Toner composition containing crystalline resin

Abstract

This invention relates to a crystalline resin-containing composition for toner with excellent electrostatic stability, and toner for electrostatic image development containing the composition. [Solution] A crystalline resin-containing composition for toner containing an amorphous polyester resin, a crystalline polyester resin, and a specific hydroxyl group-containing amide compound, wherein the amorphous polyester resin contains an amorphous polyester composite resin A in which a polyester resin segment and an addition polymerization resin segment are bonded via covalent bonds, the weight-average molecular weight of the addition polymerization resin segment is 2,000 or more and 18,000 or less, and the content of the hydroxyl group-containing amide compound is 0.4 parts by mass or more and 11 parts by mass or less per 100 parts by mass of the total amount of the amorphous polyester resin and the crystalline polyester resin, and a toner for electrostatic image development containing the composition.

Description

Technical Field

[0001] The present invention relates to a crystalline resin-containing composition for toner used for developing a latent image formed in an electrophotographic method, an electrostatic recording method, an electrostatic printing method, etc., and an electrostatic charge image developing toner containing the composition.

Background Art

[0002] In recent years, printing using toner has been used in industrial printing and commercial printing, and high-quality images such as photographs have been demanded, and it has been required to improve the charging stability of toner.

[0003] On the other hand, 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

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0005] Even when a hydroxy fatty acid amide compound is used in combination with a conventional amorphous polyester resin as a crystal nucleating agent, the dispersion of the amide compound in the amorphous polyester resin is insufficient, and it is difficult to form crystal nuclei of the crystalline polyester resin. As a result, since crystal growth proceeds with respect to a small number of crystal nuclei, coarse domains of the crystalline polyester resin are formed, and the exposure amount of the crystalline polyester resin on the toner surface increases, so there is a problem that the charge stability is likely to decrease.

[0006] The present invention relates to a crystalline resin-containing composition for toner having excellent charge stability and an electrostatic charge image developing toner containing the composition.

Means for Solving the Problems

[0007] The present invention is 〔1〕 A crystalline resin-containing composition for toner containing an amorphous polyester-based resin, a crystalline polyester-based resin, and a hydroxy group-containing amide compound, wherein the amorphous polyester-based resin contains an amorphous polyester-based composite resin A in which a polyester-based resin segment and an addition polymerization-based resin segment are bonded via a covalent bond, the weight average molecular weight of the addition polymerization-based resin segment is 2,000 or more and 18,000 or less, and the hydroxy group-containing amide compound is represented by the formula (I): R 1 -CONH-X-NHCO-R 2 (I) (In the formula, R 1 and R[[ID=2 ) 2 are each independently a hydroxyalkyl group having 12 or more and 22 or less carbon atoms, and X is a divalent hydrocarbon group having 2 or more and 12 or less carbon atoms) Or the formula (II): R 3 -CONH-R 4 (II) (In the formula, R 3 ) is a hydroxyalkyl group having 12 or more and 22 or less carbon atoms, and R 4 is a hydroxyalkyl group having 2 or more and 22 or less carbon atoms) A crystalline resin-containing composition for toner, wherein the compound represented by [formula] is such that the content of the hydroxyl group-containing amide compound is 0.4 parts by mass or more and 11 parts by mass or less, based on 100 parts by mass of the total amount of the amorphous polyester resin and the crystalline polyester resin, and [2] Toner for electrostatic image development containing the crystalline resin-containing composition for toner described in [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 electrostatic stability. [Modes for carrying out the invention]

[0009] The crystalline resin-containing toner composition of the present invention contains an amorphous polyester resin, a crystalline polyester resin, and an amide compound. A key feature of the present invention is that the amorphous polyester resin contains an amorphous polyester composite resin comprising a polyester resin segment and an addition polymerization resin segment with controlled weight-average molecular weight, and the amide compound contains a predetermined hydroxyl group-containing amide compound. The reason for the excellent electrostatic stability of the composition of the present invention is not entirely clear, but it is presumed to be as follows. Note that the following mechanism is a hypothesis and is not limited thereto.

[0010] By using a fatty acid amide containing a hydroxyl group (hydroxyl group-containing amide compound) as the amide compound, the cohesive force between amide compounds is inhibited, resulting in better dispersion of the amide compound. As a result, the effect of promoting crystal nucleation in crystalline polyester resin is greatly enhanced. In addition, in the present invention, by using an amorphous polyester-based composite resin having an addition polymerization-based resin segment, a hydrophobic addition polymerization-based resin segment serves as a dispersion field for an amide compound acting as a crystal nucleating agent, and the dispersibility of the amide compound is improved. When the weight average molecular weight of the addition polymerization-based resin segment is within an appropriate range, the function as a dispersion field is maintained, and it is considered that the improvement of the dispersibility of the amide compound is contributed by the fact that an excessive crystal nucleating agent does not excessively exist in one addition polymerization-based resin segment and functions. As a result, the number of crystal growth starting points increases, and the domain of the crystalline polyester resin becomes smaller, so that the exposed amount of the crystalline polyester resin on the toner surface decreases, and the charge stability is considered to be improved.

[0011] The amorphous polyester-based resin contains an amorphous polyester-based composite resin A in which a polyester-based resin segment and an addition polymerization-based resin segment are bonded via a covalent bond.

[0012] The polyester-based resin segment is formed by polycondensation of an alcohol component and a carboxylic acid component, which are raw material monomers of the polyester resin.

