide adducts of aromatic diols such as alkylene oxide adducts of bisphenol A; and trivalent or higher alcohols such as glycerin, pentaerythritol, and trimethylolpropane. One or more of these alcohol components may be used.

[0017] <Carboxylic acid components> The carboxylic acid component contains an aliphatic dicarboxylic acid compound. A linear aliphatic dicarboxylic acid compound is preferred as the aliphatic dicarboxylic acid compound. The number of carbon atoms in the aliphatic dicarboxylic acid compound is preferably 4 or more, preferably 14 or less, and more preferably 12 or less. Examples of preferred aliphatic dicarboxylic acid compounds include fumaric acid, sebacic acid, dodecanediic acid, and tetradecanediic acid. Among these, fumaric acid and dodecanediic acid are more preferred, and fumaric acid is even more preferred. One or more of these carboxylic acid components may be used.

[0018] The amount of aliphatic dicarboxylic acid compound is preferably 80 mol% or more, more preferably 85 mol% or more, even more preferably 90 mol% or more, even more preferably 95 mol% or more, and 100 mol% or less, and even more preferably 100 mol%, in the carboxylic acid component.

[0019] The carboxylic acid component may contain other carboxylic acid components different from aliphatic dicarboxylic acid compounds. Examples of other carboxylic acid components include aromatic dicarboxylic acid compounds such as terephthalic acid and isophthalic acid; and polycarboxylic acid compounds with a valency of three or higher. One or more of these carboxylic acid components may be used.

[0020] The equivalent ratio [COOH group / OH group] of the carboxyl group of the carboxylic acid component to the hydroxyl group of the alcohol component is preferably 0.7 or higher, more preferably 0.8 or higher, and preferably 1.3 or lower, more preferably 1.2 or lower.

[0021] <Modified silicone> The modified silicone used in the crystalline resin (A) is a modified silicone having at least one functional group selected from amino groups, carbinol groups, carboxyl groups, and epoxy groups, from the viewpoint of obtaining an electrostatic image developing toner that has excellent low-temperature fixability and image quality under high-speed printing. More preferably, it is a modified silicone having at least one functional group selected from amino groups, carbinol groups, and carboxyl groups, and even more preferably, it is a modified silicone having an amino group. Modified silicones may have these functional groups on the side chain, on one end, or on both ends. Of these, it is preferable that they be on one end or on the side chain, and more preferably on the side chain. That is, modified silicones are preferably single-end functional group modified silicones or side-chain functional group modified silicones, and more preferably side-chain functional group modified silicones.

[0022] More specifically, the modified silicone is preferably represented by the following formula (1).

[0023] [ka] [In the formula, R is independently a hydrocarbon group having 1 to 6 carbon atoms, R' is independently an alkylene group having 1 to 10 carbon atoms, a is 1 or 0, X is independently an amino group, a hydroxyl group, a hydroxyalkyloxy group, a carboxyl group, a carboxyalkyloxy group, an epoxy group, a glycidyl group, a glycidyloxy group, or an alicyclic epoxy group, R'' is a hydrocarbon group having 1 to 10 carbon atoms, s is an integer from 0 to 3, t is an integer from 0 to 3, m is an integer from 5 to 300, and n is an integer from 0 to 40, provided that at least one of s, t, and n is 1 or greater.]

[0024] In equation (1), the n repeating units and the m repeating units may be random or block-like, and are not particularly limited.

[0025] In formula (1), the number of carbon atoms in the hydrocarbon group R is 6 or less, preferably 4 or less, more preferably 3 or less, even more preferably 2 or less, and even more preferably 1. Examples of hydrocarbon groups for R include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, and phenyl groups. Among these, the methyl group is preferred.

[0026] 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, even more preferably 4 or less, even more preferably 3 or less, and preferably 1 or more. Examples of the alkylene group of R' include methanediyl group, ethane-1,2-diyl group, ethane-1,1-diyl group, n-propane-1,3-diyl group, 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 R'' is 10 or less, more preferably 8 or less, even more preferably 6 or less, even more preferably 4 or less, more preferably 3 or less, even more preferably 2 or less, and even more preferably 1. Examples of hydrocarbon groups for "R" include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, and benzyl groups.

[0027] X is an amino group, a hydroxyl group, a hydroxyalkyloxy group, a carboxyl group, a carboxyalkyloxy group, an epoxy group, a glycidyl group, a glycidyloxy group, or an alicyclic epoxy group. A hydroxyalkyloxy group may have multiple hydroxyl groups. A carboxyalkyloxy group may have multiple carboxyl groups.

[0028] s is 3 or less, preferably 2 or less, and more preferably 1 or less. t is 3 or less, preferably 2 or less, and more preferably 1 or less. When the modified silicone is a functional group-modified silicone at one end, it is preferable that s=1, t=0 and n=0, or s=0, t=1 and n=0. Furthermore, if the modified silicone is a functional group-modified silicone at both ends, it is preferable that s=t=1 and n=0. Furthermore, if the modified silicone is a side-chain functional group modified silicone, it is preferable that s=t=0 and n=1. Among these, as mentioned above, the modified silicone is preferably a one-ended functional group modified silicone or a side-chain functional group modified silicone, more preferably a side-chain functional group modified silicone, and even more preferably n=1, that is, a monofunctional side-chain functional group modified silicone. m is 300 or less, preferably 200 or less, more preferably 100 or less, even more preferably 50 or less, and 5 or more, preferably 8 or more, more preferably 10 or more. Furthermore, if 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, and even more preferably 5 or less.

[0029] The functional group equivalent of the modified silicone is preferably 300 g / mol or more, more preferably 500 g / mol or more, even more preferably 1,000 g / mol or more, even 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 even more preferably 6,000 g / mol or less. Note that functional group equivalent refers to the mass of modified silicone per mole of functional group.

[0030] The kinematic viscosity of the modified silicone is preferably 10 mm at 25°C. 2 / s or more, more preferably 20 mm 2 / s or more, more preferably 30mm 2 It is 1 / s or more, and preferably 4,000 mm 2 / s or less, more preferably 3,000 mm 2 / s or less, more preferably 2,000 mm 2 It is less than or equal to / s. The kinematic viscosity of modified silicone is measured at 25°C using a fully automated micro-kinematic viscometer (manufactured by Viscotec Co., Ltd.).

[0031] Examples of the modified silicones mentioned above include, as modified silicones having amino groups, modified silicones having amino groups in the side chain (commercial products such as "KF-864" and "KF-865" (manufactured by Shin-Etsu Chemical Co., Ltd.)), modified silicones having amino groups at both ends (commercial products such as "KF-8012" (manufactured by Shin-Etsu Chemical Co., Ltd.)), and modified silicones having an amino group at one end. Examples of modified silicones containing carboxyl groups include modified silicones having carboxyl groups in the side chain (commercial products such as "X-22-3701E" (manufactured by Shin-Etsu Chemical Co., Ltd.) and "BY16-880" (manufactured by Toray Dow Corning)), modified silicones having carboxyl groups at both ends (commercial products such as "X-22-162C" (manufactured by Shin-Etsu Chemical Co., Ltd.)), and modified silicones having a carboxyl group at one end (commercial products such as "X-22-3710" (manufactured by Shin-Etsu Chemical Co., Ltd.)). Examples of modified silicones having epoxy groups include modified silicones with epoxy groups in the side chain (commercially available products include "X-22-343" (manufactured by Shin-Etsu Chemical Co., Ltd.)), modified silicones with epoxy groups at both ends (commercially available products include "X-22-163B" and "X-22-169B" (manufactured by Shin-Etsu Chemical Co., Ltd.)), and modified silicones with epoxy groups at one end (for example, "X-22-173BX" (manufactured by Shin-Etsu Chemical Co., Ltd.)). Examples of modified silicones having a carbinol group (hydroxyl group) include modified silicones having a carbinol group in the side chain (commercially available products include "X-22-4039" (manufactured by Shin-Etsu Chemical Co., Ltd.)), modified silicones having a carbinol group at both ends (commercially available products include "KF-6003" and "KF-6002" (manufactured by Shin-Etsu Chemical Co., Ltd.)), and modified silicones having a carbinol group at one end (commercially available products include "X-22-170BX" and "X-22-170DX" (manufactured by Shin-Etsu Chemical Co., Ltd.)).

