Method for producing a crystalline resin-containing composition for toner

Abstract

The present invention relates to a method for producing a crystalline resin-containing composition for toner that has excellent bending resistance for printed materials, and a method for producing toner for electrostatic image development. [Solution] A method for producing a crystalline resin-containing composition for toner, comprising a crystalline polyester resin, an amorphous polyester resin containing amorphous polyester resin A, and a specific hydroxyl group-containing amide compound, wherein the content of the hydroxyl group-containing amide compound is 0.4 parts by mass or more and 13 parts by mass or less with respect to 100 parts by mass of the total amount of the crystalline polyester resin and the amorphous polyester resin, and comprising step Ia of mixing the amorphous polyester resin A and the hydroxyl group-containing amide compound at a temperature above the melting point of the hydroxyl group-containing amide compound, and step IIa of mixing the mixture obtained in step Ia with the crystalline polyester resin, and a method for producing toner for electrostatic image developing.

Description

Technical Field

[0001] The present invention relates to a method for producing a crystalline resin-containing composition for 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 method for producing an electrostatic charge image developing toner.

Background Art

[0002] From the viewpoints of storage stability, durability, chargeability, etc., using an amide compound as a toner raw material together with a crystalline polyester resin and an amorphous polyester resin has been studied (see Patent Documents 1 to 4).

Prior Art Documents

Patent Documents

[0003] [

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0004] On the other hand, in recent years, printing using toner has been increasingly used in industrial printing and commercial printing. In such printing, there are many applications for high print rate images such as photos, and the image parts are often used after being folded. Therefore, it is required to improve the fold resistance of printed matter, but the conventional resins for toner are not sufficient.

[0005] The present invention relates to a method for producing a crystalline resin-containing composition for toner having excellent fold resistance of printed matter and a method for producing an electrostatic charge image developing toner.

Means for Solving the Problems

[0006] The present invention relates to 〔1〕 A method for producing a crystalline resin-containing composition for toner, which contains a crystalline polyester resin, an amorphous polyester resin containing an amorphous polyester resin A, and a hydroxy group-containing amide compound, where the hydroxy group-containing amide compound is of formula (I): R 1 -CONH-X-NHCO-R 2 (I) (wherein R 1 and R 2 are each independently a hydroxyalkyl group having 12 to 22 carbon atoms, and X is a divalent hydrocarbon group having 2 to 12 carbon atoms) or formula (II): R 3 -CONH-R 4 (II) (wherein 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 is a compound represented by where the content of the hydroxy group-containing amide compound is 0.4 parts by mass or more and 13 parts by mass or less based on 100 parts by mass of the total amount of the crystalline polyester resin and the amorphous polyester resin, and includes a step Ia of mixing the amorphous polyester resin A and the hydroxy group-containing amide compound at a temperature not lower than the melting point of the hydroxy group-containing amide compound, and a step IIa of mixing the mixture obtained in the step Ia and the crystalline polyester resin, A method for producing a crystalline resin-containing composition for toner, and 〔2〕 A method for producing an electrostatic charge image developing toner, which contains a crystalline polyester resin, an amorphous polyester resin containing an amorphous polyester resin A, and a hydroxy group-containing amide compound, where the hydroxy group-containing amide compound is of formula (I): R 1 -CONH-X-NHCO-R 2 (I) (In the formula, R 1 and R 2 Each of these is independently a hydroxyalkyl group having 12 to 22 carbon atoms, and X is a divalent hydrocarbon group having 2 to 12 carbon atoms. Or formula (II): R 3 -CONH-R 4 (II) (In the formula, R 3 R is a hydroxyalkyl group having 12 to 22 carbon atoms. 4 (This is a hydroxyalkyl group having 2 to 22 carbon atoms.) It is a compound represented by the following: The content of the hydroxyl group-containing amide compound is 0.4 parts by mass or more and 13 parts by mass or less, based on 100 parts by mass of the total amount of the crystalline polyester resin and the amorphous polyester resin. The process includes step Ib of mixing the amorphous polyester resin A and the hydroxyl group-containing amide compound at a temperature above the melting point of the hydroxyl group-containing amide compound, step IIb of melt-kneading at least the mixture obtained in step Ib with the crystalline polyester resin, and step IIIb of grinding the kneaded product obtained in step IIb. Method for manufacturing toner for electrostatic image development Regarding. [Effects of the Invention]

[0007] The method of the present invention makes it possible to obtain a crystalline resin-containing toner composition with excellent bending resistance for printed materials and a toner for electrostatic image development. [Modes for carrying out the invention]

[0008] The present invention relates to a method for producing a crystalline resin-containing composition for toner containing a crystalline polyester resin, an amorphous polyester resin, and a predetermined hydroxyl group-containing amide compound, by a method comprising the step of mixing the amorphous polyester resin and the hydroxyl group-containing amide compound at a temperature above the melting point of the hydroxyl group-containing amide compound. The detailed reason why the composition obtained by the method of the present invention has excellent bending resistance for printed materials is not clear, but it is presumed to be as follows.

[0009] Even when hydroxy fatty acid amides, which act as nucleating agents, are added during melt-kneading as in conventional methods and mixed with crystalline and amorphous polyester resins, the dispersion of the nucleating agent in the amorphous polyester resin is poor, making it difficult for nuclei to form in the crystalline polyester resin. As a result, crystal growth proceeds with fewer nuclei, leading to the formation of coarse domains in the crystalline polyester, which is thought to result in poor bending resistance of printed materials. However, in this invention, by mixing an amorphous polyester resin with a hydroxyl group-containing amide compound that acts as a crystal nucleating agent at a temperature above the melting point of the hydroxyl group-containing amide compound, the crystal nucleating agent melts, and the mixing efficiency of the crystal nucleating agent and amorphous polyester can be greatly improved. As a result, the dispersion of the crystal nucleating agent in the amorphous polyester resin becomes better. Consequently, the number of crystal growth initiation points increases, and the domains of the crystalline polyester resin, which are weak against bending, become smaller, which is thought to improve the bending resistance of the printed material.

[0010] The crystalline or amorphous nature of a resin is determined by its crystallinity index. The crystallinity index is defined as the ratio of the softening point of the resin to the maximum endothermic peak temperature (softening point (°C) / maximum endothermic peak temperature (°C)) in the measurement method described in the examples below. A crystalline resin is one in which the crystallinity index is 0.6 or higher, preferably 0.7 or higher, more preferably 0.9 or higher, and 1.4 or lower, preferably 1.2 or lower, more preferably 1.1 or lower. An amorphous resin is one in which no endothermic peak is observed, or if observed, the crystallinity index is less than 0.6 or greater than 1.4. The crystallinity of a resin can be adjusted by the type and ratio of raw material monomers, as well as the manufacturing conditions (e.g., reaction temperature, reaction time, cooling rate). The maximum endothermic peak temperature refers to the temperature of the peak with the largest peak area among the observed endothermic peaks. In crystalline resins, the maximum endothermic peak temperature is defined as the melting point.

[0011] In the present invention, the crystalline resin-containing composition for toner is Step Ia involves mixing amorphous polyester resin A and a hydroxyl group-containing amide compound at a temperature above the melting point of the hydroxyl group-containing amide compound, and Step IIa involves mixing the mixture obtained in step Ia with the crystalline polyester resin. It is manufactured by a method that includes [the specified element].

