Binder resin composition for toner

Abstract

The present invention relates to a binder resin composition for toner containing the following polyester resin A, which has: a structural unit derived from an alcohol component of an alkylene oxide adduct containing bisphenol A, and a structural unit derived from a carboxylic acid component of an acid-modified product A of an amorphous α-olefin polymer having 4 or more and 18 or less carbon atoms. The present invention also relates to a binder resin composition for toner containing the following polyester resin A, which is a condensation product of an alcohol component of an alkylene oxide adduct containing bisphenol A and a carboxylic acid component of an acid-modified product A of an amorphous α-olefin polymer having 4 or more and 18 or less carbon atoms. The present invention also relates to a toner for electrostatic image development containing each of the above binder resin compositions for toner. The binder resin composition for toner of the present invention is suitable for use in a toner for electrostatic image development, which is used, for example, for developing latent images formed in electrostatic image development methods, electrostatic recording methods, electrostatic printing methods, and the like.

Description

Technical Field

[0001] The present invention relates to a binder resin composition for toner used for developing latent images formed in, for example, electrophotography, electrostatic recording, or electrostatic printing, a method for producing a polyester resin contained in the binder resin composition, and a toner for electrostatic image development containing the binder resin composition. Background Art

[0002] Patent document 1 discloses a color toner characterized in that, in a color toner comprising a toner binder (A), a wax (B), and a colorant (C), (A) is formed from a resin (D) containing 1 to 50% by weight of a hydrocarbon group having 8 or more carbon atoms, and (A) has a haze value of 70 or less.

[0003] Patent Document 2 discloses a polyester resin composition for toner, characterized in that it contains a compatibilizer. The compatibilizer is characterized in that, in a toner containing at least wax and a binder resin composed of polyester, the compatibilizer compatibilizes the polyester and the wax, and the compatibilizer is formed by reacting the polyester with a maleic anhydride-modified polyolefin.

[0004] Patent Document 3 discloses a binder resin composition for a toner, comprising: an amorphous polyester resin having a constituent portion derived from a polyester resin and a constituent portion derived from a modified polypropylene polymer A having a carboxylic acid group or a carboxylic anhydride group, wherein the constituent portion derived from the polyester resin and the constituent portion derived from the modified polypropylene polymer A are linked by a covalent bond, wherein the polymer A is a polypropylene polymer terminally modified with a carboxylic acid compound having an unsaturated bond or its anhydride, and wherein the amount of structural units derived from the polymer A in the polyester resin is 8 parts by mass or more and 30 parts by mass or less, relative to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component forming the constituent portion derived from the polyester resin.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Laid-Open No. 2000-250264

[0008] Patent Document 2: Japanese Patent Application Laid-Open No. 2005-316378

[0009] Patent Document 3: Japanese Patent Application Publication No. 2019-008185 Summary of the Invention

[0010] The present invention relates to the following aspects:

[0011] [1] A binder resin composition for toner, comprising a polyester resin A having a structural unit derived from an alcohol component comprising an alkylene oxide adduct of bisphenol A and a structural unit derived from a carboxylic acid component comprising an acid-modified product A of an amorphous α-olefin polymer having from 4 to 18 carbon atoms;

[0012] [2] A binder resin composition for toner, comprising a polyester resin A, wherein the polyester resin A is a polycondensate of an alcohol component comprising an alkylene oxide adduct of bisphenol A and a carboxylic acid component comprising an acid-modified polymer A of an amorphous α-olefin having from 4 to 18 carbon atoms;

[0013] [3] A binder resin composition for a toner, comprising a polyester resin A, wherein the polyester resin A is a polycondensate obtained by polycondensing an alcohol component comprising an alkylene oxide adduct of bisphenol A and a carboxylic acid component other than an acid-modified polymer A of an amorphous α-olefin having from 4 to 18 carbon atoms; and

[0014] [4] A toner for developing electrostatic images, comprising the binder resin composition for toner according to any one of [1] to [3] above. DETAILED DESCRIPTION

[0015] In the field of electrophotographic toners, the demand for high-speed printing and higher image quality continues to grow with the advancement of electrophotographic systems. While polyester resins, particularly linear polyester resins, are considered to have excellent low-temperature fixing properties and storage stability, they are known to have issues with charge buildup due to their high hygroscopicity in high-temperature and high-humidity environments.

[0016] Therefore, as a means of improving the moisture absorption resistance and charge buildup of polyester resins, for example, when a crystalline macromolecular monomer having a hydrophobic alkyl group, such as an acid-modified product of a C2 or C3 α-olefin polymer, is introduced into the polyester resin, a certain degree of shelf life is maintained. However, because the alkyl group has a melting point above 90°C, it does not wet and spread to completely cover the toner surface, and sufficient moisture absorption resistance cannot be achieved (see, for example, Patent Documents 2 and 3). Furthermore, when an amorphous monomer having a hydrophobic alkyl group, such as dodecenylsuccinic anhydride, is introduced into the polyester resin, a certain improvement in moisture absorption resistance is achieved, but this is not sufficient. On the other hand, even if sufficient moisture absorption resistance can be achieved by increasing the amount of the alkyl group-containing monomer added, the alkyl group plasticizes the polyester resin, lowering the glass transition temperature of the resin and thereby deteriorating shelf life (see, for example, Patent Document 1).

[0017] The present invention relates to a binder resin composition for toner having excellent moisture absorption resistance, charge buildup properties, and storage stability under high-temperature and high-humidity environments, and a toner for electrostatic image development containing the binder resin composition.

[0018] The toner for developing electrostatic images containing the binder resin composition of the present invention exhibits excellent effects in terms of moisture absorption resistance, charge buildup properties, and storage stability under high-temperature and high-humidity environments.

[0019] The binder resin composition for toners of the present invention is characterized in that it contains a polyester resin A using an acid-modified product A of an amorphous α-olefin polymer having from 4 to 18 carbon atoms. The use of such an acid-modified product A allows the hydrophobic polyolefin portion of the acid-modified product A to be uniformly dispersed in a microphase-separated state in the polyester resin into which the acid-modified product A has been introduced, thereby improving the moisture absorption resistance of the polyester resin.

