Electrostatic image developing toner

Abstract

An electrostatic image developing toner and a method for producing the toner, the electrostatic image developing toner containing a colorant, a resin composition (P) and an ester composition (C), the resin composition (P) being a resin composition obtained by condensing an amorphous polyester-based resin (A) having an acid group with an amine compound, the ester composition (C) being one or more selected from the following ester compositions (CI) and (CII). The ester composition (CI): an ester composition containing a condensate of a carboxylic acid component (CI-ac) containing 20 mol% or more of an aliphatic monobasic carboxylic acid compound having 10 to 30 carbon atoms and an alcohol component (CI-al) containing 90 mol% or more of an aliphatic alcohol having 2 or more valences having 2 to 14 carbon atoms; the ester composition (CII): an ester composition containing a condensate of an alcohol component (CII-al) containing 20 mol% or more of an aliphatic monohydric alcohol having 10 to 30 carbon atoms and a carboxylic acid component (CII-ac) containing 90 mol% or more of an aliphatic carboxylic acid compound having 2 or more valences having 2 to 14 carbon atoms.

Description

TECHNICAL FIELD

[0001] The present application relates to a toner for electrostatic image development used in development of a latent image formed in an electrophotographic process, an electrostatic recording process, an electrostatic printing process, and the like, and a manufacturing method of the toner. BACKGROUND

[0002] In the electrophotographic field, with the development of electrophotographic systems, development of toners corresponding to high image quality and high speed is sought.

[0003] For example, in Japanese Patent Application Laid-Open No. 2009-063987 (Patent Document 1), a toner composition is described, which contains a toner resin containing a polyester resin (I) composed of a linear polyester (A) and a non-linear polyester (B), and contains 5% by weight or more of a crystalline polyester (Al) having an SP value in a prescribed range in the linear polyester (A), the crystalline polyester (Al) being a polycondensation polyester resin of a carboxylic acid component and an alcohol component, the carboxylic acid component containing 40% by mole or more of one or more selected from aliphatic polybasic carboxylic acids having 9 to 30 carbon atoms and ester-forming derivatives thereof. SUMMARY

[0004] The present application relates to the following [1] and [2].

[0005] [1] A toner for electrostatic image development, which contains a colorant, a resin composition (P), and an ester composition (C),

[0006] The above resin composition (P) is a resin composition obtained by condensing an amorphous polyester-based resin (A) having an acid group with an amine compound,

[0007] The above ester composition (C) is one or more selected from the following ester composition (CI) and ester composition (CII).

[0008] Ester composition (CI): an ester composition containing a condensate of a carboxylic acid component (CI-ac) containing 20% by mole or more of an aliphatic monobasic carboxylic acid compound having 10 or more and 30 or less carbon atoms and an alcohol component (CI-al) containing 90% by mole or more of a 2 or more aliphatic alcohol having 2 or more and 14 or less carbon atoms

[0009] Ester composition (CII): an ester composition containing a condensate of an alcohol component (CII-al) containing 20% by mole or more of an aliphatic monohydric alcohol having 10 or more and 30 or less carbon atoms and a carboxylic acid component (CII-ac) containing 90% by mole or more of a 2 or more aliphatic carboxylic acid compound having 2 or more and 14 or less carbon atoms

[0010] 〔2〕 A method for producing a toner for electrostatic image development, comprising:

[0011] Process 1: a process of obtaining a resin composition (P) by condensing an amorphous polyester-based resin (A) having an acid group with an amine compound; and

[0012] Process 2: a process of melt-kneading a toner raw material including the resin composition (P) obtained in Process 1, a colorant, and an ester composition (C),

[0013] The ester composition (C) is one or more selected from the following ester compositions (CI) and (CII).

[0014] The ester composition (CI) is an ester composition containing a condensate of a carboxylic acid component (CI-ac) containing 20 mol% or more of an aliphatic monobasic carboxylic acid compound having 10 or more and 30 or less carbon atoms and an alcohol component (CI-al) containing 90 mol% or more of an aliphatic alcohol having 2 or more and 14 or less carbon atoms

[0015] The ester composition (CII) is an ester composition containing a condensate of an alcohol component (CII-al) containing 20 mol% or more of an aliphatic monohydric alcohol having 10 or more and 30 or less carbon atoms and a carboxylic acid component (CII-ac) containing 90 mol% or more of an aliphatic carboxylic acid compound having 2 or more and 14 or less carbon atoms DETAILED DESCRIPTION

[0016] In recent years, in order to reduce the cost of toner printing, it is required to reduce the amount of toner used in printing. If the amount of toner is to be reduced, the concentration of the colorant is reduced, and the image density is reduced, and thus it is necessary to increase the amount of the colorant. However, it is clear that if the amount of the colorant is increased with respect to the resin, the dispersibility of the colorant is deteriorated, and the image density expected is not obtained, and the gloss is also reduced.

[0017] In the technology of Patent Literature 1, the dispersibility of the colorant is not sufficient, and further improvement of the image density and the gloss is required.

[0018] The present application relates to a toner for electrostatic image development, which is excellent in image density and gloss, and a method for producing the toner.

[0019] The present inventors have found that by making the toner contain a resin composition obtained by condensing an amorphous polyester-based resin having an acid group with an amine compound, and an ester composition containing a condensate of a carboxylic acid component including a specified amount of an aliphatic monocarboxylic acid compound having a specified number of carbon atoms and an alcohol component including a specified amount of an aliphatic alcohol having 2 or more carbon atoms, or an ester composition containing a condensate of an alcohol component including a specified amount of an aliphatic monohydric alcohol having a specified number of carbon atoms and a carboxylic acid component including a specified amount of an aliphatic carboxylic acid compound having 2 or more carbon atoms, it is possible to provide an electrostatic image developing toner excellent in image density and gloss, a method for producing the toner, and the like.

[0020] That is, the present application relates to the embodiments of [1] to [5] as follows.

[0021] [1] An electrostatic image developing toner containing a colorant, a resin composition (P), and an ester composition (C),

[0022] The above resin composition (P) is a resin composition obtained by condensing an amorphous polyester-based resin (A) having an acid group with an amine compound,

[0023] The above ester composition (C) is one or more selected from the following ester composition (CI) and ester composition (CII).

[0024] The ester composition (CI) is an ester composition containing a condensate of a carboxylic acid component (CI-ac) including 20 mol% or more of an aliphatic monocarboxylic acid compound having 10 or more and 30 or less carbon atoms and an alcohol component (CI-al) including 90 mol% or more of an aliphatic alcohol having 2 or more and 14 or less carbon atoms

[0025] The ester composition (CII) is an ester composition containing a condensate of an alcohol component (CII-al) including 20 mol% or more of an aliphatic monohydric alcohol having 10 or more and 30 or less carbon atoms and a carboxylic acid component (CII-ac) including 90 mol% or more of an aliphatic carboxylic acid compound having 2 or more and 14 or less carbon atoms

[0026] [2] An electrostatic image developing toner containing a colorant, a resin composition (P), and an ester composition (C),

[0027] The above resin composition (P) is a resin composition obtained by condensing an amorphous polyester-based resin (A) having an acid group with an amine compound,

[0028] The above ester composition (C) is an ester composition (CI) containing a condensate of a carboxylic acid component (CI-ac) containing 20 mol% or more of an aliphatic monobasic carboxylic acid compound having 10 or more and 30 or less carbon atoms and an alcohol component (CI-al) containing 90 mol% or more of an aliphatic alcohol having 2 or more and 14 or less carbon atoms.

[0029] 〔3〕 An electrostatic image developing toner containing a colorant, a resin composition (P), and an ester composition (C),

[0030] The above resin composition (P) is a resin composition obtained by condensing an amorphous polyester-based resin (A) having an acid group with an amine compound,

[0031] The above ester composition (C) is an ester composition (CII) containing a condensate of an alcohol component (CII-al) containing 20 mol% or more of an aliphatic monohydric alcohol having 10 or more and 30 or less carbon atoms and a carboxylic acid component (CII-ac) containing 90 mol% or more of an aliphatic carboxylic acid compound having 2 or more and 14 or less carbon atoms.

[0032] 〔4〕 A method for producing an electrostatic image developing toner, comprising:

[0033] Step 1: a step of obtaining a resin composition (P) by condensing an amorphous polyester-based resin (A) having an acid group with an amine compound; and

[0034] Step 2: a step of melt-kneading toner raw materials containing the resin composition (P) obtained in Step 1, a colorant, and an ester composition (C),

[0035] The above ester composition (C) is one or more selected from the following ester composition (CI) and ester composition (CII).

[0036] Ester composition (CI): an ester composition containing a condensate of a carboxylic acid component (CI-ac) containing 20 mol% or more of an aliphatic monobasic carboxylic acid compound having 10 or more and 30 or less carbon atoms and an alcohol component (CI-al) containing 90 mol% or more of an aliphatic alcohol having 2 or more and 14 or less carbon atoms

[0037] Ester composition (CII): an ester composition containing a condensate of an alcohol component (CII-al) containing 20 mol% or more of an aliphatic monohydric alcohol having 10 or more and 30 or less carbon atoms and a carboxylic acid component (CII-ac) containing 90 mol% or more of a 2 or more valent aliphatic carboxylic acid compound having 2 or more and 14 or less carbon atoms

[0038] [5] A method for producing an electrostatic image developing toner, comprising:

[0039] Process 1: a process of obtaining a resin composition (P) by condensing an amorphous polyester-based resin (A) having an acid group with an amine compound; and

[0040] Process 2: a process of melt-kneading toner raw materials including the resin composition (P) obtained in Process 1, a colorant, and an ester composition (C),

[0041] The ester composition (C) is an ester composition (CI) containing a condensate of a carboxylic acid component (CI-ac) containing 20 mol% or more of an aliphatic monocarboxylic acid compound having 10 or more and 30 or less carbon atoms and an alcohol component (CI-al) containing 90 mol% or more of a 2 or more valent aliphatic alcohol having 2 or more and 14 or less carbon atoms.

[0042] According to the present application, it is possible to provide an electrostatic image developing toner excellent in image density and gloss, a method for producing the toner, and the like.

[0043] [Electrostatic image developing toner]

[0044] The electrostatic image developing toner of the present application (hereinafter, also simply referred to as "the toner of the present application.") contains a colorant, a resin composition (P), and an ester composition (C).

[0045] The resin composition (P) is a resin composition obtained by condensing an amorphous polyester-based resin (A) having an acid group (hereinafter, also simply referred to as "the resin (A).") with an amine compound.

[0046] Further, the ester composition (C) is one or more selected from the following ester composition (CI) and ester composition (CII).

[0047] Ester composition (CI): an ester composition containing a condensate of a carboxylic acid component (CI-ac) containing 20% by mole or more of an aliphatic monobasic carboxylic acid compound having 10 or more and 30 or less carbon atoms and an alcohol component (CI-al) containing 90% by mole or more of an aliphatic alcohol having 2 or more and 14 or less carbon atoms

[0048] Ester composition (CII): an ester composition containing a condensate of an alcohol component (CII-al) containing 20% by mole or more of an aliphatic monohydric alcohol having 10 or more and 30 or less carbon atoms and a carboxylic acid component (CII-ac) containing 90% by mole or more of an aliphatic carboxylic acid compound having 2 or more and 14 or less carbon atoms

[0049] The toner according to the present application exhibits excellent image density and gloss.

[0050] The reason why the effects of the present application are obtained is not certain, but it is considered as follows.

[0051] It is considered that the resin composition (P) contains a moiety derived from the amine compound in its structure, and functions as a dispersant for the colorant, thereby becoming a state in which the colorant is finely dispersed in the toner. In addition, the ester composition (C) contains an aliphatic hydrocarbon group derived from an aliphatic monobasic carboxylic acid or an aliphatic monohydric alcohol having a prescribed number of carbon atoms as a polyester structure, is hydrophobic and is low molecular, and thus exhibits the effect of a wetting agent for the colorant, and the dispersibility of the colorant is further improved. As a result, it is considered that the image density is improved. In addition, it is considered that since the ester composition (C) has a low melt viscosity, the printed film becomes smooth, and the gloss is also improved.

[0052] The following shows the definition of various terms in the present specification and the like.

[0053] The crystallinity of a resin is represented by the ratio of the softening point to the maximum peak temperature of endothermic obtained by a differential scanning calorimeter (DSC), that is, the crystallinity index defined by "softening point / endothermic maximum peak temperature". Generally, if this crystallinity index exceeds 1.4, the resin is amorphous, and if it is less than 0.6, the crystallinity is low and the amorphous portion is large. In the present application, "amorphous resin" means a resin having a crystallinity index exceeding 1.4 or less than 0.6, and "crystalline resin" means a resin having a crystallinity index of 0.6 or more, preferably 0.7 or more, more preferably 0.9 or more, and 1.4 or less, preferably 1.2 or less.

