Toner binder resin composition

Abstract

To provide a toner binder resin composition providing toner excellent in low temperature fixability and image heat resistance, and an electrostatic charge image development toner including the same.SOLUTION: A toner binder resin composition includes: an alcohol component including bi- or higher valent alcohol; a carboxylic acid component including a bi- or higher valent carboxylic acid compound; an amorphous resin (A) being a condensation polymer with modified silicone having a polar group; and a crystalline resin (C). The solubility parameter (SP value) (SPA) of Fedors calculated from the alcohol component and carboxylic acid component of the amorphous resin (A) is 11.0(cal / cm3)1 / 2 or less; the polar group value of the modified silicone is 10.0 mgKOH / g or more; and the SP value (SPC) of the crystalline resin (C) is 9.6(cal / cm3)1 / 2 or less.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a binder resin composition for toner used for developing a latent image formed in an electrophotographic method, an electrostatic recording method, an electrostatic printing method, etc., and an electrostatic charge image developing toner containing the binder resin composition for toner.

Background Art

[0002] In the field of electrophotography, with the development of electrophotographic systems, there is a demand for the development of an electrostatic charge image developing toner (hereinafter, also simply referred to as "toner") that can cope with high image quality and high speed. For example, in order to cope with the high speed of machines, toners are required to have excellent low-temperature fixing properties. However, when toners with good low-temperature fixing properties are used for a large amount of printing and the printed materials are stacked, they tend to be in a high-temperature environment without being cooled. Due to the softening of the fixed image, sticking between printed surfaces due to their own weight, or image roughness occurring when peeled off, the image heat resistance decreases, and unevenness in image density and gloss is likely to occur. Therefore, there is a demand for a toner that achieves both low-temperature fixing properties and image heat resistance.

[0003] For example, Patent Document 1 describes a toner having toner particles containing a binder resin and a crystalline polyester, with the binder resin containing a polyester having a silicone structure, for the purpose of providing a toner excellent in low-temperature fixing properties and image storage properties. Further, Patent Document 2 describes a binder resin for toner, which is a reaction product of an alcohol component containing a dihydric or higher alcohol, a carboxylic acid component containing a dicarboxylic or higher carboxylic acid compound, and a silicone having at least one selected from an amino group, a carboxy group, an epoxy group, and a carbinol group in its side chain, for the purpose of providing a toner excellent in low-temperature fixing properties, anti-document offset properties, and anti-filming properties.

Prior Art Documents

Patent Documents

[0004] [Patent Document 1] Japanese Patent Publication No. 2021-060582 [Patent Document 2] Japanese Patent Publication No. 2020-063412 [Overview of the project] [Problems that the invention aims to solve]

[0005] The technology described in Patent Document 1 suffers from insufficient compatibility between the obtained silicone-containing polyester and crystalline polyester during heating, leaving room for improvement in low-temperature fixability. Furthermore, while the technology described in Patent Document 2 provides a toner with excellent low-temperature fixability, document offset resistance, and filming resistance, there is still room for improvement in image heat resistance. Therefore, there is a need for the development of a toner with excellent low-temperature fixability and image heat resistance.

[0006] The present invention relates to a binder resin composition for toner that provides a toner with excellent low-temperature fixability and image heat resistance, and toner for electrostatic image development containing the toner binder resin composition. [Means for solving the problem]

[0007] The present invention relates to either [1] or [2] below. [1] A binder resin composition for toner containing an amorphous resin (A) which is a polycondensate of an alcohol component containing a divalent or higher alcohol, a carboxylic acid component containing a divalent or higher carboxylic acid compound, and a modified silicone having polar groups, and a crystalline resin (C), The solubility parameter (SP value) of Fedors is calculated from the alcohol and carboxylic acid components of the amorphous resin (A). A ) is 11.0 (cal / cm³) 3 ) 1 / 2 The following conditions apply: the polarity value of the modified silicone is 10.0 mgKOH / g or more, and the SP value of the crystalline resin (C) is (SP C ) is 9.6 (cal / cm 3 ) 1 / 2 The following is a binder resin composition for toner. 〔2〕 An electrostatic charge image developing toner, wherein the binder resin contains the toner binder resin composition described in 〔1〕. [[ID= 3]]

Advantages of the Invention

[0008] According to the present invention, there are provided a toner binder resin composition that provides a toner excellent in low-temperature fixing property and image heat resistance, and an electrostatic charge image developing toner containing the toner binder resin composition.

Modes for Carrying Out the Invention

[0009] [Toner Binder Resin Composition] The toner binder resin composition according to an embodiment of the present invention is a polycondensate of an alcohol component containing a dihydric or higher alcohol, a carboxylic acid component containing a dicarboxylic acid compound or higher, and a modified silicone having a polar group, and is an amorphous resin (A) and a crystalline resin (C). The toner binder resin composition, wherein the Fedors solubility parameter (SP value) (SP A ) calculated from the alcohol component and the carboxylic acid component of the amorphous resin (A) is 11.0 (cal / cm 3 ) 1 / 2 or less, the polar group value of the modified silicone is 10.0 mgKOH / g or more, and the SP value (SP C ) of the crystalline resin (C) is 9.6 (cal / cm 3 ) 1 / 2 or less. According to the above configuration, it is possible to provide a toner binder resin composition that provides a toner excellent in low-temperature fixing property and image heat resistance, and an electrostatic charge image developing toner containing the toner binder resin composition.

[0010] The reason for obtaining such an effect is not clear, but it is considered as follows. In order to improve the low-temperature fixing property of the toner, it is effective to use a crystalline resin having a high affinity with the amorphous resin to lower the fixing temperature of the toner. However, if the affinity between the amorphous resin and the crystalline resin is too high, there will be a problem that the crystalline resin dissolves too much in the amorphous resin, resulting in deterioration of heat resistance performance such as image heat resistance. Amorphous resin (A) has a Fedors solubility parameter (SP value) of 11.0 (cal / cm³) calculated from the alcohol and carboxylic acid components of amorphous resin (A). 3 ) 1 / 2 If the following conditions are met, the reaction between the modified silicone and the carboxylic acid component proceeds preferentially, and then the reaction product of the modified silicone and the carboxylic acid component reacts with the alcohol component, resulting in a high rate of introduction of the modified silicone into the amorphous resin (A). Furthermore, if the polarity value of the modified silicone is 10.0 mgKOH / g or higher, the modified silicone moieties introduced into the amorphous resin (A) can interact with the crystalline resin (C) via unreacted polar groups through intermolecular forces such as hydrogen bonding, and the SP value of the crystalline resin (C) becomes 9.6 (cal / cm²). 3 ) 1 / 2 Even under the following conditions, the compatibility between amorphous resin (A) and crystalline resin (C) increases. When the polar group of the modified silicone is an amino group and the crystalline resin (C) has an acidic group, the compatibility between amorphous resin (A) and crystalline resin (C) is thought to increase further due to acid-base interactions. Therefore, even if the melting point of crystalline resin (C) is relatively high, the toner can soften at low temperatures, and the low-temperature fixability of the toner is thought to improve. On the other hand, in processes where heat resistance of the image is required, crystalline resin (C), which has a relatively high melting point, is more likely to crystallize, and hardens the binder resin composition for the toner, thus improving the heat resistance of the fixed image.

