Binder resin composition for toner

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 a toner used for developing a latent image formed in, for example, an electrophotographic method, an electrostatic recording method, an electrostatic printing method, etc., and a toner for developing an electrostatic image containing the binder resin composition. [Background technology]

[0002] Patent Document 1 discloses a binder resin composition for toners that contains an amorphous resin and a crystalline resin, in which the amorphous resin contains polyester-based 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 contains polyester-based resin C which is a polycondensate of an alcohol component containing 50 mol % or more and 100 mol % or less 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 or more and 95 / 5 or less.

[0003] Patent Document 2 discloses a binder resin composition for toners, which contains an amorphous polyester A and a crystalline polyester C, in which the amorphous polyester A is an amorphous polyester obtained by polycondensing an alcohol component containing an aromatic diol and an aliphatic diol having 3 to 6 carbon atoms and a carboxylic acid component, and the crystalline polyester C is a crystalline polyester obtained by polycondensing 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) having an alcohol component (X) and a carboxylic acid component (Y) as essential constituent monomers, characterized in that 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, based on the total molar number of the carboxylic acid component (Y), and the toner binder has at least one endothermic peak derived from the crystalline resin (A) in the range of 40 to 100°C during the second heating process measured by a differential scanning calorimeter (DSC). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2019-66536 A [Patent Document 2] JP 2016-90628 A [Patent Document 3] JP 2019-159315 A Summary of the Invention [Problem to be solved by the invention]

[0006] Since crystalline polyester resin has a crystalline structure, it has high slipperiness and is expected to improve abrasion resistance, but when it is mixed with amorphous polyester resin as a binder resin for toner, if the compatibility between them is too high, the crystalline polyester resin in the printed matter will become amorphized, and the expected slipperiness will not be exhibited. In addition, the amorphized crystalline portion will have a soft and flexible structure, which will reduce the grindability of the toner. On the other hand, when the compatibility is low, the crystalline polyester resin will maintain its crystallinity even in the amorphous polyester resin, so the abrasion resistance and grindability will be relatively good, but the refractive index difference between the crystalline structure portion and the amorphous portion will be large, which will reduce the gloss of the resulting printed matter.

[0007] The present invention relates to a binder resin composition for a toner which provides an image with excellent abrasion resistance and gloss and also has good grindability, and to a toner for developing an electrostatic image which contains the binder resin composition. [Means for solving the problem]

[0008] The present invention relates to [1] A toner binder resin composition 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 and a carboxylic acid component containing an aliphatic dicarboxylic acid compound having 12 to 16 carbon atoms and an aliphatic monocarboxylic acid compound having 16 to 24 carbon atoms, the content of the aliphatic monocarboxylic acid compound being 1.5 mol % or more and 20 mol % or less in the total amount of the alcohol component and the carboxylic acid component, The amorphous polyester resin has 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 are the average number of moles of alkylene oxide added, each of which is a positive number, and the sum of x and y is 1 or more and 16 or less.) and a polycondensation product of an alkylene oxide adduct of bisphenol A represented by the formula (I) and an alcohol component containing ethylene glycol and a carboxylic acid component containing a dicarboxylic acid compound, wherein the content of ethylene glycol in the alcohol component is 10 mol % or more and 60 mol % or less; and [2] A toner for developing electrostatic images, comprising the binder resin composition for toners according to [1] above and a colorant. Regarding. Effect of the Invention

[0011] The binder resin composition for toner of the present invention exhibits excellent effects such as excellent abrasion resistance and gloss of an image and good grindability. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] The binder resin composition for toner of the present invention is a polycondensation product of raw material monomers containing ethylene glycol, such as a crystalline polyester resin and an amorphous polyester resin, and 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, which not only increases the cohesive force and facilitates crystal growth, but also promotes crystal growth by gathering the ethylene glycol moieties of the crystalline polyester at the ethylene glycol moieties of the amorphous polyester. This allows the crystalline polyester resin to be quickly recrystallized after fixing, and further promotes the formation of crystal nuclei by the moieties derived from the long-chain aliphatic dicarboxylic acid with low polarity and the long-chain aliphatic monocarboxylic acid arranged at the end. In addition, since the crystalline polyester resin has a long-chain aliphatic structure with low polarity at the end, the crystalline polyester resin is more likely to be present on the surface of the printed matter, which results in the expression of slipperiness derived from crystals and good abrasion resistance. In addition, the crystals that are formed are highly finely dispersed due to the ethylene glycol portions of the amorphous polyester resin, resulting in an increase in the number of interfaces between the crystalline and amorphous portions. Since the resin breaks at these interfaces, the grindability is improved. In addition, since the crystalline polyester resin is finely dispersed, the effect of the amorphous portions on the refractive index is suppressed, so the gloss of the obtained image is not impaired.