[0054] The above "maximum peak temperature of endothermic" means the temperature of the peak having the largest peak area in the endothermic peak observed under the conditions of the measurement method described in the examples.

[0055] The crystallinity of resin can be adjusted by the type and ratio of raw material monomers, as well as manufacturing conditions (such as reaction temperature, reaction time, and cooling rate).

[0056] "Polyester-based resins" can include polyester resins that have been modified to a degree that does not substantially impair their properties. Examples of modified polyester resins include urethane-modified polyester resins formed by modifying polyester resins with urethane bonds, epoxy-modified polyester resins formed by modifying polyester resins with epoxy bonds, and composite resins having both polyester and addition polymer resin components.

[0057] "Bisphenol A" refers to 2,2-bis(4-hydroxyphenyl)propane.

[0058] Examples of "carboxylic acid compounds" include carboxylic acids, their anhydrides, and alkyl esters with 1 to 3 carbon atoms. It should be noted that the carbon number of the alkyl group in an alkyl ester is not included in the carbon number of the carboxylic acid compound.

[0059] "The resin component of the toner" refers to the resin component contained in the toner of the present invention, which includes a resin composition (P) and an ester composition (C).

[0060] The colorant of the present invention contains a colorant, a resin composition (P) and an ester composition (C).

[0061] The colorant of the present invention contains, for example, colorant particles and external additives.

[0062] The colorant particles preferably comprise a colorant, a resin composition (P), and an ester composition (C).

[0063] Furthermore, the colorant particles may contain, for example, colorant derivatives, release agents, charge control agents, and other additives.

[0064] <Resin Composition (P)>

[0065] The resin composition (P) is a resin composition obtained by condensing an amorphous polyester resin (A) having acid groups with an amine compound. The resin composition (P) includes, for example, reactants of resin (A) and the amine compound, byproducts from the amine compound, unreacted resin (A), and unreacted amine compound. Furthermore, the reactants of resin (A) with the amine compound and byproducts from the amine compound are considered to function as dispersants of colorant in the resin composition (P).

[0066] [Amorphous polyester resin (A)]

[0067] Amorphous polyester resin (A) has acid groups.

[0068] Examples of acid groups include carboxyl and sulfonyl groups. Among these, carboxyl groups are preferred.

[0069] Examples of amorphous polyester resins (A) include amorphous polyester resins and amorphous composite resins having polyester resin segments and vinyl resin segments. Among these, the aforementioned amorphous polyester resin is preferred.

[0070] The aforementioned amorphous polyester resin is a condensation polymer of an alcohol component (A-al) and a carboxylic acid component (A-ac). The alcohol component (A-al) and carboxylic acid component (A-ac) contained in the aforementioned amorphous polyester resin will be described below.

[0071] (Alcohol component (A-al))

[0072] The alcohol component (A-al) preferably comprises at least one selected from bisphenol A alkyl oxide adducts (hereinafter also simply referred to as "BPA-AO") and aliphatic diols having 2 or more and 6 or fewer carbon atoms, and more preferably comprises BPA-AO. As BPA-AO, BPA-AO represented by formula (I) is preferably exemplified.

[0073] [Chemical Formula 1]

[0074]

[0075] In the formula, OR 11 and R 12 O is an alkeneoxy group, R 11 and R 12 Each of the alkylene groups (preferably ethylene or propylene) is independently an alkylene group with 1 or more and 4 or fewer carbon atoms. x and y are the average molar number of epoxides added, each being a positive number. The average value of the sum of x and y is preferably 1 or more, more preferably 1.5 or more, even more preferably 2 or more, and preferably 16 or less, more preferably 8 or less, even more preferably 4 or less.

[0076] BPA-AO is preferably a propylene oxide adduct of bisphenol A (hereinafter also referred to as "BPA-PO"), an ethylene oxide adduct of bisphenol A (hereinafter also referred to as "BPA-EO"), and more preferably BPA-PO. That is, the alcohol component (A-al) preferably contains BPA-PO. These BPA-AOs can be one or more.

[0077] The amount of BPA-AO in the alcohol component (A-al) is preferably 80 mol% or more, more preferably 90 mol% or more, even more preferably 95 mol% or more, even more preferably 98 mol% or more, and is 100 mol% or less, even more preferably 100 mol%.

[0078] When the alcohol component (A-al) contains BPA-PO, the amount of BPA-PO in the alcohol component (A-al) is preferably 80 mol% or more, more preferably 90 mol% or more, even more preferably 95 mol% or more, even more preferably 98 mol% or more, and is 100 mol% or less, even more preferably 100 mol%.

[0079] The alcohol component (A-al) may include other alcohol components different from BPA-AO. Examples of other alcohol components include aliphatic diols, alicyclic diols, and polyols with three or more nucleotides.

[0080] The aliphatic diol preferably has 2 or more carbon atoms, and more preferably 18 or less, more preferably 14 or less, even more preferably 10 or less, and even more preferably 6 or less.

[0081] Examples of aliphatic diols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, neopentyl glycol, 1,4-butenyl glycol, 1,2-pentanediol, 1,4-pentanediol, 2,4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 3,3-dimethyl-1,2-butanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, and 1,14-tetradecanediol.

[0082] Examples of alicyclic diols include hydrogenated bisphenol A and epoxide adducts of hydrogenated bisphenol A with 2 or more and 4 or less carbon atoms (with an average molar number of additions of 2 or more and 12 or less).

[0083] Examples of polyols with three or more components include glycerol, pentaerythritol, trimethylolpropane, sorbitol, and sorbitan anhydride.

[0084] It should be noted that, from the perspective of adjusting the molecular weight and softening point of the resin, the alcohol component (A-al) can include monohydric alcohols.

[0085] These alcohol components can be one or more.

[0086] (Carboxylic acid component (A-ac))

[0087] Examples of carboxylic acid components (A-ac) include dicarboxylic acid compounds and polycarboxylic acid compounds with three or more nucleotides.

[0088] Examples of dicarboxylic acid compounds include aromatic dicarboxylic acid compounds, aliphatic dicarboxylic acid compounds, and alicyclic dicarboxylic acid compounds.

[0089] The dicarboxylic acid compound preferably has 2 or more carbon atoms, more preferably 3 or more, and more preferably 30 or less, more preferably 20 or less.

[0090] Examples of aromatic dicarboxylic acid compounds include phthalic acid, isophthalic acid, and terephthalic acid. Among these, isophthalic acid and terephthalic acid are preferred, and terephthalic acid is more preferred.

[0091] Examples of aliphatic dicarboxylic acid compounds include oxalic acid, malonic acid, maleic acid, fumaric acid, citracic acid, itaconic acid, pentenic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanoic acid, azelaic acid, and succinic acid substituted with an aliphatic hydrocarbon group having 1 or more and 20 or fewer carbon atoms. The aliphatic hydrocarbon group preferably has 8 or more carbon atoms, more preferably 9 or more, and more preferably 16 or fewer, more preferably 14 or fewer. The aliphatic hydrocarbon group can be either straight-chain or branched, and can be either saturated or unsaturated aliphatic hydrocarbon groups. Examples of succinic acids substituted with an aliphatic hydrocarbon group having 1 or more and 20 or fewer carbon atoms include octenyl succinic acid, nonenyl succinic acid, decenyl succinic acid, undecenyl succinic acid, dodecyl succinic acid, dodecenyl succinic acid, tridecenyl succinic acid, tetradecenyl succinic acid, and tetrapropylene succinic acid.

[0092] Examples of alicyclic dicarboxylic acid compounds include cyclohexanedicarboxylic acid.

[0093] In these dicarboxylic acid compounds, the carboxylic acid component (A-ac) preferably comprises an aromatic dicarboxylic acid compound, and more preferably comprises terephthalic acid.

[0094] The amount of the aromatic dicarboxylic acid compound in the carboxylic acid component (A-ac) is preferably 50 mol% or more, more preferably 60 mol% or more, even more preferably 65 mol% or more, even more preferably 70 mol% or more, and is 100 mol% or less, even more preferably 100 mol%.

[0095] Examples of polycarboxylic acid compounds with three or more nucleotides include 1,2,4-triphenyltricarboxylic acid (triphenyltricarboxylic acid), 2,5,7-naphthotricarboxylic acid, and pyromellitic acid. Among these, trimellitic acid or its anhydride is preferred.

[0096] The content of polycarboxylic acid compounds with 3 or more ions in the carboxylic acid component (A-ac) is preferably 10 mol% or less, more preferably 5 mol% or less, even more preferably 1 mol% or less, and even more preferably 0 mol%.

[0097] It should be noted that, from the perspective of adjusting the molecular weight and softening point of the resin, the carboxylic acid component (A-ac) can contain an appropriate amount of monocarboxylic acid.

[0098] These carboxylic acid components can be one or more.

[0099] The equivalent ratio of the carboxyl group (COOH group) of the carboxylic acid component (A-ac) to the hydroxyl group (OH group) of the alcohol component (A-al) [COOH group / OH group] is preferably 0.7 or more, more preferably 0.8 or more, and preferably 1.3 or less, more preferably 1.2 or less, and even more preferably 1.0 or less.

[0100] (Physical properties of resin (A))

[0101] From the viewpoints of condensation reaction with amine compounds, enhancing interaction with colorants, and further improving image density and gloss, the acid value of resin (A) is preferably 2 mg KOH / g or more, more preferably 3 mg KOH / g or more, even more preferably 5 mg KOH / g or more, and preferably 40 mg KOH / g or less, more preferably 30 mg KOH / g or less, even more preferably 20 mg KOH / g or less, even more preferably 15 mg KOH / g or less, and even more preferably 10 mg KOH / g or less.

[0102] From the viewpoint of further improving image density and gloss, the weight-average molecular weight of resin (A) is preferably 2,000 or more, more preferably 3,000 or more, even more preferably 4,000 or more, and preferably 100,000 or less, more preferably 50,000 or less, even more preferably 10,000 or less, and even more preferably 7,000 or less.

[0103] From the viewpoint of further improving image density and gloss, the softening point of resin (A) is preferably 80°C or higher, more preferably 90°C or higher, even more preferably 95°C or higher, and preferably 130°C or lower, more preferably 120°C or lower, and even more preferably 110°C or lower.

[0104] From the viewpoint of further improving image density and gloss, the glass transition temperature of resin (A) is preferably 40°C or higher, more preferably 50°C or higher, even more preferably 55°C or higher, and preferably 90°C or lower, more preferably 80°C or lower, and even more preferably 70°C or lower.

[0105] The acid value, weight-average molecular weight, softening point, and glass transition temperature of resin (A) can be appropriately adjusted according to the type and ratio of the raw material monomers, as well as manufacturing conditions such as reaction temperature, reaction time, and cooling rate. These values ​​are obtained by the methods described in the examples below. It should be noted that when using two or more resins (A) in combination, it is preferable that the physical properties obtained in the form of a mixture of them are within the above-mentioned ranges.

[0106] (Manufacturing of Resin (A))

[0107] Resin (A) can be manufactured, for example, by a method including step (a), which involves polycondensation of a raw material monomer (A) containing an alcohol component (A-al) and a carboxylic acid component (A-ac).

[0108] In step (a), polycondensation can be carried out as needed, using esterification catalysts such as tin dioctanoate (II), dibutyltin oxide, and diisopropyl bis(triethanolamine) titanate, in an amount of 0.01 parts by mass or more and 5 parts by mass or less relative to the total amount of raw material monomer (A); and esterification co-catalysts such as gallic acid (same as 3,4,5-trihydroxybenzoic acid), in an amount of 0.001 parts by mass or more and 0.5 parts by mass or less relative to the total amount of raw material monomer (A).

[0109] Furthermore, when using monomers with unsaturated bonds such as fumaric acid in the polycondensation reaction, a free radical polymerization inhibitor, preferably 0.001 parts by mass and 0.5 parts by mass or less relative to the total amount of the raw material monomer (A), can be used as needed. Examples of free radical polymerization inhibitors include 4-tert-butylcatechol.

[0110] The temperature for the polycondensation reaction is preferably 120°C or higher, more preferably 160°C or higher, even more preferably 180°C or higher, and preferably 260°C or lower, more preferably 240°C or lower. It should be noted that the polycondensation can be carried out in an inert gas atmosphere.