[0011] 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. Regarding hydrocarbon groups, the notation "(iso or tertiary)" and "(iso)" in parentheses means both the presence and absence of these prefixes, and the absence of these prefixes indicates the normal group. "(Meth)acrylic acid" means at least one selected from acrylic acid and methacrylic acid.

[0012] The toner binder resin composition of the present invention contains an amorphous resin (A) which is a polycondensate of an alcohol component containing a divalent or higher alcohol, a carboxylic acid component containing a divalent or higher carboxylic acid compound, and a modified silicone having polar groups, and a crystalline resin (C).

[0013] [Amorphous resin (A)] Amorphous resin (A) (hereinafter also simply referred to as "resin (A)") is a polycondensate of an alcohol component, a carboxylic acid component, and a modified silicone, and includes an amorphous silicone-modified polyester resin having amorphous polyester resin segments and silicone segments.

[0014] Furthermore, resin (A) may include not only an amorphous silicone-modified polyester resin, but also an amorphous polyester resin which is a polycondensate of an unreacted alcohol component and a carboxylic acid component with the modified silicone.

[0015] <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.

[0016] The alkylene oxide adduct of an aromatic diol is preferably an alkylene oxide adduct of bisphenol A, and more preferably of formula (I):

[0017] [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, with propylene oxide adducts of bisphenol A being more 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%.

[0018] 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.

[0019] 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, 1,12-dodecanediol, 1,2-propanediol, and neopentyl glycol.

[0020] 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.

[0021] <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 mol% or more, more preferably 90 mol% or more, even more preferably 95 mol% or more, and 100 mol% 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 polyvalent carboxylic acid compounds. Among these, aromatic dicarboxylic acid compounds are preferred.

[0022] 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 80 mol% or more, more preferably 90 mol% or more, even more preferably 95 mol% or more, and 100 mol% or less, of the carboxylic acid component.

[0023] 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, fumaric acid is preferred. If a linear or branched aliphatic dicarboxylic acid compound is included, its amount is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, and preferably 90 mol% or less, more preferably 80 mol% or less, of the carboxylic acid component.

[0024] 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.

[0025] The ratio of carboxyl groups of the carboxylic acid component to hydroxyl groups of the alcohol component (COOH group / OH group) is preferably 0.6 or more, more preferably 0.7 or more, and preferably 1.1 or less, more preferably 1.0 or less.

[0026] <Modified silicone> The modified silicone used in resin (A) is, from the viewpoint of obtaining a toner binder resin composition that provides a toner with excellent low-temperature fixability and image heat resistance, a modified silicone having a polar group reactive with a hydroxyl group or a carboxyl group in its side chain, preferably a modified silicone having a polar group reactive with a hydroxyl group or a carboxyl group in its side chain, and more preferably a modified silicone having at least one polar group selected from an amino group, a carboxyl group, an epoxy group, and a hydroxyl group in its side chain.

[0027] From the viewpoint of obtaining a toner binder resin composition that provides a toner with excellent low-temperature fixability and image heat resistance, the polarity value of the modified silicone is 10.0 mg KOH / g or more, preferably 10.5 mg KOH / g or more, more preferably 11.0 mg KOH / g or more, and preferably 50.0 mg KOH / g or less, more preferably 40.0 mg KOH / g or less, and even more preferably 30.0 mg KOH / g or less. The polarity value of modified silicone is the value obtained by converting the polar groups present in 1 g of modified silicone into the number of mg of potassium hydroxide. For example, if the polar group is an amino group, the polarity value can be measured by the method of JIS K2501:2003, and if the polar group is a carboxyl group or a hydroxyl group, it can be measured by the method of JIS K0070:1992. If the polar group is an epoxy group, the polarity value can be determined by adding hydrochloric acid to a solution of modified silicone containing epoxy groups and converting the amount consumed by chlorohydrination into the number of mg of potassium hydroxide.

[0028] The modified silicone preferably has repeating units represented by formula (1) and / or a structure represented by formula (3), and repeating units represented by formula (2). More preferably, the modified silicone has repeating units represented by formula (1) and repeating units represented by formula (2), and the modified silicone has repeating units represented by formula (2) and a structure represented by formula (3) at both ends, and even more preferably, the modified silicone has repeating units represented by formula (1) and repeating units represented by formula (2).

[0029] [ka] [In formula (1), 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 a group containing an amino group, a carboxyl group, an epoxy group, or a hydroxyl group, and * is a bonding site.]

[0030] [ka] [In formula (2), R is independently a hydrocarbon group having 1 to 6 carbon atoms, and * is a bonding site.]

[0031] *-SiR 3-b (R''-X) b (3) [In formula (3), R is independently a hydrocarbon group having 1 to 6 carbon atoms, R'' is independently an alkylene group having 1 to 10 carbon atoms, b is an integer between 1 and 3, X is independently a group containing an amino group, a carboxyl group, an epoxy group, or a hydroxyl group, and * is a bonding site to the repeating unit represented by formula (2).]

[0032] The repeating units represented by equation (1) and equation (2) may be random or block-based, and are not particularly limited.

[0033] In formulas (1) to (3), 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.

[0034] In formulas (1) and (3), the number of carbon atoms in the alkylene groups R' and 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 alkylene groups for R' and 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.

[0035] Each of X is independently a group containing an amino group, a carboxyl group, an epoxy group, or a hydroxyl group, and is preferably 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, and a carboxyalkyloxy group may have multiple carboxyl groups. In particular, from the viewpoint of reactivity with the carboxyl group of a divalent or higher carboxylic acid compound, and from the viewpoint of improving the low-temperature fixability of the toner, X is preferably an amino group.

