Composition containing crystalline resin for toner

Abstract

To provide a composition containing crystalline resin for toner excellent in glossiness, and toner for electrostatic charge image development including the composition.SOLUTION: The composition containing crystalline resin for toner includes crystalline polyester resin, amorphous polyester resin and hydroxy group-containing amide compound. The crystalline polyester resin includes crystalline polyester resin C which is polycondensation product of alcohol component containing 80 mol% or more of ethylene glycol and carboxylic acid component. The hydroxy group-containing amide compound is compound represented by formula (I): R1-CONH-X-NHCO-R2 (I) or formula (II): R3-CONH-R4 (II). Content of the hydroxy group-containing amide compound is 0.5 pt.mass or more and 10 pts.mass or less with respect to total 100 pts.mass of the crystalline polyester resin and the amorphous polyester resin.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a crystalline resin-containing composition for toners used in developing latent images formed in electrophotography, electrostatic recording, electrostatic printing, etc., and to a toner for developing electrostatic images containing the composition. [Background technology]

[0002] BACKGROUND ART In recent years, printing using toner has come to be used in industrial printing and commercial printing, and there is a demand for improving the gloss of printed matter.

[0003] On the other hand, from the viewpoints of storage stability, durability, chargeability, etc., the use of an amide compound as a toner raw material together with a crystalline polyester resin and an amorphous polyester resin has been investigated (see Patent Documents 1 to 4). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2019-8249 [Patent Document 2] Japanese Patent Application Publication No. 2019-95543 [Patent Document 3] Japanese Patent Application Laid-Open No. 2009-251192 [Patent Document 4] Japanese Patent Application Laid-Open No. 2009-251193 Summary of the Invention [Problem to be solved by the invention]

[0005] It is known that crystalline polyester resins are used as binder resins that are effective in improving the low-temperature fixability of toners. However, the use of crystalline polyester resins has the problem that the gloss of printed matter tends to decrease.

[0006] The present invention relates to a crystalline resin-containing composition for toners having excellent gloss and a toner for developing electrostatic images containing the composition. [Means for solving the problem]

[0007] The present invention provides [1] A crystalline resin-containing composition for toner, which contains a crystalline polyester resin, an amorphous polyester resin, and a hydroxy group-containing amide compound, wherein the crystalline polyester resin contains a crystalline polyester resin C which is a polycondensation product of an alcohol component containing 80 mol % or more of ethylene glycol and a carboxylic acid component, and the hydroxy group-containing amide compound is a compound represented by formula (I): R 1 -CONH-X-NHCO-R 2 (I) (In the formula, R 1 and R 2 are each independently a hydroxyalkyl group having from 12 to 22 carbon atoms, and X is a divalent hydrocarbon group having from 2 to 12 carbon atoms. or formula (II): R 3 -CONH-R 4 (II) (In the formula, R 3 is a hydroxyalkyl group having 12 to 22 carbon atoms, and R 4 is a hydroxyalkyl group having 2 to 22 carbon atoms. wherein the content of the hydroxy group-containing amide compound is 0.5 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the total amount of the crystalline polyester resin and the amorphous polyester resin; and [2] A toner for developing electrostatic images, comprising the crystalline resin-containing composition for toners according to [1] above. Regarding. [Effects of the Invention]

[0008] The crystalline resin-containing composition for toner of the present invention exhibits excellent effects in terms of gloss. DETAILED DESCRIPTION OF THE INVENTION

[0009] The crystalline resin-containing composition for toner of the present invention contains a crystalline polyester resin, an amorphous polyester resin, and an amide compound, and is characterized in that the crystalline polyester resin contains a crystalline polyester resin using ethylene glycol as the main alcohol component, and the amide compound contains a specific hydroxyl group-containing amide compound. The reason why the composition of the present invention has excellent gloss is not clear, but is presumed to be as follows. Note that the following mechanism is presumed and is not limited thereto.

[0010] The decrease in gloss due to the crystalline polyester resin is presumably due to the formation of coarse domains of the crystalline polyester resin as crystal growth progresses on a small number of crystal nuclei in the printed matter after storage. In contrast, by using a specific amide compound in combination, the amide compound is expected to act as a nucleating agent, promoting the formation of crystal nuclei of the crystalline polyester resin and suppressing the formation of coarse domains. However, among amide compounds, fatty acid amides having long-chain alkyl groups have low dispersibility in amorphous polyester resins due to the strong cohesive force of the long-chain alkyl groups, and are therefore less effective in promoting crystal nucleation of crystalline polyester resins. Therefore, by using fatty acid amides containing hydroxyl groups (hydroxyl group-containing amide compounds), the cohesive force between the amide compounds is inhibited by the hydroxyl groups, improving the dispersion of the amide compounds. As a result, the effect of promoting crystal nucleation of crystalline polyester resins is enhanced. On the other hand, conventional crystalline polyester resins have long monomer chains and ester groups spaced apart, resulting in low cohesive strength of the ester bonds. Therefore, by using ethylene glycol as the main alcohol component of the crystalline polyester resin, the ester groups are densely localized, increasing the cohesive strength between the hydroxyl group-containing amide compound and the ester groups, and improving the dispersibility of the hydroxyl group-containing amide compound. As a result, the number of starting points for crystal growth increases, and the domains of the crystalline polyester resin become smaller, which is thought to suppress light scattering after storage of printed materials and improve gloss.

