Binder resin composition for toner

Abstract

A binder resin composition for toner, and an electrostatic image developing toner containing the binder resin composition for toner, the binder resin composition for toner containing a polyester resin A which is a condensate of an alcohol component and a carboxylic acid component, the alcohol component containing 80% by mole or more of an aliphatic diol having 2 or more and 6 or less carbon atoms, and the carboxylic acid component containing an aromatic dicarboxylic acid compound and an acid-modified product A of an amorphous α-olefin polymer having 4 or more and 18 or less carbon atoms. The binder resin composition for toner of the present invention is suitable for use in an electrostatic image developing toner used for development of a latent image formed in, for example, an electrostatic image developing method, an electrostatic recording method, an electrostatic printing method, or the like.

Description

Technical Field

[0001] The present invention relates to a binder resin composition for developing latent images formed, for example, in electrophotography, electrostatic recording, electrostatic printing, etc., and a toner for electrostatic image development containing the binder resin composition. Background Technology

[0002] Patent Document 1 discloses a colorant, characterized in that, in a colorant comprising a colorant 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 the haze value of (A) is 70 or less.

[0003] Patent Document 2 discloses a polyester resin composition for a toner, characterized in that it contains a compatibilizer, which is characterized in that, in a toner containing at least a wax and an adhesive resin formed from a polyester, the compatibilizer compatibilizes the polyester with 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 colorant, 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 covalently linked, wherein the polymer A is a polypropylene polymer that has been end-modified by a carboxylic acid compound having unsaturated bonds or its anhydride, wherein in the polyester resin, the amount of structural unit derived from the polymer A 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 alcohol and carboxylic acid components forming the constituent portion derived from the polyester resin.

[0005] Existing technical documents

[0006] Patent documents

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

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

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

[0010] This invention relates to the following aspects:

[0011] [1] A binder resin composition for a toner, comprising a polyester resin A, wherein the polyester resin A is a condensation polymer of an alcohol component and a carboxylic acid component, wherein the alcohol component comprises 80 mol% or more of an aliphatic diol having 2 or more and 6 or fewer carbon atoms, and the carboxylic acid component comprises an aromatic dicarboxylic acid compound and an acid-modified amorphous α-olefin polymer having 4 or more and 18 or fewer carbon atoms; and

[0012] [2] A toner for electrostatic image development, comprising the toner binder resin composition described in [1] above. Detailed Implementation

[0013] In the field of electrophotographic toners, the development of electrophotographic systems has created a demand for high-speed printing and high-quality images. While polyester resins are considered to have excellent low-temperature fixing and storage properties, their high hygroscopicity is considered a problem in terms of charge rise. Specifically, nonbis(bis) polyester resins, which do not contain a bisphenol A backbone in their alcohol content, exhibit high hygroscopicity, and their charge rise is easily and significantly reduced.

[0014] In the past, as a means to improve the moisture resistance of non-bihydric polyester resins, a method of reacting hydrophobic polyolefins with polyesters has been considered. However, when reacting with crystalline macromonomers with hydrophobic alkyl groups, such as acid-modified α-olefin polymers with 2 or 3 carbon atoms, it is difficult to disperse them sufficiently in the polyester resin, and sufficient moisture resistance cannot be obtained (for example, see Patent Documents 2 and 3).

[0015] On the other hand, when amorphous monomers with hydrophobic alkyl groups, such as dodecylene succinic anhydride, are introduced into polyester resins, a certain degree of moisture resistance is obtained, but it cannot be said to be sufficient. Assuming that sufficient moisture resistance can be obtained by increasing the amount of monomers with alkyl groups, the polyolefin is compatible with the polyester resin, the glass transition temperature of the resin decreases, and thus the shelf life deteriorates (for example, see Patent Document 1).

[0016] This invention relates to a binder resin composition for toners that exhibits excellent low-temperature fixing properties, shelf life, charge rise, and moisture resistance, as well as toners for electrostatic image development containing the binder resin composition.

[0017] The toner for electrostatic image development containing a binder resin composition of the present invention exhibits excellent effects in terms of low-temperature fixing, preservation, charge rise and moisture resistance.

[0018] The colorant binder resin composition of the present invention is characterized by comprising a polyester resin A, wherein the polyester resin A is an acid-modified derivative A of an α-olefin polymer having 4 or more carbon atoms and 18 or fewer carbon atoms. By using such an acid-modified derivative A, the hydrophobic polyolefin portion in the acid-modified derivative A can be uniformly dispersed in the polyester resin in which the acid-modified derivative A is incorporated in a microphase-separated state, thereby improving the moisture resistance of the polyester resin.

[0019] Furthermore, acid-modified compound A is amorphous. Compared to acid-modified α-olefin polymers, which are crystalline and contain carboxylic acid or carboxylic anhydride groups, the moisture resistance of the polyester resin is further improved by using amorphous acid-modified compound A. This is presumably because amorphous acid-modified compound A has no melting point, and therefore, even at low temperatures, the hydrophobic polyolefin portion wets and extends to the surface of the toner.

[0020] Similar to the crystallinity of resins described later, the crystallinity of acid-modified materials is expressed by a crystallinity index ([softening point / peak endothermic temperature]). Amorphous acid-modified materials are those with a crystallinity index greater than 1.4, preferably greater than 1.5, more preferably greater than 1.6, or those with a crystallinity index less than 0.6, preferably less than 0.5. Furthermore, substances for which no endothermic peak temperature was detected are also classified as amorphous.

[0021] Polyester resin A is a condensation polymer of alcohol and carboxylic acid components. The alcohol component includes aliphatic diols with 2 or more carbon atoms and 6 or fewer carbon atoms. The carboxylic acid component includes aromatic dicarboxylic acid compounds and acid-modified α-olefin polymers with 4 or more carbon atoms and 18 or fewer carbon atoms.

[0022] From the viewpoint of low-temperature fixing, the alcohol component includes aliphatic diols with 2 or more but 6 or fewer carbon atoms. Examples of aliphatic diols with 2 or more but 6 or fewer carbon atoms include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentanediol, and 1,6-hexanediol. Among these, it is preferable to select one or more of ethylene glycol, 1,2-propanediol, and neopentanediol, and more preferably a combination of ethylene glycol and neopentanediol. The molar ratio of ethylene glycol to neopentanediol (ethylene glycol / neopentanediol) is preferably 15 / 85 or more, more preferably 20 / 80 or more, and more preferably 60 / 40 or less, and more preferably 50 / 50 or less.