[0013] From the viewpoint of low-temperature fixing property, the alcohol component is represented by the formula (III):

[0014]

Chemical formula

[0015] (In the formula, OR 5 and R 5 O is an oxyalkylene group, R 5 is an ethylene group and / or a propylene group, x and y represent the average number of added moles of alkylene oxide, and are positive numbers respectively. The sum value 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, still more preferably 4 or less, and still more preferably 2.5 or less) It is preferable to contain an alkylene oxide adduct of bisphenol A represented by formula (III). Examples of alkylene oxide adducts of bisphenol A represented by formula (III) include polyoxypropylene adducts of 2,2-bis(4-hydroxyphenyl)propane and polyoxyethylene adducts of 2,2-bis(4-hydroxyphenyl)propane. It is preferable to use one or more of these.

[0016] The content of the bisphenol A alkylene oxide adduct represented by formula (III) is preferably 70 mol% or more, more preferably 80 mol% or more, even more preferably 90 mol% or more, and even more preferably 95 mol% or more, and 100 mol% or less, in the alcohol component.

[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, 1,7-heptanediol, 1,8-octanediol, neopentyl glycol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, and 1,12-dodecanediol, as well as trivalent or higher alcohols such as bisphenol A, hydrogenated bisphenol A, sorbitol, pentaerythritol, glycerin, and trimethylolpropane.

[0018] From the viewpoint of low-temperature fixability, the carboxylic acid component preferably 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 with one to three carbon atoms in the alkyl group. Among these, terephthalic acid is preferred from the viewpoint of low-temperature fixability.

[0020] The content of aromatic dicarboxylic acid compounds is preferably 70 mol% or more, more preferably 80 mol% or more, even more preferably 90 mol% or more, and even more preferably 95 mol% or more, and 100 mol% or less, in the carboxylic acid component.

[0021] Other carboxylic acid components include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, aliphatic dicarboxylic acids such as succinic acid, adipic acid, and sebacic acid which may be substituted with hydrocarbon groups having 1 to 20 carbon atoms, trivalent or higher carboxylic acids such as 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalentricarboxylic acid, and pyromellitic acid, anhydrides of these acids, and alkyl esters of alkyl groups having 1 to 3 carbon atoms.

[0022] The alcohol component may contain a monohydric alcohol, and the carboxylic acid component may contain a monohydric carboxylic acid compound, as appropriate.

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

[0024] The equivalent ratio (COOH group / OH group) of the carboxyl group of the carboxylic acid component to the hydroxyl group of the alcohol component is preferably 0.6 or higher, more preferably 0.7 or higher, even more preferably 0.8 or higher, and preferably 1.3 or lower, more preferably 1.2 or lower, from the viewpoint of adjusting the softening point of the polyester resin.

[0025] Polyester resin segments can be formed, 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 160°C or higher, more preferably 200°C or higher, and preferably 250°C or lower, more preferably 240°C or lower.

[0026] 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.

[0027] The addition polymerization resin segment is composed of an addition polymerization resin having a predetermined weight-average molecular weight, and is formed by the addition polymerization reaction of the raw material monomers of the addition polymerization resin.

[0028] The weight-average molecular weight of the addition polymerization resin segment is 2,000 or more, preferably 4,000 or more, more preferably 5,000 or more, and even more preferably 6,000 or more, and 18,000 or less, preferably 15,000 or less, more preferably 13,000 or less, and even more preferably 12,000 or less, from the viewpoint of dispersibility of the hydroxyl group-containing amide compound. The weight-average molecular weight of the addition polymerization resin can be adjusted by the amount of polymerization initiator and the reaction temperature. For example, increasing the amount of polymerization initiator or raising the reaction temperature increases the number of reaction initiations, and the more initiations there are, the smaller the molecular weight tends to be.

[0029] From the viewpoint of adjusting the acid value, the addition polymerization resin segment preferably contains constituent units derived from (meth)acrylic acid. In this specification, "(meth)acrylic acid" refers to acrylic acid, methacrylic acid, or both.

[0030] The content of constituent units derived from (meth)acrylic acid in the addition polymerization resin segment and the content of (meth)acrylic acid in the raw material monomer of the addition polymerization resin are preferably 9% by mass or more, more preferably 10% by mass or more, even more preferably 12% by mass or more, and preferably 20% by mass or less, more preferably 18% by mass or less, and even more preferably 16% by mass or less.

[0031] Examples of raw material monomers for addition polymerization resins other than (meth)acrylic acid include styrene compounds, alkyl (meth)acrylates, ethylenically unsaturated monoolefins such as ethylene and propylene; diolefins such as butadiene; halovinyls such as vinyl chloride; vinyl esters such as vinyl acetate and vinyl propionate; ethylenically monocarboxylic acid esters such as dimethylaminoethyl (meth)acrylate; vinyl ethers such as methyl vinyl ether; vinylidene halides such as vinylidene chloride; and N-vinyl compounds such as N-vinylpyrrolidone. Among these, styrene compounds or alkyl (meth)acrylates are preferred.

[0032] Examples of styrene-based compounds include styrene, α-methylstyrene, vinyltoluene, and other styrene derivatives, with styrene being preferred.

[0033] Examples of alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (iso)octyl (meth)acrylate, (iso)decyl (meth)acrylate, and (iso)stearyl (meth)acrylate. Among these, at least one selected from the group consisting of methyl (meth)acrylate and 2-ethylhexyl (meth)acrylate is preferred. In this specification, "(iso)" means that this group may or may not be present, and when this group is not present, it indicates that the product is normal.

[0034] The addition polymerization reaction of raw material monomers for addition polymerization resin segments can be carried out in the same reaction vessel as the polycondensation reaction of raw material monomers for polyester resins, for example, in the presence of polymerization initiators such as dibutyl peroxide and dicumyl peroxide, chain transfer agents, crosslinking agents, etc., in the presence of organic solvents or without solvents. The temperature conditions are preferably 110°C or higher, more preferably 140°C or higher, and preferably 200°C or lower, more preferably 170°C or lower.