[0011] The crystalline polyester resin contains a crystalline polyester resin C which is a polycondensate of an alcohol component containing ethylene glycol as a main component and a carboxylic acid component.

[0012] The content of ethylene glycol in the alcohol component is 80 mol % or more, preferably 90 mol % or more, more preferably 95 mol % or more, and 100 mol % or less, from the viewpoint of low-temperature fixability and hydrophilicity.

[0013] Examples of alcohol components other than ethylene glycol include aliphatic diols other than ethylene glycol such as 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, neopentyl glycol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, and 1,12-dodecanediol; aromatic diols such as alkylene oxide adducts of bisphenol A; bisphenol A, hydrogenated bisphenol A, sorbitol, pentaerythritol, glycerin, and trimethylolpropane; and trihydric or higher alcohols.

[0014] The carboxylic acid component preferably contains an aliphatic dicarboxylic acid compound.

[0015] Examples of the aliphatic dicarboxylic acid compound include 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), sebacic acid (number of carbon atoms: 10), dodecanedioic acid (number of carbon atoms: 12), tetradecanedioic acid (number of carbon atoms: 14), anhydrides of these acids, and alkyl esters of these acids having 1 to 3 carbon atoms.

[0016] From the viewpoint of heat-resistant storage stability, the carbon number of the aliphatic dicarboxylic acid compound is preferably 10 or more, more preferably 12 or more, and from the viewpoint of low-temperature fixability, it is preferably 16 or less, more preferably 14 or less. When the aliphatic dicarboxylic acid compound is an alkyl ester, the carbon number of the alkyl group is not included in the above carbon number.

[0017] From the viewpoint of hydrophobicity, the content of the aliphatic dicarboxylic acid compound in the carboxylic acid component is preferably 50 mol% or more, more preferably 60 mol% or more, even more preferably 70 mol% or more, and even more preferably 80 mol% or more, and is 100 mol% or less. When the carboxylic acid component contains an aliphatic monocarboxylic acid compound, the content is preferably 98 mol% or less, more preferably 97 mol% or less.

[0018] From the viewpoint of gloss, the carboxylic acid component preferably further contains an aliphatic monocarboxylic acid compound.

[0019] Examples of the aliphatic monocarboxylic acid compounds include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, and alkyl esters of these acids in which the alkyl group has 1 to 3 carbon atoms.

[0020] From the viewpoint of gloss, the number of carbon atoms in the aliphatic monocarboxylic acid compound is preferably 12 or more, more preferably 18 or more, and even more preferably 20 or more, and from the viewpoint of low-temperature fixability, it is preferably 30 or less, more preferably 24 or less, and even more preferably 22 or less. When the aliphatic monocarboxylic acid compound is an alkyl ester, the number of carbon atoms in the alkyl group is not included in the above carbon number.

[0021] When the carboxylic acid component contains an aliphatic monocarboxylic acid compound, the content of the aliphatic monocarboxylic acid compound in the carboxylic acid component is preferably 2 mol% or more, more preferably 3 mol% or more, and preferably 15 mol% or less, more preferably 10 mol% or less.

[0022] Examples of other carboxylic acid components include aromatic dicarboxylic acid compounds such as phthalic acid, isophthalic acid, and terephthalic acid, and trivalent or higher carboxylic acid compounds such as trimellitic acid and pyromellitic acid.

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

[0024] The equivalent ratio of the carboxyl groups of the carboxylic acid component to the hydroxyl groups of the alcohol component (COOH groups / OH groups) is preferably 0.7 or more, more preferably 0.8 or more, from the viewpoint of charging stability, and is preferably 1.3 or less, more preferably 1.2 or less, from the viewpoint of low-temperature fixability.

[0025] Crystalline polyester resin C 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 a co-catalyst, polymerization inhibitor, etc., at a temperature of preferably 120°C or higher, more preferably 180°C or higher, and preferably 230°C or lower, more preferably 220°C or lower.

[0026] Examples of the esterification catalyst include tin compounds such as dibutyltin oxide and tin(II) 2-ethylhexanoate, and titanium compounds such as titanium diisopropoxybis(triethanolaminate). 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, per 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. Examples of the co-catalyst for the esterification catalyst include gallic acid. The amount of the 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, more preferably 0.1 parts by mass or less, per 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. 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, relative to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component.

[0027] 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 Nos. 11-133668, 10-239903, and 8-20636. Among the modified polyester resins, urethane-modified polyester resins in which polyester resins are urethane-extended with a polyisocyanate compound are preferred.

[0028] The softening point of the crystalline polyester resin C is preferably 50°C or higher, more preferably 65°C or higher, and even more preferably 70°C or higher from the viewpoint of hot offset resistance, and is preferably 120°C or lower, more preferably 110°C or lower from the viewpoint of low-temperature fixability.

[0029] The crystallinity of a resin is expressed by a crystallinity index defined as the ratio of the softening point to the maximum endothermic peak temperature measured by a differential scanning calorimeter, that is, the value of [softening point / maximum endothermic peak temperature]. The crystalline resin has 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 resin has a crystallinity index of more than 1.4, preferably more than 1.5, more preferably 1.6 or more, or less than 0.6, preferably 0.5 or less. The crystallinity of a resin can be adjusted by the types and ratios of raw material monomers, and 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. For crystalline resins, the maximum endothermic peak temperature is the melting point.