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

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

[0015] Examples of 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, trihydric 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 (number of carbon atoms: 12), tetradecanedioic acid (number of carbon atoms: 14), hexadecanedioic acid (number of carbon atoms: 16), succinic acid having an alkyl or alkenyl group on the side chain, anhydrides of these acids, and alkyl esters in which the alkyl group has 1 to 3 carbon atoms, and of these, tetradecanedioic acid is preferred.

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

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

[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. Of these, stearic acid and / or behenic acid are preferred.

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

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

[0022] Examples of other carboxylic acid components include aliphatic dicarboxylic acid compounds other than the above-mentioned aliphatic dicarboxylic acid compounds, such as succinic acid (number of carbon atoms: 4), fumaric acid (number of carbon atoms: 4), adipic acid (number of carbon atoms: 6), suberic acid (number of carbon atoms: 8), azelaic acid (number of carbon atoms: 9), and sebacic acid (number of carbon atoms: 10); 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 component and the carboxylic acid component.

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

[0025] The crystalline polyester resin can be produced, for example, by polycondensing an alcohol component and a carboxylic acid component in an inert gas atmosphere, preferably in the presence of an esterification catalyst, and if necessary, in the presence of an esterification promoter, a polymerization inhibitor, etc., at a temperature of preferably 130°C or higher, more preferably 170°C or higher, and preferably 250°C or lower, more preferably 240°C or lower.

[0026] The esterification catalyst includes tin compounds and titanium compounds, and in the present invention, from the viewpoints of image heat resistance and charging stability, tin compounds are preferred.

[0027] As the tin compound, a tin(II) compound having no Sn-C bond is preferred.

[0028] As the tin(II) compound having no Sn-C bond, a tin(II) compound having no Sn-C bond but an Sn-O bond, a tin(II) compound having an Sn-X (X represents a halogen atom) bond, etc. are preferred, and a tin(II) compound having an Sn-O bond is 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) laurate, tin(II) stearate, tin(II) oleate, and other tin(II) carboxylates having a carboxylic acid group having 2 to 28 carbon atoms; alkoxytin(II) having an alkoxy group having 2 to 28 carbon atoms, such as octyloxytin(II), lauroxytin(II), stearoxytin(II), and oleyloxytin(II); tin(II) oxide; and tin(II) sulfate. Examples of tin(II) compounds having an Sn-X (X represents a halogen atom) bond include tin(II) halides such as tin(II) chloride and tin(II) bromide. Among these, the following tin(II) halides are particularly preferred from the viewpoint of catalytic activity: (R 1 COO)2Sn (where R 1 represents an alkyl or alkenyl group having 5 to 19 carbon atoms), 2 O)2Sn(where R 2 represents an alkyl or alkenyl group having 6 to 20 carbon atoms), or tin(II) oxide represented by SnO, 1 Tin(II) fatty acid 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 the esterification catalyst, preferably a tin compound, used is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more, and preferably 1.5 parts by mass or less, more preferably 1 part by mass or less, per 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component.

[0031] An example of the esterification promoter is gallic acid. The amount of the esterification promoter used is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and preferably 0.5 parts by mass or less, more preferably 0.1 parts by mass or less, based on 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. An example of the polymerization inhibitor is tert-butylcatechol. The amount of the polymerization inhibitor used is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and preferably 0.5 parts by mass or less, more preferably 0.1 parts by mass or less, based on 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component.

[0032] In the present invention, the polyester resin may be modified to such an extent that its properties are not substantially impaired. Examples of modified polyester resins include polyester resins grafted or blocked with phenol, urethane, epoxy, or the like, by the methods described in JP-A-11-133668, JP-A-10-239903, JP-A-8-20636, and the like.