[0032] From the viewpoint of obtaining a toner for electrostatic image development that has excellent low-temperature fixability and image quality under high-speed printing, the silicone is preferably a silicone having an amino group. Examples include silicone (a) having an amino group in the side chain (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 the side chain is preferred. In other words, silicone (a) is preferably represented by formula (1a), and silicone (a') is preferably represented by formula (1a').

[0033] [ka] [In the formula, R, R', R'', m, and n are defined in the same way as in formula (1) above, and the preferred ranges are also the same.]

[0034] [ka] [In the formula, R, R', R'', a, m, s, and t are defined in the same way as in formula (1) above.]

[0035] In equation (1a'), it is preferable that s=1 and t=0, s=0 and t=0, or s=t=1.

[0036] In formulas (1a) and (1a'), the group represented by *-R'-NH2 includes, for example, the substituents 1a-1 to 1a-3 listed below.

[0037] [ka]

[0038] The modified silicone used in the crystalline resin (A) is also preferably a silicone (b) having at least one selected from a carboxyl group, an epoxy group, and a carbinol group at one end, from the viewpoint of obtaining an electrostatic image developing toner that has excellent low-temperature fixability and image quality under high-speed printing. Silicone (b) is more specifically represented by formula (1b), preferably.

[0039] [ka] [In the formula, R, R', R'', a, m, and n are defined as in formula (1) above, and X' is independently a hydroxyl group, a hydroxyalkyloxy group, a carboxyl group, a carboxyalkyloxy group, an epoxy group, a glycidyl group, a glycidyloxy group, or an alicyclic epoxy group.]

[0040] If X' is a hydroxyl group or a hydroxyalkyloxy group, then *-(R') a The group represented by -X' includes, for example, the substituents 1b-1 to 1b-3 listed below. Among these, substituent 1b-1 or substituent 1b-2 is preferred, and substituent 1b-1 is more preferred.

[0041] [ka]

[0042] If X' is a glycidyl group, a glycidyloxy group, or an alicyclic epoxy group, then *-(R') a Examples of the group represented by -X' include substituents 1b-4 to 1b-6 listed below. Of these, substituent 1b-4 is preferred.

[0043] [ka]

[0044] If X' is a carboxyl group or a carboxyalkyloxy group, then *-(R') aExamples of the group represented by -X' include the substituents 1b-7 listed below.

[0045] [ka]

[0046] In the raw materials of resin A, the amount of modified silicone is greater than 0 parts by mass, preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, even more preferably 3 parts by mass or more, even more preferably 4 parts by mass or more, and preferably 30 parts by mass or less, more preferably 25 parts by mass or less, even more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less, based on the viewpoint of obtaining an electrostatic image developing toner that has excellent low-temperature fixability and image quality under high-speed printing, relative to 100 parts by mass of the total amount of alcohol and carboxylic acid components.

[0047] The above amounts are calculated based on the alcohol component, carboxylic acid component, and modified silicone, and do not take into account the amount of water removed due to condensation. Furthermore, if a modified silicone contains a hydroxyl group or a carboxyl group, it may be understood as an alcohol component or a carboxylic acid component. However, if the compound containing the hydroxyl group or carboxyl group includes a silicone skeleton, it is considered a modified silicone. For example, when calculating the total amount of alcohol and carboxylic acid components, the modified silicone containing the hydroxyl group or carboxyl group is not included in the total amount.

[0048] (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, carboxylic acid component, and modified silicone may be reacted together, or the alcohol component and carboxylic acid component may be reacted first, followed by the modified silicone; the method is not particularly limited. In this reaction, if necessary, an esterification catalyst such as di(2-ethylhexanoate)tin(II), dibutyltin oxide, or titanium diisopropylate bistriethanolamine may be used in an amount of 0.01 parts by mass to 5 parts by mass per 100 parts by mass of the total amount of the alcohol and carboxylic acid components; and an esterification co-catalyst such as gallic acid (same as 3,4,5-trihydroxybenzoic acid) may be used in an amount of 0.001 parts by mass to 0.5 parts by mass per 100 parts by mass of the total amount of the alcohol and carboxylic acid components. Furthermore, when using monomers having unsaturated bonds, such as fumaric acid, in polycondensation, a radical polymerization inhibitor may be used, preferably in an amount of 0.001 parts by mass or more and 0.5 parts by mass or less, per 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. An example of a radical polymerization inhibitor is 4-tert-butylcatechol. The reaction temperature is preferably 120°C or higher, more preferably 160°C or higher, even more preferably 180°C or higher, and preferably 250°C or lower, more preferably 240°C or lower. The reaction may also be carried out in an inert gas atmosphere.

[0049] (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, even more preferably 80°C or higher, and preferably 150°C or lower, more preferably 135°C or lower, and even more preferably 120°C or lower, from the viewpoint of obtaining a toner for electrostatic image development that has excellent low-temperature fixability and image quality under high-speed printing. The melting point of the crystalline resin (A) is preferably 50°C or higher, more preferably 70°C or higher, even more preferably 80°C or higher, even more preferably 85°C or higher, and preferably 150°C or lower, more preferably 135°C or lower, and even more preferably 120°C or lower, from the viewpoint of obtaining a toner for electrostatic image development that has excellent low-temperature fixability and image quality under high-speed printing.

[0050] Solubility parameter (SP) of crystalline polyester resin segment in crystalline resin (A) A (cal / cm3 ) 1 / 2 From the viewpoint of obtaining a toner for electrostatic image development that has excellent low-temperature fixing properties and image quality under high-speed printing, it is preferable that the following formula (2) is satisfied. 9.8≦SP A ≤11.2 (2) SP A (cal / cm 3 ) 1 / 2 Preferably 9.8 (cal / cm³) 3 ) 1 / 2 More preferably 10.0 (cal / cm²) 3 ) 1 / 2 More preferably 10.2 (cal / cm²) 3 ) 1 / 2 More preferably 10.4 (cal / cm²) 3 ) 1 / 2 The above, and preferably 11.2 (cal / cm²). 3 ) 1 / 2 More preferably, 11.0 (cal / cm 3 ) 1 / 2 More preferably, 10.8 (cal / cm³) 3 ) 1 / 2 The following applies: The solubility parameters for the crystalline polyester resin segments are those determined by the Fedors method.