[0020] Furthermore, the acid-modified product A is amorphous. Compared to crystalline acid-modified α-olefin polymers, such as modified polypropylene polymers containing carboxylic acid groups or carboxylic anhydride groups, acid-modified amorphous α-olefin polymers further improve the moisture absorption resistance of the polyester resin. This is presumably because acid-modified amorphous α-olefin polymers have no melting point, allowing the hydrophobic polyolefin portion to wet and spread onto the toner surface even at low temperatures.

[0021] Similar to the crystallinity of resins described below, the crystallinity of acid-modified products is expressed by the crystallinity index ([softening point / maximum endothermic peak temperature]). Amorphous acid-modified products are those having a crystallinity index exceeding 1.4, preferably exceeding 1.5, and more preferably 1.6 or greater, or having a crystallinity index less than 0.6, preferably 0.5 or less. Materials in which no maximum endothermic peak temperature is detected are also considered amorphous.

[0022] The polyester resin A comprises a structural unit derived from an alcohol component of an alkylene oxide adduct comprising bisphenol A, and a structural unit derived from a carboxylic acid component of an acid-modified product A comprising an amorphous α-olefin polymer having from 4 to 18 carbon atoms. The polyester resin A preferably has a structure in which a structural unit derived from an alcohol component of an alkylene oxide adduct comprising bisphenol A and a structural unit derived from a carboxylic acid component of an acid-modified product A comprising an amorphous α-olefin polymer having from 4 to 18 carbon atoms are linked via an ester bond.

[0023] From the viewpoint of storage stability and reactivity with the acid-modified product A, the alcohol component contains an alkylene oxide adduct of bisphenol A. As the alkylene oxide adduct of bisphenol A, a compound represented by formula (I) is preferred:

[0024] [Chemical Formula 1]

[0025]

[0026] (In the formula, OR and RO are oxyalkylene groups, R is ethylene and / or propylene, x and y represent the average number of added moles of alkylene oxide and are positive numbers respectively, 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 6 or less, and even more preferably 4 or less.) Examples of the alkylene oxide adduct of bisphenol A represented by formula (I) include polyoxypropylene adducts of 2,2-bis(4-hydroxyphenyl)propane and polyoxyethylene adducts of 2,2-bis(4-hydroxyphenyl)propane. It is preferred to use one or more of these.

[0027] The content of the alkylene oxide adduct of bisphenol A represented by formula (I) in the alcohol component is preferably 70 mol% or more, more preferably 80 mol% or more, even more preferably 90 mol% or more, even more preferably 95 mol% or more, and even more preferably 100 mol%. It should be noted that in this specification, the content of the compound contained in the alcohol component or the carboxylic acid component is synonymous with the ratio of the structural units derived from the compound in the polyester resin.

[0028] Examples of other alcohol components include aliphatic diols such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-butenediol, 1,3-butanediol, and neopentyl glycol; and trivalent or higher alcohols such as glycerol.

[0029] In the acid-modified product A of an α-olefin polymer having 4 or more and 18 or less carbon atoms contained in the carboxylic acid component, the α-olefin has a carbon number of 4 or more and 18 or less, preferably 10 or less, more preferably 7 or less, further preferably 5 or less, and even more preferably 4.

[0030] As the α-olefin polymer having a carbon number of 4 or more and 18 or less, polyisobutylene polymers, poly-1-butene polymers, poly-1-pentene polymers, poly-1-hexene polymers, poly-1-octene polymers, poly-4-methylpentene polymers, poly-1-dodecene polymers, poly-1-hexadecene polymers, propylene-hexene copolymers, etc. can be mentioned. Among these, polyisobutylene polymers are preferred. The above-mentioned α-olefin polymer can be a homopolymer of the above-mentioned α-olefin, or a copolymer of two or more selected from the above-mentioned α-olefins, or a copolymer of the above-mentioned α-olefin and other olefins. In addition, the copolymer can be any of a random copolymer and a block copolymer.

[0031] Examples of polyisobutylene polymers include polyisobutylene and copolymers of isobutylene and other olefins. Examples of other olefins include ethylene, butene, pentene, hexene, and 2-ethylhexene. In the case of copolymers, the proportion of isobutylene is preferably 60% by mass or greater, more preferably 80% by mass or greater, and even more preferably 90% by mass or greater, and less than 100% by mass.

[0032] On the other hand, the acid-modified product A is preferably an acid-modified product in which an α-olefin polymer having 4 to 18 carbon atoms is modified with at least one acid selected from maleic acid, fumaric acid, itaconic acid, and their anhydrides, from the viewpoint of reactivity with the polyester resin. An acid-modified product modified with maleic anhydride is more preferred. Examples of the acid-modified product include randomly grafted acid-modified products in which an acid is randomly grafted onto the α-olefin polymer, and terminal-modified acid-modified products in which the terminals of the α-olefin polymer are modified with an acid. In the present invention, terminal-modified acid-modified products are preferred from the viewpoint of low-temperature fixing properties and storage stability. A single-terminal-modified acid-modified product in which one terminal of the α-olefin polymer having 4 to 18 carbon atoms is modified with an acid is more preferred.

[0033] Randomly grafted acid-modified products are preferably modified by grafting one or more acid groups within a single polymer molecule. Whether or not a polymer is acid-modified can be determined by conventional spectroscopic measurements. For example, in the case of a randomly grafted acid-modified product using maleic anhydride, modification with maleic anhydride converts the double bonds of the maleic anhydride into single bonds, and thus can be determined by measuring the spectral changes.

[0034] The random graft-modified acid-modified product can be obtained, for example, by generating free radicals in the molecule of an α-olefin polymer and reacting the free radicals with a carboxylic acid compound having an unsaturated bond or an anhydride thereof.

[0035] For terminal-modified acid-modified products, it is preferred that one (single-terminal) or two (double-terminal) acid modifications be present within a single polymer molecule. Whether or not a polymer is acid-modified can be determined by general spectroscopic analysis. For example, in the case of a single-terminal acid-modified product using maleic anhydride, modification with maleic anhydride converts the double bond of the maleic anhydride into a single bond, allowing determination by measuring the spectral changes. Furthermore, the linked portion of the polymer side of an α-olefin also exhibits spectral changes before and after bonding, allowing determination by measuring these changes.

[0036] A single-terminal acid-modified product can be obtained, for example, by reacting an acid with the aforementioned α-olefin polymer having an unsaturated bond at one terminal to form an olefin (Ene). The aforementioned α-olefin polymer having an unsaturated bond at one terminal can be obtained by a known method, for example, using a vanadium-based catalyst, a titanium-based catalyst, a zirconium-based catalyst, or the like.