[0035] When using an organic solvent during the addition polymerization reaction, xylene, toluene, methyl ethyl ketone, acetone, etc., can be used. The amount of organic solvent used is preferably 10 to 50 parts by mass per 100 parts by mass of raw material monomers of the addition polymerization resin segment.

[0036] Furthermore, when using a pre-made addition polymerization resin in the production of a composite resin, it is preferable to produce the addition polymerization resin by bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization, and from the viewpoint of storage stability, it is more preferable to produce it by bulk polymerization. In the present invention, "bulk polymerization" refers to addition polymerization carried out under conditions in which there is substantially no solvent in the reaction system, that is, under solvent-free conditions.

[0037] Radical generators may be used in bulk polymerization. Examples of radical generators include peroxides such as di-tert-butyl peroxide, persulfates such as sodium persulfate, and azo compounds such as 2,2'-azobis(2,4-dimethylvaleronitrile).

[0038] In bulk polymerization, the concentration of the radical generator is preferably 10 parts by mass or less, more preferably 7 parts by mass or less, even more preferably 5 parts by mass or less, even more preferably 3 parts by mass or less, even more preferably 2 parts by mass or less, even more preferably 1 part by mass or less, even more preferably 0.5 parts by mass or less, and even more preferably 0 parts by mass, per 100 parts by mass of the raw material monomer of the addition polymerization resin, and is preferably carried out under catalyst-free conditions.

[0039] Bulk polymerization is preferably carried out at high temperatures under pressure above atmospheric pressure, and more preferably as continuous bulk polymerization under high temperature and high pressure. In the present invention, a pressurized state refers to a state in which the contents are heated above the boiling point at atmospheric pressure in a sealed container such as an autoclave. Under high temperatures under pressure above atmospheric pressure, radicals generated by the thermal initiation reaction of the raw material monomers function as polymerization initiators, allowing addition polymerization to proceed even under conditions with relatively few radical generators, and enabling the production of an addition polymerization resin with a narrow molecular weight distribution.

[0040] Furthermore, in the case of continuous bulk polymerization under high temperature and high pressure, it is possible to control not only the molecular weight distribution but also the monomer composition distribution, thereby obtaining a more uniform addition polymerization resin with a narrow monomer composition distribution.

[0041] From the above viewpoint, the temperature for bulk polymerization is preferably 140°C or higher, more preferably 180°C or higher, even more preferably 220°C or higher, even more preferably 260°C or higher, even more preferably 280°C or higher, and preferably 350°C or lower, more preferably 320°C or lower.

[0042] The softening point of the addition polymerization resin used in the composite is preferably 95°C or higher, more preferably 100°C or higher, and even more preferably 105°C or higher, from the viewpoint of resistance to hot offset, and preferably 140°C or lower, more preferably 135°C or lower, and even more preferably 130°C or lower, from the viewpoint of low-temperature fixation.

[0043] The glass transition temperature of the addition polymerization resin is preferably 40°C or higher, more preferably 45°C or higher, and even more preferably 50°C or higher, from the viewpoint of storage stability, and preferably 80°C or lower, more preferably 75°C or lower, and even more preferably 70°C or lower, from the viewpoint of low-temperature fixation.

[0044] The weight-average molecular weight of the addition polymerization resin is preferably 2,000 or more, more preferably 4,000 or more, even more preferably 5,000 or more, and even more preferably 6,000 or more, and also preferably 18,000 or less, more preferably 15,000 or less, even more preferably 13,000 or less, and even more preferably 12,000 or less, from the viewpoint of dispersibility of the hydroxyl group-containing amide compound.

[0045] From the viewpoint of low-temperature fixability, the acid value of the addition polymerization resin is preferably 60 mg KOH / g or more, more preferably 65 mg KOH / g or more, even more preferably 70 mg KOH / g or more, even more preferably 75 mg KOH / g or more, and preferably 130 mg KOH / g or less, more preferably 120 mg KOH / g or less, even more preferably 110 mg KOH / g or less, even more preferably 100 mg KOH / g or less, and even more preferably 90 mg KOH / g or less.

[0046] The composite resin is preferably a resin in which a polyester resin segment and an addition polymerization resin segment are covalently bonded together by reactive monomers that can react with both the raw material monomers of the polyester resin and the raw material monomers of the addition polymerization resin.

[0047] The two reactive monomers are preferably compounds having at least one functional group selected from the group consisting of hydroxyl groups, carboxyl groups, epoxy groups, primary amino groups, and secondary amino groups, preferably a hydroxyl group and / or a carboxyl group, more preferably a carboxyl group, and an ethylenically unsaturated bond within the molecule. More preferably, at least one selected from the group consisting of acrylic acid, methacrylic acid, fumaric acid, maleic acid, and maleic anhydride is preferred, and even more preferably, at least one selected from the group consisting of acrylic acid, methacrylic acid, and fumaric acid is preferred from the viewpoint of reactivity in polycondensation and addition polymerization reactions. However, when used together with a polymerization inhibitor, polycarboxylic acid compounds having an ethylenically unsaturated bond, such as fumaric acid, function as raw material monomers for polyester resins. In this case, fumaric acid, etc., are not two reactive monomers, but raw material monomers for polyester resins.

[0048] The content of both reactive monomers is preferably 1 mole or more, more preferably 2 moles or more, per 100 moles of total alcohol components of the polyester resin, from the viewpoint of improving the dispersibility of the amorphous addition polymerization resin and the amorphous polyester resin and improving the dispersibility of the raw materials in the toner, and preferably 30 moles or less, more preferably 20 moles or less, and even more preferably 10 moles or less, from the viewpoint of improving the low-temperature fixability of the toner.