[0051] Endothermic heat of dissolution of crystalline resin (A) (Q B From the viewpoint of obtaining a toner for electrostatic image development that has excellent low-temperature fixability and image quality under high-speed printing, the concentration is preferably 10 J / g or more, more preferably 30 J / g or more, even more preferably 35 J / g or more, and preferably 200 J / g or less, more preferably 150 J / g or less, and even more preferably 120 J / g or less. Endothermic heat of dissolution of crystalline resin (A) (Q B ) is measured by the method described in the examples.

[0052] The softening point, melting point, and endothermic dissolution amount of the crystalline resin (A), as well as the solubility parameter of the crystalline polyester resin segment, can be appropriately adjusted depending on the type and amount of raw material monomer used, and manufacturing conditions such as reaction temperature, reaction time, and cooling rate, and can be determined by the method described in the examples below. When two or more types of crystalline resin (A) are used in combination, it is preferable that the softening point, melting point, and endothermic dissolution amount of the crystalline resin (A) obtained as a mixture thereof, as well as the solubility parameter of the crystalline polyester resin segment, are each within the aforementioned ranges.

[0053] [Amorphous resin (B)] The toner binder resin composition of this embodiment contains an amorphous resin (B). Solubility parameter (SP) of the crystalline polyester resin segment of the crystalline resin (A) A ((cal / cm 3 ) 1 / 2 )) and the solubility parameter (SP) of the amorphous resin (B). B ((cal / cm 3 ) 1 / 2 ΔSP((cal / cm)) is the absolute value of the difference 3 ) 1 / 2 )=│SP B - SP A │ satisfies the following equation (1). Note that SP A and SP B This is the solubility parameter 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, even more preferably 0.60 or less, even more preferably 0.40 or less, even more preferably 0.25 or less, and even more preferably 0.15 or less. SP A and SP B In other words, either can be larger, but from a molecular design perspective, SP B >SP A It is preferable that this be the case.

[0054] Furthermore, the solubility parameter (SP) of amorphous resin (B) B((cal / cm 3 ) 1 / 2 From the viewpoint of obtaining a toner for electrostatic image development that has excellent low-temperature fixing properties and image quality under high-speed printing, the coefficient is preferably 10.00 (cal / cm²). 3 ) 1 / 2 More preferably 10.30 (cal / cm³) 3 ) 1 / 2 More preferably 10.50 (cal / cm³) 3 ) 1 / 2 The above, and preferably 12.50 (cal / cm²). 3 ) 1 / 2 More preferably, 12.00 (cal / cm 3 ) 1 / 2 More preferably, 11.50 (cal / cm³) 3 ) 1 / 2 The following applies:

[0055] The amorphous resin (B) (hereinafter also referred to as "resin B") is not particularly limited as long as ΔSP satisfies the above range, but from the viewpoint of compatibility with crystalline polyester resin segments, it is preferable that it be an amorphous polyester resin. Amorphous polyester resins are, for example, amorphous polyester resins that contain a polycondensate of an alcohol component and a carboxylic acid component. Examples of amorphous polyester resins include polyester resins and modified polyester resins. Examples of modified polyester resins include urethane-modified polyester resins, epoxy-modified polyester resins, and composite resins containing polyester resin segments and addition polymerization resin segments. Among these, amorphous composite resins are preferred, which are amorphous polyester resins that are polycondensates of alcohol and carboxylic acid components, or which contain a polyester resin segment that is a polycondensate of alcohol and carboxylic acid components and an addition polymerization resin segment that is an addition polymerization product of raw material monomers containing styrene compounds.

[0056] <Alcohol content> The alcohol component includes dihydric or higher alcohols. The content of dihydric or higher alcohols is preferably 80% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and 100% by mass or less, in the alcohol component. Examples of alcohols with a valency of 2 or higher include alkylene oxide adducts of aromatic diols, linear or branched aliphatic diols, alicyclic diols, and polyhydric alcohols with a valency of 3 or higher. 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.

[0057] The alkylene oxide adduct of an aromatic diol is preferably an alkylene oxide adduct of bisphenol A, and more preferably of formula (I):

[0058] [ka] (In the formula, OR 1 and R 2 O is an oxyalkylene group, R 1 and R 2 This is an alkylene oxide adduct of bisphenol A, where each is independently an ethylene group or a propylene group, x and y represent the average number of moles of alkylene oxide added, each being a positive number, 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. Examples of alkylene oxide adducts of bisphenol A include propylene oxide adducts of bisphenol A and ethylene oxide adducts of bisphenol A. One or more of these may be used. Among these, propylene oxide adducts of bisphenol A and combinations of propylene oxide adducts of bisphenol A and ethylene oxide adducts of bisphenol A are preferred. If the alcohol component contains an alkylene oxide adduct of bisphenol A, the amount is preferably 70 mol% or more, more preferably 90 mol% or more, even more preferably 95 mol% or more, and 100 mol% or less, and even more preferably 100 mol%.

[0059] As for the linear or branched aliphatic diol, aliphatic diols having a hydroxyl group bonded to a secondary carbon atom are preferred. The aliphatic diol having a hydroxyl group bonded to a secondary carbon atom preferably has 3 to 4 carbon atoms. Examples of aliphatic diols having a hydroxyl group bonded to a secondary carbon atom include 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, its amount is preferably 70 mol% or more, more preferably 90 mol% or more, even more preferably 95 mol% or more, and 100 mol% or less, and even more preferably 100 mol% of the alcohol component.

[0060] Other examples of linear or branched aliphatic diols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol.

[0061] Examples of alicyclic diols include hydrogenated bisphenol A [2,2-bis(4-hydroxycyclohexyl)propane] and alkylene oxide adducts of hydrogenated bisphenol A with 2 to 4 carbon atoms (average number of added moles: 2 to 12). Examples of polyhydric alcohols with a valency of 3 or higher include glycerin, pentaerythritol, trimethylolpropane, and sorbitol. These alcohol components may be used individually or in combination of two or more types.

[0062] <Carboxylic acid components> The carboxylic acid component includes carboxylic acid compounds with a valency of 2 or higher, such as dicarboxylic acids and polycarboxylic acids with a valency of 3 or higher. The content of divalent or greater carboxylic acid compounds is preferably 80% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and 100% by mass or less, of the carboxylic acid component. Examples of divalent or higher carboxylic acid compounds include aromatic dicarboxylic acid compounds, linear or branched aliphatic dicarboxylic acid compounds, alicyclic dicarboxylic acid compounds, and trivalent or higher polycarboxylic acid compounds. Among these, aromatic dicarboxylic acid compounds are preferred.

[0063] Examples of aromatic dicarboxylic acid compounds include phthalic acid, isophthalic acid, and terephthalic acid. Among these, isophthalic acid or terephthalic acid are preferred, and terephthalic acid is more preferred. The amount of aromatic dicarboxylic acid compound is preferably 30 mol% or more, more preferably 40 mol% or more, even more preferably 50 mol% or more, and 100 mol% or less, of the carboxylic acid component.