[0023] In the alcohol component, the content of aliphatic diols with 2 or more carbon atoms and 6 or fewer is 80 mol% or more, preferably 90 mol% or more, more preferably 95 mol% or more, and even more preferably 100 mol%.

[0024] Examples of alcohol components other than aliphatic diols with 2 or more but 6 or fewer carbon atoms include aliphatic diols with 7 or more carbon atoms such as 1,8-octanediol, aromatic diols such as polyoxypropylene adducts of 2,2-bis(4-hydroxyphenyl)propane and polyethylene oxide adducts of 2,2-bis(4-hydroxyphenyl)propane, and ternary or higher alcohols such as glycerol. In the alcohol component, the content of other alcohols is preferably 20 mol% or less, more preferably 10 mol% or less, further preferably 5 mol% or less, and even more preferably 0 mol%.

[0025] For acid-modified derivative A of an α-olefin polymer containing 4 or more and 18 or less carbon atoms in a carboxylic acid component, the α-olefin has 4 or more and 18 or less carbon atoms, preferably 10 or less, more preferably 7 or less, even more preferably 5 or less, and even more preferably 4.

[0026] Examples of α-olefin polymers having 4 or more but 18 carbon atoms include 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, and propylene-hexene copolymers. Among these, polyisobutylene polymers are preferred. The aforementioned α-olefin polymers can be homopolymers of the aforementioned α-olefins, copolymers of two or more selected from the aforementioned α-olefins, or copolymers of the aforementioned α-olefins with other olefins. Furthermore, the copolymer can be either a random copolymer or a block copolymer.

[0027] Examples of polyisobutylene-based polymers include polyisobutylene and copolymers of isobutylene with other olefins. Other olefins include, for example, ethylene, butene, pentene, hexene, and 2-ethylhexene. In the case of copolymers, the proportion of isobutylene is preferably 60% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and less than 100% by mass.

[0028] On the other hand, as acid modifier A, from the viewpoint of reactivity with polyester resin, it is preferable to be an acid-modified product in which an α-olefin polymer having 4 or more and 18 or less carbon atoms has been modified with at least one acid selected from maleic acid, fumaric acid, itaconic acid, and anhydrides of these acids, and more preferably an acid-modified product modified with maleic anhydride. Furthermore, examples of acid modifiers include: random grafted acid-modified products in which acid is randomly grafted onto the aforementioned α-olefin polymer, and end-modified acid-modified products in which the ends of the aforementioned α-olefin polymer have been modified with acid. In this invention, from the viewpoint of low-temperature fixing and storage, end-modified acid-modified products are preferred, and single-end modified acid-modified products in which an α-olefin polymer having 4 or more and 18 or less carbon atoms has been modified with acid at a single end are more preferred.

[0029] For randomly grafted acid-modified polymers, it is preferable that one or more acids are grafted onto a single molecule of the polymer. Whether or not an acid has been applied can be determined by general spectroscopic measurements. For example, in the case of randomly grafted acid-modified polymers using maleic anhydride, if modified with maleic anhydride, the double bonds of the maleic anhydride change to single bonds, and this can be determined by measuring the spectral changes.

[0030] Randomly grafted modified acid-modified compounds can be obtained, for example, by generating free radicals within the molecule of an α-olefin polymer and reacting them with a carboxylic acid compound or its anhydride that has unsaturated bonds.

[0031] For terminally modified acid-modified polymers, it is preferable that one (single-terminal) or two (double-terminal) acids modify one molecule of the polymer. Whether or not acid modification has occurred can be determined by general spectroscopic measurements. For example, in the case of a single-terminal acid-modified polymer using maleic anhydride, if modified with maleic anhydride, the double bond of the maleic anhydride changes to a single bond, and this can be determined by measuring the spectral changes. Furthermore, the linked portion on the polymer side of the α-olefin also causes spectral changes before and after bonding, and this can be determined by measuring these changes.

[0032] Acid-modified compounds with single-terminal bonds can be obtained, for example, by reacting an acid with the aforementioned α-olefin polymer having unsaturated bonds at the single terminus to form an ene. The aforementioned α-olefin polymer having unsaturated bonds at the single terminus can be obtained by known methods, such as using vanadium-based catalysts, titanium-based catalysts, zirconium-based catalysts, etc.

[0033] Based on the above, as the acid-modified α-olefin polymer A, polyisobutylene succinic anhydride with maleic anhydride modified at one end is preferred.

[0034] From the viewpoint of preservation, the weight average molecular weight of acid-modified compound A is preferably 500 or more, more preferably 700 or more, even more preferably 900 or more, and even more preferably 1,100 or more. Moreover, from the viewpoint of low-temperature fixing, it is preferably 5,000 or less, more preferably 4,000 or less, and even more preferably 3,000 or less.

[0035] From the viewpoint of charge rising and hygroscopicity, relative to the total mass of 100 parts by mass of the alcohol component and the carboxylic acid component other than acid-modified component A, the content of acid-modified component 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, even more preferably 15 parts by mass or more. Moreover, from the viewpoint of preservation, 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, even more preferably 20 parts by mass or less.

[0036] From a preservation point of view, the carboxylic acid component further contains aromatic dicarboxylic acid compounds.

[0037] Examples of aromatic dicarboxylic acid compounds include phthalic acid, isophthalic acid, terephthalic acid, the anhydrides of these acids, and alkyl esters with 1 to 3 alkyl carbons. Among these, terephthalic acid or isophthalic acid is preferred from the viewpoint of low-temperature fixing, and terephthalic acid is more preferred.

[0038] From a preservation perspective, the content of aromatic dicarboxylic acid compounds in the carboxylic acid component other than the acid-modified α-olefin polymer A is preferably 50 mol% or more, more preferably 60 mol% or more, and even more preferably 70 mol% or more. Furthermore, from a low-temperature fixing perspective, when using a carboxylic acid compound with three or more components, the content of aromatic dicarboxylic acid compounds in the carboxylic acid component is preferably 95 mol% or less, more preferably 90 mol% or less, even more preferably 85 mol% or less, and even more preferably 80 mol% or less.