[0036] The modified silicone contains 40 or fewer repeating units represented by formula (1), preferably 20 or fewer, more preferably 10 or fewer, and 1 or more. Furthermore, the repeating unit represented by formula (2) is included in a number of 500 or less, preferably 450 or less, more preferably 400 or less, and preferably 10 or more, preferably 30 or more, more preferably 50 or more.

[0037] 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 2,000 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.

[0038] The kinematic viscosity of the modified silicone is preferably 10 mm at 25°C. 2 / s or more, more preferably 30 mm 2 / s or more, more preferably 50mm 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 can be measured, for example, using a fully automated micro-kinematic viscometer (manufactured by Viscotec Co., Ltd.).

[0039] Examples of the modified silicones mentioned above include: 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.)), modified silicones having an amino group at one end; 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.)), modified silicones having a carboxyl group at one end (commercial products such as "X-22-3710" (manufactured by Shin-Etsu Chemical Co., Ltd.)); epoxy groups Examples include modified silicones having a side chain (commercially available products include "X-22-343" (manufactured by Shin-Etsu Chemical Co., Ltd.)), modified silicones having epoxy groups at both ends (commercially available products include "X-22-163B" and "X-22-169B" (manufactured by Shin-Etsu Chemical Co., Ltd.)), modified silicones having an epoxy group at one end (for example, "X-22-173BX" (manufactured by Shin-Etsu Chemical Co., Ltd.)), modified silicones having a hydroxyl group as a side chain (commercially available product includes "X-22-4039" (manufactured by Shin-Etsu Chemical Co., Ltd.)), modified silicones having hydroxyl groups at both ends (commercially available products include "KF-6003" and "KF-6002" (manufactured by Shin-Etsu Chemical Co., Ltd.)), and modified silicones having a hydroxyl group at one end (commercially available products include "X-22-170BX" and "X-22-170DX" (manufactured by Shin-Etsu Chemical Co., Ltd.)).

[0040] If the modified silicone is a modified silicone having a group containing an amino group, then in the repeating unit represented by formula (1) and the structure represented by formula (3), *-(R') a Examples of groups represented by -X and -(R''-X) include the substituents 1a-1 to 1a-3 listed below.

[0041] [ka]

[0042] If the modified silicone is a modified silicone having a group containing a hydroxyl group, then in the repeating unit represented by formula (1) and the structure represented by formula (3), *-(R') a Examples of the groups represented by -X and -(R''-X) include 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.

[0043] [ka]

[0044] When the modified silicone is a modified silicone having a group containing an epoxy group, it is preferable that X and Y in the repeating unit represented by formula (1) and the structure represented by formula (3) are a glycidyl group, a glycidyloxy group, and an alicyclic epoxy group, and *-(R') a Examples of the groups represented by -X and -(R''-X) include substituents 1b-4 to 1b-6 listed below. Of these, substituent 1b-4 is preferred.

[0045] [ka]

[0046] When the modified silicone is a modified silicone having a group containing a carboxyl group, it is preferable that X and Y in the repeating unit represented by formula (1) and the structure represented by formula (3) are carboxyl groups or carboxyalkyloxy groups, and *-(R') a Examples of the groups represented by -X and -(R''-X) include the substituents 1b-7 listed below.

[0047] [ka]

[0048] (Method of manufacturing resin (A)) 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] The amount of modified silicone added to resin (A) is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, even more preferably 1 part by mass or more, and preferably 9 parts by mass or less, more preferably 7 parts by mass or less, even more preferably 6 parts by mass or less, even more preferably 5 parts by mass or less, and even more preferably 4 parts by mass or less, based on 100 parts by mass of the theoretical yield of polyester obtained from the alcohol and carboxylic acid components in the raw materials of resin (A). If resin (A) contains an amorphous silicone-modified polyester resin which is a polycondensate of an alcohol component, a carboxylic acid component, and a modified silicone, then the amorphous polyester resin consisting of the same alcohol component and carboxylic acid component as the amorphous silicone-modified polyester resin shall be considered as resin (A).

[0050] 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.

[0051] (Physical properties of resin (A)) Solubility parameter (SP value) calculated by the Fedors method from the alcohol and carboxylic acid components of resin (A) (SP A ) is a binder resin composition for toners that provides toner with excellent low-temperature fixability and image heat resistance, with a value of 11.0 (cal / cm²). 3 ) 1 / 2 The following applies. And preferably 9.8 (cal / cm²). 3 ) 1 / 2 More preferably 10.0 (cal / cm²) 3 ) 1 / 2 More preferably 10.2 (cal / cm²) 3 ) 1 / 2 That's all.

[0052] The acid value of resin (A) is preferably 0.1 mg KOH / g or more, more preferably 0.5 mg KOH / g or more, even more preferably 1 mg KOH / g or more, and preferably 40 mg KOH / g or less, more preferably 30 mg KOH / g or less, even more preferably 20 mg KOH / g or less, and even more preferably 17 mg KOH / g or less. The hydroxyl value of resin (A) is preferably 0.1 mg KOH / g or more, more preferably 10 mg KOH / g or more, even more preferably 20 mg KOH / g or more, and preferably 90 mg KOH / g or less, more preferably 80 mg KOH / g or less, and even more preferably 70 mg KOH / g or less.

[0053] The softening point of resin (A) is preferably 70°C or higher, more preferably 80°C or higher, and even more preferably 85°C or higher, and from the viewpoint of further improving low-temperature fixability, it is preferably 130°C or lower, more preferably 120°C or lower, and even more preferably 110°C or lower. The glass transition temperature of resin (A) is preferably 40°C or higher, more preferably 45°C or higher, and even more preferably 48°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.

[0054] The number-average molecular weight (Mn) of resin (A) is preferably 500 or more, more preferably 1,000 or more, even more preferably 1,200 or more, and preferably 20,000 or less, more preferably 10,000 or less, even more preferably 7,000 or less, even more preferably 5,000 or less, and even more preferably 3,000 or less. The weight-average molecular weight (Mw) of resin (A) is preferably 500 or more, more preferably 1,000 or more, even more preferably 1,500 or more, even more preferably 3,000 or more, and preferably 50,000 or less, more preferably 20,000 or less, even more preferably 15,000 or less, and even more preferably 10,000 or less.

[0055] Solubility parameter (SP) of resin (A) A The solubility parameter (SP) of the resin (A) obtained as a mixture of two or more resins can be appropriately adjusted depending on the type and amount of raw material monomers used, as well as the manufacturing conditions such as reaction temperature, reaction time, and cooling rate, and can be determined by the method described in the examples below. A Preferably, the acid value, hydroxyl value, softening point, glass transition temperature, number average molecular weight, and weight average molecular weight are all within the above ranges.