[0111] [Amine compounds]

[0112] The amine compound is preferably a compound having an amino group (-NH2, -NHR, -NRR'). Here, R, R' represents a hydrocarbon group having 1 or more and 5 or fewer carbon atoms. The amine compound is a compound that can undergo a condensation reaction with the acid group of resin (A) and enter the molecular skeleton of resin (A).

[0113] Amine compounds may contain functional groups other than amino groups. Examples of such functional groups include hydroxyl, formyl, acetal, oxime, and thiol groups.

[0114] From the viewpoint of further improving image density and gloss, the amount of amine compound relative to 100 parts by mass of resin (A) is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, even more preferably 0.5 parts by mass or more, and preferably 20 parts by mass or less, more preferably 10 parts by mass or less, even 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, and even more preferably 2 parts by mass or less.

[0115] Examples of amine compounds include polyalkylimides, polyallylamines, (poly)ethylene polyamines, alkanolamines, and alkylamines.

[0116] The polyalkylene imide is preferably a polyalkylene imide in which the alkylene group has 1 or more and 5 or less carbon atoms, more preferably a polyalkylene imide in which the alkylene group has 2 or more and 4 or less carbon atoms, and even more preferably polyethyleneimine or polypropyleneimine, and even more preferably polyethyleneimine.

[0117] From the viewpoint of further improving image density and gloss, the number average molecular weight of polyalkylene imide is preferably 150 or more, more preferably 500 or more, even more preferably 800 or more, even more preferably 1000 or more, even more preferably 2000 or more, and preferably 10000 or less, more preferably 5000 or less, and even more preferably 4000 or less.

[0118] The number-average molecular weight value was determined using the method described in the examples.

[0119] Examples of polyallylamines include homopolymers or copolymers of allylamine compounds such as allylamine, dimethylallylamine, and diallylamine, which are polymers with amino groups in their side chains.

[0120] From the viewpoint of further improving image density and gloss, the weight-average molecular weight of polyallylamine is preferably 800 or more, more preferably 1000 or more, even more preferably 1300 or more, and preferably 10000 or less, more preferably 5000 or less, even more preferably 4000 or less, even more preferably 3000 or less, and even more preferably 2000 or less.

[0121] The weight-average molecular weight value was determined using the method described in the examples.

[0122] Examples of (poly)ethylene polyamines include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine. Among these, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine are preferred from the viewpoint of further improving image density and gloss.

[0123] As an alkanolamine, an alkanolamine having 2 or more and 9 or fewer carbon atoms is preferred. Examples of alkanolamines include primary alkanolamines such as monoethanolamine, monopropanolamine, and monobutanolamine; secondary alkanolamines such as N-methylethanolamine and N-methylpropanolamine, and secondary alkanolamines such as diethanolamine and diisopropanolamine; and tertiary alkanolamines such as N,N-dimethylethanolamine, N,N-dimethylpropanolamine, and N,N-diethylethanolamine, tertiary alkanolamines such as N-methyldiethanolamine and N-ethyldiethanolamine, and tertiary alkanolamines such as triethanolamine and triisopropanolamine. Among these, tertiary alkanolamines having 2 or more and 9 or fewer carbon atoms are preferred, tertiary alkanolamines having 2 or more and 9 or fewer carbon atoms are more preferred, and N,N-dimethylethanolamine is even more preferred.

[0124] As an alkylamine, an alkylamine having 1 or more and 6 or fewer carbon atoms is preferred. Examples of alkylamines include primary amines such as propylamine, butylamine, and hexylamine; and secondary amines such as diethylamine and dipropylamine.

[0125] One or more amine compounds may be used.

[0126] From the viewpoint of further improving image density and gloss, the amine compound preferably includes one or more of the following: polyalkylene imine, polyallylamine, (poly)ethylene polyamine, alkanolamine with 2 or more but 9 or less carbon atoms, and alkylamine with 1 or more but 6 or less carbon atoms. More preferably, it includes one or more of the following: polyalkylene imine, polyallylamine, (poly)ethylene polyamine, and tertiary alkanolamine with 2 or more but 9 or less carbon atoms. Even more preferably, it includes one or more of the following: polyalkylene imine, polyallylamine, and tertiary alkanolamine with 1 or more but 5 or less carbon atoms. Even more preferably, it includes one or more of the following: polyalkylene imine, polyallylamine, and tertiary alkanolamine with 2 or more but 9 or less carbon atoms. Even more preferably, it includes one or more of the following: polyalkylene imine, polyallylamine, and polyallylamine. Even more preferably, it includes polyalkylene imine with 1 or more but 5 or less carbon atoms. Even more preferably, it includes polyethyleneimine.

[0127] When the amine compound contains a polyalkylene imide with 1 or more and 5 or less carbon atoms in the alkylene group, the total amount of the polyalkylene imide with 1 or more and 5 or less carbon atoms in the amine compound is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and 100% by mass or less, even more preferably 100% by mass.

[0128] (Physical properties of resin composition (P))

[0129] From the viewpoint of further improving image density and gloss, the softening point of the resin composition (P) is preferably 80°C or higher, more preferably 90°C or higher, even more preferably 95°C or higher, and preferably 130°C or lower, more preferably 120°C or lower, and even more preferably 110°C or lower.

[0130] From the viewpoint of further improving image density and gloss, the glass transition temperature of the resin composition (P) is preferably 40°C or higher, more preferably 50°C or higher, even more preferably 55°C or higher, and preferably 90°C or lower, more preferably 80°C or lower, and even more preferably 70°C or lower.

[0131] The softening point and glass transition temperature of the resin composition (P) can be appropriately adjusted according to the type and ratio of raw materials, as well as manufacturing conditions such as reaction temperature, reaction time, and cooling rate. These values ​​are obtained by the methods described in the examples below. It should be noted that when two or more resin compositions (P) are used in combination, the physical properties obtained in the form of their mixtures are preferably within the above-mentioned ranges.

[0132] (Preparation of resin composition (P))

[0133] As described above, the resin composition (P) is obtained by condensing an amorphous polyester resin (A) having acid groups with an amine compound.

[0134] Methods for manufacturing the resin composition (P) include, for example:

[0135] Step 1: A step of condensing an amorphous polyester resin (A) with an acid group with an amine compound to obtain a resin composition (P).

[0136] The temperature during condensation in step 1 is preferably 50°C or higher, more preferably 100°C or higher, even more preferably 130°C or higher, and preferably 235°C or lower, more preferably 200°C or lower, and even more preferably 170°C or lower.

[0137] From the viewpoint of improving the dispersibility of the colorant and further improving the image density and gloss, the amount of amine compound in step 1 is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, even more preferably 0.5 parts by mass or more, and preferably 20 parts by mass or less, more preferably 10 parts by mass or less, even 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, and even more preferably 2 parts by mass or less.

[0138] In the toner of the present invention, from the viewpoint of improving the dispersibility of the colorant and further improving the image density and gloss, the content of the resin composition (P) is preferably 20% by mass or more, more preferably 40% by mass or more, more preferably 50% by mass or more, more preferably 55% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less, more preferably 70% by mass or less, and more preferably 65% ​​by mass or less.

[0139] <Ester Composition (C)>

[0140] As described above, the ester composition (C) is selected from one or more ester compositions (CI) and ester compositions (CII).

[0141] It is believed that because the ester composition (C) has ester groups, it has a high affinity for the resin composition (P). Furthermore, because it contains aliphatic hydrocarbon groups derived from aliphatic monocarboxylic acid compounds or aliphatic monohydric alcohols with 10 to 30 carbon atoms as a polyester structure, it is hydrophobic and has a low molecular weight, thus exhibiting a wetting agent effect on the colorant and further improving the dispersibility of the colorant. As a result, it is believed that image density and gloss can be improved. The ester composition (C) can be used in combination with ester composition (CI) and ester composition (CII), and from the above viewpoint, either ester composition (CI) or ester composition (CII) is preferred. That is, the present invention is preferably an embodiment where the ester composition (C) is ester composition (CI) or an embodiment where the ester composition (C) is ester composition (CII), and more preferably an embodiment where the ester composition (C) is ester composition (CI).

[0142] [Ester Composition (CI)]

[0143] The ester composition (CI) is an ester composition containing a condensate of a carboxylic acid component (CI-ac) and an alcohol component (CI-al), wherein the carboxylic acid component (CI-ac) comprises 20 mol% or more of an aliphatic monocarboxylic acid compound having 10 or more and 30 or fewer carbon atoms, and the alcohol component (CI-al) comprises 90 mol% or more of a divalent aliphatic alcohol having 2 or more and 14 or fewer carbon atoms.

[0144] In this invention, the carboxylic acid component (CI-ac) refers to the carboxylic acid component constituting the ester composition (CI), and the alcohol component (CI-al) refers to the alcohol component constituting the ester composition (CI).

[0145] (Carboxylic acid component (CI-ac))

[0146] From the viewpoint of further improving image density and gloss, the number of carbon atoms in the aliphatic monocarboxylic acid compound is preferably 12 or more, more preferably 14 or more, even more preferably 16 or more, and even more preferably 18 or more. Furthermore, from the viewpoint of low-temperature fixing, it is 30 or less, preferably 28 or less, more preferably 26 or less, even more preferably 24 or less, and even more preferably 22 or less.

[0147] The aliphatic monocarboxylic acid compound can be either a saturated aliphatic monocarboxylic acid compound or an unsaturated aliphatic monocarboxylic acid compound. From the viewpoint of further improving image density and gloss, a saturated aliphatic monocarboxylic acid compound is preferred.

[0148] Examples of saturated aliphatic monocarboxylic acid compounds include decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, benzyl acid, and linalic acid. Among these, stearic acid and benzyl acid are more preferred from the viewpoint of low-temperature fixing and further improving image density and gloss, with stearic acid being the most preferred.

[0149] The carboxylic acid component (CI-ac) may include carboxylic acid compounds other than aliphatic monocarboxylic acid compounds. Examples of other carboxylic acid compounds include straight-chain or branched aliphatic dicarboxylic acid compounds, aromatic dicarboxylic acid compounds and alicyclic dicarboxylic acid compounds, and polycarboxylic acid compounds with three or more members.

[0150] From the viewpoint of further improving image density and gloss, the number of carbon atoms in the aliphatic dicarboxylic acid compound is preferably 4 or more, more preferably 6 or more, and from the viewpoint of low-temperature fixing, it is preferably 14 or less, more preferably 12 or less.

[0151] Aliphatic dicarboxylic acid compounds can be either saturated or unsaturated aliphatic dicarboxylic acid compounds.

[0152] Examples of aliphatic dicarboxylic acid compounds include succinic acid, fumaric acid, adipic acid, octanoic acid, sebacic acid, dodecanoic acid, and tetradecanoic acid. Among these, sebacic acid is preferred.

[0153] Examples of aromatic dicarboxylic acid compounds, alicyclic dicarboxylic acid compounds, and polycarboxylic acid compounds with three or more members are the same as those previously illustrated.

[0154] From the viewpoint of further improving image density and gloss, the content of aliphatic monocarboxylic acid compound in the carboxylic acid component (CI-ac) is preferably 40 mol% or more, more preferably 60 mol% or more, even more preferably 70 mol% or more, even more preferably 90 mol% or more, even more preferably 95 mol% or more, and preferably 100 mol% or less, even more preferably 100 mol%.

[0155] (Alcohol component (CI-al))

[0156] From the viewpoint of image density and gloss, the aliphatic alcohol with 2 or more carbon atoms has 2 or more carbon atoms, preferably 4 or more, more preferably 6 or more, and even more preferably 8 or more carbon atoms. Furthermore, from the viewpoint of low-temperature fixing, it has 14 or less carbon atoms, preferably 12 or less, and more preferably 10 or less carbon atoms.

[0157] Aliphatic alcohols with two or more nucleotides can be categorized as straight-chain or branched aliphatic diols, alicyclic diols, and polyols with three or more nucleotides.

[0158] As a straight-chain or branched aliphatic diol, it can be either a saturated aliphatic diol or an unsaturated aliphatic diol. From the viewpoint of further improving image density and gloss, a saturated aliphatic diol is preferred.

[0159] Examples of saturated aliphatic diols include ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, 1,12-dodecanediol, and 1,14-tetradecanediol. From the viewpoints of further improving low-temperature fixing performance, image density, and gloss, ethylene glycol, 1,6-hexanediol, and 1,10-decanediol are preferred, with 1,6-hexanediol and 1,10-decanediol being more preferred.