[0049] Methods for producing amorphous polyester composite resin A, which is a composite of polyester resin segments and addition polymerization resin segments, include (i) a polymer reaction between the polyester resin and the addition polymerization resin, (ii) a reaction of the polyester resin raw materials in the presence of the addition polymerization resin, and (iii) a reaction in which a portion of the polyester resin raw materials are reacted, and then the addition polymerization resin and the remaining polyester resin raw materials are added and the reaction is carried out. When using both reactive monomers, it is preferable to use both reactive monomers together with the raw material monomers of the addition polymerization resin from the viewpoint of improving the dispersibility of the raw materials in the toner and the low-temperature fixability of the toner.

[0050] In method (i), it is preferable that the polymerization reactions of the polyester resin and the addition polymerization resin are carried out in independent reaction systems. If the polymerization reactions of the addition polymerization resin and the polyester resin are in independent reaction systems, the progress and completion of the two polymerization reactions do not need to be simultaneous in time; the reaction temperature and time can be appropriately selected according to the respective reaction mechanisms to allow the reactions to proceed and be completed. Furthermore, in the polymer reaction of method (i), there are no particular restrictions on the method of mixing the polyester resin and the addition polymerization resin. For example, one method is to isolate the polyester resin obtained by condensing the raw material monomers (alcohol component and carboxylic acid component) of the polyester resin, and then mix the polyester resin with the addition polymerization resin. Another method is to obtain a polyester resin by condensing the raw material monomers of the polyester resin, and then add and mix the resulting polyester resin with the addition polymerization resin without isolating it.

[0051] In method (ii), the raw materials for the polyester resin reacted in the presence of the addition polymerization resin may be raw material monomers (alcohol component and carboxylic acid component).

[0052] In method (iii), an example is a method in which the alcohol component is reacted with a portion of the carboxylic acid component, and then the addition polymerization resin and the remainder of the carboxylic acid component are added to carry out the reaction.

[0053] Among these methods, method (i) described above is preferred from the viewpoint of controlling molecular weight, molecular weight distribution, and copolymerizability of monomers, while maintaining excellent low-temperature fixability and broadening the fixation temperature range. In other words, amorphous polyester composite resin A is preferably produced by a method including the following steps I and II. The addition polymerization reaction in step I and the polycondensation reaction in step II are as described above. Step I: A step to obtain an addition polymerization resin by additive polymerization of raw material monomers for an addition polymerization resin, preferably by bulk polymerization. Step II: After polycondensing the raw material monomers (alcohol component and carboxylic acid component) of the polyester resin, the addition polymerization resin obtained in Step I is added and the reaction is carried out to obtain the composite resin.

[0054] In amorphous polyester composite resin A, the mass ratio of the addition polymerization resin segment to the polyester resin segment (addition polymerization resin segment / polyester resin segment) is preferably 2 / 98 or higher, more preferably 4 / 96 or higher, even more preferably 6 / 94 or higher, and preferably 45 / 55 or lower, more preferably 40 / 60 or lower, and even more preferably 35 / 65 or lower, from the viewpoint of improving the dispersibility of the raw materials in the toner. In the above calculation, the mass of the polyester resin is the amount obtained by subtracting the amount of reaction water (calculated value) dehydrated by the polycondensation reaction from the mass of the raw material monomers of the polyester resin used. The amount of the addition polymerization resin is the total amount of raw material monomers of the addition polymerization resin (including raw material monomers of the addition polymerization resin that act as both reactive monomers) and polymerization initiator.

[0055] The softening point of amorphous polyester composite resin A is preferably 90°C or higher, more preferably 100°C or higher, and even more preferably 103°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 150°C or higher, from the viewpoint of low-temperature fixability.

[0056] The crystallinity of a resin is expressed by a crystallinity index, which is defined by the ratio of the softening point to the maximum endothermic peak temperature measured by a differential scanning calorimeter, i.e., the value of [softening point / maximum endothermic peak temperature]. The amorphous resin is one in which no endothermic peak is observed, or, if observed, a resin with a crystallinity index greater than 1.4, preferably greater than 1.5, more preferably 1.6 or higher, or less than 0.6, preferably 0.5 or lower. On the other hand, the crystalline resin is a resin having a crystallinity index of 0.6 or higher, preferably 0.7 or higher, more preferably 0.9 or higher, and 1.4 or lower, preferably 1.2 or lower, more preferably 1.1 or lower. 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.

[0057] The glass transition temperature of amorphous polyester composite resin A is preferably 45°C or higher, more preferably 50°C or higher, from the viewpoint of storage stability and durability, and preferably 60°C or lower, more preferably 58°C or lower, from the viewpoint of low-temperature fixation.

[0058] The content of amorphous polyester composite resin A is preferably 60% by mass or more, more preferably 65% ​​by mass or more, even more preferably 70% by mass or more, and 100% by mass or less, in the amorphous polyester resin.

[0059] Amorphous polyester resins may be composed of resins with different softening points, from the viewpoint of low-temperature fixability and fixation width.

[0060] The difference in softening points between the amorphous polyester resin with a high softening point (resin AH) and the amorphous polyester resin with a low softening point (resin AL) is preferably 20°C or higher, more preferably 25°C or higher, even more preferably 30°C or higher, and preferably 50°C or lower, more preferably 45°C or lower, and even more preferably 40°C or lower.

[0061] The softening point of resin AH is preferably 120°C or higher, more preferably 130°C or higher, and even more preferably 135°C or higher, from the viewpoint of fixation width, and preferably 170°C or lower, more preferably 160°C or lower, and even more preferably 150°C or higher, from the viewpoint of low-temperature fixation.

