Toner binder resin composition

Abstract

To provide a binder resin composition for a toner which is excellent in scratch resistance and glossiness of an image and has good crushability, and a toner for electrostatic charge image development which contains the binder resin composition.SOLUTION: There are provided a binder resin composition for a toner which contains a crystalline polyester resin and an amorphous polyester resin, wherein the crystalline polyester resin is a polycondensate of an alcohol component containing ethylene glycol and a carboxylic acid component containing an aliphatic dicarboxylic acid-based compound having 12 or more and 16 or less carbon atoms and an aliphatic monocarboxylic acid-based compound having 16 or more and 24 or less carbon atoms, and the amorphous polyester resin is a polycondensate of an alkylene oxide adduct of bisphenol A and an alcohol component containing ethylene glycol and a carboxylic acid component containing a dicarboxylic acid-based compound; and a toner for electrostatic charge image development which contains the binder resin composition.SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] Patent Document 1 discloses a binder resin composition for toner containing an amorphous resin and a crystalline resin, wherein the amorphous resin comprises a polyester resin A which is a polycondensate of an alcohol component containing an aliphatic diol having a hydroxyl group bonded to a secondary carbon atom, a carboxylic acid component, and polyethylene terephthalate, and the crystalline resin comprises a polyester resin C which is a polycondensate of an alcohol component containing 50 mol% to 100 mol% of ethylene glycol and a carboxylic acid component, and the mass ratio of the amorphous resin to the crystalline resin (amorphous resin / crystalline resin) is 65 / 35 to 95 / 5.

[0003] Patent Document 2 discloses a binder resin composition for toner containing amorphous polyester A and crystalline polyester C, wherein amorphous polyester A is an amorphous polyester obtained by polycondensation of an alcohol component containing an aromatic diol and an aliphatic diol having 3 to 6 carbon atoms and a carboxylic acid component, and crystalline polyester C is a crystalline polyester obtained by polycondensation of an alcohol component containing an aliphatic diol having 2 to 9 carbon atoms and a carboxylic acid component.

[0004] Patent Document 3 discloses a toner binder containing a crystalline resin (A) whose essential constituent monomers are an alcohol component (X) and a carboxylic acid component (Y), wherein, based on the total number of moles of the carboxylic acid component (Y), the carboxylic acid component (Y) contains 90 to 99.49 mol% of a linear aliphatic dicarboxylic acid (y1) having 2 to 12 carbon atoms, 0.01 to 1.0 mol% of an aliphatic monocarboxylic acid (y2) having 20 carbon atoms, and 0.5 to 9.0 mol% of an aliphatic monocarboxylic acid (y3) having 22 carbon atoms, and the toner binder is characterized in that, in the second heating process by differential scanning calorimeter (DSC), the peak top temperature of the endothermic peak originating from the crystalline resin (A) is in the range of 40 to 100°C. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2019-66536 [Patent Document 2] Japanese Patent Publication No. 2016-90628 [Patent Document 3] Japanese Patent Publication No. 2019-159315 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] Crystalline polyester resins have a crystalline structure, resulting in high slipperiness and improved abrasion resistance. However, when used mixed with amorphous polyester resin as a toner binder, if the compatibility between the two is too high, the crystalline polyester resin in the printed material will become amorphous, preventing it from exhibiting the expected slipperiness. Furthermore, the amorphous crystalline portion becomes soft and flexible, reducing the toner's pulverability. On the other hand, if the compatibility is low, the crystalline polyester resin maintains its crystallinity even within the amorphous polyester resin, resulting in relatively good abrasion resistance and pulverability. However, the large refractive index difference between the crystalline and amorphous portions reduces the gloss of the resulting printed material.

[0007] The present invention relates to a binder resin composition for toner that has excellent scratch resistance and glossiness of images, as well as good pulverability, and toner for electrostatic image development containing the binder resin composition. [Means for solving the problem]

[0008] The present invention [1] A binder resin composition for toner containing a crystalline polyester resin and an amorphous polyester resin, The crystalline polyester resin is a polycondensate of an alcohol component containing 85 mol% or more of ethylene glycol, an aliphatic dicarboxylic acid compound having 12 to 16 carbon atoms, and an aliphatic monocarboxylic acid compound having 16 to 24 carbon atoms, wherein the content of the aliphatic monocarboxylic acid compound is 1.5 mol% or more and 20 mol% or less of the total amount of the alcohol component and the carboxylic acid component. The amorphous polyester resin is defined by formula (I):

[0009] [ka]

[0010] (In the formula, OR and RO are oxyalkylene groups, R is an ethylene group and / or a propylene group, x and y represent the average number of moles of alkylene oxide added, each being a positive number, and the sum of x and y is between 1 and 16.) A binder resin composition for toner, comprising a polycondensate of an alkylene oxide adduct of bisphenol A represented by and an alcohol component containing ethylene glycol and a carboxylic acid component containing a dicarboxylic acid compound, wherein the ethylene glycol content is 10 mol% or more and 60 mol% or less of the alcohol component, and [2] A toner for developing electrostatic images containing the toner binder resin composition and colorant described in [1] above. Regarding. [Effects of the Invention]

[0011] The toner binder resin composition of the present invention exhibits excellent effects such as excellent rubbing resistance and glossiness of images, and also has good pulverizability.

Mode for Carrying Out the Invention

[0012] The toner binder resin composition of the present invention is a polycondensate of a crystalline polyester resin and an amorphous polyester resin from raw material monomers containing ethylene glycol. Although the details are unknown, it is presumed that the effects of the present invention are achieved by the interaction of these raw material monomers. By using ethylene glycol in the crystalline polyester resin, two adjacent ester groups can be arranged. As a result, in addition to having high cohesive force and being easy to crystallize, the ethylene glycol sites of the crystalline polyester can gather at the ethylene glycol sites of the amorphous polyester, which can also promote crystal growth. Therefore, it becomes possible to quickly recrystallize the crystalline polyester resin after fixing. Furthermore, the generation of crystal nuclei can also be promoted by the site derived from a long-chain aliphatic dicarboxylic acid with low polarity and the long-chain aliphatic monocarboxylic acid arranged at the terminal. In addition, since the crystalline polyester resin has a long-chain aliphatic structure with low polarity at the terminal, the crystalline polyester resin is likely to exist on the surface of the printed matter, and the slipperiness derived from the crystal is expressed, resulting in good rubbing resistance. In addition, the formed crystals are in a highly micro-dispersed state due to the ethylene glycol sites of the amorphous polyester resin, and the number of heterogeneous interfaces between the crystalline sites and the amorphous sites increases. Since the resin cracks starting from this heterogeneous interface, the pulverizability is improved. At the same time, because the crystalline polyester resin is micro-dispersed, the influence on the refractive index of the amorphous site is suppressed, so the glossiness of the obtained image is not inhibited.