[0012] In step Ia, the amorphous polyester resin A to be mixed with the hydroxyl group-containing amide compound is preferably a polycondensate of an alcohol component containing an alkylene oxide adduct of bisphenol A and a carboxylic acid component.

[0013] The alkylene oxide adduct of bisphenol A is given by formula (III):

[0014] [ka]

[0015] (In the formula, OR 5 and R 5 O is an oxyalkylene group, R 5 (where x is an ethylene group and / or a propylene group, x and y represent the average number of moles of alkylene oxide added, each being a positive number, and the sum of x and y is 1 or greater, preferably 1.5 or greater, and 16 or less, preferably 8 or less, more preferably 6 or less, and even more preferably 4 or less.) Compounds represented by are preferred, including ethylene oxide adducts of bisphenol A and propylene oxide adducts of bisphenol A.

[0016] The content of the bisphenol A alkylene oxide adduct represented by formula (III) is preferably 80 mol% or more, more preferably 90 mol% or more, even more preferably 95 mol% or more, and 100 mol% or less, in the alcohol component, from the viewpoint of low-temperature fixability and hydrophilicity.

[0017] 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, as well as trivalent or higher alcohols such as bisphenol A, hydrogenated bisphenol A, and glycerin.

[0018] From the viewpoint of heat resistance and storage properties, it is preferable that the carboxylic acid component contains an aromatic dicarboxylic acid compound.

[0019] Examples of aromatic dicarboxylic acid compounds include phthalic acid, isophthalic acid, terephthalic acid, anhydrides of these acids, and alkyl esters of these acids with 1 to 3 carbon atoms. Among these, terephthalic acid is preferred.

[0020] The content of aromatic dicarboxylic acid compounds is preferably 25 mol% or more, more preferably 30 mol% or more, even more preferably 35 mol% or more, and preferably 95 mol% or less, and more preferably 90 mol% or less, of the carboxylic acid component.

[0021] Other carboxylic acid components include aliphatic dicarboxylic acid compounds and trivalent or higher carboxylic acid compounds.

[0022] Examples of aliphatic dicarboxylic acid compounds include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid and adipic acid which may be substituted with hydrocarbon groups, anhydrides of these acids, and alkyl esters of these acids with an alkyl group having 1 to 3 carbon atoms.

[0023] Examples of carboxylic acid compounds with a valency of 3 or higher include carboxylic acid compounds with a valency of 3 or higher such as 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalentricarboxylic acid, and pyromellitic acid, as well as anhydrides of these acids and alkyl esters of these acids with an alkyl group having 1 to 3 carbon atoms.

[0024] The alcohol component may contain a monohydric alcohol, and the carboxylic acid component may contain a monohydric carboxylic acid compound, as appropriate.

[0025] In this specification, macromonomers and hydroxycarboxylic acids are not included in the alcohol and carboxylic acid components.

[0026] The equivalent ratio (COOH group / OH group) of the carboxyl group of the carboxylic acid component to the hydroxyl group of the alcohol component is preferably 0.6 or higher, more preferably 0.7 or higher, even more preferably 0.8 or higher, and preferably 1.3 or lower, more preferably 1.2 or lower.

[0027] Amorphous polyester resin A can be produced, for example, by polycondensing an alcohol component and a carboxylic acid component in an inert gas atmosphere, preferably in the presence of an esterification catalyst, and optionally in the presence of a co-catalyst, polymerization inhibitor, etc., at a temperature preferably 130°C or higher, more preferably 170°C or higher, and preferably 250°C or lower, more preferably 240°C or lower.

[0028] Examples of esterification catalysts include tin compounds such as dibutyltin oxide and tin(II) 2-ethylhexanoate, and titanium compounds such as titanium diisopropoxybis(triethanolamine) and titanium dihydroxybis(triethanolamine). The amount of esterification catalyst used is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and preferably 1.5 parts by mass or less, and more preferably 1 part by mass or less, per 100 parts by mass of the total amount of alcohol and carboxylic acid components. Examples of co-catalysts for the esterification catalyst include gallic acid. The amount of co-catalyst used is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and preferably 0.5 parts by mass or less, and more preferably 0.1 parts by mass or less, per 100 parts by mass of the total amount of alcohol and carboxylic acid components. Examples of polymerization inhibitors include tert-butylcatechol. The amount of polymerization inhibitor used is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and preferably 0.5 parts by mass or less, and more preferably 0.1 parts by mass or less, based on 100 parts by mass of the total amount of alcohol and carboxylic acid components.

[0029] In this invention, the polyester resin may be a polyester resin that has been modified to such an extent that its properties are not substantially impaired. Examples of modified polyester resins include polyester resins that have been grafted or blocked with phenol, urethane, epoxy, etc., by methods described in Japanese Patent Publication No. 11-133668, Japanese Patent Publication No. 10-239903, Japanese Patent Publication No. 8-20636, etc. Among modified polyester resins, urethane-modified polyester resins obtained by urethane elongation of polyester resin with a polyisocyanate compound are preferred.

[0030] The content of amorphous polyester resin A is preferably 10% by mass or more, more preferably 50% by mass or more, even more preferably 70% by mass or more, and preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less.

[0031] The softening point of amorphous polyester resin A is preferably 70°C or higher, more preferably 80°C or higher, and even more preferably 90°C or higher, from the viewpoint of electrostatic stability, and preferably 170°C or lower, more preferably 160°C or lower, and even more preferably 155°C or lower, from the viewpoint of low-temperature fixability.

[0032] The glass transition temperature of amorphous polyester resin A is preferably 40°C or higher, more preferably 43°C or higher, from the viewpoint of storage properties, and preferably 60°C or lower, more preferably 56°C or lower, from the viewpoint of electrostatic stability.

[0033] Hydroxyl group-containing amide compounds are given by formula (I): R 1 -CONH-X-NHCO-R 2 (I) (In the formula, R 1 and R 2 Each of these is independently a hydroxyalkyl group having 12 to 22 carbon atoms, and X is a divalent hydrocarbon group having 2 to 12 carbon atoms. Or formula (II): R 3 -CONH-R 4 (II) (In the formula, R 3 R is a hydroxyalkyl group having 12 to 22 carbon atoms. 4 (This is a hydroxyalkyl group having 2 to 22 carbon atoms.) The compound is represented by [formula]. The crystalline resin-containing composition for toner obtained by the method of the present invention may contain either the compound represented by formula (I) or the compound represented by formula (II) as a hydroxyl group-containing amide compound, or it may contain both the compound represented by formula (I) and the compound represented by formula (II).

[0034] R 1 , R 2 and R 3 The number of carbon atoms in each hydroxyalkyl group is preferably 13 or more, more preferably 15 or more, and preferably 21 or less, more preferably 19 or less.

[0035] R 4 The number of carbon atoms in the hydroxyalkyl group is preferably 10 or less, more preferably 6 or less.

[0036] R 1 ~R 4 The alkyl group in this combination may be branched or linear, but it is preferably linear.

[0037] Examples of divalent hydrocarbon groups in X include divalent aliphatic hydrocarbon groups and divalent aromatic hydrocarbon groups.

[0038] Examples of divalent aliphatic hydrocarbon groups include ethylene, trimethylene, tetramethylene, and hexamethylene groups.

[0039] Examples of divalent aromatic hydrocarbon groups include phenylene groups, m-xylylene groups, and p-xylylene groups.