[0039] Examples of carboxylic acid components other than acid-modified compound A and aromatic dicarboxylic acid compounds include aliphatic dicarboxylic acid compounds and tri- or higher carboxylic acid compounds.

[0040] Examples of aliphatic dicarboxylic acid compounds include oxalic acid, malonic acid, maleic acid, fumaric acid, citracic acid, itaconic acid, pentenoic acid, succinic acid, adipic acid, and other aliphatic dicarboxylic acids that are optionally substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, as well as the anhydrides of these acids and alkyl esters having 1 to 3 carbon atoms.

[0041] Examples of carboxylic acid compounds with three or more alkyl groups include 1,2,4-benzenetricarboxylic acid (triphenyltricarboxylic acid), 2,5,7-naphthotricarboxylic acid, pyromellitic acid, the anhydrides of these acids, and alkyl esters with 1 to 3 alkyl carbons. Among these, trimellitic acid compounds are preferred.

[0042] In the carboxylic acid component, the content of trivalent or higher carboxylic acid compounds is preferably 1 mol% or more, more preferably 3 mol% or more, even more preferably 5 mol% or more, even more preferably 7 mol% or more, and preferably 30 mol% or less, more preferably 25 mol% or less.

[0043] The alcohol component may appropriately contain monohydric alcohols, and the carboxylic acid component may appropriately contain monohydric carboxylic acid compounds.

[0044] Polyester resin A can be manufactured, for example, by polycondensing an alcohol component and a carboxylic acid component in an inactive gas atmosphere, preferably in the presence of an esterification catalyst, and further, as needed, in the presence of an esterification co-catalyst, a polymerization inhibitor, etc., at a temperature preferably above 130°C, more preferably above 170°C, and more preferably below 250°C, and more preferably below 240°C.

[0045] 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 esterification catalyst used is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and more preferably 1.5 parts by mass or less, more preferably 1 part by mass or less, relative to 100 parts by mass of the total amount of the alcohol and the carboxylic acid component other than acid-modified A. Examples of esterification co-catalysts include gallic acid. The amount of esterification co-catalyst used is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and more 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 and the carboxylic acid component other than acid-modified A. Examples of polymerization inhibitors include tert-butylcatechol. The amount of polymerization inhibitor used is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and more preferably 0.5 parts by mass or less, more preferably 0.1 parts by mass or less, relative to the total amount of the alcohol component and the carboxylic acid component other than acid-modified A (100 parts by mass).

[0046] Polyester resin A can be a condensation polymer of an alcohol component and a carboxylic acid component, wherein the alcohol component includes an aliphatic diol with 2 to 6 carbon atoms, and the carboxylic acid component includes an aromatic dicarboxylic acid compound and an acid-modified α-olefin polymer with 4 to 18 carbon atoms. Polyester resin A can also be a condensation polymer obtained by condensing an acid-modified carboxylic acid component other than an acid-modified α-olefin polymer with 4 to 18 carbon atoms on an alcohol component containing an aliphatic diol with 2 to 6 carbon atoms. However, from a preservation point of view, the latter condensation polymer is preferred.

[0047] It should be noted that, in this invention, polyester resin A can be a polyester resin modified with a substance other than an acid to a degree 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 end-capping with phenols, urethanes, epoxy resins, etc., using methods described in Japanese Patent Application Publication Nos. 11-133668, 10-239903, and 8-20636. However, among the modified polyester resins, urethane-modified polyester resins obtained by urethane elongation of the polyester resin with a polyisocyanate compound are preferred.

[0048] Polyester resin A is preferably an amorphous resin. The crystallinity of the resin is represented by a crystallinity index, defined as the ratio of the softening point to the highest endothermic peak temperature obtained using differential scanning calorimetry, i.e., [softening point / highest endothermic peak temperature]. Crystalline resins are those with a crystallinity index of 0.6 or higher, preferably 0.7 or higher, more preferably 0.9 or higher, and 1.4 or lower, preferably 1.2 or lower, more preferably 1.1 or lower. On the other hand, amorphous resins are those with a crystallinity index exceeding 1.4, preferably exceeding 1.5, more preferably 1.6 or higher, or those with a crystallinity index less than 0.6, preferably 0.5 or lower. The crystallinity of the resin can be adjusted by the type and ratio of the raw material monomers, as well as manufacturing conditions (e.g., reaction temperature, reaction time, cooling rate). It should be noted that the highest endothermic peak temperature refers to the temperature of the peak at the highest temperature side among the observed endothermic peaks. For crystalline resins, the highest endothermic peak temperature is set as the melting point.

[0049] From the viewpoint of preservation stability, the softening point of polyester resin A is preferably 90°C or higher, more preferably 120°C or higher, and even more preferably 130°C or higher. Moreover, from the viewpoint of low-temperature fixing, it is preferably 160°C or lower, more preferably 150°C or lower, and even more preferably 140°C or lower.

[0050] From the viewpoint of preservation stability, the glass transition temperature of polyester resin A is preferably 50°C or higher, more preferably 60°C or higher, and from the viewpoint of low-temperature fixing, it is preferably 80°C or lower, more preferably 75°C or lower, and even more preferably 70°C or lower.

[0051] From the viewpoint of low-temperature fixing, the acid value of polyester resin A is preferably 15 mg KOH / g or more, more preferably 20 mg KOH / g or more, and even more preferably 30 mg KOH / g or more. Furthermore, from the viewpoint of moisture resistance, it is 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.

[0052] The adhesive resin composition of the present invention may further contain polyester resin B, which has a lower softening point than polyester resin A.

[0053] The difference in softening point between polyester resin A and polyester resin B is preferably 10°C or more, more preferably 15°C or more, even more preferably 20°C or more, and preferably 65°C or less, more preferably 60°C or less, and even more preferably 55°C or less.

[0054] Polyester resin B is a condensation polymer of an alcohol containing two or more diols and a carboxylic acid component containing two or more carboxylic acid compounds. The carboxylic acid component preferably includes the aforementioned acid-modifying agent A. The acid-modifying agent A used in polyester resin A and polyester resin B can be the same or different. Specific examples of the alcohol and carboxylic acid components are the same as those for polyester resin A. Furthermore, like polyester resin A, polyester resin B is preferably an amorphous resin.