[0030] The melting point of the crystalline polyester resin C is preferably 45°C or higher, more preferably 60°C or higher, and even more preferably 65°C or higher, from the viewpoint of heat-resistant storage stability, and is preferably 115°C or lower, more preferably 105°C or lower, from the viewpoint of low-temperature fixability.

[0031] The weight average molecular weight of the crystalline polyester resin C is preferably 10,000 or more, more preferably 15,000 or more, from the viewpoint of heat-resistant storage stability, and is preferably 30,000 or less, more preferably 25,000 or less, from the viewpoint of low-temperature fixability.

[0032] The content of the crystalline polyester resin C in the crystalline polyester resin is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more, and 100% by mass or less.

[0033] Furthermore, from the viewpoint of low-temperature fixability, the content of crystalline polyester resin C in the total amount of crystalline polyester resin and amorphous polyester resin is preferably 5% by mass or more, more preferably 8% by mass or more, even more preferably 10% by mass or more, and is preferably 25% by mass or less, more preferably 20% by mass or less, even more preferably 17% by mass or less.

[0034] Other crystalline polyester resins include crystalline polyester resins other than crystalline polyester resin C, and composite resins containing crystalline polyester resins and vinyl resins such as styrene-acrylic resins, epoxy resins, polycarbonates, polyurethanes, and the like.

[0035] The amorphous polyester resin preferably contains an amorphous polyester resin A which is a polycondensation product of an alcohol component containing an alkylene oxide adduct of bisphenol A and a carboxylic acid component.

[0036] Examples of alkylene oxide adducts of bisphenol A include those represented by formula (III):

[0037] [ka]

[0038] (In the formula, OR 5 and R 5 O is an oxyalkylene group, and R 5 is an ethylene group and / or a propylene group, x and y are each a positive number and represent the average number of moles of alkylene oxide added, and the sum of x and y is 1 or more, preferably 1.5 or more, and 16 or less, preferably 8 or less, more preferably 6 or less, and even more preferably 4 or less. Examples of the compound include an ethylene oxide adduct of bisphenol A and a propylene oxide adduct of bisphenol A.

[0039] The content of the alkylene oxide adduct of bisphenol A represented by formula (III) in the alcohol component is preferably 80 mol % or more, more preferably 90 mol % or more, and even more preferably 95 mol % or more, and 100 mol % or less, from the viewpoints of low-temperature fixability and hydrophilicity.

[0040] Examples of other alcohol components include aliphatic diols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-butenediol, 1,3-butanediol, and neopentyl glycol; and trihydric or higher alcohols such as bisphenol A, hydrogenated bisphenol A, and glycerin.

[0041] From the viewpoint of heat-resistant storage stability, the carboxylic acid component preferably contains an aromatic dicarboxylic acid compound.

[0042] Examples of aromatic dicarboxylic acid compounds include phthalic acid, isophthalic acid, terephthalic acid, anhydrides of these acids, and alkyl esters of these acids having a carbon number of 1 to 3. Of these, terephthalic acid is preferred.

[0043] The content of the aromatic dicarboxylic acid compound in the carboxylic acid component is preferably 25 mol% or more, more preferably 30 mol% or more, even more preferably 35 mol% or more, and is preferably 95 mol% or less, more preferably 90 mol% or less, even more preferably 85 mol% or less.

[0044] Examples of other carboxylic acid components include aliphatic dicarboxylic acid compounds and trivalent or higher carboxylic acid compounds.

[0045] Examples of the aliphatic dicarboxylic acid compound include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid which may be substituted with a hydrocarbon group, adipic acid, anhydrides of these acids, and alkyl esters of these acids in which the alkyl group has 1 to 3 carbon atoms.

[0046] Examples of trivalent or higher carboxylic acid compounds include trivalent or higher carboxylic acid compounds such as 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, and pyromellitic acid, anhydrides of these acids, and alkyl esters of these acids in which the alkyl group has 1 to 3 carbon atoms.

[0047] The alcohol component may contain a monohydric alcohol, and the carboxylic acid component may contain a monocarboxylic acid compound, as appropriate.

[0048] The equivalent ratio of the carboxyl groups of the carboxylic acid component to the hydroxyl groups of the alcohol component (COOH groups / OH groups) is preferably 0.6 or more, more preferably 0.7 or more, even more preferably 0.8 or more, and is preferably 1.3 or less, more preferably 1.2 or less.

[0049] The polycondensation reaction conditions of the alcohol component and the carboxylic acid component of the amorphous polyester resin A are the same as those of the crystalline polyester resin C, except that the preferred reaction temperature is 130°C or higher, more preferably 170°C or higher, and 250°C or lower, more preferably 240°C or lower.

[0050] The softening point of the amorphous polyester resin A is preferably 70°C or higher, more preferably 90°C or higher, and even more preferably 100°C or higher from the viewpoint of charging stability, and is preferably 170°C or lower, more preferably 160°C or lower, and even more preferably 150°C or lower from the viewpoint of low-temperature fixability.