[0040] The number of carbon atoms in the divalent hydrocarbon group of X is preferably 10 or less, more preferably 8 or less, and even more preferably 6 or less.

[0041] Specific examples of hydroxyl group-containing amide compounds represented by formula (I) include 12-hydroxystearate ethylenebisamide, 12-hydroxystearate hexamethylenebisamide, 12-hydroxystearate xylylenebisamide, and 12-hydroxypalmitate ethylenebisamide.

[0042] Specific examples of hydroxyl group-containing amide compounds represented by formula (II) include hydroxyethyl 12-hydroxystearate and hydroxyethyl 12-hydroxypalmitate.

[0043] The melting point of the hydroxyl 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 glossiness, and 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.

[0044] In step Ia, the temperature at which the amorphous polyester resin A and the hydroxyl group-containing amide compound are mixed is above the melting point of the hydroxyl group-containing amide compound, preferably at least 10°C higher than the melting point (Mp) of the hydroxyl group-containing amide compound ((Mp + 10°C) or higher), and more preferably at least (Mp + 20°C).

[0045] Furthermore, the temperature at which the amorphous polyester resin A and the hydroxyl group-containing amide compound are mixed is preferably 10°C or more higher than the softening point (Tm) of the amorphous polyester resin A ((Tm+10°C) or higher), more preferably (Tm+30°C) or higher, more preferably (Tm+40°C) or higher, and even more preferably (Tm+50°C) or higher.

[0046] On the other hand, the temperature at which the amorphous polyester resin A and the hydroxyl group-containing amide compound are mixed is preferably 260°C or lower, more preferably 230°C or lower, and even more preferably 220°C or lower, from the viewpoint of the bending resistance of the printed material.

[0047] In step Ia, the method for mixing amorphous polyester resin A and hydroxyl group-containing amide compound may be to mix amorphous polyester resin A heated to a predetermined temperature with the hydroxyl group-containing amide compound. However, in the present invention, it is preferable to add and mix the hydroxyl group-containing amide compound at a temperature above the melting point of the hydroxyl group-containing amide compound after the polycondensation reaction of the raw material monomers of amorphous polyester resin A. As in the latter method, by adding the hydroxyl group-containing amide compound at a predetermined temperature before returning the temperature in the reaction vessel to room temperature after the synthesis of amorphous polyester resin A, the two can be mixed efficiently.

[0048] As the crystalline polyester resin used in step IIa, a polycondensate of an alcohol component containing an aliphatic diol and an aliphatic dicarboxylic acid compound carboxylic acid component is preferred.

[0049] Examples of aliphatic diols include ethylene glycol, 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. Among these, ethylene glycol is preferred from the viewpoint of low-temperature fixability.

[0050] The aliphatic diol has 2 or more carbon atoms, preferably 14 or less, more preferably 10 or less, even more preferably 6 or less, even more preferably 4 or less, and even more preferably 3 or less.

[0051] From the viewpoint of low-temperature fixability and hydrophilicity, the aliphatic diol content is preferably 80 mol% or more, more preferably 90 mol% or more, even more preferably 95 mol% or more, and 100 mol% or less, in the alcohol component.

[0052] Other alcohol components include alkylene oxide adducts of bisphenol A, aromatic diols such as bisphenol A, hydrogenated bisphenol A, sorbitol, pentaerythritol, glycerin, trivalent or higher alcohols such as trimethylolpropane, etc.

[0053] Examples of aliphatic dicarboxylic acid compounds include succinic acid (4 carbon atoms), fumaric acid (4 carbon atoms), adipic acid (6 carbon atoms), suberic acid (8 carbon atoms), azelaic acid (9 carbon atoms), sebacic acid (10 carbon atoms), dodecanediic acid (12 carbon atoms), tetradecanediic acid (14 carbon atoms), anhydrides of these acids, and alkyl esters of these acids with 1 to 3 carbon atoms.

[0054] From the viewpoint of heat-resistant storage, 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 30 or less, more preferably 22 or less, more preferably 18 or less, and still more preferably 16 or less. Here, the carbon number of the alkyl group when the aliphatic dicarboxylic acid compound is an alkyl ester is not included in the above carbon number.

[0055] From the viewpoint of hydrophobicity, the content of aliphatic dicarboxylic acid compounds is preferably 50 mol% or more, more preferably 60 mol% or more, even more preferably 70 mol% or more, even more preferably 80 mol% or more, and 100 mol% or less, in the carboxylic acid component. If the carboxylic acid component includes aliphatic monocarboxylic acid compounds, the content is preferably 98 mol% or less, more preferably 97 mol% or less.

[0056] From the viewpoint of glossiness, it is preferable that the carboxylic acid component further contains an aliphatic monocarboxylic acid compound.

[0057] Examples of 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.

[0058] From the viewpoint of glossiness, the carbon number of the aliphatic monocarboxylic acid compound is preferably 12 or more, more preferably 18 or more, and even more preferably 20 or more. 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. Here, the carbon number of the alkyl group when the aliphatic monocarboxylic acid compound is an alkyl ester is not included in the above carbon number.

[0059] When the carboxylic acid component contains an aliphatic monocarboxylic acid compound, the content of the aliphatic monocarboxylic acid compound is preferably 2 mol% or more, more preferably 3 mol% or more, and preferably 15 mol% or less, and more preferably 10 mol% or less, of the carboxylic acid component.

[0060] 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.

[0061] The alcohol component may contain a monohydric alcohol, and the carboxylic acid component may contain a monohydric carboxylic acid compound, as appropriate.

[0062] The equivalent ratio of the carboxyl group of the carboxylic acid component to the hydroxyl group of the alcohol component (COOH group / OH group) is preferably 0.7 or higher, more preferably 0.8 or higher, from the viewpoint of electrostatic stability, and preferably 1.3 or lower, more preferably 1.2 or lower, from the viewpoint of low-temperature fixability.

[0063] The polycondensation reaction conditions between the alcohol component and the carboxylic acid component of the crystalline polyester resin are the same as those for the amorphous polyester resin A, except that the preferred reaction temperature is preferably 120°C or higher, more preferably 180°C or higher, and preferably 230°C or lower, and more preferably 220°C or lower.

[0064] The softening point of the crystalline polyester resin 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 preferably 120°C or lower, more preferably 110°C or lower, from the viewpoint of low-temperature fixation.

[0065] The melting point of the crystalline polyester resin 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, and preferably 115°C or lower, more preferably 105°C or lower, from the viewpoint of low-temperature fixation.

[0066] The weight-average molecular weight of the crystalline polyester resin is preferably 10,000 or more, more preferably 15,000 or more, from the viewpoint of heat-resistant storage, and preferably 30,000 or less, more preferably 25,000 or less, from the viewpoint of low-temperature fixation.

[0067] In step IIa, from the viewpoint of glossiness, it is preferable to use amorphous polyester resin B having a different softening point from amorphous polyester resin A. The difference in softening points between amorphous polyester resin B and amorphous polyester resin A is preferably 10°C or more, more preferably 15°C or more, and preferably 60°C or less, more preferably 50°C or less.

[0068] In the amorphous polyester resin used in the present invention, the softening point of the resin with the lower softening point (resin L) is preferably 70°C or higher, more preferably 85°C or higher, and even more preferably 100°C or higher, from the viewpoint of electrostatic stability, and preferably 130°C or lower, more preferably 125°C or lower, and even more preferably 120°C or lower, from the viewpoint of low-temperature fixability.