[0037] Based on the above, as the acid-modified α-olefin polymer A, polyisobutylene succinic anhydride modified at one end with maleic anhydride is preferred.

[0038] From the viewpoint of storage stability, the weight average molecular weight of the acid-modified product A is preferably 500 or more, more preferably 700 or more, further preferably 900 or more, and further preferably 1,100 or more. Furthermore, from the viewpoint of low-temperature fixing properties, it is preferably 5,000 or less, more preferably 4,000 or less, and further preferably 3,000 or less.

[0039] From the viewpoint of charge increase and hygroscopicity, the content of the acid-modified product A is preferably 3 parts by mass or more, more preferably 4 parts by mass or more, even more preferably 7 parts by mass or more, even more preferably 9 parts by mass or more, even more preferably 10 parts by mass or more, and even more preferably 15 parts by mass or more, relative to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component other than the acid-modified product A. Furthermore, from the viewpoint of storage stability, it is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, even more preferably 25 parts by mass or less, even more preferably 23 parts by mass or less, and even more preferably 20 parts by mass or less.

[0040] As the carboxylic acid component other than the acid-modified α-olefin polymer A, at least one selected from aromatic dicarboxylic acid compounds, aliphatic dicarboxylic acid compounds, and trivalent or higher carboxylic acid compounds is preferred. From the viewpoint of storage stability, an aromatic dicarboxylic acid compound is more preferably contained.

[0041] Examples of the aromatic dicarboxylic acid compound include phthalic acid, isophthalic acid, terephthalic acid, anhydrides of these acids, and alkyl esters having an alkyl group with 1 to 3 carbon atoms. Among these, terephthalic acid or isophthalic acid is preferred, and terephthalic acid is more preferred, from the viewpoint of low-temperature fixing properties.

[0042] From the viewpoint of storage stability, the content of the aromatic dicarboxylic acid compound in the carboxylic acid components other than the acid-modified α-olefin polymer A is preferably 80 mol% or more, more preferably 90 mol% or more, and even more preferably 95 mol% or more.

[0043] Examples of the aliphatic dicarboxylic acid compounds include aliphatic dicarboxylic acids such as oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, and adipic acid, and anhydrides and alkyl esters of these acids having 1 to 3 carbon atoms.

[0044] Examples of trivalent or higher carboxylic acid compounds include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, pyromellitic acid, anhydrides of these acids, and alkyl esters having 1 to 3 carbon atoms in the alkyl group. Among these, trimellitic acid compounds are preferred.

[0045] In the present invention, the polyester resin A is preferably a linear polyester resin from the perspective of low-temperature fixing properties and storage stability. Therefore, it is preferred that the polyester resin A be substantially free of trivalent or higher-valent raw material monomers (trivalent or higher-valent alcohols and trivalent or higher-valent carboxylic acid compounds) having a crosslinking effect. Here, "substantially free of trivalent or higher-valent raw material monomers" means that even if trivalent or higher-valent raw material monomers are present, their content is preferably 5 mol% or less, more preferably 3 mol% or less, even more preferably 1 mol% or less, and even more preferably 0 mol% of the total amount of the alcohol component and the carboxylic acid component.

[0046] The alcohol component may suitably contain a monovalent alcohol, and the carboxylic acid component may suitably contain a monovalent carboxylic acid compound.

[0047] The polyester resin A can be produced, for example, by polycondensing an alcohol component and a carboxylic acid component in an inert gas atmosphere, preferably in the presence of an esterification catalyst and, if necessary, in the presence of an esterification co-catalyst, a polymerization inhibitor, etc., at a temperature of preferably 130° C. or higher, more preferably 170° C. or higher, and preferably 250° C. or lower, more preferably 240° C. or lower.

[0048] Examples of esterification catalysts include tin compounds such as dibutyltin oxide and tin (II) 2-ethylhexanoate, and titanium compounds such as diisopropyl bis(triethanolamine) titanate. The amount of the esterification catalyst used is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and preferably 1.5 parts by mass or less, and more preferably 1 part by mass or less, relative to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component other than the acid-modified product A. Examples of esterification co-catalysts include gallic acid. The amount of the esterification co-catalyst used is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and preferably 0.5 parts by mass or less, and more preferably 0.1 parts by mass or less, relative to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component other than the acid-modified product A. Examples of the polymerization inhibitor include tert-butylcatechol. The amount of the polymerization inhibitor used is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and preferably 0.5 parts by mass or less, more preferably 0.1 parts by mass or less, relative to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component other than the acid-modified product A.

[0049] The polyester resin A is a polycondensate of an alcohol component comprising an alkylene oxide adduct of bisphenol A and a carboxylic acid component comprising an acid-modified product A of an amorphous α-olefin polymer having from 4 to 18 carbon atoms. It may also be a polycondensate obtained by polycondensing the acid-modified product A onto a polycondensate of an alcohol component comprising an alkylene oxide adduct of bisphenol A and a carboxylic acid component other than the acid-modified product A of an amorphous α-olefin polymer having from 4 to 18 carbon atoms. The latter polycondensate is preferred from the viewpoint of storage stability.

[0050] It should be noted that in the present invention, the polyester resin A may be a polyester resin modified with a substance other than an acid to an extent that does not substantially impair its properties. Examples of polyester resins modified with a substance other than an acid include those obtained by grafting and capping with phenol, urethane, epoxy, or the like by the methods described in Japanese Patent Application Laid-Open Nos. 11-133668, 10-239903, and 8-20636. Among these modified polyester resins, urethane-modified polyester resins obtained by urethane-stretching a polyester resin with a polyisocyanate compound are preferred.

[0051] From the viewpoint of storage stability, the softening point of the polyester resin A is preferably 80°C or higher, more preferably 90°C or higher, and from the viewpoint of low-temperature fixing property, it is preferably 150°C or lower, more preferably 140°C or lower, further preferably 120°C or lower, and even more preferably 110°C or lower.