[0033] From the viewpoint of storage stability, 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, and from the viewpoint of low-temperature fixability, it is preferably 100°C or lower, more preferably 98°C or lower.

[0034] The crystallinity of a resin is represented by a crystallinity index defined as 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 having a crystallinity index of 0.6 or more, preferably 0.7 or more, more preferably 0.9 or more, and 1.4 or less, preferably 1.2 or less, more preferably 1.1 or less. On the other hand, an amorphous resin is a resin in which no endothermic peak is observed, or if an endothermic peak is observed, the crystallinity index is greater than 1.4, preferably greater than 1.5, more preferably 1.6 or more, or less than 0.6, preferably 0.5 or less. The crystallinity of the resin can be adjusted by the type and ratio of the raw material monomers, and the production conditions (e.g., reaction temperature, reaction time, cooling rate), etc. The maximum endothermic peak temperature refers to the temperature of the peak with the largest peak area among the observed endothermic peaks. In the case of a crystalline resin, the maximum endothermic peak temperature is the melting point.

[0035] From the viewpoint of storage stability, 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, and from the viewpoint of low-temperature fixability, it is preferably 100°C or lower, more preferably 95°C or lower.

[0036] From the viewpoint of controlling crystallization, it is preferable to control the acid value of the crystalline polyester resin low, preferably 10 mgKOH / g or less, more preferably 8 mgKOH / g or less, even more preferably 6 mgKOH / g or less, and preferably 1 mgKOH / g or more.

[0037] From the viewpoint of controlling crystallization, it is preferable to control the hydroxyl value of the crystalline polyester resin to a low value, preferably 10 mgKOH / g or less, more preferably 8 mgKOH / g or less, even more preferably 6 mgKOH / g or less, and preferably 1 mgKOH / g or more.

[0038] From the viewpoint of controlling crystallization, it is preferable to control the sum of the acid value and the hydroxyl value of the crystalline polyester resin low, preferably 15 mgKOH / g or less, more preferably 12 mgKOH / g or less, and preferably 2 mgKOH / 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 is preferably 25,000 or less, more preferably 20,000 or less from the viewpoint of controlling crystallization.

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

[0041] The content of the 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 is preferably 25% by mass or less, more preferably 20% by mass or less.

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

[0043] The alkylene oxide adduct of bisphenol A has the 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 are the average number of moles of alkylene oxide added, each of which is a positive number, and the sum of x and y is 1 or more, preferably 1.5 or more, and 16 or less, preferably 8 or less, more preferably 6 or less, and even more preferably 4 or less.) From the viewpoint of grindability, a propylene oxide adduct of bisphenol A is more preferred.

[0046] The content of the propylene oxide adduct of bisphenol A in the alcohol component 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, even more preferably 70 mol% or less.

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

[0048] The content of ethylene glycol in the alcohol component is 10 mol% or more, 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] Examples of other alcohol components include aliphatic diols other than ethylene glycol, bisphenol A, hydrogenated bisphenol A, sorbitol, pentaerythritol, glycerin, trimethylolpropane and other trihydric or higher alcohols.

[0050] Examples of the dicarboxylic acid compound include aromatic dicarboxylic acid compounds and aliphatic dicarboxylic acid compounds. Among these, aromatic dicarboxylic acid compounds are preferred from the viewpoints of grindability, storage stability and charging stability.

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

[0052] From the viewpoint of charging stability, the content of the aromatic dicarboxylic acid compound 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 %.

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

[0054] Examples of the other carboxylic acid components include trivalent or higher carboxylic acid compounds.

[0055] From the viewpoint of adjusting the molecular weight and softening point of the polyester resin, the alcohol component may appropriately contain a monohydric alcohol, and the carboxylic acid component may appropriately contain a monovalent carboxylic acid compound.

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

[0057] The amorphous polyester resin can be produced, for example, by polycondensing an alcohol component and a carboxylic acid component in an inert gas atmosphere, preferably in the presence of an esterification catalyst, and if necessary, in the presence of an esterification promoter, a polymerization inhibitor, etc., at a temperature of preferably 130°C or higher, more preferably 170°C or higher, and preferably 250°C or lower, more preferably 240°C or lower.