[0013] The crystalline polyester resin is a polycondensate of an alcohol component containing ethylene glycol, a long-chain aliphatic dicarboxylic acid compound, and a carboxylic acid component containing a long-chain aliphatic monocarboxylic acid compound.

[0014] The ethylene glycol content is 85 mol% or more of the alcohol component, preferably 90 mol% or more, more preferably 95 mol% or more, even more preferably 98 mol% or more, and even more preferably 100 mol%.

[0015] Other alcohol components include aliphatic diols other than ethylene glycol such as 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, 1,12-dodecanediol, and 1,14-tetradecanediol; aromatic diols such as bisphenol A and alkylene oxide adducts of bisphenol A; hydrogenated bisphenol A; trivalent or higher alcohols such as sorbitol, pentaerythritol, glycerin, and trimethylolpropane; and aliphatic monoalcohols.

[0016] Examples of long-chain aliphatic dicarboxylic acid compounds include dodecanedioic acid (12 carbon atoms), tetradecanedioic acid (14 carbon atoms), hexadecanedioic acid (16 carbon atoms), succinic acid having an alkyl or alkenyl group in its side chain, the anhydrides of these acids, and alkyl esters having 1 to 3 carbon atoms in the alkyl group. Among these, tetradecanedioic acid is preferred.

[0017] The carbon number of the long-chain aliphatic dicarboxylic acid compound is 12 or more, preferably 14 or more, from the viewpoint of abrasion resistance, pulverability, and gloss, and 16 or less from the viewpoint of abrasion resistance, gloss, and low-temperature fixability. Here, the carbon number of the alkyl group when the long-chain aliphatic dicarboxylic acid compound is an alkyl ester is not included in the above carbon number.

[0018] From the viewpoint of glossiness and low-temperature fixability, the content of the long-chain aliphatic dicarboxylic acid compound is preferably 75 mol% or more, more preferably 80 mol% or more, even more preferably 85 mol% or more, and preferably 98 mol% or less, more preferably 96 mol% or less, and even more preferably 94 mol% or less, in the carboxylic acid component.

[0019] Examples of long-chain aliphatic monocarboxylic acid compounds include aliphatic monocarboxylic acids such as palmitic acid, stearic acid, and behenic acid, and alkyl esters of these acids in which the alkyl group has 1 to 3 carbon atoms. Among these, stearic acid and / or behenic acid are preferred.

[0020] The carbon number of the long-chain aliphatic monocarboxylic acid compound is 16 or more, preferably 18 or more, more preferably 20 or more, from the viewpoint of abrasion resistance, pulverability, and gloss, and 24 or less, preferably 22 or less, from the viewpoint of abrasion resistance, gloss, and low-temperature fixability. Here, the carbon number of the alkyl group when the long-chain aliphatic monocarboxylic acid compound is an alkyl ester is not included in the above carbon number.

[0021] The content of the long-chain aliphatic monocarboxylic acid compound is 1.5 mol% or more, preferably 2 mol% or more, and more preferably 3 mol% or more, of the total amount of alcohol and carboxylic acid components, from the viewpoint of abrasion resistance, pulverability, and gloss, and 20 mol% or less, preferably 15 mol% or less, and more preferably 13 mol% or less, from the viewpoint of abrasion resistance, gloss, and low-temperature fixability.

[0022] Other carboxylic acid components include aliphatic dicarboxylic acid compounds other than the aforementioned aliphatic dicarboxylic acid compounds such as succinic acid (4 carbon atoms), fumaric acid (4 carbon atoms), adipic acid (6 carbon atoms), suberic acid (8 carbon atoms), azelaic acid (9 carbon atoms), and sebacic acid (10 carbon atoms); aromatic dicarboxylic acid compounds such as phthalic acid, isophthalic acid, and terephthalic acid; trivalent or higher carboxylic acid compounds such as trimellitic acid and pyromellitic acid; anhydrides of these acids; and alkyl esters in which the alkyl group has 1 to 3 carbon atoms.

[0023] In this specification, macromonomers and hydroxycarboxylic acids are not included in the alcohol and carboxylic acid components.

[0024] The equivalent ratio (COOH group / OH group) of the carboxyl group of the carboxylic acid component to the hydroxyl group of the alcohol component is preferably 0.6 or higher, more preferably 0.7 or higher, even more preferably 0.75 or higher, and preferably 1.2 or lower, more preferably 1.15 or lower, from the viewpoint of adjusting the softening point of the polyester resin.

[0025] Crystalline polyester resins 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 optionally in the presence of an esterification co-catalyst, polymerization inhibitor, etc., at a temperature preferably 130°C or higher, more preferably 170°C or higher, and preferably 250°C or lower, more preferably 240°C or lower.

[0026] Examples of esterification catalysts include tin compounds and titanium compounds, and in the present invention, tin compounds are preferred from the viewpoint of image heat resistance and electrostatic stability.

[0027] As the tin compound, a tin(II) compound that does not have a Sn-C bond is preferred.

[0028] Preferred tin(II) compounds that do not have a Sn-C bond include tin(II) compounds that do not have a Sn-C bond but have a Sn-O bond, and tin(II) compounds that have a Sn-X (where X represents a halogen atom) bond, with tin(II) compounds having a Sn-O bond being more preferred.

[0029] Examples of tin(II) compounds having an Sn-O bond include tin(II) oxalate, tin(II) acetate, tin(II) octanoate, tin(II) 2-ethylhexanoate, tin(II) laurylate, tin(II) stearate, tin(II) oleate, and other tin(II) carboxylic acid groups having 2 to 28 carbon atoms; alkoxytin(II) having alkoxy groups with 2 to 28 carbon atoms, such as octyloxytin(II), lauroxytin(II), stearoxytin(II), oleyloxytin(II); tin(II) oxide; tin(II) sulfate, etc. Examples of tin(II) compounds having an Sn-X (where X represents a halogen atom) bond include tin(II) halides such as tin(II) chloride and tin(II) bromide, etc. Among these, in terms of catalytic activity, (R 1 COO)2Sn(R here) 1 (where R represents an alkyl or alkenyl group having 5 to 19 carbon atoms) Fatty acid tin(II), (R 2 O)2Sn(where R 2 (R represents an alkyl or alkenyl group having 6 to 20 carbon atoms) Preferably, alkoxytin(II) or tin(II) oxide represented by SnO is preferred, 1 Fatty acid tin(II) or tin(II) oxide represented by COO)2Sn is more preferred, and tin(II) octanoate, tin(II) 2-ethylhexanoate, tin(II) stearate, or tin(II) oxide is even more preferred.