[0055] However, in the carboxylic acid component of amorphous polyester resin AL, the content of ternary or higher carboxylic acid compounds is preferably 5 mol% or less, more preferably 3 mol% or less, and even more preferably 0 mol%.

[0056] From the viewpoint of preservation stability, the softening point of polyester resin B is preferably 80°C or higher, more preferably 85°C or higher, and from the viewpoint of low-temperature fixing, it is preferably 110°C or lower, more preferably 105°C or lower, and even more preferably 100°C or lower.

[0057] From the viewpoint of preserving stability, the glass transition temperature of polyester resin B is preferably 45°C or higher, and from the viewpoint of low-temperature fixing, it is preferably 80°C or lower, more preferably 70°C or lower, and even more preferably 60°C or lower.

[0058] From the viewpoint of low-temperature fixing, the acid value of polyester resin B is preferably 1 mg KOH / g or more, more preferably 3 mg KOH / g or more, and from the viewpoint of moisture resistance, it is preferably 15 mg KOH / g or less, more preferably 10 mg KOH / g or less, and even more preferably 5 mg KOH / g or less.

[0059] The mass ratio of polyester resin A to polyester resin B (polyester resin A / polyester resin B) is preferably 60 / 40 or more, more preferably 70 / 30 or more, and more preferably 95 / 5 or less, more preferably 90 / 10 or less.

[0060] The adhesive resin composition of the present invention may also contain polyester resins other than polyester resin A and polyester resin B, vinyl resins such as styrene-acrylic resins, epoxy resins, polycarbonates, polyurethanes, composite resins containing two or more of these resins, etc. However, when polyester resin A and polyester resin B are included, the total content of polyester resin A and polyester resin B 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 even more preferably 100% by mass.

[0061] In the toner for electrostatic image development, the content of the adhesive resin composition of the present invention is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass, and preferably less than 100% by mass, more preferably 98% by mass or less, even more preferably 95% by mass or less, and even more preferably 92% by mass or less.

[0062] In addition to the bonding resin (the bonding resin composition of the present invention), the toner for electrostatic image development of the present invention may also contain colorants, release agents, charge control agents, magnetic powders, flow improvers, conductivity modifiers, fibrous materials and other reinforcing fillers, antioxidants, cleaning agents and other additives, preferably containing colorants, release agents and charge control agents.

[0063] As a coloring agent, dyes, pigments, magnetic materials, etc., used as colorants for toning 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 diazo yellow. It should be noted that in this invention, the toning agent can be any of a black toning agent or a colored coloring agent.

[0064] From the viewpoint of improving the image concentration and low-temperature fixing properties 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 more 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.

[0065] As mold release agents (waxes), examples include aliphatic hydrocarbon waxes or their oxides such as polypropylene wax, polyethylene wax, polypropylene-polyethylene copolymer wax, microcrystalline wax, paraffin wax, Fischer-Tropsch wax, and Sasol wax; ester waxes such as carnauba wax, lignite wax or their deoxidized waxes, and fatty acid ester waxes; fatty acid amides, fatty acids, higher alcohols, and fatty acid metal salts, which can be used alone or in combination.

[0066] From the viewpoint of the transferability of the toner, 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. Furthermore, from the viewpoint of low-temperature fixing, it is preferably 130°C or lower, more preferably 125°C or lower, and even more preferably 120°C or lower.

[0067] From the viewpoints of the low-temperature fixing properties and the resistance to offset of the toner, and from the viewpoints of its dispersibility in the adhesive resin, the content of the release agent relative to 100 parts by weight of the adhesive resin is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, even more preferably 1.5 parts by weight or more, even more preferably 3 parts by weight or more, even more preferably 4 parts by weight or more, and preferably 10 parts by weight or less, more preferably 8 parts by weight or less, and even more preferably 7 parts by weight or less.

[0068] There are no particular limitations on the charge control agent; it can contain any type of positively charged charge control agent or negatively charged charge control agent.

[0069] Examples of positively charged charge control agents include: aniline black dyes such as "Nigrosine Base EX", "OILBLACK BS", "OIL BLACK SO", "BONTRON N-01", "BONTRON N-04", "BONTRON N-07", "BONTRON N-09", and "BONTRON N-11" (all manufactured by Orient Chemical Industry Co., Ltd.); triphenylmethane dyes containing tertiary amines as side chains; and quaternary ammonium salt compounds such as "BONTRON P-51" (manufactured by Orient Chemical Industry Co., Ltd.), cetyltrimethylammonium bromide, and "COPY CHARGE PX". VP435 (manufactured by Clariant Corporation), etc.; polyamine resins, such as "AFP-B" (manufactured by Orient Chemical Industry Co., Ltd.), etc.; imidazole derivatives, such as "PLZ-2001" and "PLZ-8001" (manufactured by Shikoku Chemical Industry Co., Ltd.); styrene-acrylic resins, such as "FCA-701PT" (manufactured by Fujikura Chemical Co., Ltd.), etc.

[0070] In addition, examples of negatively charged charge control agents include: metal azo dyes, such as "VARIFAST BLACK3804", "BONTRON S-31", "BONTRON S-32", "BONTRON S-34", "BONTRON S-36" (all manufactured by Orient Chemical Industry Co., Ltd.), "AIZEN SPILON BLACK TRH", and "T-77" (manufactured by Hodogaya Chemical Industry Co., Ltd.); metal compounds of diphenyl glycolic acid, such as "LR-147" and "LR-297" (manufactured by Carlit Corporation of Japan); metal compounds of salicylic acid, such as "BONTRON E-81", "BONTRON E-84", "BONTRON E-88", "BONTRON E-304" (manufactured by Orient Chemical Industry Co., Ltd.), and "TN-105" (manufactured by Hodogaya Chemical Industry Co., Ltd.); copper phthalocyanine dyes; and quaternary ammonium salts, such as "COPY CHARGE NX". VP434 (manufactured by Clariant), nitroimidazole derivatives, organometallic compounds, etc.