[0069] The weight-average molecular weight of resin L is preferably 3,000 or more, more preferably 4,000 or more, and preferably 9,000 or less, more preferably 8,000 or less.

[0070] Furthermore, the softening point of the resin with the higher softening point (resin H) is preferably 100°C or higher, more preferably 110°C or higher, from the viewpoint of fixing width, and 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 fixing properties.

[0071] The weight-average molecular weight of resin H is preferably 50,000 or more, more preferably 100,000 or more, and preferably 200,000 or less, more preferably 150,000 or less.

[0072] The mass ratio of resin L to resin H (resin L / resin H) is preferably 10 / 90 or more, more preferably 50 / 50 or more, even more preferably 70 / 30 or more, and preferably 90 / 10 or less, more preferably 85 / 15 or less, and even more preferably 80 / 20 or less.

[0073] Even if amorphous polyester resin A is resin L and amorphous polyester resin B is resin H, or amorphous polyester resin A is resin H and amorphous polyester resin B is resin L, in the present invention, the former is preferred from the viewpoint of low-temperature fixation.

[0074] The glass transition temperature of amorphous polyester resin B is preferably 40°C or higher, more preferably 50°C or higher, from the viewpoint of storage properties, and preferably 80°C or lower, more preferably 70°C or lower, from the viewpoint of electrostatic stability.

[0075] The raw material monomers (alcohol component and carboxylic acid component) and manufacturing method of amorphous polyester resin B are the same as those for amorphous polyester resin A.

[0076] The content of amorphous polyester resin B is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, and preferably 90% by mass or less, more preferably 50% by mass or less, and even more preferably 30% by mass or less.

[0077] In step IIa, the method of mixing the mixture obtained in step Ia with the crystalline polyester resin and, if necessary, the amorphous polyester resin B is not particularly limited and can be carried out as appropriate using a mixer.

[0078] In a crystalline resin-containing composition for toner, the content of the hydroxyl group-containing amide compound is 0.4 parts by mass or more, 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, even more preferably 0.8 parts by mass or more, and 13 parts by mass or less, preferably 12 parts by mass or less, more preferably 8 parts by mass or less, even more preferably 4 parts by mass or less, and even more preferably 2 parts by mass or less, based on 100 parts by mass of the total amount of crystalline polyester resin and amorphous polyester resin.

[0079] The mass ratio of the hydroxyl group-containing amide compound to the crystalline polyester resin (hydroxyl group-containing amide compound / crystalline polyester resin) is preferably 1 / 99 or more, more preferably 5 / 95 or more, even more preferably 6 / 94 or more, and 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.

[0080] From the viewpoint of low-temperature fixability, the content of crystalline 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 preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 17% by mass or less, based on the total amount of crystalline polyester resin and amorphous polyester resin.

[0081] The content of 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 preferably 95% by mass or less, more preferably 92% by mass or less, and even more preferably 90% by mass or less, based on the total amount of crystalline polyester resin and amorphous polyester resin.

[0082] The mass ratio of crystalline polyester resin to 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 preferably 25 / 75 or less, more preferably 20 / 80 or less, and even more preferably 17 / 83 or less.

[0083] The total content of crystalline polyester resin, amorphous polyester resin, and hydroxyl group-containing amide compound in the toner crystalline resin-containing composition is preferably 90% by mass or more, more preferably 95% by mass or more, even more preferably 99% by mass or more, and 100% by mass or less.

[0084] A toner for electrostatic image development can be obtained using the crystalline resin-containing composition for toner obtained by the method of the present invention. In the toner obtained by the method of the present invention, the crystalline polyester resin and amorphous polyester resin in the crystalline resin-containing composition are contained as binder resins.

[0085] The total content of crystalline polyester resin and 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, even more preferably 95% by mass or more, and 100% by mass or less.

[0086] 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.

[0087] The binder resin content 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, and even more preferably 95% by mass or less.

[0088] In addition to the crystalline resin-containing composition, the toner for electrostatic image development may also contain additives such as colorants, release agents, charge control agents, magnetic powders, flowability enhancers, conductivity modifiers, reinforcing fillers such as fibrous materials, antioxidants, and cleaning properties enhancers.

[0089] As colorants, dyes, pigments, magnetic materials, etc., used as colorants for toners can be used. Examples include carbon black, phthalocyanine blue, permanent brown FG, brilliant first 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 this invention, the toner may be either black toner or color toner.

[0090] From the viewpoint of improving the image density of the toner and its low-temperature fixability, the amount of 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 10 parts by mass or less, per 100 parts by mass of the binder resin.

[0091] Examples of mold release agents include hydrocarbon waxes and their oxides, such as polypropylene wax, polyethylene wax, ethylene propylene copolymer wax, microcrystalline wax, paraffin wax, and Fischer-Tropsch wax; ester waxes such as carnauba wax, montane wax and their deoxidizing waxes, and fatty acid ester waxes; and fatty acid amides, fatty acids, higher alcohols, fatty acid metal salts, etc., which can be used individually or in combination of two or more.

[0092] The melting point of the release agent is preferably 60°C or higher, more preferably 70°C or higher, from the viewpoint of toner transferability, and preferably 160°C or lower, more preferably 140°C or lower, even more preferably 120°C or lower, and even more preferably 110°C or lower, from the viewpoint of low-temperature fixation.

[0093] The release agent content is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, even more preferably 1.5 parts by mass or more, and 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, per 100 parts by mass of binder resin, from the viewpoint of low-temperature fixation and offset resistance of the toner and dispersibility in the binder resin.

[0094] The charge control agent is not particularly limited and may contain either a positively charged charge control agent or a negatively charged charge control agent.

[0095] Positively charged charge control agents include nigrosine dyes, such as "Nigrosine Base EX," "Oil Black BS," "Oil Black SO," "Bontron N-01," "Bontron N-04," "Bontron N-07," "Bontron N-09," and "Bontron N-11" (all manufactured by Orient Chemical Industries, Ltd.); triphenylmethane-based dyes containing tertiary amines as side chains; quaternary ammonium salt compounds, such as "Bontron P-51" (manufactured by Orient Chemical Industries, Ltd.), cetyltrimethylammonium bromide, and "COPY CHARGE PX." Examples include VP435 (manufactured by Clariant), polyamine resins such as AFP-B (manufactured by Orient Chemical Industries, Ltd.), imidazole derivatives such as PLZ-2001 and PLZ-8001 (both manufactured by Shikoku Chemicals, Ltd.), and styrene-acrylic resins such as FCA-701PT and FCA-201-PS (manufactured by Fujikura Chemicals, Ltd.).

[0096] Furthermore, as negative charge control agents, metal-containing azo dyes, such as "Barifast Black 3804," "Bontron S-31," "Bontron S-32," "Bontron S-34," and "Bontron S-36" (all manufactured by Orient Chemical Industries, Ltd.), "Eisenspiron Black TRH," and "T-77" (manufactured by Hodogaya Chemical Co., Ltd.); metal compounds of benzyl acid compounds, such as "LR-147" and "LR-297" (both manufactured by Nippon Carlit Co., Ltd.); metal compounds of salicylic acid compounds, such as "Bontron E-81," "Bontron E-84," "Bontron E-88," and "Bontron E-304" (all manufactured by Orient Chemical Industries, Ltd.), and "TN-105" (manufactured by Hodogaya Chemical Co., Ltd.); copper phthalocyanine dyes; and quaternary ammonium salts, such as "COPY CHARGE NX" Examples include VP434 (manufactured by Clariant), nitroimidazole derivatives, organometallic compounds, etc.