[0058] Examples of the esterification catalyst 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 the esterification catalyst used is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and preferably 1.5 parts by mass or less, more preferably 1 part by mass or less, relative to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. Examples of the esterification promoter include gallic acid, etc. The amount of the esterification promoter used is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and preferably 0.5 parts by mass or less, more preferably 0.1 parts by mass or less, relative to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. Examples of the polymerization inhibitor include tert-butylcatechol, etc. The amount of the polymerization inhibitor used is preferably 0.001 part by mass or more, more preferably 0.01 part by mass or more, and preferably 0.5 part by mass or less, more preferably 0.1 part by mass or less, per 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component.

[0059] From the viewpoint of storage stability, the softening point of the amorphous polyester resin is preferably 70°C or higher, more preferably 90°C or higher, and even more preferably 95°C or higher, and from the viewpoint of low-temperature fixability, 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 the 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 electrostatic stability, and is 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 mgKOH / g or less, more preferably 8 mgKOH / g or less, further preferably 5 mgKOH / g or less, and preferably 1 mgKOH / g or more.

[0062] From the viewpoint of controlling the compatibility with the crystalline polyester resin, the hydroxyl value of the amorphous polyester resin is preferably 55 mgKOH / g or less, and more preferably 50 mgKOH / 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 viewpoints of abrasion resistance and electrostatic stability, and is preferably 10,000 or less, more preferably 8,000 or less, and even more preferably 7,000 or less, from the viewpoints of grindability and glossiness.

[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 is preferably 98% by mass or less, more preferably 95% by mass or less, even more preferably 92% by mass or less.

[0065] From the viewpoint of fixing width, it is preferable that the binder resin composition for toner further contains an amorphous polyester resin AH having a higher softening point than the amorphous polyester resin (when the 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 polycondensation product of an alcohol component containing an alkylene oxide adduct of bisphenol A represented by the above formula (I) and a carboxylic acid component.

[0067] The content of the alkylene oxide adduct of bisphenol A in the alcohol 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 %.

[0068] Examples of other alcohol components include aliphatic diols, bisphenol A, hydrogenated bisphenol A, sorbitol, pentaerythritol, glycerin, trimethylolpropane and other trihydric or higher alcohols.

[0069] It is preferable that no ethylene glycol is used in the amorphous polyester resin AH, and the content of ethylene glycol in the alcohol component 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 %.

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

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

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

[0074] The glass transition temperature of the 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 electrostatic charge stability, and is 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 mgKOH / g or less, more preferably 25 mgKOH / g or less, further preferably 20 mgKOH / g or less, and preferably 10 mgKOH / g or more.

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

[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 is 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 fixability.

[0078] The content of the 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 is preferably 40% by mass or less, more preferably 35% by mass or less, even more preferably 30% by mass or less.

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

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

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

[0082] The binder resin composition may contain a resin other than the crystalline polyester resin and the amorphous polyester resin as long as the effect of the present invention is not impaired. Examples of the other resin include polyester resins other than the crystalline polyester resin and the amorphous polyester resin, vinyl resins such as styrene-acrylic resin, epoxy resin, polycarbonate, polyurethane, and composite resins containing two or more of these resins.

[0083] The total content of the crystalline polyester resin and the 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] Further, the present invention provides a toner containing the binder resin composition for toner of the present invention as a binder resin, specifically, a toner for developing electrostatic images containing the binder resin composition for toner 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 is preferably less than 100% by mass, more preferably 98% by mass or less, even more preferably 95% by mass or less.

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

[0087] In the present invention, the colorant is preferably a hydrophobic pigment, since the effect of improving the image density by improving the dispersibility of the colorant is more significant. Examples of the hydrophobic pigment include phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, naphthol pigments, and lake pigments, and among these, phthalocyanine pigments, quinacridone pigments, and 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 image density and low-temperature fixability of the toner, the content of the colorant is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and is preferably 40 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less, relative to 100 parts by mass of the binder resin composition.

[0089] The toner for developing electrostatic images of the present invention may contain additives such as a release agent, a charge control agent, a magnetic powder, a flowability improver, a conductivity adjuster, a reinforcing filler such as a fibrous substance, an antioxidant, and a cleaning property improver, in addition to the binder resin composition and the colorant, and it is preferable that the toner contains a release agent and a charge control agent.