[0056] [Amorphous resin (B)] The toner binder resin composition of the present invention may contain an amorphous resin (B) (hereinafter also referred to as "resin (B)") from the viewpoint of obtaining a toner for electrostatic image development that has excellent low-temperature fixing properties and image heat resistance.

[0057] Resin (B) is not particularly limited, but is an amorphous resin having a softening point 5°C or more higher than the softening point of amorphous resin (A), and is preferably an amorphous polyester resin (B1) (hereinafter also referred to as "resin (B1)"). The difference in softening points between resin (A) and resin (B) is preferably 10°C or higher, more preferably 20°C or higher, even more preferably 25°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 fixability and image heat resistance.

[0058] Resin (B1) is, for example, an amorphous polyester resin containing a polycondensate of an alcohol component and a carboxylic acid component. Examples of resin (B1) include polyester resin and modified polyester resin. Examples of modified polyester resins include urethane-modified polyester resin, epoxy-modified polyester resin, and composite resins containing polyester resin segments and addition polymerization resin segments. Among these, amorphous polyester resin which is a polycondensate of alcohol and carboxylic acid components is preferred.

[0059] <Alcohol content> The alcohol components include the same alcohol components listed as those for resin (A).

[0060] 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%.

[0061] <Carboxylic acid components> Examples of carboxylic acid components include those listed as the carboxylic acid component of resin (A). The carboxylic acid component includes a divalent or higher carboxylic acid compound, and its content is preferably 80 mol% or more, more preferably 90 mol% or more, even more preferably 95 mol% or more, and 100 mol% or less of the total carboxylic acid component.

[0062] 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.

[0063] As linear or branched aliphatic dicarboxylic acid compounds, 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 3 mol% or more, even more preferably 5 mol% or more, and preferably 20 mol% or less, more preferably 15 mol% or less, and even more preferably 10 mol% or less, of the carboxylic acid component.

[0064] As the polycarboxylic acid compound with a valency of 3 or higher, 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 5 mol% or more, more preferably 10 mol% or more, even more preferably 15 mol% or more, and preferably 40 mol% or less, more preferably 35 mol% or less, and even more preferably 30 mol% or less, in the carboxylic acid component.

[0065] 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.

[0066] When resin (B1) is a composite resin having a polyester resin segment and 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. For composite resins, see Japanese Patent Publication No. 2021-026129.

[0067] If the amorphous resin (B) is an amorphous polyester resin, it may be manufactured, for example, by a process of polycondensation of an alcohol component and a carboxylic acid component.

[0068] In the polycondensation step, 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 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 carboxylic acid component before 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.

[0069] (Physical properties of resin (B)) Solubility parameter (SP value) calculated by the Fedors method from the alcohol and carboxylic acid components of resin (B) (SP B From the viewpoint of obtaining a toner binder resin composition that provides a toner with excellent low-temperature fixability and image heat resistance, the coefficient is preferably 11.0 (cal / cm²). 3 ) 1 / 2 The following, and 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 That's all.

[0070] The acid value of resin (B) is preferably 0.1 mg KOH / g or more, more preferably 0.5 mg KOH / g or more, even more preferably 1 mg KOH / g or more, and preferably 40 mg KOH / g or less, more preferably 30 mg KOH / g or less, and even more preferably 20 mg KOH / g or less. The hydroxyl value of resin (B) is preferably 0.1 mg KOH / g or more, more preferably 10 mg KOH / g or more, even more preferably 20 mg KOH / g or more, and preferably 70 mg KOH / g or less, more preferably 60 mg KOH / g or less, and even more preferably 50 mg KOH / g or less.

[0071] 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, and from the viewpoint of further improving low-temperature fixability, 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, and from the viewpoint of further improving low-temperature fixation, it is preferably 80°C or lower, more preferably 75°C or lower, and even more preferably 70°C or lower.

[0072] The solubility parameters, acid value, hydroxyl value, softening point, and glass transition temperature 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 solubility parameter, acid value, hydroxyl value, softening point, and glass transition temperature obtained from the mixture thereof are all within the aforementioned ranges.

[0073] In the toner binder resin composition of the present invention, when resin (B) is included, the mass ratio of resin (B) to resin (A) (resin (B) / resin (A)) is preferably 10 / 90 or more, more preferably 15 / 85 or more, even more preferably 30 / 70 or more, and preferably 90 / 10 or less, more preferably 70 / 30 or less, even more preferably 60 / 40 or less, and even more preferably 50 / 50 or less.

[0074] [Crystalline resin (C)] The crystalline resin (C) (hereinafter also simply referred to as "resin (C)") contained in the toner binder resin composition of the present invention is preferably a crystalline polyester resin (C1) (hereinafter also referred to as "resin (C1)") which is a polycondensate of an alcohol component and a carboxylic acid component. From the viewpoint of improving the low-temperature fixability of the toner, the crystalline resin (C) is preferably said to have acidic groups.

[0075] <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, and 1,12-dodecanediol is even more preferred.

[0076] The amount of aliphatic diol is preferably 40 mol% or more, more preferably 45 mol% or more, even more preferably 50 mol% or more, and 100 mol% or less, in the alcohol component.

[0077] The alcohol component may contain other alcohol components different from aliphatic diols. Examples of other alcohol components include alkylene oxide adducts of aromatic diols such as alkylene oxide adducts of bisphenol A; trihydric or higher alcohols such as glycerin, pentaerythritol, and trimethylolpropane; and long-chain monohydric alcohols such as stearyl alcohol. One or more of these alcohol components may be used.

[0078] <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, dodecanediic acid and sebacic acid are more preferred. One or more of these carboxylic acid components may be used.

[0079] 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 of the carboxylic acid component.

[0080] 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; polycarboxylic acid compounds with a valency of 3 or higher; and long-chain monovalent carboxylic acids such as stearic acid. One or more of these carboxylic acid components may be used.

[0081] 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 1.5 or lower, more preferably 1.4 or lower. (Physical properties of resin (C))

[0082] Solubility parameter (SP value) of resin (C) by Fedors method (SP C ) is a binder resin composition for toners that provides toner with excellent low-temperature fixability and image heat resistance, with a value of 9.6 (cal / cm²). 3 ) 1 / 2 The following applies. And preferably 8.9 (cal / cm²). 3 ) 1 / 2 More preferably 9.1 (cal / cm²) 3 ) 1 / 2 More preferably 9.3 (cal / cm²) 3 ) 1 / 2 That's all.