[0071] From the viewpoint of the charge stability of the toner, the content of the charge control agent is preferably 0.01 parts by mass or more, more preferably 0.2 parts by mass or more, and preferably 10 parts by mass or less, more preferably 5 parts by mass or less, even more preferably 3 parts by mass or less, and even more preferably 2 parts by mass or less, relative to 100 parts by mass of the binder resin.

[0072] The toner of the present invention can be obtained by any known method such as melt mixing, emulsion phase inversion, or polymerization. However, from the viewpoint of productivity and colorant dispersibility, a pulverized toner obtained by melt mixing is preferred. In the case of a pulverized toner obtained by melt mixing, it can be manufactured, for example, by uniformly mixing raw materials such as binder resin, colorant, release agent, and charge control agent in a mixer such as a Henschel mixer, then melt mixing it using a closed kneader, a single-shaft or twin-shaft extruder, or an open roll mill, followed by cooling, pulverizing, and grading.

[0073] To improve transferability, the toner of the present invention preferably uses an additive. Examples of additives include inorganic particles such as silica, alumina, titanium dioxide, zirconium oxide, tin oxide, and zinc oxide, and organic particles such as resin particles such as melamine-based resin particles and polytetrafluoroethylene resin particles; two or more additives may be used in combination. Among these, silica is preferred, and from the viewpoint of the toner's transferability, hydrophobic silica that has undergone hydrophobic treatment is more preferred.

[0074] Examples of hydrophobic treatment agents used to hydrophobize the surface of silica particles include hexamethyldisilazane (HMDS), dimethyldichlorosilane (DMDS), silicone oil, octyltriethoxysilane (OTES), and methyltriethoxysilane.

[0075] From the viewpoint of the charge, flowability and transferability of the toner, the average particle size of the 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, even more preferably 150 nm or less, and even more preferably 90 nm or less.

[0076] From the viewpoint of the charge, flowability, and transferability of the toner, the content of the additive is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, even more preferably 0.3 parts by mass or more, and preferably 5 parts by mass or less, more preferably 3 parts by mass or less, relative to 100 parts by mass of the toner before treatment with the additive.

[0077] The volume median particle size (D) of the toner of the present invention 50 Preferably, the particle size is 3 μm or more, more preferably 4 μm or more, and more 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 This means that the cumulative volume frequency, calculated using volume fraction, is calculated starting from the side with the smallest particle size, which becomes the 50% particle size. Additionally, when the toner is treated with additives, the median volume particle size of the toner particles before treatment with the additives is set as the median volume particle size of the toner.

[0078] The toner of the present invention can be used as a toner for single-component development, or mixed with a carrier to be used as a two-component developer.

[0079] The present invention will now be specifically described by way of examples, but the present invention is not limited to these examples in any way. The physical properties of resins, etc., can be determined by the following methods.

[0080] [Peak endothermic temperature of acid-modified products]

[0081] Using a differential scanning calorimeter "DSC Q20" (manufactured by TA Instruments Japan Co., Ltd.), a sample of 0.01 to 0.02 g was weighed on an aluminum pan. The sample was heated from room temperature (25°C) to 200°C at a heating rate of 10°C / min, and then cooled from that temperature to -10°C at a cooling rate of 5°C / min. Next, the sample was heated to 180°C at a heating rate of 10°C / min for measurement. Samples where no endothermic peak temperature was detected were considered amorphous. In cases where an endothermic peak temperature was detected, the softening point was determined using the same method as for resins, and the crystallinity index (softening point / endothermic peak temperature) was calculated for identification.

[0082] [Weight-average molecular weight (Mw) of acid-modified α-olefin polymers]

[0083] (1) Preparation of sample solution

[0084] The sample was dissolved in tetrahydrofuran to a concentration of 0.5 g / 100 mL. Then, the solution was filtered using a fluoropolymer filter "FP-200" (manufactured by Sumitomo Electric Industries, Ltd.) with a pore size of 2 μm to remove insoluble components, thus preparing the sample solution.

[0085] (2) Determination of molecular weight distribution

[0086] Using the following apparatus and analytical column, tetrahydrofuran was flowed at a flow rate of 1 mL / min as the eluent, and the column was stabilized in a thermostat at 40°C. 100 μL of the sample solution was injected for determination. The molecular weight of the sample was calculated based on a pre-prepared calibration curve. This calibration curve used several types of monodisperse polystyrene (Tosoh Corporation's A-500, Mw 5.0 × 10⁻⁶). 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 (Mw 7.06×10) 5 F-128 (Mw 1.09×10) 6The calibration curve was prepared using the standard sample. The numbers in parentheses indicate the molecular weight.

[0087] Measurement apparatus: HLC-8220GPC (manufactured by Tosoh Corporation)

[0088] Analytical column: GMHXL+G3000HXL (manufactured by Tosoh Corporation)

[0089] [Refine softening point]

[0090] Using a flow testing machine "CFT-500D" (manufactured by Shimadzu Corporation), a 1g sample was heated at a heating rate of 6°C / min, and a load of 1.96MPa was applied using a plunger, extruding the sample from a nozzle with a diameter of 1mm and a length of 1mm. The plunger descent of the flow testing machine was plotted against temperature, and the temperature at which half of the sample flowed out was defined as the softening point.

[0091] [Peak temperature at which the resin absorbs heat]

[0092] Using a differential scanning calorimeter "Q-100" (manufactured by TA Instruments Japan Co., Ltd.), a sample of 0.01–0.02 g was weighed on an aluminum pan and cooled from room temperature (25°C) to 0°C at a cooling rate of 10°C / min, and held at 0°C for 1 minute. Subsequently, measurements were taken at a heating rate of 10°C / min. The temperature of the peak on the highest endothermic side among the observed endothermic peaks was defined as the highest endothermic peak temperature.

[0093] [Glass transition temperature of resin]

[0094] Using a differential scanning calorimeter "Q-100" (manufactured by TA Instruments Japan Co., Ltd.), weigh 0.01 to 0.02 g of the sample onto an aluminum pan, heat to 200°C, and then cool from that temperature to 0°C at a cooling rate of 10°C / min. Next, heat the sample at a heating rate of 10°C / min and measure the endothermic peak. The temperature at which the extended baseline below the highest endothermic peak temperature intersects with the tangent line representing the maximum slope from the rising portion of the peak to the apex is defined as the glass transition temperature.