[0064] The number of carbon atoms in the linear or branched aliphatic dicarboxylic acid compound is preferably 2 or more, more preferably 4 or more, even more preferably 8 or more, even more preferably 10 or more, and preferably 22 or less, more preferably 16 or less. Examples of linear or branched aliphatic dicarboxylic acid compounds include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, dodecanediic acid, tetradecanediic acid, succinic acid substituted with an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or their anhydrides or alkyl esters having 1 to 3 carbon atoms. Examples of succinic acid substituted with an aliphatic hydrocarbon group having 1 to 20 carbon atoms include dodecyl succinic acid, dodecenyl succinic acid, and octenyl succinic acid. Among these, succinic acid substituted with an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or their anhydrides, are preferred. If a linear or branched aliphatic dicarboxylic acid compound is included, its amount is preferably 2 mol% or more, more preferably 5 mol% or more, even more preferably 10 mol% or more, and preferably 30 mol% or less, more preferably 20 mol% or less, of the carboxylic acid component.

[0065] The polycarboxylic acid compounds with a valency of 3 or higher are preferably trivalent carboxylic acids, such as trimellitic acid or its anhydride. Among these, trimellitic acid or its anhydride is preferred. When a polycarboxylic acid compound with a valency of 3 or higher is included, the amount of the polycarboxylic acid compound with a valency of 3 or higher is preferably 1 mol% or more, more preferably 3 mol% or more, even more preferably 5 mol% or more, and preferably 35 mol% or less, more preferably 25 mol% or less, and even more preferably 20 mol% or less, in the carboxylic acid component. These carboxylic acid compounds may be used individually or in combination of two or more.

[0066] The ratio of carboxyl groups of the carboxylic acid component to hydroxyl groups of the alcohol component (COOH group / OH group) is preferably 0.7 or higher, more preferably 0.8 or higher, and preferably 1.3 or lower, more preferably 1.2 or lower.

[0067] If the amorphous resin (B) has an addition polymerization resin segment, the addition polymerization segment is, for example, an addition polymerization product of raw material monomers containing a styrene-based compound. Examples of styrene compounds include unsubstituted or substituted styrene. Examples of substituents that can be substituted for styrene include alkyl groups having 1 to 5 carbon atoms, halogen atoms, alkoxy groups having 1 to 5 carbon atoms, sulfonic acid groups, or salts thereof. Examples of styrene-based compounds include styrene, methylstyrene, α-methylstyrene, β-methylstyrene, tert-butylstyrene, chlorostyrene, chloromethylstyrene, methoxystyrene, styrene sulfonic acid, or salts thereof. Among these, styrene is preferred. The content of styrene compounds in the raw material monomers of the addition polymerization resin segment is preferably 50% by mass or more, more preferably 65% ​​by mass or more, even 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.

[0068] Other raw material monomers besides styrene compounds include, for example, (meth)acrylic acid esters such as alkyl (meth)acrylate, benzyl (meth)acrylate, and dimethylaminoethyl (meth)acrylate; olefins such as ethylene, propylene, and butadiene; 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; and N-vinyl compounds such as N-vinylpyrrolidone. Among these, (meth)acrylic acid esters are preferred, and alkyl (meth)acrylate is more preferred. The number of carbon atoms in the alkyl group of (meth)acrylate is preferably 1 or more, more preferably 4 or more, even more preferably 6 or more, and preferably 24 or less, more preferably 22 or less, and even more preferably 20 or less. Examples of alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, iso(or tertiary)butyl (meth)acrylate, isoamyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, isodecyl (meth)acrylate, isododecyl (meth)acrylate, isopalmityl (meth)acrylate, isostearyl (meth)acrylate, isobehenyl (meth)acrylate, and so on. Preferably, 2-ethylhexyl (meth)acrylate or stearyl (meth)acrylate is preferred, more preferably 2-ethylhexyl acrylate, stearyl methacrylate, and even more preferably 2-ethylhexyl acrylate. Note that "(iso or tertiary)" and "(iso)" refer to both cases where these prefixes are present and where they are not, and the absence of these prefixes indicates the normal form. Also, "(meth)acrylic acid" refers to acrylic acid or methacrylic acid.

[0069] The content of (meth)acrylic acid ester in the raw material monomer of the addition polymerization resin segment is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, and preferably 50% by mass or less, more preferably 35% by mass or less, and even more preferably 25% by mass or less. The total amount of styrene compounds and (meth)acrylic acid esters in the raw material monomers of the addition polymerization resin segment is preferably 80% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and even more preferably 100% by mass.

[0070] Resin B preferably has constituent units derived from both reactive monomers that are covalently bonded to the polyester resin segment and the addition polymerization resin segment. "Constituent units derived from both reactive monomers" refers to units formed by the reaction of the functional groups and addition polymerizable groups of both reactive monomers. Examples of addition polymerizable groups include carbon-carbon unsaturated bonds (ethylenically unsaturated bonds). Examples of both reactive monomers include addition polymerizable monomers having at least one functional group selected from hydroxyl groups, carboxyl groups, epoxy groups, primary amino groups, and secondary amino groups within the molecule. Among these, addition polymerizable monomers having at least one functional group selected from hydroxyl groups and carboxyl groups are preferred from the viewpoint of reactivity, and addition polymerizable monomers having carboxyl groups are more preferred. Examples of addition polymerizable monomers having a carboxyl group include acrylic acid, methacrylic acid, fumaric acid, and maleic acid. Among these, acrylic acid and methacrylic acid are preferred from the viewpoint of reactivity in both polycondensation and addition polymerization reactions, with acrylic acid being more preferred. When both reactive monomers are addition polymerizable monomers having a carboxyl group, the amount of constituent units derived from both reactive monomers is preferably 1 mol or more, more preferably 2 mol or more, even more preferably 3 mol or more, and preferably 30 mol or less, more preferably 20 mol or less, and even more preferably 10 mol or less, per 100 mol parts of the alcohol component of the polyester resin segment of resin B.

[0071] When resin B is a composite resin, the content of polyester resin segments in the composite resin is preferably 35% by mass or more, more preferably 50% by mass or more, even 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, based on the total amount of polyester resin segments and addition polymerization resin segments. Note that constituent units derived from both reactive monomers are included in the calculation of the polyester resin segments.

[0072] When resin B is a composite resin, the content of the addition polymerization resin segment in the composite resin is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, and preferably 65% ​​by mass or less, more preferably 50% by mass or less, and even more preferably 30% by mass or less, based on the total amount of the polyester resin segment and the addition polymerization resin segment. Note that the constituent units derived from both reactive monomers are included in the calculation of the polyester resin segment.

[0073] The above amounts are calculated based on the ratio of the raw material monomers for the polyester resin segment and the addition polymerization resin segment, the two reactive monomers, and the radical polymerization initiator, excluding the amount of dehydration due to polycondensation in the polyester resin segment, etc. When a radical polymerization initiator is used, the mass of the radical polymerization initiator is included in the calculation of the addition polymerization resin segment.

[0074] The amorphous resin (B) may be produced, for example, by step A, in which an alcohol component and a carboxylic acid component are polycondensed. Alternatively, if the amorphous resin (B) is a composite resin, it may be produced by a method comprising step A and step B, in which raw material monomers and both reactive monomers of an addition polymerization resin segment are addition polymerized. Process A may be performed after process B, or process B may be performed after process A, or process A and process B may be performed simultaneously. In step A, a portion of the carboxylic acid component is subjected to a polycondensation reaction, and then step B is carried out. After that, the remaining carboxylic acid component is added to the polymerization system to further advance the polycondensation reaction in step A and the polycondensation reaction with the carboxyl groups of both reactive monomers or constituent parts derived from both reactive monomers.