[0052] Polyester resin A is preferably an amorphous resin. The crystallinity of the resin is represented by a crystallinity index defined by the ratio of the maximum peak temperature of the endothermic reaction obtained by a differential scanning calorimeter to the softening point, i.e., the value of [softening point / maximum peak temperature of the endothermic reaction]. A crystalline resin is a resin having a crystallinity index of more than 0.6, preferably more than 0.7, more preferably more than 0.9, and less than 1.4, preferably less than 1.2, more preferably less than 1.1. On the other hand, an amorphous resin is a resin having a crystallinity index of more than 1.4, preferably more than 1.5, more preferably more than 1.6, or a resin having a crystallinity index of less than 0.6, preferably less than 0.5. The crystallinity of the resin can be adjusted by the type and ratio of the raw monomers, and manufacturing conditions (e.g., reaction temperature, reaction time, cooling rate), etc. It should be noted that the maximum peak temperature of the endothermic reaction refers to the temperature of the peak at the highest temperature side among the observed endothermic peaks. For a crystalline resin, the maximum peak temperature of the endothermic reaction is set to the melting point.

[0053] From the viewpoint of storage stability, the glass transition temperature of the polyester resin A is preferably 40°C or higher, more preferably 50°C or higher, and from the viewpoint of low-temperature fixing property, it is preferably 80°C or lower, more preferably 70°C or lower, and even more preferably 65°C or lower.

[0054] From the viewpoint of low-temperature fixing property, the acid value of the polyester resin A is preferably 0.5 mgKOH / g or more, more preferably 1.5 mgKOH / g or more, and from the viewpoint of moisture absorption resistance, it is preferably 15 mgKOH / g or less, more preferably 10 mgKOH / g or less, and even more preferably 5 mgKOH / g or less.

[0055] The adhesive resin composition of the present invention may also contain polyester resins other than the polyester resin A, vinyl resins such as styrene-acrylic resins, epoxy resins, polycarbonates, polyurethanes, composite resins containing two or more of these resins, etc., but the content of the polyester resin A in the adhesive resin composition is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and further preferably 100% by mass.

[0056] In the electrostatic image developing toner, the content of the binder resin composition of the present invention is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, further preferably 80% by mass, and is preferably less than 100% by mass, more preferably 98% by mass or less, further preferably 95% by mass or less, and further preferably 92% by mass or less.

[0057] In addition to the binder resin (the binder resin composition of the present invention), the electrostatic image developing colorant of the present invention may also contain additives such as colorants, release agents, charge control agents, magnetic powders, flow improvers, conductivity regulators, reinforcing fillers such as fibrous substances, antioxidants, and cleaning properties improvers, preferably containing colorants, release agents, and charge control agents.

[0058] As colorants, dyes, pigments, and magnetic substances used as toner colorants can be used. Examples include carbon black, phthalocyanine blue, Permanent Brown FG, Brilliant Fast Scarlet, Pigment Red 122, Pigment Green B, Rhodamine-B series, Solvent Red 49, Solvent Red 146, Solvent Blue 35, quinacridone, Carmine 6B, isoindoline, and disazo yellow. It should be noted that in the present invention, the toner can be either a black toner or a color colorant.

[0059] From the viewpoint of improving the image density and low-temperature fixing property of the toner, the content of the colorant is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and is preferably 40 parts by mass or less, more preferably 10 parts by mass or less, relative to 100 parts by mass of the binder resin.

[0060] Examples of release agents (waxes) include aliphatic hydrocarbon waxes such as polypropylene wax, polyethylene wax, polypropylene polyethylene copolymer wax, microcrystalline wax, paraffin wax, Fischer-Tropsch wax, and Sasol wax, or oxides thereof; ester waxes such as carnauba wax, montan wax, or deoxygenated waxes thereof, and fatty acid ester waxes; fatty acid amides, fatty acids, higher alcohols, fatty acid metal salts, and the like, which can be used alone or in combination of two or more.

[0061] From the viewpoint of toner transferability, the melting point of the release agent is preferably 80°C or higher, more preferably 85°C or higher, and even more preferably 90°C or higher. From the viewpoint of low-temperature fixing property, the melting point is preferably 130°C or lower, more preferably 125°C or lower, and even more preferably 120°C or lower.

[0062] From the viewpoint of the low-temperature fixing property and anti-offset property of the toner and the dispersibility in the binder resin, the content of the release agent is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, further preferably 1.5 parts by mass or more, further preferably 3 parts by mass or more, further preferably 4 parts by mass or more, and is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and further preferably 7 parts by mass or less, relative to 100 parts by mass of the binder resin.

[0063] The charge control agent is not particularly limited, and may contain either a positively chargeable charge control agent or a negatively chargeable charge control agent.

[0064] Examples of positively chargeable charge control agents include nigrosine dyes such as "Nigrosine Base EX," "OILBLACK BS," "OILBLACK SO," "BONTRON N-01," "BONTRON N-04," "BONTRON N-07," "BONTRON N-09," and "BONTRON N-11" (all manufactured by Orient Chemical Industries, Ltd.); triphenylmethane dyes containing a tertiary amine as a side chain; and quaternary ammonium salt compounds such as "BONTRON P-51" (manufactured by Orient Chemical Industries, Ltd.), hexadecyltrimethylammonium bromide, and "COPY CHARGE PX VP435" (manufactured by Clariant), etc.; polyamine resins, such as "AFP-B" (manufactured by Orient Chemical Industry Co., Ltd.), etc.; imidazole derivatives, such as "PLZ-2001" and "PLZ-8001" (above, manufactured by Shikoku Chemical Industry Co., Ltd.), etc.; styrene-acrylic resins, such as "FCA-701PT" (manufactured by Fujikura Chemical Co., Ltd.), etc.

[0065] Examples of negatively chargeable charge control agents include metal-containing azo dyes such as VARIFAST BLACK 3804, BONTRON S-31, BONTRON S-32, BONTRON S-34, and BONTRON S-36 (all manufactured by Orient Chemical Industries, Ltd.), AIZEN SPILON BLACK TRH, and T-77 (manufactured by Hodogaya Chemical Industries, Ltd.); metal compounds of benzilic acid compounds such as LR-147 and LR-297 (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 Industries, Ltd.); copper phthalocyanine dyes; and quaternary ammonium salts such as COPY CHARGE NX VP434" (manufactured by Clariant), nitroimidazole derivatives, etc.; organometallic compounds, etc.

[0066] From the viewpoint of the charging stability of the colorant, the content of the charge control agent is preferably 0.01 parts by mass or more, more preferably 0.2 parts by mass or more, relative to 100 parts by mass of the binder resin, and is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, further preferably 3 parts by mass or less, and further preferably 2 parts by mass or less.