[0095] [Acid value of resin]

[0096] The determination was performed based on the method of JIS K0070:1992. However, the only change was that the solvent was changed from the mixture of ethanol and diethyl ether specified in JIS K0070 to a mixture of acetone and toluene (acetone:toluene = 1:1 (volume ratio)).

[0097] [Melting point of release agent]

[0098] Using a differential scanning calorimeter "DSC Q-100" (manufactured by TA Instruments Japan Co., Ltd.), a sample of 0.01 to 0.02 g was weighed on an aluminum pan. The sample was heated to 200°C at a heating rate of 10°C / min, and then cooled to -10°C at a cooling rate of 5°C / min. Next, the sample was heated to 180°C at a heating rate of 10°C / min for measurement. The peak temperature of the endothermic reaction observed in the resulting melting endothermic curve was taken as the melting point of the release agent.

[0099] [Average particle size of the additive]

[0100] The average particle size is the exponential average particle size, which is the average of the major and minor diameters of 500 particles measured by scanning electron microscopy (SEM) images and set as their number mean.

[0101] [Volume median particle size of the toner]

[0102] Measuring instrument: Coulter Multisizer II (manufactured by Beckman Coulter Co., Ltd.)

[0103] Aperture diameter: 50μm

[0104] Analysis software: Coulter Multisizer AccuComp Ver.1.19 (manufactured by Beckman Coulter Co., Ltd.)

[0105] Electrolyte: Isoton II (manufactured by Beckman Coulter Co., Ltd.)

[0106] Dispersion: The electrolyte was prepared by dissolving EMULGEN 109P (manufactured by Kao Corporation, polyoxyethylene lauryl ether, HLB (Griffin: 13.6) in the electrolyte and adjusting the concentration to 5% by mass.

[0107] Dispersion conditions: 10 mg of the test sample was added to 5 mL of the above dispersion and dispersed for 1 minute using an ultrasonic disperser (machine name: SND Corporation US-1, output: 80 W). Then, 25 mL of the above electrolyte was added and dispersed for another 1 minute using an ultrasonic disperser to prepare the sample dispersion.

[0108] Measurement conditions: To achieve a concentration sufficient to measure the particle size of 30,000 particles within 20 seconds, the above sample dispersion was added to 100 mL of the above electrolyte, and 30,000 particles were measured. The volume median particle size (D) was determined based on the particle size distribution. 50 ).

[0109] Example 1 of resin manufacturing

[0110] The alcohol components shown in Table 1 were placed in a 10-liter four-necked flask equipped with a dehydration tube containing a nitrogen inlet, a stirrer, and a thermocouple. The mixture was heated to 100°C, and then terephthalic acid (as shown in Table 1) was added. The temperature was raised to 130°C, followed by the addition of the esterification catalyst and esterification co-catalyst (as shown in Table 1). The temperature was then raised to 185°C and reacted at 185°C for 5 hours. The temperature was then gradually increased at a rate of 5°C / hour until reaching 220°C. After confirming that the reaction rate reached over 90% at 220°C, the mixture was cooled to 160°C, and the acid modifier (as shown in Table 1) was added. The temperature was then raised again to 220°C, and a polycondensation reaction was carried out at 220°C for 5 hours. Subsequently, the mixture was cooled to 200°C, and trimellitic anhydride as shown in Table 1 was added. The polycondensation reaction was carried out at 200°C for 1 hour, and then cooled to 200°C. The reaction was carried out at 200°C and 8.0 kPa until the softening point shown in Table 1 was reached, thus obtaining amorphous polyester resins (resins A1 to A6).

[0111] Resin Manufacturing Example 2

[0112] The alcohol components shown in Table 2 were placed in a 10-liter four-necked flask equipped with a dehydration tube containing a nitrogen inlet, a stirrer, and a thermocouple. The mixture was heated to 100°C, and then terephthalic acid (as shown in Table 2) was added. The temperature was raised to 130°C, and then the esterification catalyst and esterification co-catalyst (as shown in Table 2) were added. The temperature was raised to 185°C, and the reaction was carried out at 185°C for 5 hours. The temperature was then increased in stages at a rate of 5°C / hour until reaching 220°C. After confirming that the reaction rate reached over 90% at 220°C, the temperature was cooled to 160°C, and the acid modifier (as shown in Table 2) was added. The temperature was then raised again to 220°C, and a polycondensation reaction was carried out at 220°C for 5 hours. The temperature was then lowered to 200°C, and the reaction was carried out at 200°C and 8.0 kPa until the softening point shown in Table 2 was reached, yielding amorphous polyester resins (resins B1 and B4). It should be noted that the reaction rate is the value of the amount of water produced in the reaction / the theoretical amount of water produced × 100.

[0113] Resin Manufacturing Example 3

[0114] The alcohol components shown in Table 2 were placed in a 10-liter four-necked flask equipped with a dehydration tube containing a nitrogen inlet, a stirrer, and a thermocouple. The mixture was heated to 100°C, and then terephthalic acid (as shown in Table 2) was added. The temperature was raised to 130°C, and then the esterification catalyst and esterification co-catalyst (as shown in Table 2) were added. The temperature was raised to 185°C, and after reacting at 185°C for 5 hours, the temperature was gradually increased at a rate of 5°C / hour until reaching 220°C. After confirming that the reaction rate reached over 90% at 220°C, the reaction was continued at 220°C and 8.0 kPa until the softening point shown in Table 2 was reached, yielding an amorphous polyester resin (resin B2).

[0115] Resin Manufacturing Example 4

[0116] The alcohol components shown in Table 2 were placed in a 10-liter four-necked flask equipped with a dehydration tube containing a nitrogen inlet, a stirrer, and a thermocouple. The mixture was heated to 100°C, and then terephthalic acid (as shown in Table 2) was added. The temperature was raised to 130°C, and then the esterification catalyst and esterification co-catalyst (as shown in Table 2) were added. The temperature was raised to 185°C, and the reaction was carried out at 185°C for 5 hours. The temperature was then increased in stages at a rate of 5°C / hour until reaching 220°C. After confirming that the reaction rate reached over 90% at 220°C, the mixture was cooled to 200°C, and then alkenyl succinic anhydride (as shown in Table 2) substituted with alkenyl groups having 10-14 carbon atoms was added. A polycondensation reaction was carried out at 200°C for 1 hour, and then the reaction was continued at 200°C and 8.0 kPa until the softening point shown in Table 2 was reached, yielding an amorphous polyester resin (resin B3).