[0030] The amount of esterification catalyst, preferably a tin compound, 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, more preferably 1 part by mass or less, based on 100 parts by mass of the total amount of alcohol and carboxylic acid components.

[0031] 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 preferably 0.5 parts by mass or less, and more preferably 0.1 parts by mass or less, per 100 parts by mass of the total amount of alcohol and carboxylic acid components. 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 preferably 0.5 parts by mass or less, and more preferably 0.1 parts by mass or less, per 100 parts by mass of the total amount of alcohol and carboxylic acid components.

[0032] In this invention, the polyester resin may be a polyester resin that has been modified to such an extent that its properties are not substantially impaired. Examples of modified polyester resins include polyester resins that have been grafted or blocked with phenol, urethane, epoxy, etc., by methods described in Japanese Patent Publication No. 11-133668, Japanese Patent Publication No. 10-239903, Japanese Patent Publication No. 8-20636, etc.

[0033] From the viewpoint of storage properties, the softening point of the crystalline polyester resin is preferably 50°C or higher, more preferably 60°C or higher, even more preferably 65°C or higher, and even more preferably 75°C or higher. From the viewpoint of low-temperature fixation properties, it is preferably 100°C or lower, and more preferably 98°C or lower.

[0034] The crystallinity of a resin is expressed by a crystallinity index defined by the ratio of the softening point to the maximum endothermic peak temperature measured by a differential scanning calorimeter, i.e., the value of [softening point / maximum endothermic peak temperature]. A crystalline resin is a resin 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 in which no endothermic peak is observed, or, if observed, those with a crystallinity index greater than 1.4, preferably greater than 1.5, more preferably 1.6 or higher, or less than 0.6, preferably 0.5 or lower. The crystallinity of a resin can be adjusted by the type and ratio of raw material monomers, as well as the manufacturing conditions (e.g., reaction temperature, reaction time, cooling rate). The maximum endothermic peak temperature refers to the temperature of the peak with the largest peak area among the observed endothermic peaks. In crystalline resins, the maximum endothermic peak temperature is defined as the melting point.

[0035] From the viewpoint of storage properties, the melting point of the crystalline polyester resin is preferably 50°C or higher, more preferably 60°C or higher, even more preferably 65°C or higher, and even more preferably 75°C or higher. From the viewpoint of low-temperature fixability, it is preferably 100°C or lower, and more preferably 95°C or lower.

[0036] The acid value of the crystalline polyester resin is preferably kept low from the viewpoint of controlling crystallization, preferably 10 mg KOH / g or less, more preferably 8 mg KOH / g or less, even more preferably 6 mg KOH / g or less, and preferably 1 mg KOH / g or more.

[0037] The hydroxyl value of the crystalline polyester resin is preferably kept low from the viewpoint of controlling crystallization, preferably 10 mg KOH / g or less, more preferably 8 mg KOH / g or less, even more preferably 6 mg KOH / g or less, and preferably 1 mg KOH / g or more.

[0038] The sum of the acid value and hydroxyl value of the crystalline polyester resin is preferably kept low from the viewpoint of controlling crystallization, preferably 15 mg KOH / g or less, more preferably 12 mg KOH / g or less, and preferably 2 mg KOH / g or more.

[0039] The weight-average molecular weight of the crystalline polyester resin is preferably 5,000 or more, more preferably 6,000 or more, and even more preferably 7,000 or more, from the viewpoint of storage stability, and preferably 25,000 or less, and more preferably 20,000 or less, from the viewpoint of controlling crystallization.

[0040] The molecular weight of polyester resin can be adjusted by the amount of monovalent long-chain aliphatic monomer used and the amount of trivalent or higher raw material monomers (trivalent or higher carboxylic acid compounds and trivalent or higher alcohols) used.

[0041] The content of crystalline polyester resin in the binder resin composition is preferably 2% by mass or more, more preferably 5% by mass or more, even more preferably 8% by mass or more, and preferably 25% by mass or less, more preferably 20% by mass or less.

[0042] The amorphous polyester resin is a polycondensate of an alcohol component containing an alkylene oxide adduct of bisphenol A and ethylene glycol, and a carboxylic acid component containing a dicarboxylic acid compound.

[0043] The alkylene oxide adduct of bisphenol A is given by formula (I):

[0044] [ka]

[0045] (In the formula, OR and RO are oxyalkylene groups, R is an ethylene group and / or a propylene group, x and y represent the average number of moles of alkylene oxide added, each being a positive number, and the sum of x and y is 1 or greater, preferably 1.5 or greater, and 16 or less, preferably 8 or less, more preferably 6 or less, and even more preferably 4 or less.) The compound is represented by [formula], and from the viewpoint of pulverability, the propylene oxide adduct of bisphenol A is more preferred.

[0046] The content of the bisphenol A propylene oxide adduct is preferably 30 mol% or more, more preferably 40 mol% or more, even more preferably 45 mol% or more, and preferably 90 mol% or less, more preferably 80 mol% or less, and even more preferably 70 mol% or less, in the alcohol component.

[0047] From the viewpoint of low-temperature fixability, the content of the bisphenol A alkylene oxide adduct in the alcohol component is preferably 40 mol% or more, more preferably 50 mol% or more, even more preferably 60 mol% or more, and preferably 90 mol% or less, more preferably 85 mol% or less, and even more preferably 80 mol% or less.

[0048] The ethylene glycol content is 10 mol% or more of the alcohol component, preferably 15 mol% or more, more preferably 20 mol% or more, and 60 mol% or less, preferably 50 mol% or less, and even more preferably 40 mol% or less.

[0049] Other alcohol components include aliphatic diols other than ethylene glycol, bisphenol A, hydrogenated bisphenol A, sorbitol, pentaerythritol, glycerin, trivalent or higher alcohols such as trimethylolpropane, etc.

[0050] Examples of dicarboxylic acid compounds include aromatic dicarboxylic acid compounds and aliphatic dicarboxylic acid compounds. Among these, aromatic dicarboxylic acid compounds are preferred from the viewpoint of pulverizability, storage stability, and electrostatic stability.

[0051] Examples of aromatic dicarboxylic acid compounds include phthalic acid, isophthalic acid, terephthalic acid, anhydrides of these acids, and alkyl esters of these acids with 1 to 3 carbon atoms.

[0052] The content of aromatic dicarboxylic acid compounds in the carboxylic acid component is preferably 80 mol% or more, more preferably 90 mol% or more, even more preferably 95 mol% or more, even more preferably 98 mol% or more, and even more preferably 100 mol% from the viewpoint of electrostatic stability.

[0053] Examples of aliphatic dicarboxylic acid compounds include fumaric acid, maleic acid, succinic acid, succinic acid derivatives substituted with hydrocarbon groups, glutaric acid, adipic acid, sebacic acid, anhydrides of these acids, and alkyl esters of these acids with 1 to 3 carbon atoms.