[0067] The toner of the present invention may be obtained by any of the known methods, such as melt-kneading, emulsion phase inversion, and polymerization. However, from the perspectives of productivity and colorant dispersibility, a pulverized toner obtained by melt-kneading is preferred. In the case of a pulverized toner obtained by melt-kneading, for example, raw materials such as a binder resin, colorant, release agent, and charge control agent are uniformly mixed in a mixer such as a Henschel mixer, followed by melt-kneading in a closed kneader, a single-screw or double-screw extruder, an open roll kneader, or the like, followed by cooling, pulverization, and classification.

[0068] In order to improve transferability, the toner of the present invention preferably uses an external additive. As an external additive, organic particles such as inorganic particles such as silicon dioxide, aluminum oxide, titanium dioxide, zirconium oxide, tin oxide, zinc oxide, melamine resin particles, polytetrafluoroethylene resin particles, etc. can be enumerated, and two or more thereof can also be used in combination. Among these, silicon dioxide is preferred, and from the viewpoint of the transferability of the toner, the hydrophobized silicon dioxide after the hydrophobization treatment is more preferably used.

[0069] Examples of the hydrophobizing agent for hydrophobizing the surface of the silica particles include hexamethyldisilazane (HMDS), dimethyldichlorosilane (DMDS), silicone oil, octyltriethoxysilane (OTES), and methyltriethoxysilane.

[0070] From the viewpoint of the chargeability, fluidity and transferability of the colorant, the average particle size of the external additive is preferably 10 nm or more, more preferably 15 nm or more, and preferably 250 nm or less, more preferably 200 nm or less, further preferably 150 nm or less, and further preferably 90 nm or less.

[0071] From the viewpoint of the chargeability, fluidity, and transferability of the colorant, the content of the external additive is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and even more preferably 0.3 parts by mass or more, relative to 100 parts by mass of the colorant before treatment with the external additive, and is preferably 5 parts by mass or less, and more preferably 3 parts by mass or less.

[0072] The volume median particle size (D 50 ) is preferably 3 μm or more, more preferably 4 μm or more, and preferably 15 μm or less, more preferably 10 μm or less. It should be noted that in this specification, the volume median particle size (D 50 ) refers to the particle size at which the cumulative volume frequency calculated using volume fraction reaches 50%, starting from the smaller particle size. Furthermore, when toner is treated with an external additive, the volume median particle size of the toner particles before treatment with the external additive is defined as the volume median particle size of the toner.

[0073] The toner of the present invention can be used as a one-component developing toner, or can be mixed with a carrier to be used as a two-component developer.

[0074] The present invention will be described in detail below with reference to Examples, but the present invention is not limited to these Examples. Physical properties of resins and the like can be measured by the following methods.

[0075] [Highest peak temperature of endothermic reaction of acid-modified product]

[0076] Using a differential scanning calorimeter "DSC Q20" (manufactured by TA Instruments Japan), a sample (0.01 to 0.02 g) was weighed onto an aluminum pan and heated from room temperature (25°C) to 200°C at a heating rate of 10°C / min, and then cooled from this temperature to -10°C at a cooling rate of 5°C / min. The sample was then heated to 180°C at a heating rate of 10°C / min and measured. Samples in which the maximum endothermic peak temperature was not detected were considered amorphous. If the maximum endothermic peak temperature was detected, the softening point was measured using the same method as for the resin, and the crystallinity index (softening point / maximum endothermic peak temperature) was calculated for determination.

[0077] [Weight average molecular weight (Mw) of acid-modified α-olefin polymer]

[0078] (1) Preparation of sample solution

[0079] A sample was dissolved in tetrahydrofuran to a concentration of 0.5 g / 100 mL, and the solution was filtered using a fluororesin filter "FP-200" (manufactured by Sumitomo Electric Industries, Ltd.) with a pore size of 2 μm to remove insoluble components, thereby preparing a sample solution.

[0080] (2) Molecular weight distribution determination

[0081] The following measuring device and analytical column were used, tetrahydrofuran was flowed as the eluent at a flow rate of 1 mL per minute, and the column was stabilized in a thermostatic bath at 40°C. 100 μL of the sample solution was injected into it for measurement. The molecular weight of the sample was calculated based on a pre-made calibration curve. The calibration curve at this time used several types of monodisperse polystyrene (A-500 (Mw 5.0×10 2 )、A-1000(Mw 1.01×10 3 )、A-2500(Mw 2.63×10 3 )、A-5000(Mw 5.97×10 3 )、F-1(Mw 1.02×10 4 )、F-2(Mw 1.81×10 4)、F-4(Mw 3.97×10 4 )、F-10(Mw 9.64×10 4 )、F-20(Mw 1.90×10 5 )、F-40(Mw 4.27×10 5 )、F-80(Mw7.06×10 5 )、F-128(Mw 1.09×10 6 )) was used as a calibration curve for the standard sample. Molecular weights are shown in brackets.

[0082] Measuring device: HLC-8220GPC (manufactured by Tosoh Corporation)

[0083] Analytical column: GMHXL+G3000HXL (manufactured by Tosoh Corporation)

[0084] 〔Softening point of resin〕

[0085] Using a flow tester "CFT-500D" (manufactured by Shimadzu Corporation), a 1g sample was heated at a temperature increase rate of 6°C / minute. A plunger load of 1.96 MPa was applied, and the sample was extruded from a nozzle with a diameter of 1mm and a length of 1mm. The amount of plunger descent in the flow tester was plotted against temperature, and the temperature at which half the sample had flowed out was defined as the softening point.

[0086] [The maximum peak temperature of the resin's endothermic properties]

[0087] Using a differential scanning calorimeter "Q-100" (manufactured by TA Instruments Japan), a sample (0.01-0.02 g) was weighed onto an aluminum pan and cooled from room temperature (25°C) to 0°C at a cooling rate of 10°C / min, maintaining the temperature at 0°C for 1 minute. The temperature was then raised at a heating rate of 10°C / min. The highest endothermic peak temperature was defined as the maximum endothermic peak temperature.

[0088] 〔Glass transition temperature of resin〕

[0089] Using a differential scanning calorimeter "Q-100" (manufactured by TA Instruments Japan), a sample (0.01-0.02 g) was weighed onto an aluminum pan, heated to 200°C, and then cooled from this temperature to 0°C at a cooling rate of 10°C / minute. The sample was then heated at a heating rate of 10°C / minute to measure the endothermic peak. The glass transition temperature was defined as the temperature at the intersection of an extension of the baseline below the maximum endothermic peak temperature and a tangent line showing the maximum slope from the rising portion of the peak to the peak apex.