[0062] The weight-average molecular weight of resin AH is preferably 6,000 or more, more preferably 10,000 or more, and even more preferably 50,000 or more, from the viewpoint of low-temperature fixation after long-term storage, and also preferably 3,000,000 or less, more preferably 1,000,000 or less, and even more preferably 800,000 or less.

[0063] The content of resin AH is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, and preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less, in the amorphous polyester resin.

[0064] Furthermore, the softening point of the resin AL is preferably 90°C or higher, more preferably 100°C or higher, and even more preferably 103°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 fixation.

[0065] The weight-average molecular weight of resin AL is preferably 20,000 or more, more preferably 40,000 or more, and even more preferably 50,000 or more, from the viewpoint of hot offset resistance, and preferably 300,000 or less, more preferably 200,000 or less, and even more preferably 150,000 or less, from the viewpoint of low-temperature fixation.

[0066] The content of resin AL is preferably 60% by mass or more, more preferably 65% ​​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, in the amorphous polyester resin.

[0067] Both resin AH and resin AL may be amorphous polyester composite resin A, or one of them may be amorphous polyester composite resin A. However, from the viewpoint of electrostatic stability, it is preferable that at least resin AL is amorphous polyester composite resin A.

[0068] When either resin AH or resin AL is amorphous polyester composite resin A, it is preferable that the amorphous polyester resin further contains amorphous polyester resin B other than amorphous polyester composite resin A, which has a different softening point from amorphous polyester composite resin A, and it is more preferable that resin AL is amorphous polyester composite resin A and resin AH is amorphous polyester resin B.

[0069] Examples of amorphous polyester resin B include amorphous polyester resins and amorphous polyester composite resins in which a polyester resin segment and an addition polymerization resin segment are bonded together via covalent bonds. From the viewpoint of dispersibility of hydroxyl group-containing amide compounds, amorphous polyester resins are preferred. Such amorphous polyester resins can be obtained by using the same raw material monomers (alcohol component and carboxylic acid component) as the polyester resin segment of amorphous polyester composite resin A, and adjusting the softening point by changing the raw material monomers, reaction temperature, reaction time, etc.

[0070] 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.

[0071] The glass transition temperature of amorphous polyester resin B is preferably 50°C or higher, more preferably 52°C or higher, from the viewpoint of storage and pulverability, and preferably 65°C or lower, more preferably 60°C or lower, from the viewpoint of low-temperature fixation.

[0072] Furthermore, the content of amorphous polyester resin in the total amount of amorphous polyester resin and crystalline 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.

[0073] The crystalline polyester resin is preferably a polycondensate of an alcohol component and a carboxylic acid component, and more preferably contains a crystalline polyester resin C which is a polycondensate of an alcohol component containing an aliphatic diol having 2 to 6 carbon atoms and a carboxylic acid component.

[0074] The alcohol component preferably contains an aliphatic diol.

[0075] Examples of aliphatic diols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-butenediol, 1,7-heptanediol, 1,8-octanediol, neopentyl glycol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, and 1,12-dodecanediol.

[0076] The aliphatic diol has 2 or more carbon atoms, and from the viewpoint of low-temperature fixability, it is preferably 6 or less, more preferably 4 or less.

[0077] From the viewpoint of improving the low-temperature fixability of the toner, aliphatic diols are preferably those having a hydroxyl group at the end of the carbon chain, and more preferably α,ω-linear alkanediols.

[0078] As the aliphatic diol, an aliphatic diol having 2 to 6 carbon atoms is preferred, and ethylene glycol is more preferred.

[0079] 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.

[0080] Examples of alcohol components other than aliphatic diols 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.

[0081] The carboxylic acid component preferably contains an aliphatic dicarboxylic acid compound.

[0082] 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.

[0083] 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 16 or less, more preferably 14 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.

[0084] The content of aliphatic dicarboxylic acid compounds in the carboxylic acid component 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, from the viewpoint of hydrophobicity. If the carboxylic acid component includes aliphatic monocarboxylic acid compounds, the content is preferably 98 mol% or less, more preferably 97 mol% or less.

[0085] From the viewpoint of glossiness, it is preferable that the carboxylic acid component further contains an aliphatic monocarboxylic acid compound.

[0086] 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.

[0087] 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.

[0088] 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, in the carboxylic acid component.

[0089] 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.

[0090] 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.

[0091] 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 alcohol component and carboxylic acid component of the polyester resin in amorphous polyester composite resin A, except that the preferred reaction temperature is 120°C or higher, more preferably 180°C or higher, and 230°C or lower, more preferably 220°C or lower.

[0092] 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 preferably 120°C or lower, more preferably 110°C or lower, from the viewpoint of low-temperature fixation.

[0093] 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, and preferably 115°C or lower, more preferably 105°C or lower, from the viewpoint of low-temperature fixation.

[0094] 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, and preferably 30,000 or less, more preferably 25,000 or less, from the viewpoint of low-temperature fixation.

[0095] The content of crystalline polyester resin C is preferably 80% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and 100% by mass or less in the crystalline polyester resin.

[0096] Other crystalline polyester resins include crystalline polyester resins other than crystalline polyester resin C, composite resins containing crystalline polyester resin and addition polymerization resins such as styrene-acrylic resin, epoxy resins, polycarbonate, polyurethane, and other resins.

[0097] From the viewpoint of low-temperature fixability, the content of crystalline polyester resin 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 preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 17% by mass or less.

[0098] 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.

[0099] 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 toner crystalline resin-containing composition 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).

[0100] R 1 , R 2 and R 3The 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.

[0101] R 4 The number of carbon atoms in the hydroxyalkyl group is preferably 10 or less, more preferably 6 or less.

[0102] R 1 ~R 4 The alkyl group in this combination may be branched or linear, but it is preferably linear.