[0054] Other carboxylic acid components include trivalent or higher carboxylic acid compounds.

[0055] Furthermore, the alcohol component may contain a monohydric alcohol, and the carboxylic acid component may contain a monohydric carboxylic acid compound, as appropriate, from the viewpoint of adjusting the molecular weight and softening point of the polyester resin.

[0056] The equivalent ratio (COOH group / OH group) of the carboxyl group of the carboxylic acid component to the hydroxyl group of the alcohol component is preferably 0.6 or higher, more preferably 0.7 or higher, even more preferably 0.75 or higher, and preferably 1.2 or lower, more preferably 1.15 or lower, from the viewpoint of adjusting the softening point of the polyester resin.

[0057] Amorphous polyester resins 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 optionally in the presence of an esterification co-catalyst, polymerization inhibitor, etc., at a temperature preferably 130°C or higher, more preferably 170°C or higher, and preferably 250°C or lower, more preferably 240°C or lower.

[0058] Examples of esterification catalysts include tin compounds such as dibutyltin oxide and tin(II) 2-ethylhexanoate, and titanium compounds such as titanium diisopropylate bistriethanolamine, with tin compounds being preferred. 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 preferably 1.5 parts by mass or less, and more preferably 1 part by mass or less, per 100 parts by mass of the total amount of alcohol and carboxylic acid components. 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 preferably 0.5 parts by mass or less, and more preferably 0.1 parts by mass or less, per 100 parts by mass of the total amount of alcohol and carboxylic acid components. 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 preferably 0.5 parts by mass or less, and more preferably 0.1 parts by mass or less, based on 100 parts by mass of the total amount of alcohol and carboxylic acid components.

[0059] From the viewpoint of storage properties, the softening point of amorphous polyester resin is preferably 70°C or higher, more preferably 90°C or higher, and even more preferably 95°C or higher. From the viewpoint of low-temperature fixing properties, it is preferably 130°C or lower, more preferably 125°C or lower, and even more preferably 120°C or lower.

[0060] The glass transition temperature of amorphous polyester resin is preferably 40°C or higher, more preferably 45°C or higher, and even more preferably 50°C or higher, from the viewpoint of static stability, and preferably 70°C or lower, more preferably 65°C or lower, and even more preferably 60°C or lower, from the viewpoint of controlling crystallization.

[0061] From the viewpoint of controlling crystallization, the acid value of the amorphous polyester resin is preferably 10 mg KOH / g or less, more preferably 8 mg KOH / g or less, even more preferably 5 mg KOH / g or less, and preferably 1 mg KOH / g or more.

[0062] From the viewpoint of controlling compatibility with crystalline polyester resins, the hydroxyl value of amorphous polyester resins is preferably 55 mg KOH / g or less, more preferably 50 mg KOH / g or less.

[0063] The weight-average molecular weight of the amorphous polyester resin is preferably 4,000 or more, more preferably 4,500 or more, and even more preferably 5,000 or more, from the viewpoint of abrasion resistance and electrostatic stability, and preferably 10,000 or less, more preferably 8,000 or less, and even more preferably 7,000 or less, from the viewpoint of pulverability and gloss.

[0064] The content of the amorphous polyester resin in the binder resin composition is preferably 35% by mass or more, more preferably 40% by mass or more, even more preferably 45% by mass or more, and preferably 98% by mass or less, more preferably 95% by mass or less, and even more preferably 92% by mass or less.

[0065] From the viewpoint of fixing width, the toner binder resin composition preferably further contains amorphous polyester resin AH, which has a higher softening point than the amorphous polyester resin (when amorphous polyester resin AH is used in combination, the amorphous polyester resin is also referred to as "amorphous polyester resin AL").

[0066] The amorphous polyester resin AH is preferably a polycondensate of an alcohol component containing an alkylene oxide adduct of bisphenol A represented by formula (I) and a carboxylic acid component.

[0067] The content of the bisphenol A alkylene oxide adduct is preferably 80 mol% or more, more preferably 90 mol% or more, even more preferably 95 mol% or more, even more preferably 98 mol% or more, and even more preferably 100 mol% of the alcohol component.

[0068] Other alcohol components include aliphatic diols, bisphenol A, hydrogenated bisphenol A, sorbitol, pentaerythritol, glycerin, trivalent or higher alcohols such as trimethylolpropane, etc.

[0069] Furthermore, it is preferable that ethylene glycol is not used in the amorphous polyester resin AH, and the ethylene glycol content is preferably 30 mol% or less, more preferably 20 mol% or less, even more preferably 10 mol% or less, and even more preferably 0 mol% of the alcohol component.

[0070] The equivalent ratio (COOH group / OH group) of the carboxyl group of the carboxylic acid component to the hydroxyl group of the alcohol component is preferably 0.6 or higher, more preferably 0.7 or higher, even more preferably 0.75 or higher, and preferably 1.2 or lower, more preferably 1.15 or lower, from the viewpoint of adjusting the softening point of the polyester resin.

[0071] Amorphous polyester resin AH can be manufactured in the same manner as amorphous polyester resin AL.

[0072] The difference in softening points between amorphous polyester resin AL and amorphous polyester resin AH is preferably 10°C or more, more preferably 20°C or more, even more preferably 30°C or more, and preferably 55°C or less, more preferably 50°C or less, and even more preferably 45°C or less.

[0073] The softening point of the amorphous polyester resin AH is preferably 100°C or higher, more preferably 110°C or higher, and even more preferably 120°C or higher, from the viewpoint of fixing width, and preferably 180°C or lower, more preferably 160°C or lower, and even more preferably 150°C or lower, from the viewpoint of low-temperature fixing properties.

[0074] The glass transition temperature of amorphous polyester resin AH is preferably 40°C or higher, more preferably 45°C or higher, and even more preferably 50°C or higher, from the viewpoint of static charge stability, and preferably 70°C or lower, more preferably 65°C or lower, and even more preferably 60°C or lower, from the viewpoint of controlling crystallization.

[0075] From the viewpoint of controlling crystallization, the acid value of the amorphous polyester resin AH is preferably 30 mg KOH / g or less, more preferably 25 mg KOH / g or less, even more preferably 20 mg KOH / g or less, and preferably 10 mg KOH / g or more.

[0076] The hydroxyl value of the amorphous polyester resin AH is preferably 35 mg KOH / g or less, more preferably 30 mg KOH / g or less, and more preferably 15 mg KOH / g or more, and more preferably 20 mg KOH / g or more, from the viewpoint of controlling compatibility with crystalline polyester resin.