[0090] Examples of the release agent include hydrocarbon waxes such as polypropylene wax, polyethylene wax, polypropylene-polyethylene copolymer wax, microcrystalline wax, paraffin wax, and Fischer-Tropsch wax, and oxides thereof; ester waxes such as carnauba wax, montan wax, and deacidified waxes thereof, and fatty acid ester wax; fatty acid amides, fatty acids, higher alcohols, and fatty acid metal salts. These may be used alone 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 is 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 fixability.

[0092] The content of the release agent is preferably 1 part by mass or more and preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and further preferably 3 parts by mass or less, relative to 100 parts by mass of the binder resin composition, from the viewpoints of low-temperature fixability 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 chargeable charge control agent or a negatively chargeable charge control agent.

[0094] Examples of the positively charged charge control agent 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 Co., Ltd.); triphenylmethane dyes containing a tertiary amine as a side chain; quaternary ammonium salt compounds such as "Bontron P-51" (manufactured by Orient Chemical Industries Co., Ltd.), cetyltrimethylammonium bromide, and "COPY CHARGE PX Examples of such resins include "VP435" (manufactured by Clariant), etc.; polyamine resins, such as "AFP-B" (manufactured by Orient Chemical Industry Co., Ltd.); imidazole derivatives, such as "PLZ-2001" and "PLZ-8001" (both manufactured by Shikoku Kasei Corporation); and styrene-acrylic resins, such as "FCA-701PT" and "FCA-201-PS" (manufactured by Fujikura Kasei Co., Ltd.).

[0095] Examples of the negatively chargeable charge control agent include metal-containing azo dyes such as "Varifast Black 3804", "Bontron S-31", "Bontron S-32", "Bontron S-34", and "Bontron S-36" (all manufactured by Orient Chemical Industry Co., Ltd.), "Aizenspiron Black TRH", and "T-77" (manufactured by Hodogaya Chemical Industry Co., Ltd.); metal compounds of benzilic acid compounds such as "LR-147" and "LR-297" (all 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 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 (Clariant), nitroimidazole derivatives, and organometallic compounds.

[0096] From the viewpoint of the charging 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 composition.

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

[0098] In the production of the toner, a binder resin composition in which a crystalline polyester resin and an amorphous polyester resin are mixed in advance may be used, but in the production of the toner, these resins may be directly used for mixing the raw materials.

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

[0100] Examples of hydrophobic treatment agents for hydrophobizing the surfaces of silica particles include hexamethyldisilazane (HMDS), dimethyldichlorosilane (DMDS), silicone oil, octyltriethoxysilane (OTES), and methyltriethoxysilane.

[0101] From the viewpoint of the chargeability, fluidity, and transferability of the toner, the average particle size of the external additive is preferably 10 nm or more, more preferably 15 nm or more, and is preferably 250 nm or less, more preferably 200 nm or less, and even more preferably 90 nm or less.

[0102] From the viewpoint of the electrostatic chargeability, fluidity, and transferability of the toner, the content of the external additive is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and even more preferably 0.3 parts by mass or more, relative to 100 parts by mass of the toner before being treated with the external additive, and is preferably 5 parts by mass or less, and more preferably 3 parts by mass or less.

[0103] The volume median particle size (D 50 ) is preferably 3 μm or more, more preferably 4 μm or more, and is preferably 15 μm or less, more preferably 10 μm or less. 50 ) refers to the particle size at which the cumulative volume frequency calculated by volume fraction is 50% calculated from the smallest particle size. In addition, when the toner is treated with an external additive, the volume median particle size of the toner particles before treatment with the external additive is regarded as the volume median particle size of the toner.

[0104] The toner of the present invention can be used as it is as a toner for one-component development, or as a toner for two-component development mixed with a carrier, in an image forming apparatus of a one-component development system or a two-component development system, respectively. EXAMPLES

[0105] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. Physical properties of resins and the like can be measured by the following methods.

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

[0107] [Maximum endothermic peak temperature of resin] Using a differential scanning calorimeter "Q-100" (manufactured by TA Instruments Japan, Inc.), weigh 0.01 to 0.02 g of sample into an aluminum pan, cool the sample from room temperature (20°C) to 0°C at a rate of 10°C / min, and maintain the sample at that temperature for 1 minute. Then, measure the endothermic peak while increasing the temperature to 180°C at a rate of 10°C / min. The temperature of the peak with the largest peak area among the observed endothermic peaks is regarded as the maximum endothermic peak temperature.