[0103] Examples of divalent hydrocarbon groups in X include divalent aliphatic hydrocarbon groups and divalent aromatic hydrocarbon groups.

[0104] Examples of divalent aliphatic hydrocarbon groups include ethylene, trimethylene, tetramethylene, and hexamethylene groups.

[0105] Examples of divalent aromatic hydrocarbon groups include phenylene groups, m-xylylene groups, and p-xylylene groups.

[0106] 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.

[0107] 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.

[0108] Specific examples of hydroxyl group-containing amide compounds represented by formula (II) include 12-hydroxystearate hydroxyethylamide and 12-hydroxypalmitate hydroxyethylamide.

[0109] 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.

[0110] The mass ratio of the hydroxyl group-containing amide compound to the crystalline polyester resin C (hydroxyl 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 preferably 45 / 55 or less, more preferably 35 / 65 or less, and even more preferably 20 / 80 or less.

[0111] 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 11 parts by mass or less, 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 or less, based on 100 parts by mass of the total amount of amorphous polyester resin and crystalline polyester resin.

[0112] Furthermore, the present invention provides a toner for electrostatic image development containing the crystalline resin-containing composition for toner of the present invention.

[0113] In the toner of the present invention, the crystalline polyester resin and amorphous polyester resin are contained as binder resins.

[0114] 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, and even more preferably 95% by mass or more, and 100% by mass or less.

[0115] Other binder resins include addition polymerization resins such as styrene-acrylic resin, polyamide resin, epoxy resin, polycarbonate resin, polyurethane resin, and composite resins containing two or more of these resins.

[0116] 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.

[0117] The toner of the present invention may further contain additives such as colorants, release agents, charge control agents, magnetic powders, flowability improvers, conductivity modifiers, reinforcing fillers such as fibrous materials, antioxidants, and cleaning properties improvers.

[0118] 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.

[0119] From the viewpoint of improving the toner's image density and low-temperature fixability, the colorant content is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and preferably 40 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less, per 100 parts by mass of the binder resin.

[0120] 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.

[0121] 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.

[0122] 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.

[0123] 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.

[0124] 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.).

[0125] 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.

[0126] 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.

[0127] The toner of the present invention may be obtained by any of the conventionally known methods, such as the melt-kneading method, the emulsification-coagulation method, or the suspension polymerization method, and may also be a toner having a core-shell structure. However, from the viewpoint of the miscibility of the toner components, a pulverized toner obtained by the melt-kneading method, that is, a pulverized toner obtained by a method including the steps of melt-kneading raw materials and pulverizing the resulting mixture, is preferred. Specifically, for example, a crystalline polyester resin, an amorphous polyester resin, and a hydroxyl group-containing amide compound, along with raw materials such as a colorant, mold release agent, and charge control agent as needed, can be uniformly mixed in a mixer such as a Henschel mixer, then melt-kneaded in a closed-type kneader, a single-screw or twin-screw extruder, an open-roll type kneader, etc., followed by cooling, pulverization, and classification. The crystalline polyester resin, amorphous polyester resin, and hydroxyl group-containing amide compound constituting the crystalline resin-containing composition for toner of the present invention may be used pre-mixed, or each may be used directly or mixed with other raw materials.

[0128] In order to improve the transferability of the toner of the present invention, it is preferable to use external additives. Examples of external additives include inorganic fine particles such as silica, alumina, titania, zirconia, tin oxide, and zinc oxide, and organic fine particles such as melamine resin fine particles and polytetrafluoroethylene resin fine particles, and two or more 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 treated to hydrophobicity is more preferable.

[0129] 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.

[0130] The average particle size of the external additive is preferably 5 nm or larger, more preferably 10 nm or larger, even more preferably 15 nm or larger, and preferably 250 nm or smaller, more preferably 200 nm or smaller, and even more preferably 90 nm or smaller, from the viewpoint of the toner's chargeability, fluidity, and transferability.

[0131] 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.

[0132] From the viewpoint of the toner's electrostatic properties, fluidity, and transferability, the content of the external additive is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, even more preferably 0.3 parts by mass or more, and preferably 5 parts by mass or less, and more preferably 3 parts by mass or less, per 100 parts by mass of toner particles before treatment with the external additive.

[0133] The volume-intermediate particle size (D) of the toner of the present invention 50 The volume median particle size (D) is preferably 3 μm or more, more preferably 4 μm or more, and preferably 15 μm or less, more preferably 10 μm or less. 50 ) refers to the particle size at which the cumulative volume frequency calculated using volume fractions accounts for 50% when calculated from the smallest particle size. Furthermore, if the toner is treated with an external additive, the volume median particle size of the toner particles before treatment with the external additive is taken as the volume median particle size of the toner.

[0134] The toner of the present invention can be used as is as a one-component developing toner, or as a two-component developing toner used in combination with a carrier, in image forming apparatuses using either a one-component developing method or a two-component developing method, respectively. [Examples]

[0135] 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.

[0136] [Softening point of resin] Using a flow tester "CFT-500D" (manufactured by Shimadzu Corporation), 1 g of sample is heated at a heating rate of 6°C / min while a load of 1.96 MPa is applied by a plunger, and the sample is extruded from a nozzle with a diameter of 1 mm and a length of 1 mm. The amount of plunger descent of the flow tester is plotted against temperature, and the temperature at which half of the sample has flowed out is defined as the softening point.

[0137] [Maximum peak temperature of endothermic heat 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.

[0138] [Glass transition temperature of resins] 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.

[0139] [Acid value of resins] The measurement will be performed according to the method of JIS K0070:1992. However, the measurement solvent will be changed from the mixed solvent of ethanol and ether specified in JIS K0070:1992 to a mixed solvent of acetone and toluene (acetone:toluene = 1:1 (volume ratio)).