[0083] The acid value of resin (C) is preferably 1 mg KOH / g or more, more preferably 3 mg KOH / g or more, even more preferably 5 mg KOH / g or more, and preferably 40 mg KOH / g or less, more preferably 30 mg KOH / g or less, and even more preferably 20 mg KOH / g or less, from the viewpoint of improving the low-temperature fixing performance of the toner.

[0084] The softening point of resin (C) is preferably 55°C or higher, more preferably 60°C or higher, even more preferably 65°C or higher, and preferably 110°C or lower, more preferably 100°C or lower, and even more preferably 95°C or lower. The melting point of resin (C) is preferably 50°C or higher, more preferably 60°C or higher, and even more preferably 65°C or higher, and from the viewpoint of further improving low-temperature fixability, it is preferably 100°C or lower, more preferably 95°C or lower, and even more preferably 90°C or lower.

[0085] Solubility parameter (SP) of resin (C) C The solubility parameter (SP) of the resin (C) obtained as a mixture of two or more resins (C) 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, and can be determined by the method described in the examples below. C Preferably, the acid value, softening point, and melting point are all within the aforementioned ranges.

[0086] The mass ratio of resin (C) to resin (A) (resin (C) / resin (A)) is preferably 1 / 99 or more, more preferably 5 / 95 or more, even more preferably 10 / 90 or more, and preferably 50 / 50 or less, more preferably 30 / 70 or less, and even more preferably 20 / 80 or less. Furthermore, the mass ratio of resin (C) to the total mass of resin (A) and resin (B) (resin (C) / resin (A) + resin (B)) is preferably 1 / 99 or more, more preferably 3 / 97 or more, even more preferably 5 / 95 or more, and preferably 50 / 50 or less, more preferably 40 / 60 or less, and even more preferably 30 / 70 or less.

[0087] [Toner for developing electrostatic images] An electrostatic image developing toner according to one embodiment of the present invention (hereinafter also simply referred to as "toner") is an electrostatic image developing toner containing a binder resin, wherein the binder resin contains the toner binder resin composition of the present invention described above. According to the present invention, it is possible to provide a toner for electrostatic image development that provides excellent low-temperature fixing properties and image heat resistance. The toner for developing electrostatic images contains at least the above-mentioned binder resin, and may also contain other components such as colorants, release agents, and charge control agents. Preferably, the toner for developing electrostatic images contains toner matrix particles (hereinafter also referred to as "toner particles") and external additives added to the toner matrix particles.

[0088] <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.

[0089] 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.

[0090] <Release agent> Examples of release agents include hydrocarbon waxes, ester waxes, silicone waxes, and fatty acid amide waxes.

[0091] 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.

[0092] The release agent content is preferably 0.5 parts by mass or more, more preferably 1.0 part by mass or more, even more preferably 1.5 parts by mass or more, and preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 3 parts by mass or less, based on 100 parts by mass of the total amount of binder resin.

[0093] <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.).

[0094] 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.

[0095] 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 0.5 parts by mass or more, and preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 3 parts by mass or less, based on 100 parts by mass of the total amount of binder resin.

[0096] [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, 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 resin (A) and resin (C), and optionally resin (B), colorants, release agents, and charge control agents, can be 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 method for producing toner preferably includes a step of melting and kneading a mixture containing resin (A) and resin (C), and optionally 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.

[0097] Volume-intermediate particle size of toner particles (D 50 From the viewpoint of obtaining a toner for electrostatic image development that has excellent low-temperature fixability and image heat resistance, the particle size is preferably 2 μm or more, more preferably 3 μm or more, and even more preferably 4 μm or more. From the viewpoint of hot offset resistance, the particle size is 8 μm or less, preferably 7 μm or less, and more preferably 6.8 μm or less.

[0098] 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 external additives include inorganic material nanoparticles such as hydrophobic silica, titanium dioxide nanoparticles, alumina nanoparticles, cerium oxide nanoparticles, and carbon black, as well as polymer nanoparticles such as polycarbonate, polymethyl methacrylate, and silicone resin. Among these, hydrophobic silica is preferred. When using external additives, the amount of external additive added is preferably 0.5 parts by mass or more, preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and even more preferably 3 parts by mass or less, per 100 parts by mass of toner particles.

[0099] 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]

[0100] 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.

[0101] [Measurement method] [Acid value and hydroxyl value of resins] The acid value and hydroxyl value of the resins were measured according to the method of JIS K0070:1992. However, the measurement solvent was changed from the ethanol and ether mixed solvent specified in JIS K0070:1992 to an acetone and toluene mixed solvent [acetone:toluene = 1:1 (volume ratio)] for amorphous resins, and to chloroform for crystalline resins.

[0102] [Amine value of modified silicone] The total amine value of the modified silicone was measured according to the ASTM D2073 method. However, the measurement solvent was changed from ethanol to toluene as specified in ASTM D2073.

[0103] [Number-average molecular weight and weight-average molecular weight of resins] The molecular weight distribution was measured by gel permeation chromatography (GPC), obtained using the following method, and the number-average molecular weight and weight-average molecular weight were determined. (1) Preparation of sample solution The sample was dissolved in tetrahydrofuran (for amorphous resins) or chloroform (for crystalline resins) at 25°C to a concentration of 0.5 g / 100 mL. This solution was then filtered using a fluoropolymer filter "DISMIC-25JP" (manufactured by ADVANTEC) with a pore size of 0.2 μm to remove undissolved material and obtain the sample solution. (2) Molecular weight measurement Using the measurement apparatus and analytical column described below, tetrahydrofuran (amorphous resin) or chloroform (crystalline resin) was flowed as the eluent at a flow rate of 1 mL / min, and the column was stabilized in a constant temperature bath at 40°C. 100 μL of the sample solution was injected into the column and measurements were performed. The molecular weight of the sample was calculated based on a calibration curve prepared in advance. The calibration curve used in this case included several types of monodisperse polystyrene "A-500" (5.0 × 10⁻¹⁰). 2 ), "A-1000" (1.01 x 10 3 ), "A-2500" (2.63 x 10 3 ), "A-5000" (5.97 x 10 3 ), "F-1" (1.02×10 3 ), "F-2" (1.81×10 4 ), "F-4" (3.97×10 4 ), "F-10" (9.64×10 4 ), "F-20" (1.90×10 5 ), "F-40" (4.27×10 5 ), "F-80" (7.06×10 5 ), "F-128" (1.09×10 6 The above samples were prepared using Tosoh Corporation's standard sample. Measuring device: "HLC-8220CPC" (manufactured by Tosoh Corporation) Analysis columns: "GMHXL" + "G3000HXL" (manufactured by Tosoh Corporation)

[0104] [Softening point of resin] 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.