[0108] [Glass transition temperature of resin] Using a differential scanning calorimeter "Q-100" (manufactured by TA Instruments Japan), 0.01 to 0.02 g of sample is weighed into an aluminum pan, heated from room temperature (20°C) to 200°C at a heating rate of 10°C / min, and cooled from that temperature to 0°C at a heating 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 top of the peak is taken as the glass transition temperature.

[0109] [Acid value and hydroxyl value of crystalline polyester resin] Measure based on the method of JIS K0070:1992, except that the measurement solvent is 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, except that the measurement solvent is changed from the ethanol and ether mixture specified in JIS K0070:1992 to a mixture 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, except that the measurement solvent is changed from the mixed solvent of ethanol and ether specified in JIS K0070:1992 to tetrahydrofuran.

[0112] [Weight average molecular weight of resin] The weight average molecular weight is determined by gel permeation chromatography (GPC) according to the following method. (1) Preparation of sample solution The sample is dissolved in tetrahydrofuran (amorphous resin) or chloroform (crystalline resin) at 40° C. so that the concentration becomes 0.5 g / 100 mL. Next, this solution is filtered using a PTFE type membrane filter "DISMIC-25JP" (manufactured by Toyo Roshi Kaisha, Ltd.) with a pore size of 0.20 μm to remove insoluble components, and the sample solution is obtained. (2) Molecular weight measurement The following measuring equipment and analytical column are used, and tetrahydrofuran (amorphous resin) or chloroform (crystalline resin) is passed as the eluent at a flow rate of 1 mL per minute. The column is stabilized in a thermostatic bath at 40°C. 100 μL of the sample solution is injected into the column for measurement. The molecular weight of the sample is calculated based on a calibration curve that has been prepared in advance. The calibration curve used here is a series of monodisperse polystyrenes (A-500 (5.0 x 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 )) was used as a standard sample. The numbers in parentheses indicate the molecular weight. Measuring device: HLC-8220GPC (Tosoh Corporation) Analytical column: TSKgel GMHXL + TSKgel G3000HXL (manufactured by Tosoh Corporation)

[0113] [Melting point of release agent] Using a differential scanning calorimeter "DSC Q-100" (manufactured by TA Instruments Japan Co., Ltd.), 0.01 to 0.02 g of sample is weighed into an aluminum pan, heated to 200°C at a heating rate of 10°C / min, and cooled to -10°C at a heating rate of 5°C / min. The sample is then heated to 180°C at a heating rate of 10°C / min and measured. The maximum endothermic peak temperature observed in the melting endothermic curve obtained is taken as the melting point of the wax.

[0114] [Average particle size of external additives] The average particle size refers to the number-average particle size, and is calculated by measuring the particle sizes (average of major and minor diameters) of 500 particles in a scanning electron microscope (SEM) photograph and averaging these by number.

[0115] [Volume Median Particle Size of Toner] Measuring instrument: Coulter Multisizer III (manufactured by Beckman Coulter, Inc.) Aperture diameter: 50μm Analysis software: Multisizer III version 3.51 (Beckman Coulter, Inc.) Electrolyte: "Isoton (registered trademark) II" (manufactured by Beckman Coulter, Inc.) Dispersion liquid: Polyoxyethylene lauryl ether "Emulgen (registered trademark) 109P" (manufactured by Kao Corporation, HLB (Griffin) = 13.6) was dissolved in the electrolyte to adjust the concentration to 5% by mass. Dispersion conditions: 10 mg of the measurement sample is added to 5 mL of the dispersion liquid, and dispersed for 1 minute using an ultrasonic disperser (machine name: US-1, manufactured by SND Co., Ltd., output: 80 W). Then, 25 mL of electrolyte is added, and the mixture is further dispersed for 1 minute using the ultrasonic disperser to prepare a sample dispersion liquid. Measurement conditions: The sample dispersion was added to 100 mL of the electrolyte to adjust the concentration so that the particle size of 30,000 particles could be measured in 20 seconds. Then, 30,000 particles were measured, and the volume median particle size (D 50 ) is required.