[0140] [Weight-average molecular weight of resins] 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)

[0141] [Weight-average molecular weight of addition polymerization resin segments in composite resins] The weight-average molecular weight of the addition polymerization resin segment is determined by the following method. (1) Separation of addition polymerization resin segments The resin is dissolved in tetrahydrofuran to a concentration of 5 g / 100 mL, and 10 g of 5% by mass sodium hydroxide aqueous solution is added and mixed to hydrolyze the polyester resin segment. Then, ethanol is added in small amounts to reprecipitation and separate only the addition polymerization resin segment. (2) Measurement of weight-average molecular weight Using the measurement apparatus and analytical column described below, tetrahydrofuran 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 (Mw: 5.0 × 10) manufactured by Tosoh Corporation). 2 ), A-1000 (Mw: 1.01 × 10 3 ), A-2500 (Mw: 2.63 × 10 3 ), A-5000 (Mw: 5.97 × 10 3 ), F-1 (Mw: 1.02 × 10 4 ), F-2 (Mw: 1.81×10 4 ), F-4 (Mw: 3.97×10 4 ), F-10 (Mw: 9.64×10 4 ), F-20 (Mw: 1.90×10 5 ), F-40 (Mw: 4.27×10 5 ), F-80 (Mw: 7.06×10 5 ), F-128 (Mw: 1.09 × 10 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)

[0142] [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.

[0143] [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.

[0144] [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 )

[0145] Resin manufacturing example 1 The raw material monomers shown in Table 1 were placed in an autoclave equipped with a stainless steel stirring rod, and polymerized under pressurized heating conditions (300°C) for 2 hours. The precipitated resin was recovered by returning the reaction system to atmospheric pressure and room temperature to obtain addition polymerization resins (resins A1 and A2).

[0146] [Table 1]

[0147] Resin manufacturing example 2 The raw material monomers, esterification catalysts, and co-catalysts for polyester resins other than adipic acid, as shown in Tables 2 and 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. 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, adipic acid was added, and the mixture was heated to 220°C over 2 hours. The mixture was then reacted at 220°C for 1 hour, followed by a reaction at 8 kPa for 2 hours. Subsequently, resin A1, as shown in Tables 2 and 3, was added at 220°C, held at 220°C for 4 hours, and then reacted at 8 kPa until the softening point described in Tables 2 and 3 was reached, yielding amorphous polyester composite resins (resins 1, 3, 4, 9, and 10). In this specification, the reaction rate refers to the value of (mol) of reaction water produced / (mol) of theoretical reaction water produced × 100.

[0148] Resin manufacturing example 3 The raw material monomers, esterification catalyst, and co-catalyst for polyester resins other than adipic acid, as shown in Table 2, 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 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 added, and the mixture was heated to 220°C over 2 hours. The mixture was then reacted at 220°C for 1 hour, followed by a reaction at 8 kPa for 2 hours. Subsequently, resin A2, as shown in Table 2, was added at 220°C, the mixture was held at 220°C for 4 hours, and the reaction was carried out at 8 kPa until the softening point shown in Table 2 was reached, yielding amorphous polyester composite resin (resin 2).

[0149] Resin manufacturing example 4 The raw material monomers for polyester resins other than adipic acid, as shown in Table 2, were placed in a 10-liter four-necked flask equipped with a thermometer, stainless steel stirring rod, dehydration tube, condenser, and nitrogen inlet tube. Under a nitrogen atmosphere and in a mantle heater, a mixed solution of the raw material monomers for the addition polymerization resins shown in Table 2, both reactive monomers, and polymerization initiator was added dropwise over 1 hour at 160°C. After maintaining the temperature at 160°C for 30 minutes, the temperature was raised to 200°C, and the reaction was carried out under reduced pressure of 8 kPa for 1 hour, after which it was cooled to 160°C. Then, the esterification catalyst and co-catalyst shown in Table 2 were added and the temperature was raised to 235°C over 2 hours. After confirming that the reaction rate reached 95% or more at 235°C, it was cooled to 180°C. Then, adipic acid was added and the temperature was raised to 220°C over 2 hours. After reacting at 220°C for 1 hour, the reaction was carried out under 8 kPa until the softening point shown in Table 2 was reached, yielding amorphous polyester composite resins (resins 5 and 6).

[0150] Resin manufacturing example 5 The raw material monomers, esterification catalysts, and co-catalysts for polyester resins other than dodecenyl succinic anhydride, as 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. 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 over 95% at 235°C, the mixture was cooled to 180°C and then heated to 220°C over 2 hours. The mixture was then reacted at 220°C for 1 hour, followed by a reaction at 8 kPa for 2 hours. Subsequently, resin A1, as shown in Table 3, was added at 220°C, and the mixture was held at 220°C for 4 hours. The reaction was then carried out at 8 kPa until the softening point shown in Table 3 was reached, yielding an amorphous polyester composite resin (resin 8).

[0151] Resin manufacturing example 6 The raw material monomers for polyester resins other than adipic acid and trimellitic anhydride, esterification catalysts, and co-catalysts 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, and then adipic acid and trimellitic anhydride were added. The mixture was then 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 11).

[0152] Resin manufacturing example 7 The raw material monomers for polyester resins other than adipic acid, the esterification catalyst, and the co-catalyst, as 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. 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, 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 12).