[0090] 〔Acid value of resin〕

[0091] The measurement was performed according to the method of JIS K0070: 1992. However, the measurement solvent was simply changed from the mixed solvent of ethanol and diethyl ether specified in JIS K0070 to a mixed solvent of acetone and toluene (acetone:toluene = 1:1 (volume ratio)).

[0092] 〔Melting point of release agent〕

[0093] Using a differential scanning calorimeter "DSC Q-100" (manufactured by TA Instruments Japan), a sample (0.01-0.02 g) was weighed onto an aluminum pan and heated to 200°C at a heating rate of 10°C / min. The sample was then cooled from this temperature to -10°C at a cooling rate of 5°C / min. The sample was then heated to 180°C at a heating rate of 10°C / min and measured. The maximum endothermic peak temperature observed in the resulting melting endothermic curve was defined as the melting point of the release agent.

[0094] 〔Average particle size of external additives〕

[0095] The average particle size refers to a number average particle size, and the particle sizes (average value of the major diameter and the minor diameter) of 500 particles are measured from a scanning electron microscope (SEM) photograph, and the number average value thereof is taken as the average value.

[0096] [Volume median particle size of toner]

[0097] Measuring machine: Coulter Multisizer II (manufactured by Beckman Coulter, Inc.)

[0098] Aperture diameter: 50μm

[0099] Analysis software: Coulter Multisizer AccuComp Ver.1.19 (manufactured by Beckman Coulter, Inc.)

[0100] Electrolyte: Isoton II (Beckman Coulter)

[0101] Dispersion: EMULGEN 109P (manufactured by Kao Corporation, polyoxyethylene lauryl ether, HLB (Griffin): 13.6) dissolved in an electrolyte solution to adjust to 5% by mass

[0102] Dispersion conditions: 10 mg of the measurement sample was added to 5 mL of the above dispersion and dispersed for 1 minute using an ultrasonic disperser (machine name: US-1 manufactured by SND Co., Ltd., output: 80 W). Subsequently, 25 mL of the above electrolyte was added and further dispersed for 1 minute using an ultrasonic disperser to prepare a sample dispersion.

[0103] Measurement conditions: The sample dispersion was added to 100 mL of the electrolyte solution at a concentration that allowed the measurement of the particle size of 30,000 particles within 20 seconds. 30,000 particles were measured and the volume median particle size (D) was calculated based on the particle size distribution. 50 ).

[0104] Resin Production Example 1

[0105] The alcohol components listed in Table 1 were placed in a 10-liter four-necked flask equipped with a dehydration tube equipped with a nitrogen inlet tube, a stirrer, and a thermocouple. The temperature was raised to 100°C, and then the terephthalic acid listed in Table 1 was added. The temperature was then raised to 160°C. The esterification catalyst and esterification co-catalyst listed in Table 1 were added, and the temperature was raised to 235°C. The reaction was allowed to proceed at 235°C for 10 hours, and then at 235°C and 8.0 kPa for 1 hour. The reaction was then cooled to 160°C, and the acid-modified product listed in Table 1 was added. The temperature was again raised to 235°C, and a polycondensation reaction was carried out at 235°C for 5 hours. The reaction was then continued at 235°C and 8.0 kPa until the softening point shown in Table 1 was reached, thereby obtaining amorphous polyester resins (resins A1 to A5).

[0106] Resin Production Example 2

[0107] The alcohol components listed in Table 1 were placed in a 10-liter four-necked flask equipped with a dehydration tube equipped with a nitrogen inlet tube, a stirrer, and a thermocouple. The temperature was raised to 100°C, and then the terephthalic acid listed in Table 1 was added. The temperature was raised to 160°C. The esterification catalyst and esterification co-catalyst listed in Table 1 were added, and the temperature was raised to 235°C. After reacting at 235°C for 10 hours, the reaction was continued at 235°C and 8.0 kPa for 1 hour to obtain an amorphous polyester resin (resin A6).

[0108] Resin Production Example 3

[0109] The alcohol components listed in Table 1 were placed in a 10-liter four-necked flask equipped with a dehydration tube equipped with a nitrogen inlet tube, a stirrer, and a thermocouple. The flask was heated to 100°C, and then the terephthalic acid listed in Table 1 was added. The temperature was then raised to 160°C. The esterification catalyst and esterification co-catalyst listed in Table 1 were added, and the temperature was then raised to 235°C. The flask was reacted at 235°C for 10 hours, and then reacted at 235°C and 8.0 kPa for 1 hour. The flask was cooled to 160°C, and then the alkenyl succinic anhydride substituted with an alkenyl group having 10 to 14 carbon atoms listed in Table 1 was added. The temperature was again raised to 235°C, and a polycondensation reaction was carried out at 235°C for 5 hours. The reaction was then continued at 235°C and 8.0 kPa until the softening point shown in Table 1 was reached, thereby obtaining an amorphous polyester resin (Resin A7).

[0110] Resin Production Example 4

[0111] The alcohol components listed in Table 1 were placed in a 10-liter four-necked flask equipped with a dehydration tube equipped with a nitrogen inlet tube, a stirrer, and a thermocouple. The temperature was raised to 100°C, and then the terephthalic acid listed in Table 1 was added. The temperature was then raised to 160°C. The esterification catalyst and esterification co-catalyst listed in Table 1 were added, and the temperature was raised to 235°C. The reaction was allowed to proceed at 235°C for 10 hours, and then at 235°C and 8.0 kPa for 1 hour. The reaction was then cooled to 160°C, and the acid-modified product listed in Table 1 was added. The temperature was again raised to 235°C, and a polycondensation reaction was carried out at 235°C for 5 hours. The reaction was then continued at 235°C and 8.0 kPa until the softening point shown in Table 1 was reached, thereby obtaining an amorphous polyester resin (Resin A8).