[0116] Resin manufacturing example 1 The raw material monomers shown in Tables 1 and 2 were placed in a 10-liter four-neck flask equipped with a thermometer, a stainless steel stirring rod, a downflow condenser, and a nitrogen inlet tube, and the temperature was raised to 200°C over 8 hours in a nitrogen atmosphere in a mantle heater. Then, an esterification catalyst and an esterification promoter were added, and the temperature was raised to 210°C over 1 hour, and the reaction was continued at 8.0 kPa until the softening points shown in Tables 1 and 2 were reached, to obtain crystalline polyester resins (resins C1 to C10).

[0117] [Table 1]

[0118] [Table 2]

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

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

[0121] [Table 3]

[0122] Examples 1 to 7 and Comparative Examples 1 to 6 As the binder resin, 15 parts by mass of resin C, 60 parts by mass of resin AL, and 25 parts by mass of resin AH shown in Table 4, 5 parts by mass of colorant "ECB-301" (manufactured by Dainichi Seikagaku Kogyo Co., Ltd., copper phthalocyanine pigment), 1 part by mass of charge control agent "LR-147" (manufactured by Nippon Carlit Co., Ltd.), and 2 parts by mass of release agent "HNP-9" (manufactured by Nippon Seiro Co., Ltd., paraffin wax, melting point: 75 ° C.) were thoroughly stirred with a Henschel mixer, and then melt-kneaded using a co-rotating twin-screw extruder with a total length of 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 in the screw was 90 ° C., the temperature of the kneaded material was 140 ° C., the feed rate of the kneaded material was 10 kg / h, and the average residence time was about 18 seconds. The obtained kneaded product was cooled from 140°C to 50°C in 1.5 hours, rolled and cooled at 50°C with a cooling roller, pulverized in a jet mill, classified, and the volume median particle size (D 50 ) Toner particles of 5.5 μm 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 mixed in a Henschel mixer at 3600 r / min for 5 minutes to perform external additive treatment and obtain a toner.

[0124] Example 8 15 parts by mass of resin C1 and 85 parts by mass of resin AL1 as binder resins, 5 parts by mass of colorant "ECB-301" (manufactured by Dainichi Seikagaku Kogyo Co., Ltd., copper phthalocyanine pigment), 1 part by mass of charge control agent "LR-147" (manufactured by Nippon Carlit Co., Ltd.), and 2 parts by mass of release agent "HNP-9" (manufactured by Nippon Seiro Co., Ltd., paraffin wax, melting point: 75°C) were thoroughly stirred with a Henschel mixer, and then melt-kneaded using a co-rotating twin-screw extruder with a total length of 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 in the screw was 90°C, the temperature of the kneaded material was 125°C, the feed rate of the kneaded material was 10 kg / h, and the average residence time was about 18 seconds. The kneaded product obtained was cooled from 125°C to 50°C in 1.5 hours, rolled and cooled at 50°C with a cooling roller, pulverized in a jet mill, classified, and the volume median particle size (D 50 ) Toner particles of 5.5 μm were obtained.

[0125] 100 parts by mass of the obtained toner particles were subjected to external addition treatment in the same manner as in Example 1 to obtain a toner.

[0126] Test Example 1 [Abrasion resistance] A halftone image (2 dots 2 spaces halftone image) consisting of 2 dots of printed areas (points) and 2 dots of non-printed areas (blanks) was printed at a resolution of 600 dpi on coated paper "OK ​​Topcoat+" (Oji Paper Co., Ltd.) using a commercially available printer "Microline (registered trademark) 5400" (Oki Data Co., Ltd.). The resulting print was applied to a cellulose nonwoven fabric "Bencotto M3-II" (Asahi Kasei Co., Ltd.) with a load of 2 kg (contact area 900 mm2). 2 The reflective image density of the printed matter before and after rubbing was measured using a colorimeter "SpectroEye" (GretagMacbeth, light irradiation conditions: standard light source D 50 The measurements were made using a 2° observation field, density standard DINNB, and absolute white standard. The average of the values ​​measured at three arbitrary points on each image was taken as the image density, and the amount of change in image density before and after rubbing [(image density before rubbing - image density after rubbing)] was calculated. The results are shown in Table 4. The smaller the amount of change in image density before and after rubbing, the more excellent the abrasion resistance.