[0105] [Glass transition temperature of amorphous resins] Using a differential scanning calorimeter "Q-20" (manufactured by T.A. Instruments Japan Co., Ltd.), 0.01 to 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. Next, the sample was heated at a rate of 10°C / min, and the temperature at the intersection of the extension of the baseline below the highest endothermic peak temperature and the tangent line showing the maximum slope from the rise of the peak to the peak apex was defined as the glass transition temperature.

[0106] [Melting point of crystalline resins] Using a differential scanning calorimeter "Q-100" (manufactured by T.A. Instruments Japan Co., Ltd.), 0.01 to 0.02 g of the sample was weighed into an aluminum pan and cooled from room temperature to -10°C at a rate of 10°C / min, holding the temperature for 1 minute. Next, the sample was heated to 200°C at a rate of 10°C / min, and then cooled from that temperature to -30°C at a rate of 10°C / min. Then, the sample was heated again at a rate of 10°C / min, and the peak temperature on the highest endothermic side of the observed endothermic peaks was defined as the melting point.

[0107] [Melting point of release agent] Using a differential scanning calorimeter "Q-100" (manufactured by T.A. Instruments Japan Co., Ltd.), 0.02 g of the sample was weighed into an aluminum pan, heated to 200°C, and then cooled from 200°C to 0°C at a rate of 10°C / min. Next, the sample was heated again at a rate of 10°C / min, and the amount of heat was measured. The maximum peak temperature of the obtained endothermic reaction was defined as the melting point.

[0108] [Toner particle volume median particle size (D 50 )〕 Volume-intermediate particle size of toner particles (D 50 The following measurements were taken: • Measuring device: "Coulter Multisizer (registered trademark) III" (manufactured by Beckman Coulter, Inc.) • Aperture diameter: 50 μm • Analysis software: "Coulter Multisizer (registered trademark) III version 3.51" (manufactured by Beckman Coulter, Inc.) • Electrolyte: "Isoton (registered trademark) II" (manufactured by Beckman Coulter, Inc.) • Dispersion: "Emulgen (registered trademark) 109P" [polyoxyethylene lauryl ether, manufactured by Kao Corporation, HLB (Hydrophile-Lipophile Balance, Griffin method) = 13.6] was dissolved in the electrolyte to obtain a dispersion with a concentration of 5% by mass. • Dispersion conditions: 10 mg of the sample was added to 5 mL of the dispersion, dispersed for 1 minute using an ultrasonic disperser, then 25 mL of electrolyte was added, and dispersed again for 1 minute using an ultrasonic disperser to prepare the sample dispersion. • Measurement conditions: In a beaker, the sample dispersion is added to 100 mL of the electrolyte to adjust the concentration to a level that allows for the measurement of 30,000 particle sizes in 20 seconds. Then, the 30,000 particles are measured, and the median particle size (D) is determined from the obtained particle size distribution. 50 ) was sought.

[0109] [Toner Evaluation] [Minimum fixing temperature] A modified fuser unit of the "AR-505" copier (manufactured by Sharp Corporation) was modified to allow for external fixing, and toner was installed in this modified unit. A printed document was obtained in an unfixed state (print area: 2cm x 12cm, adhesion amount: 0.5mg / cm²). 2 Subsequently, using a fuser (fixing speed 300 mm / sec) adjusted to a total fixing pressure of 30 kgf, fixing tests were performed on unfixed printed materials at each temperature, while sequentially increasing the temperature of the fixing roll from 100°C to 240°C in 5°C increments. Cellophane adhesive tape "UNICEF Cellophane" (manufactured by Mitsubishi Pencil Co., Ltd., width: 18 mm, JIS Z 1522) was attached to the image portion of the obtained printed material, and after passing it through a fixing roller set to 30°C, the tape was removed. The paper used for printing was "CopyBond SF-70NA" (manufactured by Sharp Corporation, 75 g / m²). 2 ) was used. The optical reflectance density before and after tape application was measured using a reflectance densitometer "RD-915" (Gretag Macbeth Corporation). The minimum fixing temperature was defined as the temperature of the fixing roller at which the ratio of the two (after peeling / before application × 100) first exceeded 90%. A lower minimum fixing temperature indicates superior low-temperature fixing performance.

[0110] [Image heat resistance] A modified fuser unit of the "AR-505" copier (manufactured by Sharp Corporation) was modified to allow for external fixing, and toner was installed in this modified unit. A printed document was obtained in an unfixed state (print area: 2cm x 12cm, adhesion amount: 0.5mg / cm²). 2 Subsequently, a fuser (fixing speed 300 mm / sec) adjusted to achieve a total fixing pressure of 30 kgf was used, and the temperature of the fuser roll was set to 140°C to fix the unfixed printed material. The paper used for printing was "CopyBond SF-70NA" (manufactured by Sharp Corporation, 75 g / m²). 2 ) was used. The fixed images are superimposed, and 100g / cm² 2 Under the conditions of weight, temperature of 60°C, and humidity of 50%, the samples were left for one day, and the presence or absence of document offset was visually checked after peeling them off after one day. The obtained results were evaluated according to the following criteria. A: The document offset cannot be confirmed. B: No peeling of the fixed image was observed, but slight sticking occurred when peeling it off. C: When peeling, sticking may occur, resulting in slight peeling (white spots, etc.) in the fixed image. D: When peeling it off, it sticks, and white areas are clearly visible in the fixed image. E: The papers are stuck together and will be damaged if you try to separate them.

[0111] [Resin manufacturing] Manufacturing example A1 (Manufacturing of resin A-1) The alcohol component, carboxylic acid component, amino-modified silicone, esterification catalyst, and esterification co-catalyst shown in Table 1-1 were placed in a 10-liter four-necked flask equipped with a thermometer, stainless steel stirring rod, fractionation column, dehydration tube, condenser, and nitrogen inlet tube. The mixture was heated to 235°C in a mantle heater under a nitrogen atmosphere and reacted at atmospheric pressure for 4 hours. Subsequently, the reaction was carried out under reduced pressure at 235°C and 8 kPa until the desired acid value and softening point were reached, yielding silicone-modified amorphous polyester resin A-1. Various physical properties are shown in Table 1-1.