[0153] Resin manufacturing example 8 The raw material monomers for polyester resins other than adipic acid, as 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. Under a nitrogen atmosphere and in a mantle heater, a mixed solution of the raw material monomers for the addition polymerization resin shown in Table 3, both reactive monomers, and polymerization initiator was added dropwise over 1 hour at 170°C. After maintaining the temperature at 170°C for 30 minutes, the temperature was raised to 200°C, and the reaction was carried out under reduced pressure of 8 kPa for 1 hour, after which it was cooled to 160°C. Then, the esterification catalyst and co-catalyst shown in Table 3 were added and the temperature was raised to 235°C over 2 hours. After confirming that the reaction rate reached 95% or more at 235°C, the temperature was cooled to 180°C, adipic acid was added, and the temperature was raised to 220°C over 2 hours. After reacting at 220°C for 1 hour, the reaction was carried out under 8 kPa until the softening point shown in Table 3 was reached, yielding an amorphous polyester composite resin (resin 13).

[0154] Resin manufacturing example 9 The raw material monomers for polyester resins other than adipic acid, as shown in Tables 2 and 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. Under a nitrogen atmosphere and in a mantle heater, a mixed solution of the raw material monomers for the addition polymerization resins shown in Tables 2 and 3, both reactive monomers, and polymerization initiators was added dropwise over 1 hour at 150°C. After maintaining the temperature at 150°C for 30 minutes, the temperature was raised to 200°C, and the reaction was carried out under reduced pressure of 8 kPa for 1 hour, after which it was cooled to 160°C. Then, the esterification catalyst and co-catalyst shown in Tables 2 and 3 were added and the temperature was raised to 235°C over 2 hours. After confirming that the reaction rate reached 95% or more at 235°C, the temperature was cooled to 180°C, adipic acid was added, and the temperature was raised to 220°C over 2 hours. Subsequently, the reaction was carried out at 220°C for 1 hour, and then at 8 kPa until the softening point shown in Tables 2 and 3 was reached, yielding amorphous polyester composite resins (resins 7 and 14).

[0155] [Table 2]

[0156] [Table 3]

[0157] 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, and then a polycondensation reaction was carried out at 200°C for 1 hour. Furthermore, the esterification catalyst and co-catalyst shown in Table 4 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 15-21).

[0158] [Table 4]

[0159] Examples 1-23 and Comparative Examples 1-6 100 parts by mass of the binder resin shown in Tables 5 and 6, 1 part by mass of the amide compound, 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 in the rolls of 100°C. The feed rate of the mixture was 20 kg / h, and the average residence time was approximately 18 seconds. The obtained molten mixture 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.

[0160] Toner was obtained by adding 1 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.

[0161] Test example [Static stability] Under conditions of 25°C and 50% relative humidity, 0.6g of toner and 19.4g of silicone ferrite carrier (manufactured by Kanto Denka Kogyo Co., Ltd., average particle size 90μm) were placed in a 50mL polyethylene container and mixed at 250r / min using a ball mill. The charge level of the toner was then measured using a Q / M meter (manufactured by EPPING) by the following method. After a mixing time of 60 or 600 seconds, a specified amount of toner and carrier mixture was placed in the cell attached to the Q / M meter, and only the toner was drawn through a 32 μm mesh sieve (stainless steel, twill weave, wire diameter: 0.0035 mm) for 90 seconds. The voltage change on the carrier that occurred at that time was monitored, and the value of [total electric charge after 90 seconds (μC) / amount of toner drawn (g)] was defined as the charge amount (μC / g). The ratio of the charge amount after 60 seconds of mixing to the charge amount after 600 seconds of mixing (charge amount after 60 seconds of mixing / charge amount after 600 seconds of mixing) was calculated to evaluate the charge stability. The results are shown in Tables 5 and 6. A higher value indicates better charge stability.

[0162] [Table 5]

[0163] [Table 6]

[0164] From the above results, it can be seen that the toners of Examples 1 to 23 exhibit superior electrostatic stability compared to the toners of Comparative Example 1, which contains an amorphous polyester resin instead of an amorphous polyester composite resin; Comparative Examples 2 and 3, in which the weight-average molecular weight of the addition polymerization resin segment in the composite resin is outside the predetermined range; Comparative Example 4, which contains an amide compound that does not contain a hydroxyl group; and Comparative Examples 5 and 6, which do not contain a predetermined amount of a hydroxyl group-containing amide compound. [Industrial applicability]

[0165] The toner for electrostatic image development containing the crystalline resin-containing composition for toner of the present invention is suitably used for developing latent images formed in electrostatic image development methods, electrostatic recording methods, electrostatic printing methods, and the like.

Claims

1. A crystalline resin-containing composition for toner containing an amorphous polyester resin, a crystalline polyester resin, and a hydroxyl group-containing amide compound, wherein the amorphous polyester resin contains an amorphous polyester composite resin A in which a polyester resin segment and an addition polymerization resin segment are bonded via covalent bonds, the weight-average molecular weight of the addition polymerization resin segment is 2,000 or more and 18,000 or less, and 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.) A crystalline resin-containing composition for toner, wherein the compound represented by [formula] is such that the content of the hydroxyl group-containing amide compound is 0.4 parts by mass or more and 11 parts by mass or less, based on 100 parts by mass of the total amount of the amorphous polyester resin and the crystalline polyester resin.

2. The crystalline resin-containing composition for toner according to claim 1, wherein the crystalline polyester resin C is a polycondensate of an alcohol component containing an aliphatic diol having 2 to 6 carbon atoms and a carboxylic acid component.

3. The crystalline resin-containing composition for toner according to claim 1, wherein the crystalline polyester resin contains a crystalline polyester resin C which is a polycondensate of an alcohol component containing ethylene glycol and a carboxylic acid component.

4. A crystalline resin-containing composition for toner according to any one of claims 1 to 3, wherein the mass ratio of the addition polymerization resin segment to the polyester resin segment in the amorphous polyester composite resin A is 2 / 98 or more and 45 / 55 or less.

5. A toner for developing electrostatic images containing the crystalline resin-containing composition for toner according to any one of claims 1 to 3.

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