[0160] Examples of alicyclic diols and polyols with three or more nucleotides are the same as those previously illustrated. Glycerol is preferred among polyols with three or more nucleotides.

[0161] From the viewpoint of further improving image density and gloss, the content of aliphatic alcohols with two or more components in the alcohol component (CI-al) is preferably 95 mol% or more, more preferably 97 mol% or more, and preferably 100 mol% or less, more preferably 100 mol%.

[0162] From the perspective of further improving low-temperature fixing performance and image density and gloss, the ester composition (CI) is preferably a synthetic ester composition containing a compound having two ester groups in its molecule (hereinafter also referred to as "dieseryl compound"). It is believed that diester compounds have low melt viscosity, and in the case of manufacturing toners by melt mixing, in addition to the effect of the wetting agent mentioned above, during the wetting process of dispersing the colorant, the diester compound penetrates into the gaps between the colorant particle aggregates, reducing the cohesive force of the colorant particles and making them easier to break apart by the mechanical force of the disperser. As a result, it is believed that the dispersibility of the colorant is improved, and the image density and gloss are further improved. From this perspective, the ester composition (CI) preferably comprises a condensation compound of an aliphatic monocarboxylic acid compound having 10 or more and 30 or less carbon atoms and an aliphatic diol having 2 or more and 14 or less carbon atoms, more preferably a condensation compound of an aliphatic monocarboxylic acid compound having 16 or more and 24 or less carbon atoms and an aliphatic diol having 2 or more and 14 or less carbon atoms, and even more preferably a condensation compound of an aliphatic monocarboxylic acid compound having 16 or more and 24 or less carbon atoms and an aliphatic diol having 6 or more and 14 or less carbon atoms.

[0163] [Ester Composition (CII)]

[0164] The ester composition (CII) is an ester composition containing a condensate of an alcohol component (CII-al) and a carboxylic acid component (CII-ac), wherein the alcohol component (CII-al) comprises 20 mol% or more of an aliphatic monohydric alcohol having 10 or more and 30 or fewer carbon atoms, and the carboxylic acid component (CII-ac) comprises 90 mol% or more of a divalent aliphatic carboxylic acid compound having 2 or more and 14 or fewer carbon atoms.

[0165] In this invention, the alcohol component (CII-al) refers to the alcohol component constituting the ester composition (CII), and the carboxylic acid component (CII-ac) refers to the carboxylic acid component constituting the ester composition (CII).

[0166] (Alcohol component (CII-al))

[0167] From the viewpoint of further improving image density and gloss, the number of carbon atoms in the aliphatic monohydric alcohol is preferably 12 or more, more preferably 14 or more, even more preferably 16 or more, and even more preferably 18 or more. Furthermore, from the viewpoint of low-temperature fixing, it is 30 or less, preferably 28 or less, more preferably 26 or less, even more preferably 24 or less, and even more preferably 22 or less.

[0168] The aliphatic monohydric alcohol can be either saturated or unsaturated. From the viewpoint of further improving image density and gloss, saturated aliphatic monohydric alcohols are preferred.

[0169] Examples of aliphatic monohydric alcohols include decanol, lauryl alcohol, stearyl alcohol, palmitol, and behenyl alcohol. Among these, stearyl alcohol and behenyl alcohol are preferred, and stearyl alcohol is more preferred.

[0170] The alcohol component (CII-al) may include alcohols other than aliphatic monohydric alcohols. Examples of other alcohols include straight-chain or branched aliphatic diols, alicyclic diols, and polyols with three or more nucleotides.

[0171] Examples of straight-chain or branched aliphatic diols, alicyclic diols, and polyols with three or more nucleotides are the same as those previously illustrated.

[0172] Among them, alcohols other than aliphatic monohydric alcohols are preferably saturated aliphatic diols, and more preferably 1,12-dodecanediol.

[0173] From the viewpoint of further improving image density and gloss, the content of aliphatic monohydric alcohol in the alcohol component (CII-al) is preferably 30 mol% or more, more preferably 40 mol% or more, even more preferably 50 mol% or more, even more preferably 60 mol% or more, even more preferably 70 mol% or more, even more preferably 80 mol% or more, even more preferably 90 mol% or more, even more preferably 95 mol% or more, and preferably 100 mol% or less, even more preferably 100 mol%.

[0174] (Carboxylic acid component (CII-ac))

[0175] From the viewpoint of further improving image density and gloss, the number of carbon atoms in the aliphatic carboxylic acid compound with 2 or more atoms is preferably 4 or more, more preferably 6 or more, and even more preferably 8 or more. Furthermore, from the viewpoint of low-temperature fixing, it is preferably 12 or less.

[0176] Examples of aliphatic carboxylic acid compounds with two or more members include straight-chain or branched aliphatic dicarboxylic acid compounds and aliphatic carboxylic acid compounds with three or more members.

[0177] Aliphatic dicarboxylic acid compounds can be either saturated or unsaturated aliphatic dicarboxylic acid compounds.

[0178] Examples of aliphatic dicarboxylic acid compounds include succinic acid, fumaric acid, adipic acid, octanoic acid, sebacic acid, dodecanoic acid, and tetradecanoic acid.

[0179] Examples of aliphatic carboxylic acid compounds with three or more elements include aconitic acid.

[0180] From the perspective of low-temperature fixing and further improving image density and gloss, aliphatic carboxylic acid compounds with more than 2 nucleotides are preferred, and saturated aliphatic dicarboxylic acid compounds are more preferred, and sebacic acid is preferred.

[0181] The carboxylic acid component (CII-ac) may include other carboxylic acid compounds besides aliphatic carboxylic acid compounds with more than two members. Examples of other carboxylic acid compounds include aromatic dicarboxylic acid compounds and alicyclic dicarboxylic acid compounds. Examples of aromatic dicarboxylic acid compounds and alicyclic dicarboxylic acid compounds are the same as those previously illustrated.

[0182] From the viewpoint of further improving image density and gloss, the content of aliphatic carboxylic acid compounds with 2 or more moles in the carboxylic acid component (CII-ac) is preferably 95 mol% or more, more preferably 97 mol% or more, and preferably 100 mol% or less, more preferably 100 mol%.

[0183] From the viewpoint of further improving image density and gloss, the ester composition (CII) is preferably a synthetic ester composition comprising a diester compound having two ester groups in its molecule. It is believed that this diester compound has a low melt viscosity, and similarly to the diester compound in the aforementioned ester composition (CI), the dispersibility of the colorant is improved, further enhancing image density and gloss. From this viewpoint, as the ester composition (CII), it is preferable to include a condensation compound comprising an aliphatic monohydric alcohol having 10 or more and 30 or fewer carbon atoms and an aliphatic dicarboxylic acid compound having 2 or more and 14 or fewer carbon atoms; more preferably, a condensation compound comprising an aliphatic monohydric alcohol having 16 or more and 24 or fewer carbon atoms and an aliphatic dicarboxylic acid compound having 2 or more and 14 or fewer carbon atoms; and even more preferably, a condensation compound comprising an aliphatic monohydric alcohol having 16 or more and 24 or fewer carbon atoms and an aliphatic dicarboxylic acid compound having 6 or more and 14 or fewer carbon atoms.

[0184] As described above, the ester composition (C) is further preferably an ester composition (CI) comprising a condensate of an aliphatic monocarboxylic acid compound having 10 or more and 30 or less carbon atoms and an aliphatic diol having 2 or more and 14 or less carbon atoms as the diester compound, or an ester composition (CII) comprising a condensate of an aliphatic monocarboxylic acid compound having 10 or more and 30 or less carbon atoms and an aliphatic dicarboxylic acid compound having 2 or more and 14 or less carbon atoms as the diester compound, and is further preferably an ester composition (CI) comprising a condensate of an aliphatic monocarboxylic acid compound having 10 or more and 30 or less carbon atoms and an aliphatic diol having 2 or more and 14 or less carbon atoms as the diester compound.

[0185] [Physical properties of ester composition (C)]

[0186] From the viewpoint of further improving image density and gloss, the acid value of the ester composition (C) is preferably 0.2 mg KOH / g or more, more preferably 1 mg KOH / g or more, even more preferably 2 mg KOH / g or more, even more preferably 3 mg KOH / g or more, and preferably 45 mg KOH / g or less, more preferably 40 mg KOH / g or less, even more preferably 30 mg KOH / g or less, even more preferably 20 mg KOH / g or less, even more preferably 10 mg KOH / g or less, and even more preferably 5 mg KOH / g or less.

[0187] When the ester composition (C) is an ester composition (CI), from the viewpoint of further improving image density and gloss, the acid value of the ester composition (C) is preferably 0.2 mg KOH / g or more, more preferably 1 mg KOH / g or more, even more preferably 2 mg KOH / g or more, even more preferably 3 mg KOH / g or more, and preferably 45 mg KOH / g or less, more preferably 40 mg KOH / g or less, even more preferably 30 mg KOH / g or less, even more preferably 10 mg KOH / g or less, and even more preferably 5 mg KOH / g or less.

[0188] When the ester composition (C) is an ester composition (CII), from the viewpoint of further improving image density and gloss, the acid value of the ester composition (C) is preferably 1 mg KOH / g or more, more preferably 3 mg KOH / g or more, even more preferably 5 mg KOH / g or more, even more preferably 10 mg KOH / g or more, even more preferably 15 mg KOH / g or more, and preferably 45 mg KOH / g or less, more preferably 40 mg KOH / g or less, even more preferably 30 mg KOH / g or less, and even more preferably 20 mg KOH / g or less.

[0189] From the viewpoint of further improving image density and gloss, the weight-average molecular weight of the ester composition (C) is preferably 300 or more, more preferably 500 or more, even more preferably 700 or more, even more preferably 1000 or more, and from the viewpoint of low-temperature fixing, it is preferably 10000 or less, more preferably 7000 or less, even more preferably 5000 or less, even more preferably 3000 or less, even more preferably 2000 or less, even more preferably 1500 or less.

[0190] The softening point of the ester composition (C) is preferably 60°C or higher, more preferably 65°C or higher, even more preferably 70°C or higher, and preferably 100°C or lower, more preferably 90°C or lower, even more preferably 80°C or lower.

[0191] The ester composition (C) is preferably crystalline and has a melting point. From the viewpoint of further improving image density and gloss, the melting point of the ester composition (C) is preferably 50°C or higher, more preferably 55°C or higher, and even more preferably 60°C or higher. Furthermore, from the viewpoint of low-temperature fixing, it is preferably 100°C or lower, more preferably 90°C or lower, and even more preferably 80°C or lower.

[0192] The acid value, weight-average molecular weight, softening point, and melting point of the ester composition (C) can be appropriately adjusted according to the type and ratio of the raw material monomers, as well as manufacturing conditions such as reaction temperature, reaction time, and cooling rate. These values ​​are obtained by the methods described in the examples below. It should be noted that when two or more ester compositions (C) are used in combination, the physical properties obtained as a mixture of them are preferably within the above-mentioned ranges.

[0193] [Preparation of ester composition (C)]

[0194] Ester composition (C) can be obtained by manufacturing ester composition (CI) or ester composition (CII). For example, ester composition (CI) can be manufactured by condensing a starting monomer containing an alcohol component (CI-al) and a carboxylic acid component (CI-ac) in an inactive gas atmosphere, preferably in the presence of an esterification catalyst, and further, as needed, in the presence of an esterification co-catalyst, a free radical polymerization inhibitor, etc., at a temperature preferably above 130°C, more preferably above 170°C, and preferably below 250°C, more preferably below 240°C. Ester composition (CII) can be manufactured in the same way as ester composition (CI) using a starting monomer containing an alcohol component (CII-al) and a carboxylic acid component (CII-ac).

[0195] Examples of esterification catalysts and esterification co-catalysts used in the manufacture of ester compositions (CI) and (CII) are the same as those previously illustrated. Examples of free radical polymerization inhibitors include 4-tert-butylcatechol. The amounts of these components used in the manufacture of ester compositions (CI) and (CII) are as follows.

[0196] The amount of esterification catalyst used is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and preferably 1 part by mass or less, more preferably 0.5 parts by mass or less, relative to 100 parts by mass of the raw material monomer.

[0197] The amount of esterification co-catalyst used relative to 100 parts by mass of the raw material monomer is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and preferably 0.5 parts by mass or less, more preferably 0.1 parts by mass or less.

[0198] The amount of free radical polymerization inhibitor used relative to 100 parts by mass of the raw material monomer is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and preferably 0.5 parts by mass or less, more preferably 0.1 parts by mass or less.