[0075] In step A, if necessary, an esterification catalyst such as di(2-ethylhexanoate)tin(II), dibutyltin oxide, or titanium diisopropoxybis(triethanolamine) may be used in an amount of 0.01 parts by mass to 5 parts by mass per 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component; and an esterification co-catalyst such as gallic acid (same as 3,4,5-trihydroxybenzoic acid) may be used in an amount of 0.001 parts by mass to 0.5 parts by mass per 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component for polycondensation. Furthermore, when using monomers having unsaturated bonds, such as fumaric acid, in polycondensation, a radical polymerization inhibitor may be used, preferably in an amount of 0.001 parts by mass or more and 0.5 parts by mass or less, per 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. An example of a radical polymerization inhibitor is 4-tert-butylcatechol. The temperature of the polycondensation reaction is preferably 120°C or higher, more preferably 160°C or higher, even more preferably 180°C or higher, and preferably 250°C or lower, more preferably 240°C or lower. The polycondensation may be carried out in an inert gas atmosphere.

[0076] Examples of radical polymerization initiators for the addition polymerization in step B include peroxides such as dibutyl peroxide, persulfates such as sodium persulfate, and azo compounds such as 2,2'-azobis(2,4-dimethylvaleronitrile). The amount of radical polymerization initiator used is preferably 1 to 20 parts by mass per 100 parts by mass of raw material monomers of 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, and even more preferably 210°C or lower.

[0077] (Physical properties of resin B) The softening point of resin B is preferably 70°C or higher, more preferably 90°C or higher, and even more preferably 100°C or higher. Furthermore, from the viewpoint of further improving low-temperature fixation, it is preferably 160°C or lower, more preferably 150°C or lower, and even more preferably 145°C or lower. The glass transition temperature of resin B is preferably 40°C or higher, more preferably 50°C or higher, and even more preferably 55°C or higher. From the viewpoint of further improving low-temperature fixation, it is preferably 80°C or lower, more preferably 70°C or lower, and even more preferably 65°C or lower.

[0078] From the viewpoint of obtaining a toner for electrostatic image development that has excellent low-temperature fixing properties and image quality under high-speed printing, it is preferable to use a combination of an amorphous resin BL having a low softening point and an amorphous resin BH having a high softening point that is 5°C or more higher than the amorphous resin BL. The difference in softening points between amorphous resin BL and amorphous resin BH is preferably 10°C or higher, more preferably 20°C or higher, even more preferably 30°C or higher, and preferably 80°C or lower, more preferably 60°C or lower, and even more preferably 50°C or lower, from the viewpoint of obtaining a toner for electrostatic image development that has excellent low-temperature fixing properties and image quality under high-speed printing. When amorphous resin BL and amorphous resin BH are used in combination, the mass ratio BL / BH of amorphous resin BL to amorphous resin BH is preferably 0.1 or higher, more preferably 0.2 or higher, even more preferably 0.4 or higher, and preferably 10 or lower, more preferably 5 or lower, even more preferably 2.5 or lower, and even more preferably 1 or lower, from the viewpoint of obtaining a toner for electrostatic image development that has excellent low-temperature fixing properties and image quality under high-speed printing.

[0079] 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, as well as manufacturing conditions such as reaction temperature, reaction time, and cooling rate. These values ​​can be determined by the method described in the examples. Furthermore, when using two or more types of resin B in combination, it is preferable that the values ​​of the softening point, glass transition temperature, and solubility parameters obtained from the mixture are within the aforementioned ranges.

[0080] In the binder resin composition of this embodiment, the mass ratio of crystalline resin (A) to amorphous resin (B) (crystalline resin (A) / amorphous resin (B)) is preferably 1 / 99 or more, more preferably 3 / 97 or more, even more preferably 5 / 95 or more, even more preferably 8 / 92 or more, 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.

[0081] [Toner for developing electrostatic images] 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 contains the toner binder resin composition of this embodiment described above. According to the present invention, it is possible to provide a toner for electrostatic image development that exhibits excellent low-temperature fixing properties and image quality under high-speed printing conditions. The toner for developing electrostatic images contains at least a binder resin and a colorant, and may also contain other components such as a mold release agent and a charge control agent. Preferably, the toner for developing electrostatic images contains toner matrix particles and an external additive added to the toner matrix particles (hereinafter also referred to as "toner particles").

[0082] <Coloring agent> As a coloring agent, all dyes, pigments, etc. used as coloring agents 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., and the toner of the present invention may be either a black toner or any other color toner.

[0083] From the viewpoint of improving the image density of the toner, the colorant content is preferably 0.3 parts by mass or more, more preferably 1 part by mass or more, and preferably 20 parts by mass or less, and more preferably 10 parts by mass or less, per 100 parts by mass of the total amount of binder resin. Furthermore, from the viewpoint of improving the image density of the toner, the colorant content is preferably 0.3% by mass or more, more preferably 1% by mass or more, and preferably 20% by mass or less, and more preferably 10% by mass or less, relative to the toner particles.

[0084] <Release agent> Examples of release agents include hydrocarbon waxes, ester waxes, silicone waxes, and fatty acid amide waxes.

[0085] The melting point of the release agent is preferably 60°C or higher, more preferably 70°C or higher, and more preferably 160°C or lower, more preferably 150°C or lower, and even more preferably 140°C or lower. Furthermore, when using two or more release agents in combination, it is preferable that the melting points of each release agent are within the aforementioned range. In the present invention, the crystalline resin (A) does not need to contain a release agent because the silicone segment contributes to its release properties. The release agent content is preferably 1 part by mass or less, more preferably 0.5 parts by mass or less, even more preferably 0.1 parts by mass or less, and preferably 0 parts by mass or more, per 100 parts by mass of the total amount of binder resin.

[0086] <Charge control agent> The charge control agent may contain either a positively charged charge control agent or a negatively charged charge control agent. Examples of positively charged charge control agents include nigrosine dyes, such as "Nigrosine Base EX," "Oil Black BS," "Oil Black SO," "Bontron N-01," "Bontron N-04," "Bontron N-07," "Bontron N-09," "Bontron N-11," and "Bontron N-79" (all manufactured by Orient Chemical Industries, Ltd.); triphenylmethane-based dyes containing tertiary amines as side chains, quaternary ammonium salt compounds, such as "Bontron P-51" (manufactured by Orient Chemical Industries, Ltd.), cetyltrimethylammonium bromide, and "COPY CHARGE PX VP435" (manufactured by Clariant); polyamine resins, such as "AFP-B" (manufactured by Orient Chemical Industries, Ltd.); imidazole derivatives, such as "PLZ-2001" and "PLZ-8001" (both manufactured by Shikoku Chemicals, Ltd.); and styrene-acrylic resins, such as "FCA-701PT" (manufactured by Fujikura Chemicals, Ltd.).

[0087] Examples of negatively charged charge control agents include metal-containing azo dyes, such as "Barifast Black 3804," "Bontron S-31," "Bontron S-32," "Bontron S-34," and "Bontron S-36" (all manufactured by Orient Chemical Industries, Ltd.), "Eisenspiron Black TRH," and "T-77" (manufactured by Hodogaya Chemical Co., Ltd.); metal compounds of benzyl acid compounds, such as "LR-147" and "LR-297" (both manufactured by Nippon Carlit Co., Ltd.); metal compounds of salicylic acid compounds, such as "Bontron E-81," "Bontron E-84," "Bontron E-88," and "Bontron E-304" (all manufactured by Orient Chemical Industries, Ltd.), and "TN-105" (manufactured by Hodogaya Chemical Co., Ltd.); copper phthalocyanine dyes; quaternary ammonium salts, such as "COPY CHARGE NX VP434" (manufactured by Clariant), nitroimidazole derivatives, etc.; and organometallic compounds. The charge control agent to be used should be selected appropriately according to the characteristics of the printing press using toner and the type of colorant used.