[0117] [Table 1]

[0118]

[0119] [Table 2]

[0120]

[0121] Examples 1-7 and Comparative Examples 1-3

[0122] 100 parts by weight of the binder resin shown in Table 3, 6 parts by weight of the colorant "Fastogen Supermagenda R" (CI Pigment Red 122, manufactured by Dai Nippon Ink Chemical Industry Co., Ltd.), 1 part by weight of the charge control agent "LR-147" (manufactured by Carlit Corporation of Japan), and 4 parts by weight of the release agent "SP-105" (manufactured by Kato Hiroko Co., Ltd., Fischer-Tropsch wax, melting point: 105°C) were thoroughly mixed using a Henschel mixer. The mixture was then melt-blended using a co-rotating twin-screw extruder with a total length of 1560 mm, a screw diameter of 42 mm, and a barrel inner diameter of 43 mm. The roller rotation speed was 200 r / min, the roller heating setting temperature was 100°C, the mixture temperature was 160°C, the mixture feed rate was 10 kg / h, and the average residence time was approximately 18 seconds. After cooling, the volume median particle size (D) was obtained using a spray mill. 50 6.5μm toner particles.

[0123] Add 2 parts by mass of "Aerosil R-972" (hydrophobic silica, manufactured by Aerosil Corporation of Japan, hydrophobic treatment agent: DMDS, average particle size: 16nm) as an additive to 100 parts by mass of the obtained toner particles, and mix with a Henschel mixer at 3600 r / min for 5 minutes to obtain the toner.

[0124] Experimental Example 1 [Low Temperature Fixing]

[0125] The toner was installed in the color printer "C612dnw" (trade name, manufactured by Oki Data Co., Ltd.), and the image was output in an unfixed state (printing area: 6cm×6cm, 0.5mg / cm). 2 ).

[0126] The fuser of the above-mentioned printer is used offline, and the unfused image is fusing by increasing the temperature by 5°C from 100°C at a rate of 100mm / second. It should be noted that J paper (manufactured by Fuji Xerox, weight per unit area: 82g / m²) was used as the fusing paper. 2 (Paper thickness: 97μm).

[0127] A UNICEF Cellophane tape (Mitsubishi Pencil Corporation, width: 18mm, JISZ-1522) was adhered to the fixing image and passed through a fixing roller set to 30°C before being peeled off. Optical reflectance density was measured using a reflectance density meter RD-915 (Macbeth Process Measurements) before and after tape application. The temperature of the fixing roller at which the ratio (after peeling / before application) first exceeded 90% was set as the lowest fixing temperature to evaluate low-temperature fixing performance. The results are shown in Table 3.

[0128] Test Example 2 [Moisture Resistance]

[0129] After the resin used in the bonding resin was sized to be 150–250 μm, it was dried in a vacuum dryer at 40 °C and 60 torr for 12 hours, and the mass of the dried resin was measured (resin mass a). 2.00 g of the dried resin was evenly spread on a glass dish and placed in a high-temperature and high-humidity environment at 40 °C and 85% humidity for 12 hours, and the mass was measured again (resin mass b).

[0130] The lower the moisture absorption rate (%) calculated by (resin mass b - resin mass a) / resin mass a × 100, the better the moisture absorption resistance. The moisture absorption resistance is evaluated according to the following evaluation criteria. The results are shown in Table 3.

[0131] <Evaluation Criteria>

[0132] A: The moisture absorption rate is less than 0.50%, which does not affect the charge of the toner.

[0133] B: The moisture absorption rate is above 0.50% and below 0.60%, which may slightly reduce the charge of the toner.

[0134] C: The moisture absorption rate is above 0.60% and below 0.90%, which may reduce the charge of the toner.

[0135] D: A moisture absorption rate of 0.90% or higher increases the likelihood of reducing the charge of the toner, or reduces the charge of the toner, which can lead to poor development.

[0136] Experimental Example 3 [Charged Ascent]

[0137] Four parts by mass (0.4 g) of toner and 96 parts by mass (9.6 g) of silicone-coated ferrite carrier (manufactured by Kanto Denka Kogyo Co., Ltd.) with an average particle size of 90 μm were placed in a 20 mL polypropylene container and mixed in a ball mill for 0.5 minutes at 25°C and 50% relative humidity. The charge was measured using a q / m Meter MODEL 210HS (manufactured by TREK). The mixture was stirred for another 2.5 minutes, and the charge was measured again. The ratio of the two charges (charge at 0.5 minutes / charge at 2.5 minutes) 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 3.

[0138] <Evaluation Criteria>

[0139] A: The calculated value is above 0.60, so even at high speed (more than 50 sheets), there will be no printing defects caused by poor development, or sometimes printing defects caused by poor development may occur at high speed.

[0140] B: A calculated value of 0.40 or higher but less than 0.60 will result in printing defects caused by poor development during high-speed printing.

[0141] C: The calculated value is less than 0.40, which means that printing will not be possible at high speeds due to poor development.

[0142] Experimental Example 4 [Preservation]

[0143] 5g of toner was placed in a cylindrical container and placed in a high-temperature environment of 50°C and 50% relative humidity for 72 hours. After that, the toner was passed through a 200-mesh sieve (75μm mesh) and the mass of the toner that passed through was weighed. The greater the mass of toner that passed through, the better the shelf life. The shelf life was evaluated according to the following evaluation criteria. The results are shown in Table 3.

[0144] <Evaluation Criteria>

[0145] A: The toner that passes through the sieve is 80% or more by mass, and there is no printing defect caused by toner agglomeration, or there is a slight possibility of printing defect caused by toner agglomeration.

[0146] B: If the toner passing through the sieve is more than 20% by mass but less than 80% by mass, there is a high possibility of printing defects caused by toner agglomeration.

[0147] C: If less than 20% by mass of the toner passes through the sieve, printing defects will occur due to the aggregation of the toner.