[0199] In the toner of the present invention, from the viewpoint of improving the dispersibility of the colorant and further improving the image density and gloss, the content of the ester composition (C) is preferably 1% by mass or more, more preferably 2% by mass or more, more preferably 3% by mass or more, and preferably 20% by mass or less, more preferably 10% by mass or less, and more preferably 7% by mass or less.

[0200] In the colorant of the present invention, the mass ratio of the content of ester composition (C) to resin composition (P) [ester composition (C) / resin composition (P)] is preferably 0.01 or more, more preferably 0.03 or more, even more preferably 0.05 or more, and preferably 1 or less, more preferably 0.5 or less, even more preferably 0.3 or less, and even more preferably 0.1 or less.

[0201] In addition to the resin composition (P) and ester composition (C), the resin component of the toner of the present invention may also contain other resins such as amorphous polyester resin and crystalline polyester resin. In the toner of the present invention, the total content of the resin composition (P) and ester composition (C) is preferably 40% by mass or more, more preferably 50% by mass or more, further preferably 60% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less, and further preferably 70% by mass or less.

[0202] <Amorphous Polyester Resin (B)>

[0203] From the viewpoint of further improving image density and gloss, the toner of the present invention preferably further contains an amorphous polyester resin (B) (hereinafter also simply referred to as "resin (B)") in addition to the resin composition (P) and the ester composition (C). The resin (B) may be the same as the resin (A) described above, but preferably has a softening point different from that of the resin (A), and more preferably has a softening point higher than that of the resin (A).

[0204] The resin (B) is preferably an amorphous polyester resin that is a condensation polymer of an alcohol component (B-al) and a carboxylic acid component (B-ac).

[0205] The examples of alcohol components (B-al) and carboxylic acid components (B-ac) of resin (B) are the same as those of alcohol components (A-al) and carboxylic acid components (A-ac) of resin (A) described above.

[0206] BPA-AO is preferred as the alcohol component (B-al).

[0207] BPA-AO is preferably BPA-PO or BPA-EO, and more preferably BPA-PO. That is, the alcohol component (B-al) preferably contains BPA-PO.

[0208] As the carboxylic acid component (B-ac), aromatic dicarboxylic acid compounds, aliphatic dicarboxylic acid compounds, and polycarboxylic acid compounds with three or more elements are preferred.

[0209] As aromatic dicarboxylic acid compounds, isophthalic acid and terephthalic acid are preferred, and terephthalic acid is more preferred.

[0210] The amount of the aromatic dicarboxylic acid compound in the carboxylic acid component (B-ac) is preferably 20 mol% or more, more preferably 30 mol% or more, even more preferably 40 mol% or more, and preferably 70 mol% or less, more preferably 60 mol% or less, and even more preferably 50 mol% or less.

[0211] Adipic acid is preferred as an aliphatic dicarboxylic acid compound.

[0212] The amount of the aliphatic dicarboxylic acid compound in the carboxylic acid component (B-ac) is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, and preferably 60 mol% or less, more preferably 50 mol% or less, and even more preferably 40 mol% or less.

[0213] As a polycarboxylic acid compound with three or more elements, trimellitic acid or its anhydride is preferred.

[0214] The amount of the polycarboxylic acid compound with 3 or more components in the carboxylic acid component (B-ac) is preferably 1 mol% or more, more preferably 10 mol% or more, even more preferably 20 mol% or more, and preferably 40 mol% or less, more preferably 35 mol% or less, and even more preferably 30 mol% or less.

[0215] (Physical properties of resin (B))

[0216] The acid value of resin (B) is preferably 2 mg KOH / g or more, more preferably 5 mg KOH / g or more, even more preferably 10 mg KOH / g or more, and preferably 40 mg KOH / g or less, more preferably 30 mg KOH / g or less, and even more preferably 25 mg KOH / g or less.

[0217] From the viewpoint of further improving image density and gloss, the softening point of resin (B) is preferably 80°C or higher, more preferably 90°C or higher, even more preferably 100°C or higher, even more preferably 110°C or higher, even more preferably 115°C or higher, even more preferably 120°C or higher, even more preferably more than 120°C, and preferably 170°C or lower, more preferably 160°C or lower, even more preferably 150°C or lower, even more preferably 140°C or lower, even more preferably 130°C or lower.

[0218] When the softening point of resin (A) is 80°C or higher and 120°C or lower, the softening point of resin (B) is preferably higher than 120°C, more preferably higher than 125°C, even more preferably higher than 130°C, and preferably lower than 170°C, more preferably lower than 150°C, and even more preferably lower than 140°C.

[0219] The difference in softening point between resin (A) and resin (B) is preferably 5°C or more, more preferably 10°C or more, even more preferably 20°C or more, even more preferably 30°C or more, and preferably 60°C or less, more preferably 50°C or less, and even more preferably 40°C or less.

[0220] The glass transition temperature of resin (B) is preferably 40°C or higher, more preferably 45°C or higher, even more preferably 50°C or higher, and preferably 90°C or lower, more preferably 80°C or lower, even more preferably 70°C or lower, and even more preferably 60°C or lower.

[0221] The acid value, softening point, and glass transition temperature of resin (B) can be appropriately adjusted according to the type and ratio of the raw material monomers, as well as manufacturing conditions such as reaction temperature, reaction time, and cooling rate. These values ​​are obtained by the methods described in the examples below. It should be noted that when using two or more resins (B) in combination, it is preferable that the physical properties obtained in the form of a mixture of them are within the above-mentioned ranges.

[0222] In the toner of the present invention, the content of resin (B) is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, and preferably 60% by mass or less, more preferably 50% by mass or less, and further preferably 40% by mass or less, based on the total amount of resin components in the toner.

[0223] In the colorant of the present invention, the total content of the resin component of the colorant is preferably 50% by mass or more, more preferably 65% ​​by mass or more, even more preferably 80% by mass or more, and preferably 98% by mass or less, more preferably 94% by mass or less, and even more preferably 90% by mass or less.

[0224] <Coloring agent>

[0225] The colorant can be either a pigment or a dye.

[0226] Examples of pigments include azo pigments, phthalocyanine pigments, fused polycyclic pigments, and lake pigments.

[0227] Examples of azo pigments include insoluble azo pigments such as CI Pigment Red 3, soluble azo pigments such as CI Pigment Red 48:1, and condensed azo pigments such as CI Pigment Red 144.

[0228] Examples of phthalocyanine pigments include copper phthalocyanine pigments such as CI Pigment Blue 15:3 and zinc polyhalogen phthalocyanine pigments such as CI Pigment Green 58.

[0229] Examples of fused polycyclic pigments include anthraquinone pigments such as CI Pigment Red 177, perylene pigments such as CI Pigment Red 123, pyrene pigments such as CI Pigment Orange 43, quinacridone pigments such as CI Pigment Red 122, naphthol pigments such as CI Pigment Red 269, dioxazine pigments such as CI Pigment Violet 23, isoindolineone pigments such as CI Pigment Yellow 139 and 185, isoindoline pigments such as CI Pigment Orange 66, quinolineone pigments such as CI Pigment Yellow 138, nickel azo complex pigments such as CI Pigment Yellow 150, indigo pigments such as CI Pigment Red 88, metal complex pigments such as CI Pigment Green 8, and diketopyrrolopyrrole pigments such as CI Pigment Red 254, CI Pigment Red 255, and CI Pigment Orange 71.

[0230] As a lake pigment, CI Pigment Red 57:1 can be cited as an example.

[0231] Among these, from the viewpoint of further improving image density and gloss, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, naphthol pigments, and lake pigments are preferred, phthalocyanine pigments, quinacridone pigments, and isoindolinone pigments are more preferred, phthalocyanine pigments are even more preferred, and copper phthalocyanine pigments such as CI Pigment Blue 15:3 are even more preferred.

[0232] It should be noted that, in the toner of the present invention, when a pigment is used as a colorant, as described above, the resin composition (P) improves the microdispersion of the pigment in the toner, and further, through the wetting effect of the ester composition (C) on the colorant, the dispersibility of the pigment is improved. Therefore, good pigment dispersibility can be obtained not only for phthalocyanine pigments, but also for quinacridone-based pigments and naphthol-based pigments, which have historically been considered to have insufficient pigment dispersibility.

[0233] Examples of dyes include azine dyes, anthraquinone dyes, pyrenone dyes, and rhodamine dyes. More specifically, examples of dyes include CI Solvent Black 5, CI Solvent Black 7, Spirit Black SB, toluidine blue, CI Solvent Blue 11, CI Solvent Blue 12, CI Solvent Blue 35, CI Solvent Blue 59, CI Solvent Blue 74, 1-aminoanthraquinone, 2-aminoanthraquinone, hydroxyethylaminoanthraquinone, CI Solvent Violet 47, Solvent Orange 60, Solvent Orange 78, Solvent Orange 90, Solvent Violet 29, Solvent Red 135, Solvent Red 162, Solvent Red 179, and basic rhodamine B.

[0234] From the viewpoint of further enjoying the effects of the present invention, the colorant is preferably a pigment. The hue of the colorant is not particularly limited; colored pigments such as yellow, magenta, cyan, blue, red, orange, and green can all be used. One or more of these can be used.

[0235] From the viewpoint of increasing the image concentration of the toner, the content of the colorant relative to the total amount of resin component of the toner is preferably 1 part by mass or more, more preferably 2 parts by mass or more, even more preferably 3 parts by mass or more, even more preferably 5 parts by mass or more, even more preferably 7 parts by mass or more, even more preferably 10 parts by mass or more, even more preferably more than 10 parts by mass, and preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 15 parts by mass or less.

[0236] <Colorant Derivatives>

[0237] The colorant of the present invention may contain colorant derivatives. Examples of colorant derivatives include colorants or their salts that have incorporated acidic or basic groups.

[0238] The colorant derivative is preferably a colorant containing a sulfonium group or a salt thereof.

[0239] As a colorant, and as a colorant derivative used with CI Pigment Blue 15:3, it is preferable to introduce a copper phthalocyanine compound or its salt containing a sulfonium group.

[0240] Examples of salts include halide salts, amine salts, and quaternary ammonium salts.

[0241] As a colorant derivative, sulfonated copper phthalocyanine or its salt is preferred.

[0242] Commercially available products that are colorant derivatives include, for example, the "SOLSPERS" series of "5000S" and "22000" (both manufactured by Lubrizol Co., Ltd. of Japan).

[0243] When the toner of the present invention contains a colorant derivative, from the viewpoint of increasing the image concentration of the toner, the content of the colorant derivative is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, further preferably 2 parts by mass or more, and preferably 15 parts by mass or less, more preferably 10 parts by mass or less, relative to 100 parts by mass of the colorant.

[0244] <Mold Release Agent>

[0245] The colorant of this invention may contain a release agent.

[0246] Examples of release agents include polypropylene wax, polyethylene wax, and polypropylene-polyethylene copolymer wax; hydrocarbon waxes such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax, and saxoline wax, or their oxides; ester waxes such as carnauba wax, lignite wax, or their deoxidized waxes, and fatty acid ester waxes; fatty acid amides, fatty acids, higher alcohols, and fatty acid metal salts. One or more of these can be used.

[0247] The melting point of the release agent is preferably above 60°C, more preferably above 70°C, even more preferably above 75°C, and preferably below 150°C, more preferably below 130°C, and even more preferably below 100°C.

[0248] The content of the release agent relative to 100 parts by weight of the total resin component of the colorant is preferably 0.1 parts by weight or more, more preferably 0.5 parts by weight or more, even more preferably 0.8 parts by weight or more, and preferably 10 parts by weight or less, more preferably 8 parts by weight or less, and even more preferably 5 parts by weight or less.

[0249] <Charge Control Agent>

[0250] The toner of the present invention may contain a charge control agent. The charge control agent may contain either a positively charged charge control agent or a negatively charged charge control agent.

[0251] Examples of positively charged charge control agents include aniline black dyes such as "Nigrosine base EX", "OilBlack BS", "Oil Black SO", "BONTRON (registered trademark) N-01", "BONTRON (registered trademark) N-04", "BONTRON (registered trademark) N-07", "BONTRON (registered trademark) N-09", and "BONTRON (registered trademark) N-11" (all manufactured by Orient Chemical Industry Co., Ltd.); triphenylmethane dyes containing tertiary amines as side chains; quaternary ammonium salt compounds such as "BONTRON (registered trademark) P-51" (manufactured by Orient Chemical Industry Co., Ltd.); hexadecyltrimethylammonium bromide; and "COPY CHARGE PX". VP435 (manufactured by Clariant Corporation), etc.; polyamine resins, such as "AFP-B" (manufactured by Orient Chemical Industry Co., Ltd.), etc.; imidazole derivatives, such as "PLZ-2001" and "PLZ-8001" (manufactured by Shikoku Chemical Industry Co., Ltd.), etc.; styrene-acrylic resins, such as "FCA-701PT" (manufactured by Fujikura Chemical Co., Ltd.), etc.