[0077] The weight-average molecular weight of the amorphous polyester resin AH is preferably 30,000 or more, more preferably 50,000 or more, and even more preferably 60,000 or more, from the viewpoint of hot offset resistance, and preferably 150,000 or less, more preferably 120,000 or less, and even more preferably 100,000 or less, from the viewpoint of low-temperature fixation.

[0078] The content of amorphous polyester resin AH in the binder resin composition is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 25% by mass or more, and preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less.

[0079] When amorphous polyester resin AH is included, the content of amorphous polyester resin AL in the binder resin composition is preferably 35% by mass or more, more preferably 45% by mass or more, even more preferably 50% by mass or more, and preferably 88% by mass or less, more preferably 80% by mass or less, and even more preferably 75% by mass or less.

[0080] The total content of amorphous polyester resin AL and amorphous polyester resin AH in the binder resin composition is preferably 75% by mass or more, more preferably 80% by mass or more, and preferably 98% by mass or less, more preferably 95% by mass or less, and even more preferably 92% by mass or less.

[0081] The mass ratio of crystalline polyester resin to the total amount of amorphous polyester resin (crystalline polyester resin / amorphous polyester resin) is preferably 2 / 98 or higher, more preferably 5 / 95 or higher, and even more preferably 8 / 92 or higher, from the viewpoint of abrasion resistance and image density, and preferably 25 / 75 or lower, more preferably 20 / 80 or lower, from the viewpoint of electrostatic stability.

[0082] The binder resin composition may contain resins other than the crystalline polyester resin and amorphous polyester resin mentioned above, to the extent that they do not impair the effects of the present invention. Examples of other resins include polyester resins other than the crystalline polyester resin and amorphous polyester resin, vinyl resins such as styrene-acrylic resin, epoxy resins, polycarbonate, polyurethane, and composite resins containing two or more of these resins.

[0083] The total content of the crystalline polyester resin and amorphous polyester resin in the binder resin composition is preferably 80% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, even more preferably 98% by mass or more, and even more preferably 100% by mass.

[0084] Furthermore, the present invention provides a toner containing the toner binder resin composition of the present invention as a binder resin, specifically, a toner for electrostatic image development containing the toner binder resin composition of the present invention and a colorant.

[0085] The content of the binder resin composition in the toner 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 or more, and preferably less than 100% by mass, more preferably 98% by mass or less, and even more preferably 95% by mass or less.

[0086] As a coloring agent, dyes, pigments, magnetic materials, etc., used as coloring agents for toners can be used. In the present invention, the toner may be either black toner or color toner.

[0087] In the present invention, hydrophobic pigments are preferred as colorants because the effect of improving image density by improving the dispersibility of the colorant is more pronounced. Examples of hydrophobic pigments include phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, naphthol pigments, and lake pigments. Among these, phthalocyanine pigments, quinacridone pigments, or naphthol pigments are preferred, phthalocyanine pigments are more preferred, and copper phthalocyanine pigments such as CI Pigment Blue 15:3 are even more preferred.

[0088] From the viewpoint of improving the toner's image density and low-temperature fixability, the colorant content is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and preferably 40 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less, per 100 parts by mass of the binder resin composition.

[0089] In addition to the binder resin composition and colorant, the toner for electrostatic image development of the present invention may contain additives such as a mold release agent, a charge control agent, magnetic powder, a fluidity improver, a conductivity modifier, a reinforcing filler such as a fibrous material, an antioxidant, and a cleaning performance improver, and it is preferable that it contains a mold release agent and a charge control agent.

[0090] Examples of mold release agents include hydrocarbon waxes and their oxides, such as polypropylene wax, polyethylene wax, polypropylene-polyethylene copolymer wax, microcrystalline wax, paraffin wax, and Fischer-Tropsch wax; ester waxes such as carnauba wax, montane wax and their deoxidizing waxes, and fatty acid ester waxes; and fatty acid amides, fatty acids, higher alcohols, fatty acid metal salts, etc., which can be used individually or in combination of two or more.

[0091] The melting point of the release agent is preferably 60°C or higher, more preferably 70°C or higher, from the viewpoint of toner transferability, and preferably 160°C or lower, more preferably 140°C or lower, even more preferably 120°C or lower, and even more preferably 110°C or lower, from the viewpoint of low-temperature fixation.

[0092] The amount of release agent is preferably 1 part by mass or more, more preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 3 parts by mass or less, per 100 parts by mass of the binder resin composition, from the viewpoint of low-temperature fixation and offset resistance of the toner and dispersibility in the binder resin composition.

[0093] The charge control agent is not particularly limited and may contain either a positively charged charge control agent or a negatively charged charge control agent.

[0094] Positively charged charge control agents include nigrosine dyes, such as "Nigrosine Base EX," "Oil Black BS," "Oil Black SO," "Bontron N-01," "Bontron N-04," "Bontron N-07," "Bontron N-09," and "Bontron N-11" (all manufactured by Orient Chemical Industries, Ltd.); triphenylmethane-based dyes containing tertiary amines as side chains; quaternary ammonium salt compounds, such as "Bontron P-51" (manufactured by Orient Chemical Industries, Ltd.), cetyltrimethylammonium bromide, and "COPY CHARGE PX." Examples include VP435 (manufactured by Clariant), polyamine resins such as AFP-B (manufactured by Orient Chemical Industries, Ltd.), imidazole derivatives such as PLZ-2001 and PLZ-8001 (both manufactured by Shikoku Chemicals, Ltd.), and styrene-acrylic resins such as FCA-701PT and FCA-201-PS (manufactured by Fujikura Chemicals, Ltd.).

[0095] Furthermore, as negative charge control agents, metal-containing azo dyes, such as "Barifast Black 3804," "Bontron S-31," "Bontron S-32," "Bontron S-34," and "Bontron S-36" (all manufactured by Orient Chemical Industries, Ltd.), "Eisenspiron Black TRH," and "T-77" (manufactured by Hodogaya Chemical Co., Ltd.); metal compounds of benzyl acid compounds, such as "LR-147" and "LR-297" (both manufactured by Nippon Carlit Co., Ltd.); metal compounds of salicylic acid compounds, such as "Bontron E-81," "Bontron E-84," "Bontron E-88," and "Bontron E-304" (all manufactured by Orient Chemical Industries, Ltd.), and "TN-105" (manufactured by Hodogaya Chemical Co., Ltd.); copper phthalocyanine dyes; and quaternary ammonium salts, such as "COPY CHARGE NX" Examples include VP434 (manufactured by Clariant), nitroimidazole derivatives, organometallic compounds, etc.

[0096] From the viewpoint of the charge control 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, per 100 parts by mass of the binder resin composition.