[0097] From the viewpoint of the charge stability of the toner, the content of the charge control agent is preferably 0.01 parts by mass or more, more preferably 0.2 parts by mass or more, and preferably 10 parts by mass or less, more preferably 5 parts by mass or less, even more preferably 3 parts by mass or less, and even more preferably 2 parts by mass or less, per 100 parts by mass of the binder resin.

[0098] The toner may be obtained by any known method such as melt-kneading, emulsification-coagulation, or polymerization, and may be either pulverized toner or polymerized toner. However, it is preferable that the toner is pulverized toner obtained by a process that includes melt-kneading raw materials such as a crystalline resin-containing composition, a colorant, a mold release agent, and a charge control agent, and a process that includes pulverizing the resulting mixture, and further classifying it as appropriate.

[0099] When manufacturing the toner, the crystalline resin-containing composition obtained by the method of the present invention may be mixed with a colorant or the like beforehand, or the mixture obtained in step Ia and the crystalline polyester resin may be used directly or mixed with other raw materials.

[0100] Accordingly, the present invention further provides a method for producing a toner for electrostatic image development, comprising an amorphous polyester resin containing the crystalline polyester resin and amorphous polyester resin A, and a predetermined amount of the hydroxyl group-containing amide compound, The process includes step Ib of mixing the amorphous polyester resin A and the hydroxyl group-containing amide compound at a temperature above the melting point of the hydroxyl group-containing amide compound, step IIb of melt-kneading at least the mixture obtained in step Ib with the crystalline polyester resin, and step IIIb of grinding the kneaded product obtained in step IIb. This invention provides a method for manufacturing toner for electrostatic image development.

[0101] Step Ib is the same as step Ia, and preferably step Ib is a step in which, after the polycondensation reaction of the raw material monomers of amorphous polyester resin A, a hydroxyl group-containing amide compound is added and mixed at a temperature above the melting point of the hydroxyl group-containing amide compound. The mixture obtained in step Ia and the mixture obtained in step Ib are synonymous.

[0102] It is preferable that amorphous polyester resin B, colorants, charge control agents, release agents, etc., be melt-kneaded together with the crystalline polyester resin in step IIb.

[0103] In step IIb, the raw materials to be melted and kneaded may be kneaded all at once or in portions, but it is preferable to mix them beforehand in a mixer such as a Henschel mixer or ball mill before supplying them to the kneader.

[0104] For melt mixing, known mixing machines such as closed-type kneaders, single-screw or twin-screw extruders, and open-roll type mixers can be used.

[0105] The melt-mixing temperature is not particularly limited as long as it is the temperature at which the resin melts and the raw materials mix together.

[0106] After step IIb, the resulting mixture is cooled appropriately until it reaches a hardness suitable for pulverization, and then subjected to the subsequent step IIIb. Here, cooling refers to cooling the mixture to 0°C to 50°C, or to a temperature below the glass transition temperature of the binder resin in the mixture.

[0107] In step IIIb, the kneaded material may be ground all at once to the desired particle size, or ground in stages. However, from the viewpoint of efficient and more uniform grinding, it is preferable to perform the grinding in two stages: coarse grinding and fine grinding.

[0108] Examples of grinders used for coarse grinding include hammer mills, cutter mills, atomizers, and Rotoplexes.

[0109] Examples of grinders used for fine grinding include counter-jet mills, fluidized bed jet mills, impact plate jet mills, and other types of jet mills, as well as mechanical mills.

[0110] The degree of fine grinding is preferably adjusted as appropriate according to the desired particle size of the toner particles.

[0111] After step IIIb, a classification step (step IVb) is performed as needed.

[0112] Classifiers used for classification include air-flow classifiers, inertial classifiers, and sieve classifiers. During the classification process, any pulverized material that is removed due to insufficient pulverization may be subjected to the pulverization process again, and the pulverization process (process IIIb) and the classification process (process IVb) may be repeated as needed.

[0113] In the present invention, from the viewpoint of further improving transferability, it is preferable to perform a step of mixing the obtained toner particles with an external additive after the grinding step or classification step.

[0114] Examples of external additives include inorganic fine particles such as silica, alumina, titania, zirconia, tin oxide, and zinc oxide, and organic fine particles such as melamine resin fine particles and polytetrafluoroethylene resin fine particles. Two or more types may be used in combination. Among these, silica is preferred, and from the viewpoint of toner transferability, hydrophobic silica that has been hydrophobicized is more preferred.

[0115] Examples of hydrophobic agents used to hydrophobize the surface of silica particles include hexamethyldisilazane (HMDS), dimethyldichlorosilane (DMDS), cyclic silazane, silicone oil, aminosilane, octyltriethoxysilane (OTES), and methyltriethoxysilane.

[0116] The average particle size of the external additive is preferably 10 nm or more, more preferably 15 nm or more, and preferably 250 nm or less, more preferably 200 nm or less, and even more preferably 90 nm or less, from the viewpoint of the toner's chargeability, fluidity, and transferability.

[0117] External additive treatment, which involves mixing toner particles with external additives, can be carried out according to conventional methods, and a mixer such as a Henschel mixer can be used.

[0118] From the viewpoint of the toner's electrostatic properties, fluidity, and transferability, the amount of external additive used is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, even more preferably 0.3 parts by mass or more, and preferably 5 parts by mass or less, and more preferably 3 parts by mass or less, per 100 parts by mass of toner particles before treatment with the external additive.

[0119] The volume median particle size (D) of the toner obtained by the present invention 50 The volume median particle size (D) is preferably 3 μm or more, more preferably 4 μm or more, and preferably 15 μm or less, more preferably 10 μm or less. 50) refers to the particle size at which the cumulative volume frequency calculated using volume fractions accounts for 50% when calculated from the smallest particle size. Furthermore, when 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.

[0120] The toner obtained by the method of the present invention can be used as a one-component developing toner, or mixed with a carrier to form a two-component developing agent. [Examples]

[0121] The present invention will be specifically described below with reference to examples, but the present invention is not limited in any way by these examples. The physical properties of resins, etc., can be measured by the following methods.

[0122] [Softening point of resins and mixtures of resins and amide compounds] Using a flow tester "CFT-500D" (manufactured by Shimadzu Corporation), 1 g of sample is heated at a heating rate of 6°C / min while a load of 1.96 MPa is applied by a plunger, and the sample is extruded from a nozzle with a diameter of 1 mm and a length of 1 mm. The amount of plunger descent of the flow tester is plotted against temperature, and the temperature at which half of the sample has flowed out is defined as the softening point.

[0123] [Maximum endothermic peak temperature of resins, amide compounds, and mixtures of resins and amide compounds] Using a differential scanning calorimeter "Q-100" (manufactured by T.A. Instruments Japan Co., Ltd.), 0.01 to 0.02 g of the sample is weighed into an aluminum pan, cooled from room temperature (25°C) at a rate of 10°C / min to 0°C, and maintained at 0°C for 1 minute. Then, measurements are taken at a rate of 10°C / min. Among the observed endothermic peaks, the temperature of the peak with the largest peak area is defined as the maximum endothermic peak temperature. For crystalline resins and amide compounds, the maximum endothermic peak temperature is defined as the melting point.