[0112] Manufacturing examples A2-A4 and A6, and comparative manufacturing examples A'2 and A'3 (manufacturing of resins A-2-A-4 and A-6, and resins A'-2 and A'-3) Except for changing the types and amounts of alcohol component, carboxylic acid component, amino-modified silicone, esterification catalyst, and esterification co-catalyst as shown in Tables 1-1 and 1-2, the reaction was carried out under the same conditions as in Production Example A1 until the desired acid value and softening point were obtained, yielding silicone-modified amorphous polyester resins A-2 to A-4, A-6, and resins A'-2 and A'-3. Various physical properties are shown in Tables 1-1 and 1-2.

[0113] Manufacturing example A5 (Manufacturing of resin A-5) The alcohol components, terephthalic acid, amino-modified silicone, esterification catalyst, and esterification co-catalyst shown in Table 1-1 were placed in a 10-liter four-necked flask equipped with a thermometer, stainless steel stirring rod, fractionation column, dehydration tube, condenser, and nitrogen inlet tube. The mixture was heated to 235°C in a mantle heater under a nitrogen atmosphere and reacted under reduced pressure of 8 kPa for 1 hour. After cooling to 180°C at atmospheric pressure, fumaric acid and radical polymerization inhibitors shown in Table 1-1 were added, and the temperature was gradually increased to 210°C at a rate of 10°C / h. Subsequently, the reaction was carried out under reduced pressure at 210°C and 16 kPa to the desired softening point, yielding silicone-modified amorphous polyester resin A-5. Various physical properties are shown in Table 1-1.

[0114] Comparative manufacturing example A'1 (Manufacturing of resin A'-1) The alcohol component, carboxylic acid component, esterification catalyst, and esterification co-catalyst shown in Table 1-2 were placed in a 10-liter four-necked flask equipped with a thermometer, stainless steel stirring rod, fractionation column, dehydration tube, condenser, and nitrogen inlet tube. The reaction was carried out under the same conditions as in Production Example A1 until the desired acid value and softening point were reached, yielding amorphous polyester resin A'-1. Various physical properties are shown in Table 1-2.

[0115] The amino-modified silicones used in Tables 1-1 and 1-2 have the following composition. • KF-864: Modified silicone "KF-864" (a modified silicone having monoamino groups in its side chains, kinematic viscosity (25℃) = 1,700 mmHg) 2 ( / s, molecular weight = 30,000, functional group equivalent = 3,800 g / mol, total amine value 14.7 mg KOH / g, manufactured by Shin-Etsu Chemical Co., Ltd.) • KF-865: Modified silicone oil "KF-865" (modified silicone with monoamino groups in its side chains, kinematic viscosity (25℃) = 110 mmHg) 2 ( / s, Molecular weight = 5,000, Functional group equivalent = 5,000 g / mol, Total amine value 11.2 mg KOH / g, 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, Molecular weight = 4,400, Functional group equivalent = 2,200 g / mol, Total amine value 25.5 mg KOH / g, Manufactured by Shin-Etsu Chemical Co., Ltd.) • KF-8008: Modified silicone oil "KF-8008" (silicone with amino groups at both ends, kinematic viscosity (25℃) = 450 mm) 2 ( / s, Molecular weight = 11,400, Functional group equivalent = 5,700 g / mol, Total amine value 9.8 mg KOH / g, Manufactured by Shin-Etsu Chemical Co., Ltd.)

[0116] [Table 1-1] [Table 1-2]

[0117] Manufacturing example B1 (Manufacturing of resin B-1) 2450 g of bisphenol A propylene oxide (2.2) adduct and 2275 g of bisphenol A ethylene oxide (2.2) adduct as alcohol components, 1322 g of terephthalic acid and 188 g of dodecenyl succinic anhydride as carboxylic acid components, 20.4 g of tin(II) di(2-ethylhexanoate) as an esterification catalyst, and 2.04 g of gallic acid monohydrate as an esterification co-catalyst were placed in a 10-liter four-necked flask equipped with a thermometer, stainless steel stirring rod, distillation column, dehydration tube, condenser, and nitrogen inlet tube. The mixture was heated to 235°C in a mantle heater while stirring under a nitrogen atmosphere, and the reaction was carried out at atmospheric pressure for 2.5 hours, followed by a reaction under reduced pressure of 8 kPa for 1 hour. After that, the mixture was cooled to 190°C at atmospheric pressure, 554 g of trimellitic anhydride was added, and the temperature was gradually increased to 210°C at a rate of 10°C / h. Subsequently, the reaction was carried out at 8 kPa until the desired softening point was reached, yielding amorphous polyester resin B-1. Various physical properties are shown in Table 2.

[0118] [Table 2]

[0119] Manufacturing Example C1 (Manufacturing of Resin C1-1) The alcohol component, carboxylic acid component, esterification catalyst, and polymerization inhibitor shown in Table 3 were placed in a 10-liter four-necked flask equipped with a thermometer, stainless steel stirring rod, fractionation column, dehydration tube, condenser, and nitrogen inlet tube. The mixture was heated to 140°C in a mantle heater under a nitrogen atmosphere and reacted for 5 hours. After that, the temperature was gradually increased to 200°C at a rate of 10°C / h. The reaction was then carried out at 8 kPa until the desired softening point was reached, yielding crystalline polyester resin C1-1. Various physical properties are shown in Table 3.

[0120] Manufacturing example C2 and comparative manufacturing example C'1 (manufacturing of resins C1-2 and C1'-1) The reaction was carried out under the same conditions as in Production Example C1 until the desired softening point was reached, except that the types and charged amounts of the alcohol component, carboxylic acid component, esterification catalyst, and polymerization inhibitor were changed as shown in Table 3, and crystalline polyester resins C1-2 and C1'-1 were obtained. Various physical properties are shown in Table 3.