[0097] The toner of the present invention may be obtained by any of the conventionally known methods, such as the melt-kneading method, the emulsification-phase inversion method, or the polymerization method, but from the viewpoint of productivity and dispersibility of the colorant, pulverized toner obtained by the melt-kneading method is preferred. In the case of pulverized toner obtained by the melt-kneading method, for example, raw materials such as a binder resin (binder resin composition) and a colorant, and optionally a mold release agent and a charge control agent, can be uniformly mixed in a mixer such as a Henschel mixer, and then melt-kneaded in a closed-type kneader, a single-screw or twin-screw extruder, an open-roll type kneader, etc., followed by cooling, pulverization, and classification to produce the toner.

[0098] In the manufacture of toner, a binder resin composition in which crystalline polyester resin and amorphous polyester resin are pre-mixed may be used, or these resins may be directly mixed with the raw materials during the manufacturing of the toner.

[0099] In order to improve the transferability of the toner of the present invention, it is preferable to use external additives. Examples of external additives include inorganic fine particles such as silica, alumina, titania, zirconia, tin oxide, and zinc oxide, and organic fine particles such as melamine resin fine particles and polytetrafluoroethylene resin fine particles, and two or more types may be used in combination. Among these, silica is preferred, and from the viewpoint of the transferability of the toner, hydrophobic silica that has been hydrophobized is more preferred.

[0100] Examples of hydrophobic agents used to hydrophobize the surface of silica particles include hexamethyldisilazane (HMDS), dimethyldichlorosilane (DMDS), silicone oil, octyltriethoxysilane (OTES), and methyltriethoxysilane.

[0101] The average particle size of the external additive is preferably 10 nm or larger, more preferably 15 nm or larger, and more preferably 250 nm or smaller, more preferably 200 nm or smaller, and even more preferably 90 nm or smaller, from the viewpoint of the toner's chargeability, fluidity, and transferability.

[0102] From the viewpoint of the toner's electrostatic properties, fluidity, and transferability, the content of the external 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, and more preferably 3 parts by mass or less, per 100 parts by mass of toner before treatment with the external additive.

[0103] The volume-intermediate particle size (D) of the toner of the present invention 50 The volume median particle size (D) is preferably 3 μm or more, more preferably 4 μm or more, and preferably 15 μm or less, more preferably 10 μm or less. 50 ) refers to the particle size at which the cumulative volume frequency calculated using volume fractions accounts for 50% when calculated from the smallest particle size. Furthermore, if the toner is treated with an external additive, the volume median particle size of the toner particles before treatment with the external additive is taken as the volume median particle size of the toner.

[0104] The toner of the present invention can be used as is as a one-component developing toner, or as a two-component developing toner used in combination with a carrier, in image forming apparatuses using either a one-component developing method or a two-component developing method, respectively. [Examples]

[0105] The present invention will be specifically described below with reference to examples, but the present invention is not limited in any way by these examples. The physical properties of resins, etc., can be measured by the following methods.

[0106] [Softening point of resin] Using a flow tester "CFT-500D" (manufactured by Shimadzu Corporation), 1 g of sample is heated at a heating rate of 6°C / min while a load of 1.96 MPa is applied by a plunger, and the sample is extruded from a nozzle with a diameter of 1 mm and a length of 1 mm. The amount of plunger descent of the flow tester is plotted against temperature, and the temperature at which half of the sample has flowed out is defined as the softening point.

[0107] [Maximum peak temperature of endothermic resin] Using a differential scanning calorimeter "Q-100" (manufactured by T.A. Instruments Japan Co., Ltd.), 0.01 to 0.02 g of the sample is weighed into an aluminum pan and cooled from room temperature (20°C) to 0°C at a rate of 10°C / min. The sample is then maintained at this temperature for 1 minute. Subsequently, the endothermic peaks are measured while the temperature is increased to 180°C at a rate of 10°C / min. Among the observed endothermic peaks, the temperature of the peak with the largest peak area is defined as the maximum endothermic peak temperature.

[0108] [Glass transition temperature of resins] Using a differential scanning calorimeter "Q-100" (manufactured by T.A. Instruments Japan), 0.01 to 0.02 g of the sample is weighed into an aluminum pan and heated from room temperature (20°C) to 200°C at a heating rate of 10°C / min, and then cooled to 0°C at a cooling rate of 10°C / min. Next, the sample is heated to 180°C at a heating rate of 10°C / min, and the endothermic peak is measured. The temperature at the intersection of the extension of the baseline below the maximum endothermic peak temperature and the tangent line showing the maximum slope from the rising part of the peak to the peak apex is defined as the glass transition temperature.

[0109] [Acid value and hydroxyl value of crystalline polyester resins] The measurement will be performed according to the method of JIS K0070:1992. However, the measurement solvent will be changed from the mixed solvent of ethanol and ether specified in JIS K0070:1992 to tetrahydrofuran.

[0110] [Acid value of amorphous polyester resin] Measure based on the method of JIS K0070:1992. However, only change the measurement solvent from the mixed solvent of ethanol and ether specified in JIS K0070:1992 to a mixed solvent of acetone and toluene (acetone:toluene = 1:1 (volume ratio)).

[0111] [Hydroxyl value of amorphous polyester resin] Measure based on the method of JIS K0070:1992. However, only change the measurement solvent from the mixed solvent of ethanol and ether specified in JIS K0070:1992 to tetrahydrofuran.

[0112] [Weight-average molecular weight of resin] Determine the weight-average molecular weight by gel permeation chromatography (GPC) method according to the following method. (1) Preparation of sample solution Dissolve the sample in tetrahydrofuran (amorphous resin) or chloroform (crystalline resin) at 40°C so that the concentration becomes 0.5 g / 100 mL. Then, filter this solution using a PTFE type membrane filter "DISMIC-25JP" with a pore size of 0.20 μm (manufactured by Toyo Roshi Kaisha, Ltd.) to remove insoluble components and obtain a sample solution. (2) Molecular weight measurement Using the following measuring device and analytical column, flow tetrahydrofuran (amorphous resin) or chloroform (crystalline resin) as the eluent at a flow rate of 1 mL per minute, and stabilize the column in a constant temperature bath at 40°C. Inject 100 μL of the sample solution there and perform the measurement. The molecular weight of the sample is calculated based on a calibration curve prepared in advance. For this calibration curve, several types of monodisperse polystyrene (A-500 (5.0×10 2 ), A-1000 (1.01×10 3 ), A-2500 (2.63×10 3 ), A-5000 (5.97×10 3 ), F-1 (1.02×10 4 ), F-2 (1.81×10 4 ), F-4 (3.97×10 4 ), F-10 (9.64×10 4 ), F-20 (1.90×105 ), F-40 (4.27×10 5 ), F-80 (7.06×10 5 ), F-128 (1.09×10 6 The sample prepared using )) as a standard sample is used. The value in parentheses indicates the molecular weight. Measuring device: HLC-8220GPC (manufactured by Tosoh Corporation) Analytical columns: TSKgel GMHXL + TSKgel G3000HXL (manufactured by Tosoh Corporation)

[0113] [Melting point of release agent] Using a differential scanning calorimeter "DSC Q-100" (manufactured by T.A. Instruments Japan Co., Ltd.), 0.01 to 0.02 g of the sample is weighed into an aluminum pan, 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 is heated to 180°C at a heating rate of 10°C / min and measured. The maximum endothermic peak temperature observed from the resulting melting endothermic curve is defined as the melting point of the wax.