[0252] Examples of negatively charged charge control agents include metal azo dyes such as "VALIFAST Black 3804", "BONTRON S-31", "BONTRON S-32", "BONTRON S-34", "BONTRON S-36" (all manufactured by Orient Chemical Industry Co., Ltd.), and "AizenSpilon Black". Examples of charge control agents include: TRH, T-77 (manufactured by Hodogaya Chemical Industry Co., Ltd.); metal compounds of diphenyl glycolic acid, such as LR-147 and LR-297 (manufactured by Carlit Corporation of Japan); metal compounds of salicylic acid, such as BONTRON E-81, BONTRON E-84, BONTRON E-88, BONTRONE-304 (manufactured by Orient Chemical Industry Co., Ltd.), and TN-105 (manufactured by Hodogaya Chemical Industry Co., Ltd.); copper phthalocyanine dyes; quaternary ammonium salts, such as COPY CHARGE PX VP434 (manufactured by Clariant), nitroimidazole derivatives, etc.; and organometallic compounds. One or more of these charge control agents may be used.

[0253] The content of the charge control agent relative to 100 parts by weight of the total resin component of the colorant is preferably 0.01 parts by weight or more, more preferably 0.2 parts by weight or more, even more preferably 0.5 parts by weight or more, and preferably 10 parts by weight or less, more preferably 5 parts by weight or less, even more preferably 3 parts by weight or less, and even more preferably 2 parts by weight or less.

[0254] <Other Additives>

[0255] In addition to other additives, the colorant particles may also contain appropriate amounts of magnetic powder, flowability improvers, conductivity modifiers, fibrous materials, and other reinforcing fillers, antioxidants, anti-aging agents, and cleaning agents.

[0256] In the toner of the present invention, the content of toner particles is preferably 80% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and preferably 100% by mass or less, preferably 99% by mass or less.

[0257] The volume median particle size (D) of toner particles 50 Preferably, the particle size is 2 μm or more, more preferably 3 μm or more, even more preferably 4 μm or more, and preferably 20 μm or less, more preferably 15 μm or less, even more preferably 10 μm or less. In this specification, the volume median particle size (D...) 50 () refers to the cumulative volume frequency calculated as a volume fraction, starting from the smaller particle size side and reaching 50% of the particle size.

[0258] <External Additives>

[0259] To improve fluidity, the colorant of the present invention may further contain external additives. Examples of external additives include inorganic material particles such as silica, alumina, titanium dioxide, zirconium oxide, tin oxide, and zinc oxide, as well as organic particles such as melamine-based resin particles and polytetrafluoroethylene resin particles. One or more of these can be used. Among these external additives, silica is preferred, and hydrophobic silica treated with a hydrophobicating agent is more preferred.

[0260] Examples of hydrophobicating agents include hexamethyldisilazane (HMDS), dimethyldichlorosilane (DMDS), silicone oil, octyltriethoxysilane (OTES), and methyltriethoxysilane. Among these, hexamethyldisilazane is preferred.

[0261] When surface treatment of the toner particles is performed using external additives, from the viewpoint of the charge and flowability of the toner, the content of the external additive in the toner of the present invention is preferably 0.05 parts by mass or more, more preferably 0.08 parts by mass or more, even more preferably 0.1 parts by mass or more, and preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 2 parts by mass or less.

[0262] [Method for manufacturing toners]

[0263] The colorant of the present invention can be any colorant obtained by any known method such as melt mixing, emulsion phase inversion, suspension polymerization, emulsion coagulation, etc. From the viewpoint of productivity and colorant dispersibility, a pulverized colorant based on melt mixing is preferred.

[0264] In this invention, the melt blending method is a method of manufacturing a toner by melt blending a toner raw material containing a colorant, a resin composition (P) and an ester composition (C), and then pulverizing the resulting melt blend.

[0265] In the case of pulverizing the toner, the method for manufacturing the toner includes, for example:

[0266] Step 1: A step of condensing an amorphous polyester resin (A) with an acid group with an amine compound to obtain a resin composition (P);

[0267] Step 2: A step of melt-blending the toner raw material obtained in Step 1, which includes resin composition (P), colorant, and ester composition (C); and

[0268] Step 3: The process of crushing and classifying the molten compound obtained in Step 2 to obtain colorant particles.

[0269] In step 2, the colorant raw materials may include other additives such as charge control agents. These colorant raw materials are preferably pre-mixed using a mixer such as a Henschel mixer or a ball mill before being supplied to the mixing mill.

[0270] From the viewpoints of improving the dispersibility of colorants, charge control agents, and other additives in the binder resin, reducing the mechanical force during melt mixing, suppressing heat generation, and improving the productivity of colorants, the melt mixing temperature is preferably 80°C or higher, more preferably 90°C or higher, even more preferably 95°C or higher, and preferably 160°C or lower, more preferably 130°C or lower.

[0271] The residence time during melt mixing also depends on the mixer used and the scale of the colorant raw material. It is preferably 10 seconds or more, more preferably 13 seconds or more, even more preferably 15 seconds or more, and preferably 30 minutes or less, more preferably 10 minutes or less, even more preferably 5 minutes or less, even more preferably 1 minute or less, and even more preferably 30 seconds or less. The average residence time refers to the time from when the colorant raw material is supplied to the mixer until it is discharged.

[0272] The melt mixing in step 2 can be performed using known mixing machines such as a closed kneader, a single-screw extruder, a twin-screw extruder, or an open mill roll mixer. From the viewpoint of melting and mixing crystals, a twin-screw extruder that can be set to high-temperature conditions is preferred, and a co-rotating twin-screw extruder whose shafts can rotate in the same direction is more preferred.

[0273] The mixing section of a twin-screw extruder is enclosed, allowing the materials to be easily melted using the heat generated during mixing.

[0274] The set temperature of a twin-screw extruder is not affected by the melting characteristics of the material due to the structure of the extruder, and it is easy to perform melt mixing at the desired temperature.

[0275] The set temperature (barrel set temperature) of the twin-screw extruder is preferably adjusted to be the same as the temperature range of the melt mixing process described above.

[0276] From the viewpoint of improving the dispersibility of other additives such as charge control agents and colorants in the toner, and from the viewpoint of reducing mechanical force and suppressing heat generation during melt mixing, in the case of a co-rotating twin-screw extruder, the rotational circumferential speed of the twin-screw extruder is preferably 5 m / min or more, more preferably 10 m / min or more, even more preferably 15 m / min or more, and preferably 50 m / min or less, more preferably 40 m / min or less, and even more preferably 30 m / min or less.

[0277] After the molten compound obtained in step 2 is cooled to a degree that it can be crushed, it is supplied to the next step 3.

[0278] The pulverization in step 3 can be carried out in multiple stages. For example, the resin compound obtained by solidifying the molten compound can be coarsely pulverized to a size of 1 mm or more but less than 5 mm, and then further pulverized to the desired particle size.

[0279] It should be noted that in step 3, the pulverizers used for coarse and fine grinding, as well as the classifiers used for grading, can be appropriately selected from known devices. For example, hammer mills, atomizers, and rotoplexes are suitable pulverizers for coarse grinding. Fluidized bed jet mills, impact plate jet mills, and rotary mechanical mills are suitable pulverizers for fine grinding. From the viewpoint of grinding efficiency, fluidized bed jet mills and impact plate jet mills are preferred, and impact plate jet mills are more preferred.

[0280] Classifiers used in step 3 (grading) include air classifiers, inertial classifiers, and sieve classifiers. During grading, the pulverized material that is removed due to insufficient pulverization can be fed back for pulverization, or it can be repeatedly pulverized and graded as needed.

[0281] The method for manufacturing the toner of the present invention may further include a step of mixing the obtained toner particles with external additives.

[0282] The mixing of colorant particles and external additives is preferably done using a mixer equipped with stirring tools such as rotating blades, preferably a high-speed mixer such as a Henschel mixer or a super mixer, and even more preferably a Henschel mixer.

[0283] The toner of this invention is used for developing latent images formed in electrophotography, electrostatic recording, electrostatic printing, and the like. This toner can be used as a single-component developer or mixed with a carrier to serve as a two-component developer.

[0284] Regarding the above embodiments, the present invention further discloses the following toner for electrostatic image development and a method for manufacturing the toner for electrostatic image development.

[0285] <1> A toner for electrostatic image development, comprising a colorant, a resin composition (P), and an ester composition (C),

[0286] The resin composition (P) is a resin composition obtained by condensing an amorphous polyester resin (A) having acid groups with an amine compound.

[0287] The ester composition (C) is selected from one or more of the following ester compositions (CI) and ester compositions (CII).

[0288] Ester composition (CI): An ester composition comprising a condensate of a carboxylic acid component (CI-ac) and an alcohol component (CI-al), wherein the carboxylic acid component (CI-ac) comprises 20 mol% or more of an aliphatic monocarboxylic acid compound having 10 or more and 30 or fewer carbon atoms, and the alcohol component (CI-al) comprises 90 mol% or more of a divalent or more aliphatic alcohol having 2 or more and 14 or fewer carbon atoms.

[0289] Ester composition (CII): An ester composition comprising an alcohol component (CII-al) and a carboxylic acid component (CII-ac), wherein the alcohol component (CII-al) comprises 20 mol% or more of an aliphatic monohydric alcohol having 10 or more and 30 or fewer carbon atoms, and the carboxylic acid component (CII-ac) comprises 90 mol% or more of a divalent or more aliphatic carboxylic acid compound having 2 or more and 14 or fewer carbon atoms.

[0290] <2> According to the electrostatic image developing toner described in <1> above, the weight-average molecular weight of the resin (A) is preferably 2000 or more, more preferably 3000 or more, even more preferably 4000 or more, and preferably 100000 or less, more preferably 50000 or less, even more preferably 10000 or less, and even more preferably 7000 or less.

[0291] <3> According to the electrostatic image developing toner described in <1> or <2> above, the softening point of the resin (A) is preferably 80°C or higher, more preferably 90°C or higher, even more preferably 95°C or higher, and preferably 130°C or lower, more preferably 120°C or lower, even more preferably 110°C or lower.

[0292] <4> The toner for electrostatic image development according to any one of <1> to <3> above, wherein the amine compound preferably comprises one or more selected from polyalkylene imines, polyallylamines, (poly)ethylene polyamines, alkanolamines with 1 or more and 5 or less carbon atoms, and alkylamines with 1 or more and 6 or less carbon atoms, more preferably comprising polyalkylene imines, polyallylamines, (poly)ethylene polyamines, and carbon atoms with 1 or more and 5 or less carbon atoms. The amine comprises one or more of tertiary alkyl alcoholamines having 2 or more and 9 or less carbon atoms, and more preferably includes one or more of polyalkylene imines, polyallylamines, and tertiary alkyl alcoholamines having 2 or more and 9 or less carbon atoms selected from alkylene groups, more preferably includes one or more of polyalkylene imines having 1 or more and 5 or less carbon atoms selected from alkylene groups, and polyallylamines, more preferably includes polyalkylene imines having 1 or more and 5 or less carbon atoms selected from alkylene groups, and more preferably includes polyethyleneimine.

[0293] <5> The toner for electrostatic image development according to any one of <1> to <4> above, wherein the amount of amine compound relative to 100 parts by weight of resin (A) is preferably 0.05 parts by weight or more, more preferably 0.1 parts by weight or more, even more preferably 0.5 parts by weight or more, and preferably 20 parts by weight or less, more preferably 10 parts by weight or less, even more preferably 7 parts by weight or less, even more preferably 5 parts by weight or less, even more preferably 3 parts by weight or less, even more preferably 2 parts by weight or less.

[0294] <6> The toner for electrostatic image development according to any one of <1> to <5> above, wherein the softening point of the resin composition (P) is preferably 80°C or higher, more preferably 90°C or higher, even more preferably 95°C or higher, and preferably 130°C or lower, more preferably 120°C or lower, even more preferably 110°C or lower.

[0295] <7> The toner for electrostatic image development according to any one of <1> to <6> above, wherein the content of the resin composition (P) is preferably 20% by mass or more, more preferably 40% by mass or more, further preferably 50% by mass or more, further preferably 55% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less, further preferably 70% by mass or less, and further preferably 65% ​​by mass or less.