[0124] [Glass transition temperatures of resins and mixtures of resins and amide compounds] Using a differential scanning calorimeter "Q-100" (manufactured by T.A. Instruments Japan Co., Ltd.), 0.01 to 0.02 g of the sample is weighed into an aluminum pan and heated from room temperature (20°C) to 200°C at a heating rate of 10°C / min, and then cooled to 0°C at a cooling rate of 10°C / min. Next, the sample is heated at a heating rate of 10°C / min and the endothermic peak is measured. The temperature at the intersection of the extension of the baseline below the maximum endothermic peak temperature and the tangent line showing the maximum slope from the rising part of the peak to the peak apex is defined as the glass transition temperature.

[0125] [Weight-average molecular weight of resins and mixtures of resins and amide compounds] The molecular weight distribution is measured by gel permeation chromatography (GPC) using 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. Then, this solution is filtered using a PTFE type membrane filter "DISMIC-25JP" (manufactured by Toyo Roshi Co., Ltd.) with a pore size of 0.20 μm to remove insoluble components and obtain the sample solution. (2) Molecular weight measurement Using the measuring apparatus and analytical column described below, tetrahydrofuran (amorphous resin) or chloroform (crystalline resin) is flowed as the eluent at a flow rate of 1 mL / min, and the column is stabilized in a constant temperature bath at 40°C. 100 μL of the sample solution is then injected and the measurement is performed. The molecular weight of the sample is calculated based on a calibration curve prepared in advance. The calibration curve used in this case includes several types of monodisperse polystyrene (A-500 (5.0 × 10) manufactured by Tosoh Corporation). 2 ), A-1000 (1.01 x 10 3 ), A-2500 (2.63 x 10 3 ), A-5000 (5.97 x 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 The sample prepared using )) as a standard sample is used. The value in parentheses indicates the molecular weight. Measuring device: HLC-8220GPC (manufactured by Tosoh Corporation) Analysis column: TSKgel GMH XL +TSKgel G3000H XL (Manufactured by Tosoh Corporation)

[0126] [Melting point of release agent] Using a differential scanning calorimeter "Q-100" (manufactured by T.A. Instruments Japan Co., Ltd.), 0.02 g of the 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. Next, the sample is heated at a rate of 10°C / min and the heat quantity is measured, with the maximum endothermic peak temperature being defined as the melting point.

[0127] [Average particle size of external additives] The average particle diameter refers to the number-average particle diameter, which is calculated by measuring the particle size (average of the major and minor axes) of 500 particles from scanning electron microscope (SEM) images and using the number-average value of these measurements.

[0128] [Toner volume medium particle size (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" (manufactured by Beckman Coulter, Inc.) • Electrolyte: "Isoton (registered trademark) II" (manufactured by Beckman Coulter, Inc.) • Dispersion: Prepared by dissolving polyoxyethylene lauryl ether "Emulgen (registered trademark) 109P" [manufactured by Kao Corporation, HLB (Griffin) = 13.6] in the electrolyte to adjust the concentration to 5% by mass. • Dispersion conditions: Add 10 mg of the sample to 5 mL of the dispersion and disperse for 1 minute using an ultrasonic disperser (machine name: US-1 manufactured by SND Corporation, output: 80W). Then, add 25 mL of electrolyte and disperse for another minute using the ultrasonic disperser to prepare the sample dispersion. • Measurement conditions: The sample dispersion is added to 100 mL of the electrolyte to adjust the concentration so that the particle size of 30,000 particles can be measured in 20 seconds. Then, the 30,000 particles are measured, and the volume median particle size (D) is determined from the particle size distribution. 50 )

[0129] Resin manufacturing example 1 The alcohol components, carboxylic acid components other than adipic acid, esterification catalysts, and co-catalysts shown in Tables 1-3 were placed in a 10-liter four-necked flask equipped with a thermometer, stainless steel stirring rod, dehydration tube, condenser, and nitrogen inlet tube, and the mixture was heated to 235°C over 2 hours in a mantle heater under a nitrogen atmosphere. After confirming that the reaction rate reached 95% or more at 235°C, the mixture was cooled to 180°C. Then, adipic acid was added, and the mixture was heated to 220°C over 2 hours. After reacting at 220°C for 1 hour, the reaction was carried out at 8 kPa until the softening point shown in Tables 1-3 was reached to obtain amorphous polyester resins (resins A1-A4, A8-A9, A12-A13, A14-A16). Subsequently, the resin was cooled to 180°C, the amide compounds shown in Tables 1-3 were added, and the mixture was melt-mixed at 180°C for 30 minutes to obtain mixtures of resin and amide compounds (mixtures 1-4, 8-9, 12-13, 14-16). The physical properties of the resin, measured by taking a portion of the obtained resin, are shown in Tables 1-3. In this specification, the reaction rate refers to the value of (mol) of reaction water produced / (mol) of theoretical reaction water produced × 100.

[0130] Resin manufacturing example 2 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-necked flask equipped with a thermometer, stainless steel stirring rod, dehydration tube, condenser, and nitrogen inlet tube, and heated to 235°C over 2 hours in a mantle heater under a nitrogen atmosphere. After confirming that the reaction rate reached over 95% 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 carried out at 8 kPa until the softening point shown in Table 1 was reached to obtain amorphous polyester resin (resin A5). The resin was then cooled to 145°C, the amide compound shown in Table 1 was added, and the mixture was melt-mixed at 145°C for 30 minutes to obtain a mixture of the resin and the amide compound (mixture 5). The physical properties of the resin, measured by taking a sample of the obtained resin, are shown in Table 1.

[0131] Resin manufacturing example 3 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-necked flask equipped with a thermometer, stainless steel stirring rod, dehydration tube, condenser, and nitrogen inlet tube, and heated to 235°C over 2 hours in a mantle heater under a nitrogen atmosphere. After confirming that the reaction rate reached 95% or more at 235°C, the mixture was cooled to 180°C. Then, adipic acid was added, and the mixture was heated to 220°C over 2 hours. After reacting at 220°C for 1 hour, the reaction was carried out at 8 kPa until the softening point shown in Table 1 was reached to obtain amorphous polyester resin (resin A6). The resin was then heated to 235°C, the amide compound shown in Table 1 was added, and the mixture was melt-mixed at 235°C for 30 minutes to obtain a mixture of the resin and the amide compound (mixture 6). The physical properties of the resin, measured by taking a sample of the obtained resin, are shown in Table 1.

[0132] Resin manufacturing example 4 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-necked flask equipped with a thermometer, stainless steel stirring rod, dehydration tube, condenser, and nitrogen inlet tube, and heated to 235°C over 2 hours in a mantle heater under a nitrogen atmosphere. After confirming that the reaction rate reached 95% or more at 235°C, the mixture was cooled to 180°C. Then, adipic acid was added, and the mixture was heated to 220°C over 2 hours. After reacting at 220°C for 1 hour, the reaction was carried out at 8 kPa until the softening point shown in Table 1 was reached to obtain amorphous polyester resin (resin A7). The resin was then cooled to 110°C, the amide compound shown in Table 1 was added, and the mixture was melt-mixed at 110°C for 30 minutes to obtain a mixture of resin and amide compound (mixture 7). The physical properties of the resin, measured by taking a sample of the obtained resin, are shown in Table 1.