[0114] [Average particle size of external additives] The average particle diameter refers to the number-average particle diameter, which is calculated by measuring the particle size (average of the major and minor axes) of 500 particles from scanning electron microscope (SEM) images and using the number-average value of these measurements.

[0115] [Medium particle size in toner volume] • Measuring instrument: Coulter Multisizer III (manufactured by Beckman Coulter, Inc.) • Aperture diameter: 50 μm • Analysis software: Multisizer III version 3.51 (manufactured by Beckman Coulter, Inc.) • Electrolyte: "Isoton (registered trademark) II" (manufactured by Beckman Coulter, Inc.) • Dispersion: Prepared by dissolving polyoxyethylene lauryl ether "Emulgen (registered trademark) 109P" [manufactured by Kao Corporation, HLB (Griffin) = 13.6] in the electrolyte to adjust the concentration to 5% by mass. • Dispersion conditions: Add 10 mg of the sample to 5 mL of the dispersion and disperse for 1 minute using an ultrasonic disperser (machine name: US-1 manufactured by SND Corporation, output: 80W). Then, add 25 mL of electrolyte and disperse for another minute using the ultrasonic disperser to prepare the sample dispersion. • Measurement conditions: The sample dispersion is added to 100 mL of the electrolyte to adjust the concentration so that the particle size of 30,000 particles can be measured in 20 seconds. Then, the 30,000 particles are measured, and the volume median particle size (D) is determined from the particle size distribution. 50 )

[0116] Resin manufacturing example 1 The raw material monomers shown in Tables 1 and 2 were placed in a 10-liter four-necked flask equipped with a thermometer, stainless steel stirring rod, a fall-flow condenser, and a nitrogen inlet tube. The mixture was heated to 200°C over 8 hours in a mantle heater under a nitrogen atmosphere. Subsequently, the esterification catalyst and esterification co-catalyst were added, and the mixture was heated to 210°C over 1 hour. The reaction was then carried out at 8.0 kPa until the softening point shown in Tables 1 and 2 was reached, yielding crystalline polyester resins (resins C1-C10).

[0117] [Table 1]

[0118] [Table 2]

[0119] Resin manufacturing example 2 As shown in Table 3, the raw material monomers, esterification catalyst, and esterification co-catalyst were placed in a 10-liter four-necked flask equipped with a thermometer, stainless steel stirring rod, fall-flow condenser, and nitrogen inlet tube. The mixture was heated to 235°C in a mantle heater under a nitrogen atmosphere, and then polycondensation was carried out at 235°C for 6 hours. After that, the temperature was lowered to 210°C, and the reaction was carried out under reduced pressure of 8.0 kPa at 210°C until the softening point shown in Table 3 was reached, yielding amorphous polyester resins (resins AL1 to AL4).

[0120] Resin manufacturing example 3 As shown in Table 3, the raw material monomers other than adipic acid and trimellitic anhydride, the esterification catalyst, and the esterification co-catalyst were placed in a 10-liter four-necked flask equipped with a thermometer, stainless steel stirring rod, fall-flow condenser, and nitrogen inlet tube. The mixture was heated to 235°C under a nitrogen atmosphere and then polycondensed at 235°C for 6 hours. After that, the temperature was lowered to 210°C, adipic acid and trimellitic anhydride were added, and the mixture was reacted at 210°C for 2 hours. Then, the reaction was carried out at 210°C under reduced pressure of 10 kPa until the softening point shown in Table 3 was reached to obtain amorphous polyester resin (resin AH1).

[0121] [Table 3]

[0122] Examples 1-7 and Comparative Examples 1-6 As a binder resin, 15 parts by mass of resin C, 60 parts by mass of resin AL, and 25 parts by mass of resin AH, as shown in Table 4, were mixed with 5 parts by mass of the coloring agent "ECB-301" (manufactured by Dainichi Seika Kogyo Co., Ltd., copper phthalocyanine pigment), 1 part by mass of the charge control agent "LR-147" (manufactured by Nippon Carlit Co., Ltd.), and 2 parts by mass of the release agent "HNP-9" (manufactured by Nippon Seiro Co., Ltd., paraffin wax, melting point: 75℃). The mixture was thoroughly mixed in a Henschel mixer, and then melt-kneaded using a co-rotating twin-screw extruder with a total length of 1560 mm in the mixing section, a screw diameter of 42 mm, and a barrel inner diameter of 43 mm. The screw rotation speed was 200 r / min, the heating setting temperature inside the screw was 90℃, the temperature of the kneaded material was 140℃, the feed rate of the kneaded material was 10 kg / h, and the average residence time was approximately 18 seconds. The resulting mixture is cooled from 140°C to 50°C in 1.5 hours, then rolled and cooled at 50°C using cooling rollers, followed by grinding and classification using a jet mill to obtain the medium volume particle size (D 50 ) 5.5 μm toner particles were obtained.

[0123] To 100 parts by mass of the obtained toner particles, 1.5 parts by mass of "Aerosil R-972" (hydrophobic silica, manufactured by Nippon Aerosil Co., Ltd., hydrophobic treatment agent: DMDS, average particle size: 16 nm) and 1.0 part by mass of "RY-50" (hydrophobic silica, manufactured by Nippon Aerosil Co., Ltd., hydrophobic treatment agent: silicone oil, average particle size: 40 nm) were added as external additives, and the mixture was treated with external additives by mixing in a Henschel mixer at 3600 r / min for 5 minutes to obtain toner.

[0124] Example 8 As a binder, 15 parts by mass of resin C1 and 85 parts by mass of resin AL1, along with 5 parts by mass of the coloring agent "ECB-301" (manufactured by Dainichi Seika Kogyo Co., Ltd., copper phthalocyanine pigment), 1 part by mass of the charge control agent "LR-147" (manufactured by Nippon Carlit Co., Ltd.), and 2 parts by mass of the release agent "HNP-9" (manufactured by Nippon Seiro Co., Ltd., paraffin wax, melting point: 75℃), were thoroughly mixed in a Henschel mixer. The mixture was then melt-kneaded using a co-rotating twin-screw extruder with a total mixing section length of 1560 mm, a screw diameter of 42 mm, and a barrel inner diameter of 43 mm. The screw rotation speed was 200 r / min, the heating setting temperature inside the screw was 90℃, the temperature of the kneaded material was 125℃, the feed rate of the kneaded material was 10 kg / h, and the average residence time was approximately 18 seconds. The resulting mixture is cooled from 125°C to 50°C in 1.5 hours, then rolled and cooled at 50°C using cooling rollers, followed by grinding and classification using a jet mill to obtain the medium volume particle size (D 50 ) 5.5 μm toner particles were obtained.