[0127] Test Example 2 [Crushability] In the toner manufacturing process, 1 kg of the molten kneaded material (approximately 3 cm square plate piece) was collected and put into a Rotoplex (manufactured by Hosokawa Micron Corporation, model R20 / 10) equipped with a screen with a mesh size of 3 mm, and pulverized. The pulverized molten kneaded material was classified into particles with a particle size of 850 μm to 1000 μm using wire mesh sieves (manufactured by Iida Manufacturing Co., Ltd.) with mesh sizes of 1000 μm and 850 μm as specified in JIS Z 8801-1:2000. 20 g of the classified particles were pulverized for 10 seconds with a coffee mill (manufactured by PHILIPS, HR-2170 type), and then passed through a 150 μm sieve, and the weight A (g) of the toner that passed through was precisely weighed. The pulverizability was calculated from the weighed weight using the following formula, and this operation was performed three times to obtain the average value. The results are shown in Table 4. The higher the value, the better the pulverizability. Grindability (%) = (A [g] / 20.0 [g]) x 100

[0128] Test Example 3 [Gloss] The toner was mounted on a copy machine "AR-505" (manufactured by Sharp Corporation) whose fixing unit was modified to enable fixing outside the machine, and a printout was obtained in an unfixed state (print area: 2 cm × 12 cm, adhesion amount: 0.3 mg / cm 2 ). Thereafter, a fixing machine (fixing speed 300 mm / sec) adjusted to a total fixing pressure of 40 kgf was used, and the temperature of the fixing roll was set to the minimum fixing temperature + 20°C to fix the unfixed printed matter. The paper used for printing was coated paper "OK ​​Topcoat+" (manufactured by Oji Paper Co., Ltd.). After leaving the resulting printed matter at a temperature of 45°C for one day, the gloss was measured using a gloss meter "IG-330" (manufactured by Horiba, Ltd.) with cardboard placed under the image and the light irradiation condition set at 60°. The results are shown in Table 4. The higher the value, the higher the gloss.

[0129] [Table 4]

[0130] From the above results, it is apparent that the toners of Examples 1 to 8 have good grindability during the production process and are also excellent in abrasion resistance and gloss. In contrast, the toner of Comparative Example 1 containing a crystalline polyester resin using 1,6-hexanediol instead of ethylene glycol, the toner of Comparative Example 5 containing a crystalline polyester resin using a small amount of ethylene glycol, and the toner of Comparative Example 6 containing an amorphous polyester resin not using ethylene glycol are all insufficient in terms of grindability, abrasion resistance, and gloss. Also, the toner of Comparative Example 2 containing a crystalline polyester resin using sebacic acid having a carbon number of 10 as an aliphatic dicarboxylic acid compound, the toner of Comparative Example 3 containing a crystalline polyester resin not using an aliphatic monocarboxylic acid compound, and the toner of Comparative Example 4 containing a crystalline polyester resin using lauric acid having a carbon number of 12 as an aliphatic monocarboxylic acid compound are good in gloss but lack grindability and abrasion resistance. [Industrial Applicability]

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

Claims

1. A toner binder resin composition containing a crystalline polyester resin and an amorphous polyester resin, wherein 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 a carboxylic acid component containing an aliphatic monocarboxylic acid compound having 16 to 24 carbon atoms, and the content of the aliphatic monocarboxylic acid compound is 1.5 mol% or more and 20 mol% or less in the total amount of the alcohol component and the carboxylic acid component, the amorphous polyester resin is represented by the formula (I): 【Chemical 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 is a positive number, and the value of the sum of x and y is 1 or more and 16 or less) a polycondensate of an alkylene oxide adduct of bisphenol A represented by the formula and an alcohol component containing ethylene glycol and a carboxylic acid component containing a dicarboxylic acid compound, and the content of ethylene glycol is 10 mol% or more and 60 mol% or less in the alcohol component, a toner binder resin composition.

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

3. The toner binder resin composition according to claim 1, wherein the acid value of the crystalline polyester resin is 10 mgKOH / 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 softening point of the amorphous polyester resin is 70°C or more and 130°C or less.

6. An electrostatic charge image developing toner containing the toner binder resin composition according to any one of claims 1 to 5 and a colorant.

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