[0112] [Table 1]

[0113]

[0114] Examples 1 to 5 and Comparative Examples 1 to 3

[0115] 100 parts by mass of the binder resin shown in Table 2, 6 parts by mass of the colorant "Fastogen Supermagenda R" (CI Pigment Red 122, manufactured by Dainippon Ink & Chemicals Co., Ltd.), 1 part by mass of the charge control agent "LR-147" (manufactured by Japan Carlit Co., Ltd.), and 4 parts by mass of the release agent "SP-105" (manufactured by Kato Yoko Co., Ltd., Fischer-Tropsch wax, melting point: 105°C) were fully stirred using a Henschel mixer, and then melt-kneaded using a co-rotating twin-screw extruder with a total length of 1560 mm for the kneading part, a screw diameter of 42 mm, and an inner diameter of the barrel of 43 mm. The rotation speed of the roller was 200 r / min, the heating setting temperature in the roller was 100°C, the temperature of the kneaded material was 160°C, the supply rate of the kneaded material was 10 kg / hour, and the average residence time was about 18 seconds. After cooling, the volume median particle size (D 50 )6.5μm colorant particles.

[0116] To 100 parts by mass of the obtained toner particles, 2 parts by mass of "Aerosil R-972" (hydrophobic silica, manufactured by Nippon Aerosil Co., Ltd., hydrophobizing agent: DMDS, average particle size: 16 nm) was added as an external additive, and the mixture was mixed at 3600 rpm for 5 minutes using a Henschel mixer to perform external additive treatment, thereby obtaining a toner.

[0117] Test Example 1 [Low-temperature fixability]

[0118] The toner was loaded into a color printer "C612dnw" (trade name, manufactured by Oki Data Co., Ltd.), and an image was output in an unfixed state (printing area: 6 cm×6 cm, 0.5 mg / cm 2 ).

[0119] The unfixed image was fixed using the fixing machine of the above printer in an offline manner, with the temperature raised by 5°C at a speed of 100 mm / s from 100°C. It should be noted that J paper (manufactured by Fuji Xerox, basis weight: 82 g / m2) was used as the fixing paper. 2 , paper thickness: 97μm).

[0120] "UNICEF Cellophane" (Mitsubishi Pencil Co., Ltd., width: 18 mm, JIS Z-1522) was applied to the fixed image and passed through a fixing roller set at 30°C, after which the tape was peeled off. The optical reflection density was measured using a reflection densitometer "RD-915" (Macbeth Process Measurements) before and after the tape was peeled off. Low-temperature fixability was evaluated by defining the fixing roller temperature at which the ratio (after peeling / before adhesion) first exceeded 90%. The results are shown in Table 2.

[0121] Test Example 2 [Moisture Absorption Resistance]

[0122] The resin used in the binder resin was sized to a particle size of 150 to 250 μm and then dried in a vacuum dryer at 40°C and 60 torr for 12 hours. The mass after drying was measured (resin mass a). 2.00 g of the dried resin was evenly spread on a glass dish and left in a high-temperature, high-humidity environment at 40°C and 85% humidity for 12 hours. The mass was then measured again (resin mass b).

[0123] The smaller the moisture absorption rate (%) calculated from (resin mass b - resin mass a) / resin mass a × 100, the better the moisture absorption resistance. The moisture absorption resistance was evaluated according to the following evaluation criteria. The results are shown in Table 2.

[0124] <Evaluation Criteria>

[0125] A: The moisture absorption rate is less than 0.30%, and the charging performance of the toner is not affected.

[0126] B: The moisture absorption rate is 0.30% or more and less than 0.50%. Although the charging performance of the toner may be slightly reduced, it has no substantial influence.

[0127] C: The moisture absorption rate is 0.50% or more and less than 0.70%, and there is a possibility that the charging performance of the toner is reduced.

[0128] D: The moisture absorption rate is 0.70% or more and less than 1.20%, and there is a high possibility that the charging performance of the toner is deteriorated.

[0129] E: The moisture absorption rate is 1.2% or more, which reduces the charging performance of the toner and causes poor development.

[0130] Test Example 3〔Charge Rising Properties〕

[0131] After placing 4 parts by mass (0.4 g) of toner and 96 parts by mass (9.6 g) of a silicone-coated ferrite carrier (manufactured by Kanto Denka Kogyo Co., Ltd.) with an average particle size of 90 μm in a 20 mL polypropylene container, the mixture was mixed with a ball mill for 0.5 minutes at a temperature of 25°C and a relative humidity of 50%, and the charge was measured using a "q / m Meter MODEL 210HS" (manufactured by TREK). The mixture was further stirred for 2.5 minutes and the charge was measured. The ratio of the two charge amounts (0.5 minute charge amount / 2.5 minute charge amount) was calculated. The larger the calculated value, the better the charge rise. The charge rise was evaluated according to the following evaluation criteria. The results are shown in Table 2.

[0132] <Evaluation Criteria>

[0133] A: The calculated value is 0.80 or higher, and printing defects due to poor development do not occur even during high-speed printing (50 sheets or more).

[0134] B: The calculated value is 0.60 or more and less than 0.80. There is a slight possibility that printing defects due to development defects may occur during high-speed printing, but there is substantially no problem.

[0135] C: The calculated value is 0.40 or more and less than 0.60, and printing defects due to poor development occur during high-speed printing.

[0136] D: The calculated value is less than 0.40, and printing is impossible due to poor development during high-speed printing.

[0137] Test Example 4〔Storage〕

[0138] 5 g of toner was placed in a cylindrical container and left in a high-temperature environment at 50°C and 50% relative humidity for 72 hours. The container was then passed through a 200-mesh sieve (75 μm opening) and the mass of the toner that passed through was measured. The greater the mass of toner that passed through, the better the shelf life. Shelf life was evaluated according to the following criteria. The results are shown in Table 2.

[0139] <Evaluation Criteria>

[0140] A: The toner passing through the sieve accounts for 90% by mass or more, and no printing failure due to toner aggregation occurs.

[0141] B: The toner passing through the sieve is 80% by mass or more and less than 90% by mass. There is a slight possibility of printing failure due to toner aggregation, but there is substantially no problem.

[0142] C: The toner passing through the sieve is 20% by mass or more and less than 80% by mass, and there is a high possibility that printing defects due to toner aggregation will occur.

[0143] D: The toner passing through the sieve is less than 20% by mass, and printing failure occurs due to toner aggregation.

[0144] [Table 2]

[0145] Table 2

[0146]

[0147] The above results demonstrate that the toners of Examples 1 to 5 maintain good low-temperature fixing properties and exhibit excellent moisture absorption resistance, charge buildup, and storage stability under high-temperature and high-humidity environments. In particular, the toners of Examples 4 and 5, which contain a polyester resin and contain an acid-modified substance A content of 15 parts by mass or greater relative to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component other than the acid-modified substance A, exhibit particularly excellent moisture absorption resistance and charge buildup.