[0125] Toner was obtained by subjecting 100 parts by mass of the obtained toner particles to an external additive treatment in the same manner as in Example 1.

[0126] Test Example 1 [Abrasion Resistance] A halftone image (2 dots 2 spaces halftone image) was printed on coated paper "OK ​​Topcoat+" (manufactured by Oji Paper Co., Ltd.) using a commercially available printer "Microline® 5400" (manufactured by Oki Data Corporation) at a resolution of 600 dpi, consisting of two printed areas (dots) and two unprinted areas (blank spaces). The resulting print was then subjected to a 2 kg load (contact area 900 mm²) on a cellulose nonwoven fabric "Bencott M3-II" (manufactured by Asahi Kasei Corporation). 2 A friction test was conducted by applying a 100-back-back pass of a colorimeter (GretagMacbeth, Inc., light emission conditions: standard light source D) to the printed material before and after friction. 50 Measurements were taken using a 2° field of view, DINNB density standard, and absolute white standard. The average value of three arbitrary points measured on the image was used as the image density, and the change in image density before and after scraping [(image density before scraping - image density after scraping)] was calculated. The results are shown in Table 4. The smaller the change in image density before and after scraping, the better the scraping resistance.

[0127] Test Example 2 [Crushability] During the toner manufacturing process, 1 kg of molten mixture (approximately 3 cm square plate pieces) was taken and placed into a Rotoplex (Hosokawa Micron Corporation, model R20 / 10) fitted with a 3 mm mesh screen for grinding. The ground molten mixture was classified into particles between 850 μm and 1000 μm using wire mesh sieves with mesh sizes of 1000 μm and 850 μm (Iida Seisakusho Co., Ltd.) as specified in JIS Z 8801-1:2000. 20 g of the classified particles were ground for 10 seconds in a coffee mill (Philips, HR-2170 type), then passed through a 150 μm sieve, and the toner weight A (g) that passed through was accurately weighed. The grindability was calculated from the weighed weight using the following formula, and this operation was repeated three times to obtain the average value. The results are shown in Table 4. A higher value indicates better grindability. Grinding capacity (%) = (A [g] / 20.0 [g]) × 100

[0128] Test Example 3 [Glossiness] A modified fuser unit of the "AR-505" copier (manufactured by Sharp Corporation) was modified to allow for external fixing, and toner was installed in this modified unit. A printed document was obtained in an unfixed state (print area: 2cm x 12cm, adhesion amount: 0.3mg / cm²). 2 Subsequently, a fuser (fixing speed 300 mm / sec) adjusted to a total fixing pressure of 40 kgf was used to fix the unfixed printout by setting the fuser roll temperature to the minimum fixing temperature + 20°C. The paper used for printing was coated paper "OK ​​Topcoat+" (manufactured by Oji Paper Co., Ltd.). After leaving the resulting printout at 45°C for one day, the glossiness was measured using a gloss meter "IG-330" (manufactured by Horiba, Ltd.) with cardboard placed beneath the image and the light emission condition set to 60°. The results are shown in Table 4. A higher value indicates higher glossiness.

[0129] [Table 4]

[0130] From the above results, it can be seen that the toners of Examples 1 to 8 have good pulverizability during the manufacturing process and also exhibit excellent abrasion resistance and gloss. In contrast, the toner of Comparative Example 1, which contains a crystalline polyester resin using 1,6-hexanediol instead of ethylene glycol, the toner of Comparative Example 5, which contains a crystalline polyester resin with a small amount of ethylene glycol, and the toner of Comparative Example 6, which contains an amorphous polyester resin without ethylene glycol, are found to be insufficient in terms of pulverability, abrasion resistance, and gloss. Furthermore, the toner of Comparative Example 2, which contains a crystalline polyester resin using sebacic acid with 10 carbon atoms as the aliphatic dicarboxylic acid compound, the toner of Comparative Example 3, which contains a crystalline polyester resin without the use of an aliphatic monocarboxylic acid compound, and the toner of Comparative Example 4, which contains a crystalline polyester resin using lauric acid with 12 carbon atoms as the aliphatic monocarboxylic acid compound, have good gloss, but lack pulverability and abrasion resistance. [Industrial applicability]

[0131] The toner for electrostatic image development containing the toner binder resin composition of the present invention is suitably used for developing latent images formed in electrostatic image development methods, electrostatic recording methods, electrostatic printing methods, and the like.

Claims

1. A binder resin composition for toner containing a crystalline polyester resin and an amorphous polyester resin, The crystalline polyester resin is a polycondensate of an alcohol component containing 85 mol% or more of ethylene glycol, an aliphatic dicarboxylic acid compound having 12 to 16 carbon atoms, and an aliphatic monocarboxylic acid compound having 16 to 24 carbon atoms, wherein the content of the aliphatic monocarboxylic acid compound is 1.5 mol% or more and 20 mol% or less of the total amount of the alcohol component and the carboxylic acid component. The amorphous polyester resin is defined by formula (I): 【Chemistry 1】 (In the formula, OR and RO are oxyalkylene groups, R is an ethylene group and / or a propylene group, x and y represent the average number of moles of alkylene oxide added, each being a positive number, and the sum of x and y is between 1 and 16.) A binder resin composition for toner, comprising a polycondensate of an alkylene oxide adduct of bisphenol A represented by and an alcohol component containing ethylene glycol and a carboxylic acid component containing a dicarboxylic acid compound, wherein the ethylene glycol content is 10 mol% or more and 60 mol% or less of the alcohol component.

2. The toner binder resin composition according to claim 1, wherein the aliphatic dicarboxylic acid compound having 12 to 16 carbon atoms is tetradecanediic acid.

3. The toner binder resin composition according to claim 1, wherein the acid value of the crystalline polyester resin is 10 mg KOH / g or less.

4. The toner binder resin composition according to claim 1, wherein the content of the alkylene oxide adduct of bisphenol A in the alcohol component of the amorphous polyester resin is 40 mol% or more and 90 mol% or less in the alcohol component.

5. The toner binder resin composition according to Claim 1, wherein the amorphous polyester resin has a softening point of 70°C or more and 130°C or less.

6. A toner for electrostatic image development, comprising the toner binder resin composition and colorant described in any one of claims 1 to 5.

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