[0148] [Table 3]

[0149] Table 3

[0150]

[0151] Based on the results above, it can be seen that the toners of Examples 1 to 7 maintain good low-temperature fixing properties, and are excellent in any of the following aspects: moisture resistance, charge rise, and storage properties.

[0152] In contrast, the toner of Comparative Example 1, which contains polyester resin without acid modification, has low moisture resistance and is prone to leakage, thus its charge rise is insufficient. Furthermore, the toner of Comparative Example 2, which uses an amorphous monomer (alkenyl succinic anhydride) with hydrophobic alkyl groups instead of acid modification, shows improved moisture resistance and charge rise compared to Comparative Example 1, but its shelf life deteriorates due to the lower glass transition temperature of the resin. Additionally, the toner of Comparative Example 3, which contains a polyester resin with a hydrophobic alkyl crystalline macromonomer such as an acid-modified α-olefin polymer with two or three carbon atoms, is insufficient in terms of charge rise and moisture resistance compared to Example 7.

[0153] The binder resin composition for toners of the present invention is suitable for use as a toner for electrostatic image development, which is used for developing latent images formed, for example, in electrostatic image development, electrostatic recording, electrostatic printing, etc.

Claims

1. A binder resin composition for toner, comprising a polyester resin A which is a polycondensate of an alcohol component containing 80% by moles or more of an aliphatic diol having 2 or more and 6 or less carbon atoms and a carboxylic acid component containing an aromatic dicarboxylic acid compound and an acid-modified product A of an amorphous α-olefin polymer having 4 or more and 18 or less carbon atoms, the amorphous α-olefin polymer having 4 or more and 18 or less carbon atoms is a polyisobutenyl polymer, the acid-modified product A of the amorphous α-olefin polymer having 4 or more and 18 or less carbon atoms has a weight average molecular weight of 500 or more and 5,000 or less.

2. The toner binder resin composition according to claim 1, wherein, the polyester resin A is: the polycondensate obtained by polycondensing the acid-modified product A on a polycondensate of an alcohol component containing 80% by moles or more of an aliphatic diol having 2 or more and 6 or less carbon atoms and a carboxylic acid component other than the acid-modified product A of the amorphous α-olefin polymer having 4 or more and 18 or less carbon atoms.

3. The toner binder resin composition according to claim 1 or 2, wherein, the acid-modified product A of the amorphous α-olefin polymer having 4 or more and 18 or less carbon atoms has a weight average molecular weight of 500 or more and 4,000 or less.

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

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

6. The toner binder resin composition according to claim 1 or 2, wherein, the acid-modified product A of the amorphous α-olefin polymer having 4 or more and 18 or less carbon atoms is an acid-modified product in which the single terminal of the α-olefin polymer having 4 or more and 18 or less carbon atoms is modified with an acid.

7. The toner binder resin composition according to claim 1 or 2, wherein, the acid-modified product A of the amorphous α-olefin polymer having 4 or more and 18 or less carbon atoms is a polyisobutenyl succinic anhydride in which the single terminal is modified with maleic anhydride.

8. The toner binder resin composition according to claim 1 or 2, wherein, the aliphatic diol having 2 or more and 6 or less carbon atoms is one or more selected from the group consisting of ethylene glycol, 1,2-propanediol and neopentyl glycol.

9. The toner binder resin composition according to claim 1 or 2, wherein, the content of the acid-modified product A of the amorphous α-olefin polymer having 4 or more and 18 or less carbon atoms is 3 parts by mass or more and 40 parts by mass or less with respect 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.

10. The toner binder resin composition according to claim 1 or 2, wherein, the aliphatic diol having 2 or more and 6 or less carbon atoms contains ethylene glycol and neopentyl glycol.

11. The toner binder resin composition according to claim 10, wherein the mole ratio of ethylene glycol to neopentyl glycol, i.e., ethylene glycol / neopentyl glycol is 15 / 85 or more and 60 / 40 or less.

12. The toner binder resin composition according to claim 1 or 2, wherein, the aromatic dicarboxylic acid compound contains terephthalic acid.

13. The toner binder resin composition according to claim 1 or 2, wherein, the softening point of the polyester resin A is 90°C or more and 160°C or less.

14. The toner binder resin composition according to claim 1 or 2, wherein, the glass transition temperature of the polyester resin A is 50°C or more and 80°C or less.

15. The toner binder resin composition according to claim 1 or 2, wherein, the acid value of the polyester resin A is 15 mgKOH / g or more and 70 mgKOH / g or less.

16. The toner binder resin composition according to claim 1 or 2, wherein, in the binder resin composition, the content of the polyester resin A is 80% by mass or more.

17. The binder resin composition for toner according to claim 1, further comprising a polyester resin B having a lower softening point than the polyester resin A.

18. The toner binder resin composition according to claim 17, wherein The difference between the softening points of the polyester resin A and the polyester resin B is 15°C or more and 65°C or less.

19. The toner binder resin composition according to claim 17 or 18, wherein, In the binder resin composition, the total content of the polyester resin A and the polyester resin B is 80 mass% or more.

20. A toner for electrostatic image development, comprising the binder resin composition for toner according to any one of claims 1 to 19.

21. The electrostatic image developing toner according to claim 20, wherein In the toner, the content of the binder resin composition is 50 mass% or more and less than 100 mass%.

22. The toner for electrostatic image development according to claim 20 or 21, further comprising 1 mass part or more and 40 mass parts or less of a colorant per 100 mass parts of the binder resin composition.

23. The toner for electrostatic image development according to claim 20 or 21, further comprising a release agent having a melting point of 80°C or more and 130°C or less.

24. The toner for electrostatic image development according to claim 20 or 21, further comprising 0.5 mass part or more and 10 mass parts or less of a release agent per 100 mass parts of the binder resin composition.

25. The toner for electrostatic image development according to claim 20 or 21, further comprising 0.01 mass part or more and 10 mass parts or less of a charge control agent per 100 mass parts of the binder resin composition.

26. The toner for electrostatic image development according to claim 20 or 21, which is a pulverized toner obtained by a melt-kneading method.

27. The toner for electrostatic image development according to claim 20 or 21, having a volume median particle diameter of 3 μm or more and 15 μm or less.

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