[0051] From the viewpoints of low-temperature fixability and fixation width, the amorphous polyester resin A preferably comprises amorphous polyester resins having different softening points. The difference in softening point between the two amorphous polyester resins is preferably 10°C or more, more preferably 15°C or more, and is preferably 60°C or less, more preferably 50°C or less.

[0052] The softening point of the amorphous polyester resin A (resin AH) having a higher softening point is preferably 100°C or higher, more preferably 110°C or higher, from the viewpoint of fixing width, and is preferably 170°C or lower, more preferably 160°C or lower, and even more preferably 150°C or lower, from the viewpoint of low-temperature fixability.

[0053] The weight average molecular weight of Resin AH is preferably 50,000 or more, more preferably 100,000 or more, and preferably 200,000 or less, more preferably 150,000 or less.

[0054] Furthermore, the softening point of the amorphous polyester resin A (resin AL) having a lower softening point is preferably 70°C or higher, more preferably 90°C or higher, from the viewpoint of charging stability, and is preferably 120°C or lower, more preferably 110°C or lower, and even more preferably 100°C or lower, from the viewpoint of low-temperature fixability.

[0055] The weight average molecular weight of the resin AL is preferably 3,000 or more, more preferably 4,000 or more, and preferably 9,000 or less, more preferably 8,000 or less.

[0056] The mass ratio of resin AL to resin AH (resin AL / resin AH) is preferably 55 / 45 or more, more preferably 60 / 40 or more, even more preferably 65 / 35 or more, and is preferably 90 / 10 or less, more preferably 85 / 15 or less, even more preferably 80 / 20 or less.

[0057] The glass transition temperature of the amorphous polyester resin A is preferably 40°C or higher, more preferably 50°C or higher, from the viewpoint of storage stability, and is preferably 80°C or lower, more preferably 70°C or lower, from the viewpoint of charging stability.

[0058] The content of the amorphous polyester resin A in the amorphous polyester resin is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more, and 100% by mass or less.

[0059] Furthermore, from the viewpoint of low-temperature fixability, the content of amorphous polyester resin A in the total amount of crystalline polyester resin and amorphous polyester resin is preferably 75% by mass or more, more preferably 80% by mass or more, even more preferably 83% by mass or more, and is preferably 95% by mass or less, more preferably 92% by mass or less, even more preferably 90% by mass or less.

[0060] Other amorphous polyester resins include amorphous polyester resins other than amorphous polyester resin A, and composite resins containing an amorphous polyester resin and a vinyl resin such as a styrene-acrylic resin, an epoxy resin, a polycarbonate, a polyurethane, and the like.

[0061] The mass ratio of the crystalline polyester resin to the amorphous polyester resin (crystalline polyester resin / amorphous polyester resin) is preferably 5 / 95 or more, more preferably 8 / 92 or more, even more preferably 10 / 90 or more, and is preferably 25 / 75 or less, more preferably 20 / 80 or less, even more preferably 17 / 83 or less.

[0062] Furthermore, the mass ratio of crystalline polyester resin C to amorphous polyester resin A (crystalline polyester resin C / amorphous polyester resin A) is preferably 5 / 95 or more, more preferably 8 / 92 or more, even more preferably 10 / 90 or more, and is preferably 25 / 75 or less, more preferably 20 / 80 or less, even more preferably 17 / 83 or less.

[0063] The hydroxy group-containing amide compound has the formula (I): R 1 -CONH-X-NHCO-R 2 (I) (In the formula, R 1 and R 2 are each independently a hydroxyalkyl group having from 12 to 22 carbon atoms, and X is a divalent hydrocarbon group having from 2 to 12 carbon atoms. or formula (II): R3 -CONH-R 4 (II) (In the formula, R 3 is a hydroxyalkyl group having 12 to 22 carbon atoms, and R 4 is a hydroxyalkyl group having 2 to 22 carbon atoms. The crystalline resin-containing composition for toner of the present invention may contain, as the hydroxy group-containing amide compound, either the compound represented by formula (I) or the compound represented by formula (II), or may contain both the compound represented by formula (I) and the compound represented by formula (II).

[0064] R 1 , R 2 and R 3 From the viewpoint of further improving the glossiness of printed matter after storage, the number of carbon atoms in the hydroxyalkyl groups is preferably 13 or more, more preferably 15 or more, and is preferably 21 or less, more preferably 19 or less, independently.

[0065] R 4 The number of carbon atoms in the hydroxyalkyl group is preferably 10 or less, more preferably 6 or less, from the viewpoint of further improving the glossiness of printed matter after storage.

[0066] R 1 ~R 4 The alkyl group in may be either branched or straight chain, but is preferably straight chain, and the hydroxy group is preferably at the terminal of the alkyl group.

[0067] Examples of the divalent hydrocarbon group for X include a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group.

[0068] Examples of the divalent aliphatic hydrocarbon group include an ethylene group, a trimethylene group, a tetramethylene group, and a hexamethylene group.

[0069] Examples of the divalent aromatic hydrocarbon group include a phenylene group, an m-xylylene group, and a p-xylylene group.

[0070] The divalent hydrocarbon group of X preferably has 10 or less carbon atoms, more preferably 8 or less carbon atoms, and even more preferably 6 or less carbon atoms.

[0071] Specific examples of the hydroxy group-containing amide compound represented by formula (I) include 12-hydroxystearic acid ethylene bisamide, 12-hydroxystearic acid hexamethylene bisamide, 12-hydroxystearic acid xylylene bisamide, and 12-hydroxypalmitic acid ethylene bisamide.