[0296] <8> The toner for electrostatic image development according to any one of <1> to <7> above, wherein the ester composition (C) is the ester composition (CI) described above.

[0297] <9> According to the electrostatic image developing toner described in <8> above, the aliphatic monocarboxylic acid compound preferably has 12 or more carbon atoms, more preferably 14 or more, even more preferably 16 or more, even more preferably 18 or more, and preferably 28 or less, more preferably 26 or less, even more preferably 24 or less, even more preferably 22 or less.

[0298] <10> According to the electrostatic image developing toner described in <8> or <9> above, the content of the aliphatic monocarboxylic acid compound in the carboxylic acid component (CI-ac) is preferably 40 mol% or more, more preferably 60 mol% or more, even more preferably 70 mol% or more, even more preferably 90 mol% or more, even more preferably 95 mol% or more, and preferably 100 mol% or less, even more preferably 100 mol%.

[0299] <11> The toner for electrostatic image development according to any one of <8> to <10> above, wherein the aliphatic alcohol with 2 or more carbon atoms preferably has 4 or more carbon atoms, more preferably 6 or more carbon atoms, even more preferably 8 or more carbon atoms, and preferably 12 or less carbon atoms, more preferably 10 or less carbon atoms.

[0300] <12> The toner for electrostatic image development according to any one of <8> to <11> above, wherein the content of aliphatic alcohols of 2 or more is preferably 95 mol% or more in the alcohol component (CI-al), more preferably 97 mol% or more, and preferably 100 mol% or less, and even more preferably 100 mol%.

[0301] <13> The toner for electrostatic image development according to any one of <1> to <7> above, wherein the ester composition (C) is the above-mentioned ester composition (CII).

[0302] <14> According to the electrostatic image developing toner described in <13> above, the aliphatic monohydric alcohol preferably has 12 or more carbon atoms, more preferably 14 or more, even more preferably 16 or more, even more preferably 18 or more, and preferably 28 or less, more preferably 26 or less, even more preferably 24 or less, even more preferably 22 or less.

[0303] <15> According to the electrostatic image developing toner described in <13> or <14> above, the content of aliphatic monohydric alcohol in the alcohol component (CII-al) is preferably 30 mol% or more, more preferably 40 mol% or more, even more preferably 50 mol% or more, even more preferably 60 mol% or more, even more preferably 70 mol% or more, even more preferably 80 mol% or more, even more preferably 90 mol% or more, even more preferably 95 mol% or more, and preferably 100 mol% or less, even more preferably 100 mol%.

[0304] <16> The toner for electrostatic image development according to any one of <13> to <15> above, wherein the aliphatic carboxylic acid compound with 2 or more carbon atoms preferably has 4 or more carbon atoms, more preferably 6 or more carbon atoms, even more preferably 8 or more carbon atoms, and preferably 12 or less carbon atoms.

[0305] <17> The toner for electrostatic image development according to any one of <13> to <16> above, wherein the content of the aliphatic carboxylic acid compound of 2 or more is preferably 95 mol% or more in the alcohol component (CII-ac), more preferably 97 mol% or more, and preferably 100 mol% or less, and even more preferably 100 mol%.

[0306] <18> The toner for electrostatic image development according to any one of <13> to <17> above, wherein the aliphatic carboxylic acid compound with 2 or more elements is a saturated aliphatic dicarboxylic acid compound.

[0307] <19> The electrostatic image developing toner according to any one of <1> to <18> above, wherein the melting point of the ester composition (C) is preferably 50°C or higher, more preferably 55°C or higher, even more preferably 60°C or higher, and preferably 100°C or lower, more preferably 90°C or lower, even more preferably 80°C or lower.

[0308] <20> The toner for electrostatic image development according to any one of <1> to <19> above, wherein the content of the ester composition (C) is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 3% by mass or more, and preferably 20% by mass or less, more preferably 10% by mass or less, and further preferably 7% by mass or less.

[0309] <21> The toner for electrostatic image development according to any one of <1> to <20> above, wherein the mass ratio of the ester composition (C) to the content of the resin composition (P) in the toner [ester composition (C) / resin composition (P)] is preferably 0.01 or more, more preferably 0.03 or more, even more preferably 0.05 or more, and preferably 1 or less, more preferably 0.5 or less, even more preferably 0.3 or less, and even more preferably 0.1 or less.

[0310] <22> The toner for electrostatic image development according to any one of <1> to <21> above, wherein the total content of the resin composition (P) and the ester composition (C) is preferably 40% by mass or more, more preferably 50% by mass or more, further preferably 60% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less, and further preferably 70% by mass or less.

[0311] <23> The electrostatic image developing toner according to any one of <1> to <22> above further contains an amorphous polyester resin (B), which preferably has a softening point different from that of the resin (A), and more preferably has a softening point higher than that of the resin (A).

[0312] <24> According to the electrostatic image developing toner described in <23> above, when the softening point of resin (A) is 80°C or higher and 120°C or lower, the softening point of resin (B) is preferably higher than 120°C, more preferably higher than 125°C, even more preferably higher than 130°C, and preferably lower than 170°C, more preferably lower than 150°C, and even more preferably lower than 140°C.

[0313] <25> The toner for electrostatic image development according to any one of <23> or <24> above, wherein the content of resin (B) is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, and preferably 60% by mass or less, more preferably 50% by mass or less, and further preferably 40% by mass or less.

[0314] <26> The toner for electrostatic image development according to any one of <1> to <25> above, wherein the content of the colorant is preferably 1 part by mass or more, more preferably 2 parts by mass or more, further preferably 3 parts by mass or more, further preferably 5 parts by mass or more, further preferably 7 parts by mass or more, further preferably 10 parts by mass or more, further preferably more than 10 parts by mass, and preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and further preferably 15 parts by mass or less.

[0315] <27> Toner for electrostatic image development according to any one of <1> to <26>, wherein the toner for electrostatic image development is a pulverized toner based on a melt-blending method.

[0316] <28> Use of the toner described in any one of <1> to <27> above, mixed with a single-component developer or a carrier, as a two-component developer.

[0317] <29> A method for manufacturing a toner for electrostatic image development, comprising:

[0318] Step 1: A step of condensing an amorphous polyester resin (A) with an acid group with an amine compound to obtain a resin composition (P); and

[0319] Step 2: A step of melt-blending the toner raw material, which includes the resin composition (P) obtained in Step 1, the colorant, and the ester composition (C).

[0320] The above-mentioned ester composition (C) is selected from one or more of the following ester compositions (CI) and ester compositions (CII).

[0321] Ester composition (CI): An ester composition comprising a condensate of a carboxylic acid component (CI-ac) and an alcohol component (CI-al), wherein the carboxylic acid component (CI-ac) comprises 20 mol% or more of an aliphatic monocarboxylic acid compound having 10 or more and 30 or fewer carbon atoms, and the alcohol component (CI-al) comprises 90 mol% or more of a divalent or more aliphatic alcohol having 2 or more and 14 or fewer carbon atoms.

[0322] Ester composition (CII): An ester composition comprising an alcohol component (CII-al) and a carboxylic acid component (CII-ac), wherein the alcohol component (CII-al) comprises 20 mol% or more of an aliphatic monohydric alcohol having 10 or more and 30 or fewer carbon atoms, and the carboxylic acid component (CII-ac) comprises 90 mol% or more of a divalent or more aliphatic carboxylic acid compound having 2 or more and 14 or fewer carbon atoms.

[0323] <30> The method for manufacturing toner for electrostatic image development according to <29> above further includes step 3: crushing and classifying the molten compound obtained in step 2 to obtain toner particles.

[0324] <31> The method for manufacturing toner for electrostatic image development according to <29> or <30> above, wherein the ester composition (C) is an ester composition (CI).

[0325] <32> The method for manufacturing toner for electrostatic image development according to <29> or <30> above, wherein the ester composition (C) is an ester composition (CII).

[0326] <33> A toner for electrostatic image development, comprising a colorant, a resin composition (P), and an ester composition (C),

[0327] The resin composition (P) is a resin composition formed by condensing an amorphous polyester resin (A) having acid groups with an amine compound.

[0328] The aforementioned amorphous polyester resin (A) is a condensation polymer of an alcohol component (A-al) containing an epoxide adduct of bisphenol A and a carboxylic acid component (A-ac).

[0329] The above-mentioned amine compounds include polyalkylene imides with 1 or more but less than 5 carbon atoms in the alkylene group.

[0330] The ester composition (C) is an ester composition (CI) comprising a condensate of an aliphatic monocarboxylic acid compound having 10 or more and 30 or fewer carbon atoms and an aliphatic diol having 2 or more and 14 or fewer carbon atoms.

[0331] <34> A toner for electrostatic image development, comprising a colorant, a resin composition (P), and an ester composition (C),

[0332] The resin composition (P) is a resin composition formed by condensing an amorphous polyester resin (A) having acid groups with an amine compound.

[0333] The aforementioned amorphous polyester resin (A) is a condensation polymer of an alcohol component (A-al) containing an epoxide adduct of bisphenol A and a carboxylic acid component (A-ac).

[0334] The above-mentioned amine compounds include polyalkylene imides with 1 or more but less than 5 carbon atoms in the alkylene group.

[0335] The ester composition (C) is an ester composition (CII) comprising a condensate of an aliphatic monohydric alcohol having 10 or more and 30 or fewer carbon atoms and an aliphatic dicarboxylic acid compound having 2 or more and 14 or fewer carbon atoms.

[0336] Example

[0337] The properties of raw materials, etc., are measured and evaluated using the following methods.

[0338] [Measurement]

[0339] [Acid value of the resin and ester composition]

[0340] The acid value was determined based on the method of JIS K0070:1992. However, in this method, in the case of amorphous polyester resins, only the solvent was changed from a mixture of ethanol and diethyl ether to a mixture of acetone and toluene [acetone:toluene = 1:1 (volume ratio)], and in the case of ester compositions, only the solvent was changed from a mixture of ethanol and ether to chloroform.

[0341] [Weight-average molecular weight of the resin and ester composition]

[0342] The molecular weight distribution was determined using gel permeation chromatography (GPC) obtained by the following method, and the weight-average molecular weight was calculated.

[0343] (1) Preparation of sample solution

[0344] The sample was dissolved in tetrahydrofuran (in the case of amorphous polyester resin) or chloroform (in the case of ester composition) at 25°C to a concentration of 0.5 g / 100 mL. Next, the solution was filtered to remove insoluble components using a 0.2 μm fluoropolymer filter "DISMIC-25JP" (manufactured by ADVANTEC) or a 2 μm fluoropolymer filter "FP-200" (manufactured by Sumitomo Electric Industries, Ltd.) (in the case of ester composition) to prepare the sample solution.

[0345] (2) Molecular weight determination

[0346] Using the following apparatus and analytical column, tetrahydrofuran (in the case of amorphous polyester resins) or chloroform (in the case of ester compositions) as the eluent is flowed at a flow rate of 1 mL per minute, and the column is stabilized in a thermostat at 40°C. 100 μL of the sample solution is injected for determination. The molecular weight of the sample is calculated based on a pre-prepared standard curve. The standard curve used here is based on various monodisperse polystyrene “A-500” (5.0 × 10⁻⁶).2 ), "A-1000" (1.01×10 3 ), "A-2500" (2.63×10 3 ), "A-5000" (5.97×10 3 ), "F-1" (1.02×10 4 ), "F-2" (1.81×10 4 ), "F-4" (3.97×10 4 ), "F-10" (9.64×10 4 ), "F-20" (1.90×10 5 ), "F-40" (4.27×10 5 ), "F-80" (7.06×10 5 ), "F-128" (1.09×10 6 (The above is a standard curve prepared using Tosoh Corporation as a standard sample. The numbers in parentheses indicate molecular weight.)

[0347] Measuring apparatus: "HLC-8220CPC" (manufactured by Tosoh Corporation) (in the case of amorphous polyester resins), "CO-8010" (manufactured by Tosoh Corporation) (in the case of ester compositions).

[0348] Analytical column: "GMHXL" + "G3000HXL" (manufactured by Tosoh Corporation)

[0349] [Softening point of resins, resin compositions and ester compositions]

[0350] Using a flow testing apparatus "CFT-500D" (manufactured by Shimadzu Corporation), a 1g sample was heated at a heating rate of 6°C / min while a load of 1.96MPa was applied using a plunger, and the sample was extruded from a nozzle with a diameter of 1mm and a length of 1mm. The plunger descent of the flow testing apparatus was plotted against temperature, and the temperature at which half of the sample flowed out was taken as the softening point.