[0121] [Table 3]

[0122] [Manufacture of Toner] Example 1 60 parts by mass of amorphous resin A-1, 30 parts by mass of amorphous resin B-1, 10 parts by mass of crystalline polyester resin C1-1, 5 parts by mass of colorant "ECB-301" (manufactured by Dainichi Seika Kogyo Co., Ltd.), 1 part by mass of charge control agent "LR-147" (manufactured by Nippon Carlit Co., Ltd.), and 2 parts by mass of mold release agent "HNP-9" (manufactured by Nippon Seiro Co., Ltd., paraffin wax, melting point: 75°C) were thoroughly stirred with a Henschel mixer and then melt-kneaded using a co-rotating twin-screw extruder with a total length of the kneading part of 1560 mm, a screw diameter of 42 mm, and a barrel inner diameter of 43 mm. The rotational speed of the screw was 200 r / min, the heating set temperature in the screw was 90°C, the temperature of the kneaded product was 140°C, the supply rate of the kneaded product was 10 kg / h, and the average residence time was about 18 seconds. The obtained kneaded product was cooled from 140°C to 50°C in 1.5 hours, rolled and cooled with a cooling roller at 50°C, left standing at 45°C for 4 hours, and then pulverized and classified with a jet mill to obtain toner particles with a volume median diameter (D 50 ) of 5.5 μm. To 100 parts by mass of the obtained toner particles, 1.0 part by mass of external additive "AEROSIL NAX 50" (manufactured by Nippon Aerosil Co., Ltd., hydrophobic silica, hydrophobizing agent: HMDS, number average particle diameter: about 3 nm) was added and mixed with a Henschel mixer at 3600 r / min for 5 minutes to perform an external addition treatment to obtain toner. The minimum fixing temperature and image heat resistance were evaluated by the method described in the above [Toner Evaluation]. The evaluation results are shown in Table 4.

[0123] Examples 2 to 8 and Comparative Examples 1 to 5 Except for changing the binder resin as shown in Table 4, toners for Examples 2-8 and Comparative Examples 1-5 were obtained in the same manner as in Example 1. The evaluation results are shown in Table 4.

[0124] [Table 4]

[0125] The results from the examples and comparative examples show that the electrostatic image developing toner containing the toner binder resin composition of the present invention exhibits excellent low-temperature fixing properties and image heat resistance. On the other hand, as a crystalline resin (C), the SP value is 9.6 (cal / cm³). 3 ) 1 / 2 Comparative Examples 1 and 2, which used a toner binder resin composition containing a larger resin C1'-1, exhibited inferior image heat resistance. Furthermore, Comparative Example 3's toner uses a toner binder resin composition containing resin A'-1, which does not contain modified silicone-derived parts, instead of amorphous resin (A); Comparative Example 4's toner uses a toner binder resin composition containing resin A'-2, which contains modified silicone-derived parts with a total amine value of less than 10.0 mgKOH / g, as amorphous resin (A); and amorphous resin (A) has an SP value of 11.0 (cal / cm²). 3 ) 1 / 2 The toner of Comparative Example 5, which used a binder resin composition for toner containing resin A'-3, which is larger than the specified resin, had a high minimum fixing temperature and poor low-temperature fixing performance. This is thought to be due to insufficient compatibility between the amorphous resin and the crystalline resin. Furthermore, from the results of Examples 4 and 5 and the Comparative Examples, SP A and SP C Regardless of the magnitude of the difference (ΔSP), it can be seen that a toner for electrostatic image development with excellent low-temperature fixing properties and image heat resistance can be obtained if the SP values ​​of the amorphous resin (A) and the crystalline resin (C) contained in the toner binder resin composition are within a specific range.

Claims

1. A method for producing a binder resin composition for toner, comprising an amorphous resin (A) which is a polycondensate of an alcohol component containing a divalent or higher alcohol, a carboxylic acid component containing a divalent or higher carboxylic acid compound, and a modified silicone having a polar group, and a crystalline resin (C), The aforementioned polar group is one of an amino group, a carboxyl group, a hydroxyl group, or an epoxy group. The solubility parameter (SP value) of Fedors calculated from the alcohol component and carboxylic acid component of the amorphous resin (A) (SP Ａ ) is 11.0 (cal / cm³) ３ ) １／２ The following conditions apply: the polarity value of the modified silicone is 10.0 mg KOH / g or more, and the SP value of the crystalline resin (C) is SP Ｃ ) is 9.6 (cal / cm³) ３ ) １／２ The following: A method for producing a binder resin composition for toner, wherein the polarity value of the modified silicone is the value obtained by converting the polar groups of 1 g of the modified silicone into the number of mg of potassium hydroxide.

2. The method for producing a toner binder resin composition according to claim 1, wherein the modified silicone has repeating units represented by formula (1) and repeating units represented by formula (2). 【Chemistry 1】 [In formula (1), 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 a group containing an amino group, a carboxyl group, an epoxy group, or a hydroxyl group, and * is a bonding site.] 【Chemistry 2】 [In formula (2), R is independently a hydrocarbon group having 1 to 6 carbon atoms, and * is a bonding site.]

3. A method for producing a binder resin composition for toner according to claim 2, wherein X is an amino group.

4. A method for producing a binder resin composition for toner according to any one of claims 1 to 3, wherein the amount of modified silicone added to the amorphous resin (A) is 0.1 parts by mass or more and 9 parts by mass or less with respect to 100 parts by mass of the theoretical yield of polyester obtained from the alcohol component and carboxylic acid component in the raw materials of the amorphous resin (A).

5. A method for producing a binder resin composition for toner according to any one of claims 1 to 3, wherein the crystalline resin (C) is a crystalline polyester resin (C1).

6. A method for producing a binder resin composition for toner according to any one of claims 1 to 3, wherein the mass ratio of the crystalline resin (C) to the amorphous resin (A) (crystalline resin (C) / amorphous resin (A)) is 1 / 99 or more and 50 / 50 or less.

7. Step I for producing a binder resin composition for toner, comprising an amorphous resin (A) which is a polycondensate of an alcohol component containing a divalent or higher alcohol, a carboxylic acid component containing a divalent or higher carboxylic acid compound, and a modified silicone having polar groups, and a crystalline resin (C), and A method for producing toner for electrostatic image developing, comprising step II of mixing raw materials containing the toner binder resin composition, melt-kneading, cooling, grinding, and classifying, The aforementioned polar group is one of an amino group, a carboxyl group, a hydroxyl group, or an epoxy group. In the step I, the solubility parameter (SP value) (SP Ａ ) calculated from the alcohol component and carboxylic acid component of the amorphous resin (A) is 11.0 (cal / cm ３ ), １／２ is 11.0 (cal / cm Ｃ ) or less, the polar group value of the modified silicone is 10.0 mgKOH / g or more, and the SP value (SP ３ ) of the crystalline resin (C) is 9.6 (cal / cm １／２ ) or less, A method for producing toner for electrostatic image developing, wherein the polarity value of the modified silicone is the value obtained by converting the polar groups present in 1 g of the modified silicone into the number of mg of potassium hydroxide.

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