[0072] Specific examples of the hydroxy group-containing amide compound represented by formula (II) include 12-hydroxystearic acid hydroxyethylamide, 12-hydroxypalmitic acid hydroxyethylamide, and the like.

[0073] The melting point of the hydroxy group-containing amide compound is preferably 100°C or higher, more preferably 110°C or higher, and even more preferably 120°C or higher, from the viewpoint of gloss, and is preferably 180°C or lower, more preferably 170°C or lower, and even more preferably 160°C or lower, from the viewpoint of low-temperature fixability.

[0074] The content of the hydroxy group-containing amide compound is 0.5 parts by mass or more, preferably 0.6 parts by mass or more, more preferably 0.7 parts by mass or more, even more preferably 0.8 parts by mass or more, relative to 100 parts by mass of the total amount of the crystalline polyester resin and the amorphous polyester resin, and is 10 parts by mass or less, preferably 7 parts by mass or less, more preferably 4 parts by mass or less, even more preferably 2 parts by mass.

[0075] Furthermore, the content of the hydroxy group-containing amide compound is preferably 0.5 parts by mass or more, more preferably 0.6 parts by mass or more, even more preferably 0.7 parts by mass or more, and even more preferably 0.8 parts by mass or more, relative to 100 parts by mass of the total amount of crystalline polyester resin C and amorphous polyester resin A, and is preferably 10 parts by mass or less, more preferably 7 parts by mass or less, even more preferably 4 parts by mass or less, and even more preferably 2 parts by mass.

[0076] The mass ratio of the hydroxy group-containing amide compound to the crystalline polyester resin C (hydroxy group-containing amide compound / crystalline polyester resin C) is preferably 1 / 99 or more, more preferably 5 / 95 or more, even more preferably 7 / 93 or more, and is preferably 80 / 20 or less, more preferably 50 / 50 or less, even more preferably 35 / 65 or less, and even more preferably 20 / 80 or less.

[0077] Furthermore, the present invention provides a toner for developing electrostatic images, which contains the crystalline resin-containing composition for toners of the present invention.

[0078] In the toner of the present invention, the crystalline polyester resin and the amorphous polyester resin are contained as binder resins.

[0079] The total content of the crystalline polyester resin and the amorphous polyester resin in the binder resin is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and even more preferably 95% by mass or more, and is 100% by mass or less.

[0080] Furthermore, the total content of the crystalline polyester resin C and the amorphous polyester resin A in the binder resin is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and even more preferably 95% by mass or more, and is 100% by mass or less.

[0081] Other binder resins include vinyl resins such as styrene acrylic resin, polyamide resin, epoxy resin, polycarbonate resin, polyurethane resin, and composite resins containing two or more of these resins.

[0082] The content of the binder resin in the toner is preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably 75% by mass or more, and preferably 99.5% by mass or less, more preferably 98% by mass or less, even more preferably 95% by mass or less.

[0083] The toner of the present invention may further contain additives such as a colorant, 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.

[0084] As the colorant, dyes, pigments, magnetic materials, etc. used as toner colorants can be used. Examples include carbon black, phthalocyanine blue, permanent brown FG, brilliant fast scarlet, pigment red 122, pigment green B, rhodamine-B base, solvent red 49, solvent red 146, solvent blue 35, quinacridone, carmine 6B, isoindoline, disazo yellow, etc. In the present invention, the toner may be either a black toner or a color toner.

[0085] 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 preferably 40 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less, relative to 100 parts by mass of the binder resin.

[0086] Examples of the release agent include hydrocarbon waxes such as polypropylene wax, polyethylene wax, ethylene-propylene 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, and these may be used alone or in combination of two or more.

[0087] 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.

[0088] The content of the release agent is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 1.5 parts by mass or more, relative to 100 parts by mass of the binder resin, from the viewpoints of the low-temperature fixability and offset resistance of the toner and the dispersibility in the binder resin, and is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and even more preferably 7 parts by mass or less.

[0089] 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.

[0090] Positively chargeable 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 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 suitable resins include "VP435" (manufactured by Clariant), etc.; polyamine resins, such as "AFP-B" (manufactured by Orient Chemical Industries Co., Ltd.); imidazole derivatives, such as "PLZ-2001" and "PLZ-8001" (both manufactured by Shikoku Chemical Industry Co., Ltd.); and styrene-acrylic resins, such as "FCA-701PT" and "FCA-201-PS" (manufactured by Fujikura Chemical Co., Ltd.).

[0091] Examples of negatively chargeable charge control agents include metal-containing azo dyes such as "Balifast 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 benzilic acid compounds such as "LR-147" and "LR-297" (manufactured by Nippon Carlit Co., Ltd.); metal compounds of salicylic acid compounds such as "Bontron E-81," "Bontron E-84," "Bontron E-88," and "Bontron E-304" (all manufactured by Orient Chemical Industries, Ltd.), and "TN-105" (manufactured by Hodogaya Chemical Co., Ltd.); copper phthalocyanine dyes; and quaternary ammonium salts such as "COPY CHARGE NX VP434 (manufactured by Clariant), nitroimidazole derivatives, etc.; organometallic compounds, etc.

[0092] 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.