[0133] Resin manufacturing example 5 As shown in Table 2, the alcohol component, carboxylic acid components other than dodecenyl succinic anhydride, esterification catalyst, and co-catalyst were placed in a 10-liter four-necked flask equipped with a thermometer, stainless steel stirring rod, dehydration tube, condenser, and nitrogen inlet tube, and heated to 235°C over 2 hours in a mantle heater under a nitrogen atmosphere. After confirming that the reaction rate reached 95% or more at 235°C, the mixture was cooled to 180°C. Then, dodecenyl succinic anhydride was added, and the mixture was heated to 220°C over 2 hours. After reacting at 220°C for 1 hour, the reaction was carried out at 8 kPa until the softening point shown in Table 2 was reached to obtain amorphous polyester resin (resin A10). The resin was then cooled to 180°C, the amide compound shown in Table 2 was added, and the mixture was melt-mixed at 180°C for 30 minutes to obtain a mixture of resin and amide compound (mixture 10). The physical properties of the resin, measured by taking a sample of the obtained resin, are shown in Table 2.

[0134] Resin manufacturing example 6 As shown in Table 2, the alcohol component, carboxylic acid components other than adipic acid and trimellitic anhydride, esterification catalyst, and co-catalyst were placed in a 10-liter four-necked flask equipped with a thermometer, stainless steel stirring rod, dehydration tube, condenser, and nitrogen inlet tube, and heated to 235°C over 2 hours in a mantle heater under a nitrogen atmosphere. After confirming that the reaction rate reached 95% or more at 235°C, the mixture was cooled to 180°C. Then, adipic acid and trimellitic anhydride were added, and the mixture was heated to 220°C over 2 hours. After reacting at 220°C for 1 hour, the reaction was carried out at 8 kPa until the softening point shown in Table 2 was reached to obtain amorphous polyester resin (resin A11). The resin was then cooled to 190°C, the amide compound was added, and the mixture was melt-mixed at 190°C for 30 minutes to obtain a mixture of the resin and the amide compound (mixture 11). The physical properties of the resin, measured by taking a sample of the obtained resin, are shown in Table 2.

[0135] Resin manufacturing example 7 The alcohol component, carboxylic acid component other than adipic acid, esterification catalyst, and co-catalyst shown in Table 3 were placed in a 10-liter four-necked flask equipped with a thermometer, stainless steel stirring rod, dehydration tube, condenser, and nitrogen inlet tube, and heated to 235°C over 2 hours in a mantle heater under a nitrogen atmosphere. After confirming that the reaction rate reached 95% or more at 235°C, the mixture was cooled to 180°C. Then, adipic acid was added, and the mixture was heated to 220°C over 2 hours. After reacting at 220°C for 1 hour, the reaction was carried out at 8 kPa until the softening point shown in Table 3 was reached to obtain amorphous polyester resin (resin A17). The resin was then cooled to 120°C, an amide compound was added, and the mixture was melt-mixed at 120°C for 30 minutes to obtain a mixture of the resin and the amide compound (mixture 17). The physical properties of the resin, measured by taking a sample of the obtained resin, are shown in Table 3.

[0136] Resin manufacturing example 8 The alcohol component, carboxylic acid component other than adipic acid, esterification catalyst, and co-catalyst shown in Table 3 were placed in a 10-liter four-necked flask equipped with a thermometer, stainless steel stirring rod, dehydration tube, condenser, and nitrogen inlet tube, and the mixture was heated to 235°C over 2 hours in a mantle heater under a nitrogen atmosphere. After confirming that the reaction rate reached 95% or more at 235°C, the mixture was cooled to 180°C. Then, adipic acid was 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 3 was reached, yielding amorphous polyester resin (resin A18).

[0137] Resin manufacturing example 9 The alcohol components, carboxylic acid components other than adipic acid and trimellitic anhydride, esterification catalyst, and co-catalyst shown in Table 3 were placed in a 10-liter four-necked flask equipped with a thermometer, stainless steel stirring rod, dehydration tube, condenser, and nitrogen inlet tube, and the mixture was heated to 235°C over 2 hours in a mantle heater under a nitrogen atmosphere. After confirming that the reaction rate reached 95% or more at 235°C, the mixture was cooled to 180°C. Then, adipic acid and trimellitic anhydride were 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 3 was reached, yielding amorphous polyester resin (resin B1).

[0138] Details of the amide compounds used are as follows: 12-Hydroxystearate ethylenebisamide: ITOHWAX J-530 (manufactured by Ito Oil Co., Ltd.), melting point 142℃ 12-Hexamethylenebisamide hydroxystearate: ITOHWAX J-630 (manufactured by Ito Oil Co., Ltd.), melting point 135℃ 12-Hydroxystearate xylylenebisamide: ITOHWAX J-700 (manufactured by Ito Oil Co., Ltd.), melting point 125℃ 12-Hydroxyethyl hydroxystearate: ITOHWAX J-420 (manufactured by Ito Oil Co., Ltd.), melting point 105℃ Ethylenebisamide stearate: Kao Wax EB-P (manufactured by Kao Corporation), melting point 143℃

[0139] [Table 1]

[0140] [Table 2]

[0141] [Table 3]

[0142] Resin manufacturing example 10 The alcohol and carboxylic acid components shown in Table 4 were placed in a 10-liter four-necked flask equipped with a thermometer, stainless steel stirring rod, dehydration tube, condenser, and nitrogen inlet tube. The mixture was then kept at 140°C for 1 hour in a mantle heater under a nitrogen atmosphere, followed by a 10°C / h increase in temperature from 140°C to 200°C. A polycondensation reaction was then carried out at 200°C for 1 hour. An esterification catalyst and co-catalyst were added, and the reaction was carried out at 200°C and 8 kPa until the softening point shown in Table 4 was reached to obtain crystalline polyester resins (resins C1-C7).

[0143] [Table 4]

[0144] Examples 1-21, Comparative Examples 2-5 100 parts by mass of the crystalline resin-containing composition shown in Table 5, 1 part by mass of the negative charge control agent "Bontron E-81" (manufactured by Orient Chemical Industry Co., Ltd.), 5 parts by mass of the coloring agent "Pigment blue 15:3" (manufactured by Dainichi Seika Kogyo Co., Ltd., phthalocyanine blue), and 2 parts by mass of the release agent "HNP-9" (manufactured by Nippon Seiro Co., Ltd., paraffin wax, melting point: 75°C) were thoroughly mixed in a Henschel mixer. Then, using a twin-screw extruder with a total length of 1560 mm in the mixing section, a screw diameter of 42 mm, and a barrel inner diameter of 43 mm, the mixture was melt-kneaded at a roll rotation speed of 200 r / min and a heating temperature of 100°C in the rolls (resin temperature: 120°C). The feed rate of the mixture was 20 kg / h, and the average residence time was approximately 18 seconds. The resulting kneaded material was cooled and coarsely ground, then ground in a jet mill and classified to obtain the medium particle size (D) by volume. 50 ) yielded toner particles with a diameter of 8 μm.

[0145] Toner was obtained by adding 1.0 part by mass of hydrophobic silica "AEROSIL NAX 50" (manufactured by Nippon Aerosil Co., Ltd., hydrophobic treatment agent: HMDS, average particle size: approximately 30 nm) as an external additive to 100 parts by mass of the obtained toner particles and mixing them in a Henschel mixer.