[0088] The charge control agent content is preferably 0.01 parts by mass or more, more preferably 0.2 parts by mass or more, even more preferably 1 part by mass or more, and preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 3 parts by mass or less, based on 100 parts by mass of the total amount of binder resin.

[0089] [Toner manufacturing method] The toner may be obtained by any known method such as the melt-kneading method, the emulsification-phase inversion method, the polymerization method, or the emulsification-coagulation method, but from the viewpoint of productivity and other factors, pulverized toner obtained by the melt-kneading method is preferred. In the case of pulverized toner produced by the melt-kneading method, for example, raw materials such as crystalline resin (A), amorphous resin (B), colorant, and charge control agent are uniformly mixed in a mixer such as a Henschel mixer, then melt-kneaded in a closed-type kneader, a single-screw or twin-screw extruder, an open-roll type kneader, etc., followed by cooling, pulverization, and classification. The toner manufacturing method preferably includes a step of melting and kneading a mixture containing a crystalline resin (A), an amorphous resin (B), etc., at a temperature in the range of 80°C to 200°C. The melting and 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. A method for producing toner preferably includes the step of grinding and classifying a mixture obtained by melt kneading to obtain toner particles. This grinding and classification can be carried out by known methods.

[0090] Volume-intermediate particle size of toner particles (D 50 From the viewpoint of obtaining an electrostatic image developing toner with excellent low-temperature fixing properties and image quality under high-speed printing, the toner is preferably 2 μm or more, more preferably 3 μm or more, and even more preferably 4 μm or more. From the viewpoint of resistance to hot offset, it is 8 μm or less, preferably 7 μm or less, and more preferably 6.8 μm or less.

[0091] It is preferable that the toner is treated by adding fluidizing agents or the like as external additives to the surface of the toner particles. Examples of the external additive include fine particles of inorganic materials such as hydrophobic silica, titanium oxide fine particles, alumina fine particles, cerium oxide fine particles, carbon black, and polymer fine particles such as polycarbonate, polymethyl methacrylate, and silicone resin. Among these, hydrophobic silica is preferable. When using an external additive, the addition amount of the external additive is preferably 0.5 parts by mass or more, and preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and still more preferably 3 parts by mass or less with respect to 100 parts by mass of the toner particles.

[0092] The storage elastic modulus G'(Pa) at 120°C when the toner is heated at 5°C / min is preferably 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 from the viewpoint of obtaining an electrostatic charge image developing toner excellent in low-temperature fixing property and image quality under high-speed printing, and preferably 2.0×10 4 or less, more preferably 1.5×10 4 or less, still more preferably 1.2×10 4 or less. Further, the storage elastic modulus G'(Pa) at 80°C when the toner is heated to 200°C and then rapidly cooled at 20°C / min 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 from the viewpoint of obtaining an electrostatic charge image developing toner excellent in low-temperature fixing property and image quality under high-speed printing, and 10×10 5 Pa or less, more preferably 9.0×10 5 Pa or less, still more preferably 8.0×10 5 Pa or less. The storage elastic modulus G' is measured by the method described in the examples.

[0093] The crystal recovery rate (%) of the crystalline resin in the toner is preferably 5% or more, more preferably 10% or more, and even more preferably 15% or more, from the viewpoint of obtaining a toner for electrostatic image development that has excellent low-temperature fixing properties and image quality under high-speed printing. There is no particular upper limit, but from the viewpoint of ease of manufacturing, it is preferably 80% or less, and more preferably 70% or less. The crystal recovery rate (%) represents the extent to which the crystalline resin exhibits crystallization ability in the toner, and the endothermic peak area originating from the crystalline resin, observed in the measurement of the endothermic heat of dissolution of the toner, is used to determine the endothermic heat of dissolution Q. A (J / g), the endothermic peak area of ​​the crystalline resin (A) before tonerization is the amount of heat absorbed by dissolution Q. B When expressed as (J / g), the appropriate calculation is performed using the following formula. Crystal recovery rate (%)=(Q A / Q B ) × 100 In detail, it is measured and calculated by the method described in the examples.

[0094] Toner is used, for example, in developing latent images formed in electrophotography, electrostatic recording, and electrostatic printing. Toner can be used as a one-component developer or mixed with a carrier to form a two-component developer. [Examples]

[0095] The present invention will be specifically described below with reference to examples, but the present invention is not limited in any way by these examples. The physical properties of the resin and the like were measured by the following methods. In notations such as "alkylene oxide (X)," the number X in parentheses represents the average number of moles of alkylene oxide added.

[0096] [Measurement method] [Kinematic viscosity of modified silicone] The kinematic viscosity of the modified silicones was taken from the catalog values ​​for each product.

[0097] [Equivalent of functional groups in modified silicone] The functional group equivalents of the modified silicones were taken from the catalog values ​​for each product.

[0098] [Softening point, crystallinity index, melting point, and glass transition temperature of resins] (1) Softening point Using a flow tester "CFT-500D" (manufactured by Shimadzu Corporation), 1 g of sample was heated at a heating rate of 6°C / min while a load of 1.96 MPa was applied by a plunger, and the sample was extruded from a nozzle with a diameter of 1 mm and a length of 1 mm. The amount of plunger descent of the flow tester was plotted against temperature, and the temperature at which half of the sample flowed out was defined as the softening point. (2) Crystallinity index 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 and cooled to 0°C at a cooling rate of 10°C / min. The sample was then left to stand still for 1 minute, and then heated to 180°C at a heating rate of 10°C / min, and the amount of heat was measured. Among the observed endothermic peaks, the temperature of the peak with the largest peak area was defined as the maximum endothermic peak temperature (1), and the crystallinity index was determined by (softening point (°C)) / (maximum endothermic peak temperature (1) (°C)). (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 then cooled to 0°C at a rate of 10°C / min. The sample was then heated again at a rate of 10°C / min, and the amount of heat was measured. Among the observed endothermic peaks, the temperature of the peak with the largest peak area was defined as the maximum endothermic peak temperature (2). In the case of crystalline resins, this peak temperature was defined as the melting point. Furthermore, in the case of amorphous resins, if a peak was observed, the temperature of that peak was defined as the glass transition temperature. If no peak was observed but a step was observed, the temperature at the intersection of the tangent line showing the maximum slope of the curve in the step portion and the extension of the baseline on the low-temperature side of the step was defined as the glass transition temperature.

[0099] [Dissolution endothermic amount] Each sample was heated from room temperature (20°C) to 180°C at a heating rate of 10°C / min using a differential scanning calorimeter "Q-100" (manufactured by TA Instruments Japan Co., Ltd.), and the observed endothermic peak area originating from the crystalline resin (A) was defined as the dissolution endothermic amount. The dissolution endothermic amount of the resin before tonerization was defined as dissolution endothermic amount Q. B The values ​​are shown in Table 1 as (J / g).