[0093] The toner of the present invention may be a toner obtained by any conventional method, such as melt-kneading, emulsion aggregation, or suspension polymerization, or may have a core-shell structure. However, from the viewpoint of the mixability of the toner components, a pulverized toner obtained by melt-kneading is preferred. In the case of a pulverized toner obtained by melt-kneading, for example, a crystalline polyester resin, an amorphous polyester resin, and a hydroxyl-containing amide compound, as well as, if necessary, a colorant, 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 kneader, or the like, followed by cooling, pulverization, and classification. The crystalline polyester resin, amorphous polyester resin, and hydroxyl-containing amide compound constituting the crystalline resin-containing toner composition of the present invention may be used as a premix, or may be used directly or mixed with other raw materials.

[0094] In order to improve the transferability of the toner of the present invention, it is preferable to use an external additive. Examples of the external additive include inorganic fine particles such as silica, alumina, titania, zirconia, tin oxide, and zinc oxide, and organic fine particles such as melamine-based resin fine particles and polytetrafluoroethylene resin fine particles, and two or more of these 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 subjected to a hydrophobic treatment is more preferred.

[0095] Examples of hydrophobic treatment agents for hydrophobizing the surfaces of silica particles include hexamethyldisilazane (HMDS), dimethyldichlorosilane (DMDS), cyclic silazanes, silicone oils, aminosilanes, octyltriethoxysilane (OTES), and methyltriethoxysilane.

[0096] From the viewpoint of the chargeability, fluidity, and transferability of the toner, the average particle diameter of the external additive is preferably 5 nm or more, more preferably 10 nm or more, and even 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.

[0097] The external addition treatment by mixing the toner particles with the external additives can be carried out in accordance with a conventional method, and a mixer such as a Henschel mixer can be used.

[0098] From the viewpoint of the 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 particles before treatment with the external additive, and is preferably 5 parts by mass or less, and more preferably 3 parts by mass or less.

[0099] 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 ) means the particle size at which the cumulative volume frequency calculated by volume fraction is 50% starting 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 taken as the volume median particle size of the toner.

[0100] The toner of the present invention can be used as a toner for one-component development as it is, 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. [Example]

[0101] The present invention will be described in more 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.

[0102] [Softening point of resin] Using a flow tester "CFT-500D" (Shimadzu Corporation), 1 g of sample is heated at a temperature increase rate of 6°C / min while applying a load of 1.96 MPa with the plunger, and extruding it from a nozzle 1 mm in diameter and 1 mm in length. The plunger depression distance of the flow tester is plotted against the temperature, and the temperature at which half of the sample flows out is taken as the softening point.

[0103] [Maximum endothermic peak temperature of resin and amide compound] Using a differential scanning calorimeter "Q-100" (TA Instruments Japan Co., Ltd.), weigh 0.01-0.02 g of sample into an aluminum pan, cool from room temperature (25°C) to 0°C at a rate of 10°C / min, and maintain at 0°C for 1 minute. Then, measure at a rate of 10°C / min. The temperature of the peak with the largest peak area among the observed endothermic peaks is taken as the maximum endothermic peak temperature. For crystalline resins and amide compounds, the maximum endothermic peak temperature is taken as the melting point.

[0104] [Glass transition temperature of resin] Using a differential scanning calorimeter "Q-100" (TA Instruments Japan), 0.01-0.02 g of sample is weighed into an aluminum pan, heated from room temperature (20°C) at a heating rate of 10°C / min to 200°C, and then cooled from that temperature at a heating rate of 10°C / min to 0°C. Next, the sample is heated at a heating rate of 10°C / min, and the endothermic peak is measured. The glass transition temperature is the temperature at the intersection of an extension of the baseline below the maximum endothermic peak temperature and a tangent line showing the maximum slope from the rising part of the peak to the peak apex.

[0105] [Weight average molecular weight of resin (Mn)] The molecular weight distribution is measured by gel permeation chromatography (GPC) according to the following method, and the weight average molecular weight is determined. (1) Preparation of sample solution The sample is dissolved in tetrahydrofuran (amorphous resin) or chloroform (crystalline resin) at 40°C to a concentration of 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 resulting solution is used as the sample solution. (2) Molecular weight measurement The following measurement 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 sample solution is injected into the column for measurement. The molecular weight of the sample is calculated based on a calibration curve prepared in advance. The calibration curve used here is a series of monodisperse polystyrenes (A-500 (5.0 × 10) manufactured by Tosoh Corporation) 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(1.90×10 5 ), 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 molecular weight is indicated in parentheses. Measuring device: HLC-8220GPC (manufactured by Tosoh Corporation) Analytical column: TSKgel GMH XL +TSKgel G3000H XL (Manufactured by Tosoh Corporation)

[0106] [Melting point of release agent] Using a differential scanning calorimeter "Q-100" (TA Instruments Japan), 0.02 g of sample is weighed into an aluminum pan, heated to 200°C, and then cooled from 200°C to 0°C at a rate of 10°C / min. The sample is then heated at a rate of 10°C / min, and the calorific value is measured. The maximum endothermic peak temperature is taken as the melting point.

[0107] [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 values ​​of major and minor axes) of 500 particles in a scanning electron microscope (SEM) photograph and averaging these values ​​by number.