[0146] Comparative Example 1 100 parts by mass of the crystalline resin-containing composition shown in Table 5, 1 part by mass of the negative charge control agent "Bontron E-81" (manufactured by Orient Chemical Industry Co., Ltd.), 5 parts by mass of the coloring agent "Pigment blue 15:3" (manufactured by Dainichi Seika Kogyo Co., Ltd., phthalocyanine blue), 2 parts by mass of the release agent "HNP-9" (manufactured by Nippon Seiro Co., Ltd., paraffin wax, melting point: 75℃), and 1 part by mass of 12-hydroxystearate ethylenebisamide "ITOHWAX J-530" (manufactured by Ito Oil Co., Ltd., melting point: 142℃) were thoroughly mixed in a Henschel mixer. Then, using a twin-screw extruder with a total length of 1560 mm in the mixing section, a screw diameter of 42 mm, and a barrel inner diameter of 43 mm, the mixture was melt-kneaded at a roll rotation speed of 200 r / min and a heating temperature in the rolls of 100℃ (resin temperature: 120℃). The mixture was fed at a rate of 20 kg / h, and the average residence time was approximately 18 seconds. The resulting kneaded material was cooled, coarsely ground, then ground in a jet mill, and classified to obtain the medium volume particle size (D 50 ) yielded toner particles with a diameter of 8 μm.

[0147] Toner was obtained by adding 1.0 part by mass of hydrophobic silica "AEROSIL NAX 50" (manufactured by Nippon Aerosil Co., Ltd., hydrophobic treatment agent: HMDS, average particle size: approximately 30 nm) as an external additive to 100 parts by mass of the obtained toner particles and mixing them in a Henschel mixer.

[0148] Test example [Bending resistance of printed materials] A modified fuser unit of the "AR-505" copier (manufactured by Sharp Corporation) was modified to allow for external fixing. Toner was then installed in this modified unit, and a printout was obtained in an unfixed state (print area: 20cm x 20cm, adhesion amount: 0.5mg / cm²). 2 ). Subsequently, the image was fixed using a fuser (fixing speed 300 mm / sec) adjusted to achieve a total fixing pressure of 40 kgf, with the fixing roll temperature set to 160°C. This image was then fixed at 50 g / cm². 2The maximum width of the image defect after folding the paper inward for 30 seconds, unfolding it again, and wiping away the damaged image with a soft cloth was used as an indicator of the print's bending resistance. The results are shown in Table 6. The smaller the maximum width of the image defect, the better the print's bending resistance. The fuser paper used was "CopyBond SF-70NA" (manufactured by Sharp Corporation, 75g / m²). 2 ) was used.

[0149] [Table 5]

[0150] [Table 6]

[0151] From the above results, it can be seen that the toners obtained in Examples 1 to 21 have good bending resistance when compared to Comparative Example 1, in which the hydroxyl group-containing amide compound was directly mixed with amorphous polyester resin and crystalline polyester resin without pre-mixing with amorphous polyester resin at a temperature above the melting point of the hydroxyl group-containing amide compound; Comparative Example 2, which used an amide compound that does not contain hydroxyl groups; Comparative Examples 3 and 4, in which the hydroxyl group-containing amide compound was not used in a predetermined amount; and Comparative Example 5, in which the hydroxyl group-containing amide compound was pre-mixed with amorphous polyester resin at a temperature below the melting point of the hydroxyl group-containing amide compound. [Industrial applicability]

[0152] The toner containing the crystalline resin-containing composition for toner obtained by the method of the present invention is suitably used for developing latent images formed in electrostatic image development, electrostatic recording, electrostatic printing, and the like.

Claims

1. A method for producing a crystalline resin-containing composition for toner containing a crystalline polyester resin, an amorphous polyester resin containing amorphous polyester resin A, and a hydroxyl group-containing amide compound, The hydroxyl group-containing amide compound is of formula (I): R １ -CONH-X-NHCO-R ２ (I) (In the formula, R １ and R ２ Each of these is independently a hydroxyalkyl group having 12 to 22 carbon atoms, and X is a divalent hydrocarbon group having 2 to 12 carbon atoms. Or formula (II): R ３ -.ONH-R ４ (-I) (In the formula, R ３ R is a hydroxyalkyl group having 12 to 22 carbon atoms. ４ (This is a hydroxyalkyl group having 2 to 22 carbon atoms.) It is a compound represented by the following: The content of the hydroxyl group-containing amide compound is 0.4 parts by mass or more and 13 parts by mass or less, based on 100 parts by mass of the total amount of the crystalline polyester resin and the amorphous polyester resin. The process includes step Ia, in which the amorphous polyester resin A and the hydroxyl group-containing amide compound are mixed at a temperature above the melting point of the hydroxyl group-containing amide compound, and step IIa, in which the mixture obtained in step Ia is mixed with the crystalline polyester resin. A method for producing a crystalline resin-containing composition for toner.

2. The method for producing a crystalline resin-containing composition for toner according to claim 1, wherein step Ia is a step of adding and mixing a hydroxyl group-containing amide compound at a temperature above the melting point of the hydroxyl group-containing amide compound after the polycondensation reaction of the raw material monomers of amorphous polyester resin A.

3. A method for producing a crystalline resin-containing composition for toner according to claim 1 or 2, wherein the temperature at which the amorphous polyester resin A and the hydroxyl group-containing amide compound are mixed is 30°C or more higher than the softening point of the amorphous polyester resin A.

4. A method for producing a crystalline resin-containing composition for toner according to claim 1 or 2, wherein the crystalline polyester resin is a polycondensate of an alcohol acid component containing an aliphatic diol and a carboxylic acid component containing an aliphatic dicarboxylic acid compound.

5. A method for producing a crystalline resin-containing composition for toner according to claim 4, wherein the aliphatic diol has 2 to 6 carbon atoms.

6. A method for producing a crystalline resin-containing composition for toner according to claim 4, wherein the aliphatic dicarboxylic acid compound has 12 or more carbon atoms and 30 or less carbon atoms.

7. A method for producing a toner for electrostatic image development containing a crystalline polyester resin, an amorphous polyester resin containing amorphous polyester resin A, and a hydroxyl group-containing amide compound, The hydroxyl group-containing amide compound is of formula (I): R １ -CONH-X-NHCO-R ２ (I) (In the formula, R １ and R ２ Each of these is independently a hydroxyalkyl group having 12 to 22 carbon atoms, and X is a divalent hydrocarbon group having 2 to 12 carbon atoms. Or formula (II): R ３ -.ONH-R ４ (-I) (In the formula, R ３ R is a hydroxyalkyl group having 12 to 22 carbon atoms. ４ (This is a hydroxyalkyl group having 2 to 22 carbon atoms.) It is a compound represented by the following: The content of the hydroxyl group-containing amide compound is 0.4 parts by mass or more and 13 parts by mass or less, based on 100 parts by mass of the total amount of the crystalline polyester resin and the amorphous polyester resin. The process includes step Ib of mixing the amorphous polyester resin A and the hydroxyl group-containing amide compound at a temperature above the melting point of the hydroxyl group-containing amide compound, step IIb of melt-kneading at least the mixture obtained in step Ib with the crystalline polyester resin, and step IIIb of grinding the kneaded product obtained in step IIb. A method for manufacturing toner for developing electrostatic images.

8. The method for producing electrostatic image developing toner according to claim 7, wherein step Ib is a step of adding and mixing a hydroxyl group-containing amide compound at a temperature above the melting point of the hydroxyl group-containing amide compound after the polycondensation reaction of raw material monomers of amorphous polyester resin A.

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