[0100] [Storage modulus of toner (G')] Measurements were taken using a viscoelasticity measuring device (rheometer) "MCR-302" (manufactured by Anton Paar) at a shear strain of 0.05% and a frequency of 1 Hz. A 25mm diameter parallel plate was heated to 100°C and left standing. A pellet with a diameter of 20mm and a thickness of 5mm was obtained by pressurizing 2.0g of the sample at 30MPa. This pellet was placed on the parallel plate at 100°C, sandwiched from above with an 8mm parallel plate, and then cooled to 40°C. The temperature was then increased at 5°C / min to 200°C, and the storage modulus at 120°C [G'(T=120°C)] was determined. The temperature was then further decreased from 200°C to 40°C at 20°C / min, and the storage modulus at 80°C [G'(T=80°C)] was determined.

[0101] [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 the extent to which the crystalline resin in the toner exhibited its inherent crystallization ability. Each toner is measured according to the aforementioned method for measuring the amount of heat absorbed by dissolution, and the observed endothermic peak area derived from the crystalline resin is used to determine the amount of heat absorbed by dissolution Q. A The expression was given as (J / g). Furthermore, by dividing by the amount of crystalline resin (A) in the toner, the heat endothermic amount Q was calculated. A The following was determined. Meanwhile, the crystalline resin (A) before toner production was heated under similar conditions, and the endothermic peak area originating from the crystalline resin (A) was used to determine the amount of heat absorbed by dissolution Q. B The crystal recovery property is determined by the dissolution heat endurance Q. A and the heat absorbed by dissolution Q B It was defined using the following formula. Crystal recovery rate (%)=(Q A / Q B) × 100 The crystal recovery rate is expressed as a numerical value between 100 and 0, with higher values ​​indicating more accelerated crystallization of the crystalline polyester resin in the toner. The results are shown in Table 3.

[0102] Test Example 1 [Low Temperature Fixation] A modified "HL-2040" printer (manufactured by Brother Industries, Ltd.) capable of capturing unfixed images was loaded with toner, and an unfixed solid 2cm square image was printed. Using an external fuser unit modified from "OKI MICROLINE 3010" (manufactured by OKI Data Corporation), the fuser roll rotation speed was set to 100mm / sec, and the fuser roll temperature was increased by 5°C increments from 100°C to 230°C. The unfixed image was then fixed at each temperature to obtain a fixed image. Mending tape (manufactured by Sumitomo 3M Limited) was attached to the image obtained at each fixing temperature, and a 500g cylindrical weight was placed on top to ensure the tape adhered sufficiently to the fixed image. After that, the mending tape was slowly peeled off the fixed image. The image density before and after peeling was measured using the image density meter "GRETAG SPM50" (manufactured by GRETAG). The temperature at which the ratio of image density before and after rubbing ([image density after rubbing / image density before rubbing] × 100) first exceeded 90% was defined as the minimum fixing temperature and used as an indicator of low-temperature fixing performance. A smaller value indicates better low-temperature fixing performance.

[0103] Test Example 2 [Image Quality in High-Speed ​​Printing] The printer, external fuser, and unfixed image used were the same as in Test Example 1, except the print speed was set to 200 mm / sec. A fixed image was obtained at a set temperature of the minimum fixing temperature obtained in Test Example 1 + 20°C. The quality of the obtained fixed image was evaluated according to the criteria shown below. Rating A: No visible scratches or streaks are present in the fixed image. Rating B: Scratches and defects are only visible at the edges of the fixed image. Rating C: Visible scratches and streaks are visible in the fixed image.

[0104] [Resin manufacturing] Manufacturing Example 1 (Resin A-1) A 10 L four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer, and thermocouple was purged with nitrogen. 4,790 g of 1,6-hexanediol, 4,710 g of fumaric acid, 425 g of silicone "X-22-170BX" (manufactured by Shin-Etsu Chemical Co., Ltd.), and 5 g of polymerization inhibitor (tert-butylcatechol) were added. Under a nitrogen atmosphere, the mixture was heated to 140°C with stirring and held for 1 hour. Subsequently, the temperature was increased at 10°C / h until 200°C was reached, at which point 28 g of tin(II) di(2-ethylhexanoate) was added and the mixture was held for 1 hour. After holding, the pressure inside the flask was reduced, and the reaction was carried out at 8 kPa until the desired softening point was reached to obtain crystalline resin A-1. The physical properties are shown in Table 1.

[0105] Production examples 2 to 7, comparative production examples 1 and 2 (resin 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. Their physical properties are shown in Table 1.

[0106] Manufacturing example 8 (Resin A-8) A 10 L four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer, and thermocouple was purged with nitrogen. 2,190 g of ethylene glycol, 7,310 g of dodecanedioic acid, and 440 g of silicone "KF-864" (manufactured by Shin-Etsu Chemical Co., Ltd.) were added. Under a nitrogen atmosphere, the mixture was heated to 140°C with stirring and held for 1 hour. Subsequently, the temperature was increased at 10°C / h until 200°C was reached, at which point 28 g of tin(II) di(2-ethylhexanoate) was added and the mixture was held for 1 hour. After holding, the pressure inside the flask was reduced, and the reaction was carried out at 8 kPa until the desired softening point was reached to obtain crystalline resin A-8. The physical properties are shown in Table 1.

[0107] The modified and unmodified silicones used in Manufacturing Examples 1 to 8 and Comparative Manufacturing Example 2 are as follows. • X-22-170BX: Modified silicone oil "X-22-170BX" (silicone with a carbinol group (hydroxyl group) at one end, kinematic viscosity (25℃) = 40 mm) 2 ( / s, functional group equivalent 2,800 g / mol, manufactured by Shin-Etsu Chemical Co., Ltd.) • X-22-170DX: Modified silicone oil "X-22-170DX" (silicone with a carbinol group (hydroxyl group) at one end, kinematic viscosity (25℃) = 65 mm) 2 ( / s, functional group equivalent 4,670 g / mol, manufactured by Shin-Etsu Chemical Co., Ltd.) • KF-865: Modified silicone oil "KF-865" (silicone with monoamino groups in its side chains, kinematic viscosity (25℃) = 110 mm) 2 ( / s, functional group equivalent = 5,000 g / mol, manufactured by Shin-Etsu Chemical Co., Ltd.) • KF-8012: Modified silicone oil "KF-8012" (silicone with amino groups at both ends, kinematic viscosity (25℃) = 90 mm) 2 ( / s, functional group equivalent = 2,200 g / mol, manufactured by Shin-Etsu Chemical Co., Ltd.) • X-22-3710: Modified silicone oil "X-22-3710" (a silicone having a carboxyl group at one end on average, kinematic viscosity (25℃) = 60 mm) 2 ( / s, functional group equivalent 1,450 g / mol, manufactured by Shin-Etsu Chemical Co., Ltd.) • KF-864: Modified silicone "KF-864" (silicone with monoamino groups in its side chains, kinematic viscosity (25℃) = 1,700 mmHg) 2 ( / s, functional group equivalent = 3,800 g / mol, manufactured by Shin-Etsu Chemical Co., Ltd.) • KF96-50cs: Unmodified silicone oil "KF96-50cs" (silicone oil (dimethyl silicone oil), kinematic viscosity (25℃) 50mm 2 (Manufactured by Shin-Etsu Chemical Co., Ltd.)