[0108] [Volume median particle size of toner (D 50 ) Measuring instrument: "Coulter Multisizer (registered trademark) III" (manufactured by Beckman Coulter, Inc.) Aperture diameter: 50 μm Analysis software: "Multisizer (registered trademark) III Version 3.51" (Beckman Coulter, Inc.) Electrolyte: "Isoton (registered trademark) II" (manufactured by Beckman Coulter, Inc.) Dispersion: Polyoxyethylene lauryl ether "Emulgen (registered trademark) 109P" (manufactured by Kao Corporation, HLB (Griffin) = 13.6) dissolved in the electrolyte to adjust the concentration to 5% by mass Dispersion conditions: 10 mg of the measurement sample was added to 5 mL of the dispersion, and the mixture was dispersed for 1 minute using an ultrasonic disperser (machine name: US-1 manufactured by SND Corporation, output: 80 W). 25 mL of electrolyte was then added, and the mixture was further dispersed for 1 minute using the ultrasonic disperser to prepare a sample dispersion. 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 found.

[0109] Resin manufacturing example 1 The alcohol component, carboxylic acid component other than adipic acid, esterification catalyst, and co-catalyst shown in Table 1 were placed in a 10-liter four-neck flask equipped with a thermometer, stainless steel stirring rod, dehydration tube, condenser, and nitrogen inlet tube. The mixture was heated to 235°C over 2 hours in a nitrogen atmosphere in a mantle heater. After confirming that the reaction rate had reached 95% or more at 235°C, the mixture was cooled to 180°C. Adipic acid was then added, and the mixture was heated to 220°C over 2 hours. After reacting at 220°C for 1 hour, the reaction was continued at 8 kPa until the softening point shown in Table 1 was reached, yielding an amorphous polyester resin (Resin AL1). Note that the "reaction rate" in this specification refers to the value calculated by dividing the amount of water produced by reaction (mol) by the theoretical amount of water produced (mol) × 100.

[0110] Resin manufacturing example 2 The alcohol component, carboxylic acid component other than dodecenyl succinic anhydride, esterification catalyst, and co-catalyst shown in Table 1 were placed in a 10-liter four-neck flask equipped with a thermometer, a stainless steel stirring rod, a dehydration tube, a condenser, and a nitrogen inlet tube, and the temperature was raised to 235°C over 2 hours in a nitrogen atmosphere in a mantle heater. After confirming that the reaction rate had reached 95% or more at 235°C, the mixture was cooled to 180°C. Dodecenyl succinic anhydride was then added, and the temperature was raised to 220°C over 2 hours. After reacting at 220°C for 1 hour, the reaction was continued at 8 kPa until the softening point shown in Table 1 was reached, yielding an amorphous polyester resin (Resin AL2).

[0111] Resin manufacturing example 3 The alcohol component, carboxylic acid components other than adipic acid and trimellitic anhydride, esterification catalyst, and co-catalyst shown in Table 1 were placed in a 10-liter four-neck flask equipped with a thermometer, a stainless steel stirring rod, a dehydration tube, a condenser, and a nitrogen inlet tube, and the temperature was raised to 235°C over 2 hours in a nitrogen atmosphere in a mantle heater. After confirming that the reaction rate had reached 95% or more at 235°C, the mixture was cooled to 180°C. Adipic acid and trimellitic anhydride were then added, and the temperature was raised to 220°C over 2 hours. After reacting at 220°C for 1 hour, the reaction was continued at 8 kPa until the softening point shown in Table 1 was reached, yielding an amorphous polyester resin (Resin AH1).

[0112] [Table 1]

[0113] Resin manufacturing example 4 The alcohol components and carboxylic acid components shown in Table 2 were placed in a 10-liter four-neck flask equipped with a thermometer, a stainless steel stirring rod, a dehydration tube, a condenser, and a nitrogen inlet tube, and the mixture was kept at 140°C for 1 hour in a nitrogen atmosphere in a mantle heater. The temperature was then increased from 140°C to 200°C at a rate of 10°C / hr, and the mixture was reacted at 200°C for 1 hour. An esterification catalyst was then added, and the reaction was continued at 200°C and 8 kPa until the softening point shown in Table 2 was reached, thereby obtaining crystalline polyester resins (resins C1 to C7).

[0114] [Table 2]

[0115] Examples 1 to 13 and Comparative Examples 1 to 5 100 parts by mass of the binder resin and amide compound shown in Table 3 were thoroughly mixed in a Henschel mixer with 1 part by mass of a negatively chargeable charge control agent "Bontron E-81" (manufactured by Orient Chemical Industry Co., Ltd.), 5 parts by mass of a colorant "Pigment Blue 15:3" (manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd., phthalocyanine blue), and 2 parts by mass of a release agent "HNP-9" (manufactured by Nippon Seiro Co., Ltd., paraffin wax, melting point: 75°C). The mixture was 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 at a roll rotation speed of 200 r / min and a heating temperature of 100°C inside the roll. The mixture was fed at a rate of 20 kg / h and had an average residence time of approximately 18 seconds. The resulting kneaded product was cooled, coarsely crushed, crushed in a jet mill, and classified to determine the volume median particle size (D 50 ) toner particles of 8 μm were obtained.