[0148] In contrast, the toner of Comparative Example 1, which contains a polyester resin without an acid modifier, has high resistance to moisture absorption in high-temperature, high-humidity environments and is prone to leakage, thus being insufficient in terms of charge rise. Furthermore, the toner of Comparative Example 2, which contains a polyester resin using an amorphous monomer (alkenyl succinic anhydride) with a hydrophobic alkyl group instead of an acid modifier, has improved charge rise, but its storage stability deteriorates due to a decrease in the glass transition temperature of the resin. Furthermore, the toner of Comparative Example 3, which contains a polyester resin using a crystalline macromonomer with a hydrophobic alkyl group, such as an acid modifier of an α-olefin polymer with 2 or 3 carbon atoms, has a certain degree of storage stability, but is insufficient in terms of moisture absorption resistance and charge rise in high-temperature, high-humidity environments.

[0149] The binder resin composition for toner of the present invention is suitably used in a toner for developing electrostatic images, which is used for developing latent images formed in, for example, electrostatic image developing methods, electrostatic recording methods, and electrostatic printing methods.

Claims

1. A binder resin composition for toner, comprising a polyester resin A having: a structural unit derived from an alcohol component of an alkylene oxide adduct comprising bisphenol A, and a structural unit derived from a carboxylic acid component of an acid-modified product A comprising an amorphous α-olefin polymer having 4 to 18 carbon atoms, wherein the α-olefin polymer having 4 to 18 carbon atoms is a polyisobutylene polymer; The softening point of the polyester resin A is 80° C. or higher and 150° C. or lower.

2. The binder resin composition for toner according to claim 1, wherein The polyester resin A is a polyester resin having a structure in which a structural unit derived from an alcohol component of an alkylene oxide adduct containing bisphenol A and a structural unit derived from a carboxylic acid component of an acid-modified product A containing an amorphous α-olefin polymer having 4 to 18 carbon atoms are linked via an ester bond.

3. The binder resin composition for toner according to claim 1 or 2, wherein Polyester resin A is: A polycondensate obtained by polycondensing an alcohol component comprising an alkylene oxide adduct of bisphenol A and a carboxylic acid component other than an acid-modified polymer A of an amorphous α-olefin having 4 to 18 carbon atoms into a polycondensate of the acid-modified polymer A.

4. The binder resin composition for toner according to claim 1 or 2, wherein The weight average molecular weight of the acid-modified amorphous α-olefin polymer having 4 to 18 carbon atoms is 500 to 5000.

5. The binder resin composition for toner according to claim 1 or 2, wherein The acid-modified amorphous α-olefin polymer having 4 to 18 carbon atoms A is an α-olefin polymer having 4 to 18 carbon atoms modified with at least one acid selected from maleic acid, fumaric acid, itaconic acid, and anhydrides of these acids.

6. The binder resin composition for toner according to claim 1 or 2, wherein The acid-modified product A of an amorphous α-olefin polymer having 4 to 18 carbon atoms is an acid-modified product of an α-olefin polymer having 4 to 18 carbon atoms whose terminals are modified with an acid.

7. The binder resin composition for toner according to claim 1 or 2, wherein The acid-modified product A of an amorphous α-olefin polymer having 4 to 18 carbon atoms is an acid-modified product of an α-olefin polymer having 4 to 18 carbon atoms in which one terminal is modified with an acid.

8. The binder resin composition for toner according to claim 1 or 2, wherein The acid-modified product A of an amorphous α-olefin polymer having 4 to 18 carbon atoms is polyisobutylene succinic anhydride modified at one end with maleic anhydride.

9. The binder resin composition for toner according to claim 1 or 2, wherein The content of the acid-modified amorphous α-olefin polymer having 4 to 18 carbon atoms is 3 to 40 parts by mass based on 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component other than the acid-modified product A.

10. The binder resin composition for toner according to claim 1 or 2, wherein The alkylene oxide adduct of bisphenol A is a compound represented by formula (I). In the formula, OR and RO are oxyalkylene groups, R is ethylene and / or propylene, x and y represent the average number of added moles of alkylene oxide, each of which is a positive number, and the sum of x and y is 1 or more and 16 or less. The content of the alkylene oxide adduct of bisphenol A represented by the formula (I) in the alcohol component is 70 mol% or more.

11. The binder resin composition for toner according to claim 1 or 2, wherein The carboxylic acid component further contains an aromatic dicarboxylic acid compound.

12. The binder resin composition for toner according to claim 11, wherein The aromatic dicarboxylic acid compound is terephthalic acid.

13. The binder resin composition for toner according to claim 1 or 2, wherein Polyester resin A is a linear polyester resin.

14. The binder resin composition for toner according to claim 1 or 2, wherein The glass transition temperature of the polyester resin A is 40° C. or higher and 80° C. or lower.

15. The binder resin composition for toner according to claim 1 or 2, wherein The acid value of the polyester resin A is 0.5 mgKOH / g or more and 15 mgKOH / g or less.

16. The binder resin composition for toner according to claim 1 or 2, wherein In the adhesive resin composition, the content of the polyester resin A is 80% by mass or more. 17 . A toner for developing electrostatic images, comprising the binder resin composition for toner according to claim 1 .

18. The electrostatic image developing toner according to claim 17, wherein In the toner, the content of the binder resin composition is 50% by mass or more and less than 100% by mass. 19 . The electrostatic image developing toner according to claim 17 , further comprising 1 part by mass or more and 40 parts by mass or less of a colorant based on 100 parts by mass of the binder resin composition. 20 . The electrostatic image developing toner according to claim 17 , further comprising a releasing agent having a melting point of 80° C. to 130° C. 21 . The electrostatic image developing toner according to claim 17 , further comprising 0.5 parts by mass or more and 10 parts by mass or less of a release agent relative to 100 parts by mass of the binder resin composition. 22 . The electrostatic image developing toner according to claim 17 , further comprising 0.01 parts by mass or more and 10 parts by mass or less of a charge control agent based on 100 parts by mass of the binder resin composition.

23. The toner for electrostatic image development according to claim 17 or 18, which is a pulverized toner obtained by a melt-kneading method. 24 . The electrostatic image developing toner according to claim 17 , wherein the toner has a volume median particle size of 3 μm or more and 15 μm or less.

Images