[0108] [Table 1]

[0109] Production example 9 (resin B-1) A 10 L four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer, and thermocouple was purged with nitrogen. 7,250 g of bisphenol A propylene oxide (2.2) adduct, 2,750 g of terephthalic acid, and 50 g of tin(II) di(2-ethylhexanoate) were added. Under a nitrogen atmosphere, the mixture was stirred and heated to 235°C. After holding at 235°C for 6 hours, the pressure inside the flask was reduced, and the reaction was carried out at 8 kPa until the desired softening point was reached to obtain amorphous resin B-1. The physical properties are shown in Table 2.

[0110] Production example 10 (resin B-2) A 10 L four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer, and thermocouple was purged with nitrogen. The raw material monomers for the polyester resin (excluding trimellitic anhydride) and the esterification catalyst shown in Table 2 were added. Under a nitrogen atmosphere, the temperature was raised to 160°C while stirring, and a mixed solution of the raw material monomers for the addition polymerization resin, both reactive monomers, and the radical polymerization initiator shown in Table 2 was added dropwise over 1 hour. After that, the mixture 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 carried out under reduced pressure of 8 kPa for 1 hour. After that, the temperature was raised to 235°C over 30 minutes, polycondensation occurred at 235°C for 5 hours, and the reaction was carried out under 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 the reaction was carried out for 1 hour, and then the crosslinking reaction was carried out at 8 kPa until the predetermined softening point was reached to obtain amorphous resin B-2. The physical properties are shown in Table 2.

[0111] Production example 11 (resin B-3) A 10 L four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer, and thermocouple was purged with nitrogen. 4,860 g of bisphenol A propylene oxide (2.2) adduct, 1,935 g of bisphenol A ethylene oxide (2.2) adduct, 1,515 g of terephthalic acid, 1,120 g of dodecenyl succinic anhydride (DDSA-C), and 50 g of tin(II) di(2-ethylhexanoate) were added. Under a nitrogen atmosphere, the mixture was stirred and heated to 235°C, where it was maintained for 6 hours. After that, the pressure inside the flask was reduced and maintained at 8 kPa for 1 hour. After returning to atmospheric pressure, the mixture was cooled to 220°C, 570 g of trimellitic anhydride was added, and the reaction was carried out at 220°C for 0.5 hours. Then, the pressure inside the flask was reduced and the reaction was carried out at 20 kPa until the desired softening point was reached to obtain amorphous resin B-3. The physical properties are shown in Table 2.

[0112] Comparative production examples 3 and 4 (resin B-4, 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 composition was changed as shown in Table 2. The physical properties are shown in Table 2. The KF-6000 used in comparative manufacturing example 3 is as follows: • KF-6000: Modified silicone oil "KF-6000" (silicone with carbinol groups (hydroxyl groups) at both ends, kinematic viscosity (25℃) = 35 mm) 2 ( / s, functional group equivalent 470 g / mol, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0113] Comparative production example 5 (resin B-6) Amorphous resin B-6 was obtained in the same manner as in Manufacturing Example 11, except that the raw material composition was changed as shown in Table 2. The physical properties are shown in Table 2.

[0114] [Table 2]

[0115] 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 positively charged charge control agent "Bontron N-79" (manufactured by Orient Chemical Industry Co., Ltd.), and 6.0 parts by mass of the coloring agent "Regal 330R" (manufactured by Cabot, carbon black) were added and thoroughly pre-mixed in a Henschel mixer. Then, the mixture was melt-kneaded using a co-rotating twin-screw extruder at a roll rotation speed of 200 r / min (peripheral speed 0.3 m / min) and a heating temperature in the rolls of 100°C. After the obtained melt-kneaded material was cooled and coarsely ground, it was melt-kneaded again using a co-rotating twin-screw extruder with a total length of 1,560 mm, a screw diameter of 42 mm, and a barrel inner diameter of 43 mm. The screw rotation speed was 200 r / min (peripheral speed 0.3 m / min), the heating setting temperature in the rolls was 100°C, the temperature of the mixture was 160°C, the mixture supply rate was 10 kg / h, and the average residence time was approximately 18 seconds.

[0116] After cooling the mixture, it was coarsely ground to approximately 1 mm using a hammer mill (manufactured by Hosokawa Micron Corporation). The resulting coarsely ground material was then finely ground using an impact plate type jet mill IDS-2 (manufactured by Nippon Pneumatic Mfg. Co., Ltd.) at a feed rate of 4.0 kg / h to obtain the desired medium volume particle size (D 50 The particle size was set to 6.5 μm, and the grinding pressure was adjusted to obtain toner particles.

[0117] Toner was obtained by adding 1.0 part by mass of hydrophobic silica "NAX-50" (manufactured by Nippon Aerosil Co., Ltd., hydrophobic treatment agent: HMDS, average particle size: 30 nm) to 100 parts by mass of the obtained toner particles and mixing them in a Henschel mixer.

[0118] [Table 3]

[0119] From the results of the examples and comparative examples, the electrostatic image developing toner containing the toner binder resin composition of the present invention exhibited excellent low-temperature fixing properties and produced high-quality images even during high-speed printing. On the other hand, in Comparative Example 1, in which amorphous polyester resin was modified with silicone, and in Comparative Example 2, in which unmodified silicone was used, image defects occurred during high-speed printing, and high-quality images could not be obtained. Also, ΔSP is 1.11 (cal / cm²). 3 ) 1 / 2 It is 1.05 (cal / cm³). 3 ) 1 / 2 Comparative Example 3, which exceeded the specified range, exhibited poor low-temperature fixation. This is thought to be due to insufficient compatibility between the crystalline resin (A) and the amorphous resin (B).

Claims

1. This is 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 carboxyl group, an epoxy group, and a carbinol group. The solubility parameter (SP Ｂ , ３ , １／２ , Ａ ((cal / cm ３ )) of the crystalline polyester resin segment of the crystalline resin (A), and the solubility parameter (SP １／２ )) of the amorphous resin (B), and the absolute value of the difference ΔSP ((cal / cm Ｂ ((cal / cm ３ )) is ΔSP ((cal / cm １／２ )) = │SP ３ - SP １／２ │ satisfies the following formula (1), a binder resin composition for toner.​​​​ 0 ≤ ΔSP ≤ 1.05 (1)

2. The toner binder resin composition according to claim 1, wherein the modified silicone has at least one of an amino group, a carbinol group, and a carboxyl group as a functional group.

3. The toner binder resin composition according to claim 1 or 2, wherein the modified silicone is a one-end functional group modified silicone or a side-chain functional group modified silicone.

4. The toner binder resin composition according to any one of claims 1 to 3, wherein the amount of modified silicone in the crystalline resin (A) is greater than 0 parts by mass and less than or equal to 30 parts by mass, based on 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component.

5. The solubility parameter (SP) of the crystalline polyester resin segment in the crystalline resin (A) Ａ ((cal / cm ３ ) １／２ A toner binder resin composition according to any one of claims 1 to 4, wherein )) satisfies the following formula (2). 9.8≦SP Ａ ≦11.2 (2)

6. The toner binder resin composition according to any one of claims 1 to 5, wherein the amorphous resin (B) is an amorphous polyester resin.

7. The toner binder resin composition according to any one of claims 1 to 6, wherein 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.

8. A toner for developing electrostatic images, comprising a binder resin and a colorant, wherein the binder resin comprises the toner binder resin composition described in any one of claims 1 to 7.

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