[0116] To 100 parts by mass of the obtained toner particles, 1 part by mass of hydrophobic silica "AEROSIL NAX 50" (manufactured by Nippon Aerosil Co., Ltd., hydrophobic treatment agent: HMDS, average particle diameter: approximately 30 nm) was added as an external additive, and the mixture was mixed using a Henschel mixer to obtain a toner.

[0117] Test example [Glossiness of printed matter after storage] (1) Measurement of the minimum fixing temperature The toner was loaded into a copy machine "AR-505" (manufactured by Sharp Corporation) with a modified fuser that enabled off-machine fusing, and an unfused image was obtained. The fuser was then adjusted to a total fusing pressure of 40 kgf (fusing speed: 390 mm / sec), and the temperature was raised in 5°C increments from 80°C to 240°C. A fusing test of the unfused image was then performed at each temperature. "UNICEF Cellophane" (Mitsubishi Pencil Co., Ltd., width: 18 mm, JIS Z-1522) was applied to the fixed image, and the image was passed through a fusing roller set at 30°C. The tape was then peeled off. The optical reflection density before and after tape application was measured using a reflection densitometer "RD-915" (manufactured by Macbeth Co., Ltd.). The temperature of the fusing roller at which the ratio (after peeling / before application) first exceeded 90% was defined as the minimum fusing temperature. The results are shown in Table 3. The paper used for the fusing test was CopyBond SF-70NA (75 g / m) manufactured by Sharp Corporation.2 )

[0118] (2) Gloss measurement The toner was installed in a copy machine "AR-505" (manufactured by Sharp Corporation) with a modified fuser that allows for external fusing, and the unfixed printed matter (printed area: 2 cm x 12 cm, toner adhesion amount: 0.3 mg / cm) was printed. 2 ) was obtained. The unfixed print was then fixed using a fixing machine (fixing speed 300 mm / sec) adjusted to a total fixing pressure of 40 kgf, with the fixing roll temperature set to the minimum fixing temperature + 20°C. The paper used for printing was coated paper "OK ​​Topcoat+" (Oji Paper Co., Ltd.). The resulting print was left at a temperature of 50°C for one week, after which the gloss was measured using a gloss meter "IG-330" (Horiba, Ltd.) with cardboard placed under the image and light irradiation conditions of 60°. The results are shown in Table 3. A higher value indicates higher gloss.

[0119] [Table 3]

[0120] From the above results, it can be seen that the toners of Examples 1 to 13 produce images with excellent glossiness, compared to Comparative Example 1, which is a toner containing an amide compound that does not contain a hydroxy group, Comparative Examples 2 and 3, which are toners that do not contain a specified amount of a hydroxy group-containing amide compound, and Comparative Examples 4 and 5, which are toners that do not contain ethylene glycol in the alcohol component of the crystalline polyester resin. Furthermore, in Comparative Examples 4 and 5, in which ethylene glycol was not used as the alcohol component of the crystalline polyester resin, there was almost no difference in glossiness depending on whether or not an aliphatic monocarboxylic acid compound was present. This shows that the gloss-improving effect of an aliphatic monocarboxylic acid compound is achieved when a crystalline polyester resin using ethylene glycol is included. [Industrial Applicability]

[0121] The electrostatic image developing toner containing the crystalline resin-containing composition for toner of the present invention is suitably used for developing latent images formed in electrostatic image developing methods, electrostatic recording methods, electrostatic printing methods, etc.

Claims

1. A crystalline resin-containing composition for toner, comprising a crystalline polyester resin, an amorphous polyester resin, and a hydroxy group-containing amide compound, wherein the crystalline polyester resin comprises a crystalline polyester resin C which is a polycondensate of an alcohol component containing 80 mol % or more of ethylene glycol and a carboxylic acid component, and the hydroxy group-containing amide compound is a compound represented by formula (I): R １ -CONH-X-NHCO-R ２ (I) (In the formula, R １ and R ２ are each independently a hydroxyalkyl group having from 12 to 22 carbon atoms, and X is a divalent hydrocarbon group having from 2 to 12 carbon atoms. Or formula (II): R ３ -.ONH-R ４ (-I) (In the formula, R ３ is a hydroxyalkyl group having 12 to 22 carbon atoms, and R ４ is a hydroxyalkyl group having 2 to 22 carbon atoms. and the content of the hydroxy group-containing amide compound is 0.5 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the total amount of the crystalline polyester resin and the amorphous polyester resin.

2. 2. The crystalline resin-containing composition for toner according to claim 1, wherein the carboxylic acid component of the crystalline polyester resin C contains an aliphatic monocarboxylic acid compound having 12 to 30 carbon atoms.

3. The amorphous polyester resin is represented by formula (III): 【Chemical 1】 (In the formula, OR ５ and R ５ O is an oxyalkylene group, and R ５ represents 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 more and 16 or less.

3. The crystalline resin-containing composition for toner according to claim 1, further comprising an amorphous polyester resin A which is a polycondensation product of an alcohol component containing an alkylene oxide adduct of bisphenol A represented by the formula:

4. 3. The crystalline resin-containing composition for toner according to claim 1, wherein the content of the crystalline polyester resin C is 5% by mass or more and 25% by mass or less of the total amount of the crystalline polyester resin and the amorphous polyester resin.

5. 3. A toner for developing electrostatic images, comprising the crystalline resin-containing composition for toners according to claim 1 or 2.

Images