[0351] [Glass transition temperature of the resin or resin composition]

[0352] Using a differential scanning calorimeter "Q-20" (manufactured by TA Instruments Japan Co., Ltd.), 0.01 to 0.02 g of sample was weighed in an aluminum pan and heated to 200°C. The sample was then cooled to 0°C at a rate of 10°C / min. Next, the sample was heated at a rate of 10°C / min, and the temperature at which the extension of the baseline below the highest endothermic peak temperature intersects with the tangent line representing the maximum slope from the rising portion of the peak to the apex of the peak was taken as the glass transition temperature.

[0353] [Maximum peak temperature of heat absorption]

[0354] Using a differential scanning calorimeter "Q-20" (manufactured by TA Instruments Japan Co., Ltd.), a sample cooled from room temperature (20°C) to 0°C at a cooling rate of 10°C / min was held at that temperature for 1 minute. Then, the sample was heated to 180°C at a heating rate of 10°C / min while measuring the heat. The temperature of the peak with the largest peak area among the observed endothermic peaks was taken as the maximum peak temperature of the endothermic reaction.

[0355] [Melting point of the ester composition]

[0356] Using a differential scanning calorimeter "Q-100" (manufactured by TA Instruments Japan Co., Ltd.), a sample cooled from room temperature (20°C) to 0°C at a cooling rate of 10°C / min was held at that temperature for 1 minute. Then, the sample was heated to 180°C at a heating rate of 10°C / min while measuring the heat. The temperature of the largest peak on the high-temperature side of the observed endothermic peaks (i.e., the peak with the largest peak area) was taken as the melting point.

[0357] [Number-average molecular weight (Mn) of polyalkylimide and weight-average molecular weight (Mw) of polyallylamine]

[0358] The molecular weight distribution was determined by gel permeation chromatography (GPC) as shown below, and the number-average molecular weight and weight-average molecular weight were calculated.

[0359] (1) Preparation of sample solution

[0360] Polyalkylimide or polyallylamine was dissolved in the following solution at a concentration of 0.2 g / 100 mL: a solution prepared by dissolving 0.15 mol / L Na₂SO₄ in a 1% (w / w) aqueous acetic acid solution. Next, the solution was filtered using a 0.2 μm fluoropolymer filter "FP-200" (manufactured by Sumitomo Electric Industries, Ltd.) to remove insoluble components, resulting in a sample solution.

[0361] (2) Molecular weight determination

[0362] Using the following analytical apparatus and column, a solution of 0.15 mol / L Na₂SO₄ dissolved in 1% acetic acid aqueous solution was passed through at a flow rate of 1 mL / min as the eluent. The column was stabilized in a thermostat at 40°C. 100 μL of the sample solution was then injected for determination. The molecular weight of the sample was calculated based on a pre-prepared standard curve. This standard curve used multiple standard pullulan polysaccharides "P-5" (5.9 × 10⁻⁶). 3 ), "P-50" (4.73×10 4 ), "P-200" (2.12×105 ), "P-800" (7.08×10 5 (The above is a standard curve prepared using Showa Denko Co., Ltd.) as a standard sample. The numbers in parentheses indicate the molecular weight.

[0363] Measurement device: "HLC-8320GPC" (manufactured by Tosoh Corporation)

[0364] Analysis column: “α” + “α-M” + “α-M” (Tosoh Corporation)

[0365] [Melting point of release agent]

[0366] Using a differential scanning calorimeter "Q-100" (manufactured by TA Instruments Japan Co., Ltd.), a 0.02 g sample was weighed in an aluminum pan, heated to 200 °C, and then cooled to 0 °C at a cooling rate of 10 °C / min. Next, the sample was heated at a rate of 10 °C / min, and the heat was measured. The maximum peak temperature of the endothermic reaction was taken as the melting point.

[0367] [Volume median particle size (D) of toner particles] 50 )

[0368] The volume median particle size (D) of toner particles 50 The following measurements were taken.

[0369] • Measuring device: “Coulter Multisizer (registered trademark) III” (manufactured by Beckman Coulter Co., Ltd.)

[0370] • Aperture: 50μm

[0371] • Analysis software: "Coulter Multisizer (registered trademark) III version 3.51" (manufactured by Beckman Coulter Co., Ltd.)

[0372] Electrolyte: "ISOTON (registered trademark) II" (manufactured by Beckman Coulter Co., Ltd.)

[0373] • Dispersion: Dissolve “EMULGEN (registered trademark) 109P” [polyoxyethylene lauryl ether, manufactured by Kao Corporation, HLB (Hydrophile-Lipophile Balance, Griffin method) = 13.6] in the above electrolyte to obtain a dispersion with a concentration of 5% by mass.

[0374] • Dispersion conditions: Add 10 mg of the test sample to 5 mL of the above dispersion and disperse it for 1 minute using an ultrasonic disperser. Then, add 25 mL of the above electrolyte and disperse it for another 1 minute using an ultrasonic disperser to prepare the sample dispersion.

[0375] • Measurement conditions: In a beaker, the above sample dispersion was added to 100 mL of the above electrolyte. After adjusting the particle size of 30,000 particles to a concentration that could be measured within 20 seconds, the particle size was measured. The volume median particle size (D) was determined based on the obtained particle size distribution. 50 ).

[0376] [Manufacturing of Resin (A) and Resin (B)]

[0377] Manufacturing Example A1 (Manufacturing of Resin A-1)

[0378] The raw monomers and esterification catalyst shown in Table 1 were added to a 20-liter four-necked flask equipped with a thermometer, a stainless steel stir bar, a downflow condenser, and a nitrogen inlet tube. Under a nitrogen atmosphere, the temperature was raised to 235°C in a covered heater over 2 hours. Then, the reaction rate was confirmed to be over 90% at 235°C. The reaction was continued at 235°C and a reduced pressure of 40 kPa until the desired softening point was reached, yielding resin A-1. Various physical properties were measured and are shown in Table 1.

[0379] Manufacturing Example B1 (Manufacturing of Resin B-1)

[0380] The raw material monomers shown in Table 1, excluding adipic acid and trimellitic anhydride, and the esterification catalyst were added to a 20-liter four-necked flask equipped with a thermometer, a stainless steel stir bar, a downflow condenser, and a nitrogen inlet tube. Under a nitrogen atmosphere, the temperature was raised to 235°C in a jacketed heater over 2 hours. Then, after confirming a reaction rate of over 90% at 235°C, the temperature was cooled to 190°C, and the adipic acid and trimellitic anhydride shown in Table 1 were added. The temperature was then raised to 210°C over 2 hours. After reacting at 210°C for 1 hour, the reaction was continued under reduced pressure of 40 kPa until the desired softening point was reached, yielding amorphous polyester resin B-1. Various physical properties were measured and are shown in Table 1.

[0381] [Table 1]

[0382] Table 1

[0383]

[0384] *1 BPA-P0: Propylene oxide (2.1) adduct of bisphenol A

[0385] *2 indicates the molar ratio when the total amount of alcohol in the raw material monomers is set to 100 moles.

[0386] *3 Amount (parts by mass) relative to the total amount of alcohol and carboxylic acid components of the raw material monomers per 100 parts by mass.

[0387] [Preparation of resin composition (P)]

[0388] Manufacturing Examples P1 to P8 (Manufacturing of Resin Compositions P-1 to P-8)

[0389] The raw materials shown in Table 2 were added to a 20-liter four-necked flask equipped with a thermometer, a stainless steel stir bar, a flow-down condenser, and a nitrogen inlet tube. The mixture was heated to 150°C over 2 hours in a covered heater under a nitrogen atmosphere. The reaction was then carried out at 150°C for 3 hours to obtain resin compositions P-1 to P-8. Various physical properties were measured and are shown in Table 2.

[0390] [Table 2]

[0391]

[0392] [Preparation of ester compositions (C) (ester compositions (CI) and (CII))]

[0393] Manufacturing Examples C1 to C8 (Manufacturing of ester compositions CI-1 to CI-3, CII-1 to CII-5)

[0394] The raw material monomers shown in Tables 3 and 4 were added to a 10-liter four-necked flask equipped with a thermometer, a stainless steel stirring rod, a flow-down condenser, and a nitrogen inlet tube. The temperature was raised from 130°C to 200°C in a covered heater under a nitrogen atmosphere over 8 hours, and then reacted at 200°C for 2 hours. An esterification catalyst was then added, and the reaction was carried out under reduced pressure of 8 kPa until the desired softening point was reached, yielding ester compositions CI-1 to CI-3 and CII-1 to CII-5.

[0395] [Table 3]

[0396] Table 3

[0397]

[0398] *1 Amount (parts by mass) relative to the total amount of alcohol and carboxylic acid components of the raw material monomers, expressed as 100 parts by mass.

[0399] [Table 4]

[0400]

[0401] [The manufacture of toners]

[0402] Examples 1-15, Comparative Examples 1-2 (Toners 1-15, 51-52)

[0403] The resin components in the proportions shown in Table 5 (total 100 parts by weight), the negatively charged charge control agent "BONTRONE-81" (manufactured by ORIENT Chemical Industry Co., Ltd.), the colorant "phthalocyanine blue 4927" (manufactured by Daihatsu Seika Co., Ltd., CI pigment blue 15:3), and the release agent "HNP-9" (manufactured by Nippon Seika Co., Ltd., paraffin wax, melting point: 80℃) were thoroughly mixed using a Henschel mixer. The mixture was then melt-blended using a co-rotating twin-screw extruder with a total length of 1560 mm, a screw diameter of 42 mm, and a barrel inner diameter of 43 mm, at a screw speed of 200 r / min and a barrel temperature of 100℃. The feed rate of the mixture was 20 kg / h, and the average residence time was approximately 18 seconds. The resulting melt-blended mixture was cooled, coarsely pulverized, and then pulverized and classified using a jet mill to obtain the volumetric median particle size (D). 50 The toner particles are 8μm in size.

[0404] Add 1 part by mass of hydrophobic silica “AEROSIL NAX 50” (manufactured by AEROSIL Corporation of Japan, hydrophobic treatment agent: HMDS, average particle size: about 30 nm) as an external additive to 100 parts by mass of the obtained toner particles, and mix with a Henschel mixer to obtain toners 1-15 and 51-52.

[0405] [Toner Evaluation]

[0406] [Image density]

[0407] Using a commercially available printer, the Microline 5400 (manufactured by Oki Data Co., Ltd.), on Dowling paper "J Paper A4 Size" (manufactured by Fuji Xerox Co., Ltd.), the toner adhesion amount on the paper is 0.42–0.48 mg / cm². 2 A solid image is used to obtain a printed product.

[0408] Next, set the temperature of the fixer to 130°C and fix the toner along the A4 length at a speed of 1.5 seconds per sheet to obtain the printed material.

[0409] The reflectance image density of the fixed image portion of the printed material was measured using a SpectroEye colorimeter (manufactured by GretagMacbeth, under the following lighting conditions: standard light source D50, viewing field 2°, density reference DINNB, and absolute white reference). A higher reflectance image density value indicates better image density. The results are shown in Table 5.

[0410] 〔luster〕

[0411] Thick paper was placed under the fixed image portion of the printed material, output using the same method as for evaluating image density. The gloss of the printed material was measured using a gloss meter (manufactured by Horiba Manufacturing Co., Ltd., trade name: "IG-330") under light conditions with an incident angle of 60°. Higher gloss indicates better gloss; a gloss of 25 or higher is preferred, more preferably 35 or higher, and even more preferably 40 or higher. The results are shown in Table 5.

[0412] [Table 5]

[0413]

[0414] As shown in Table 5, it can be seen that the toners of the embodiments containing the specific resin composition have superior image density and gloss compared to the toners of the comparative examples.

Claims

1. A toner for electrostatic image development, comprising a colorant, a release agent, a resin composition P, and an ester composition C. The resin composition P is a resin composition formed by condensing an amorphous polyester resin A with acid groups with an amine compound. The ester composition C is selected from one or more of the following ester compositions C1 and CII. Ester composition CI: An ester composition containing a condensate of a carboxylic acid component CI-ac and an alcohol component CI-al, wherein the carboxylic acid component CI-ac comprises 20 mol% or more of an aliphatic monocarboxylic acid compound having 10 or more and 30 or less carbon atoms, and the alcohol component CI-al comprises 90 mol% or more of a divalent aliphatic alcohol having 2 or more and 14 or less carbon atoms. Ester composition CII: An ester composition containing a condensate of an alcohol component CII-al and a carboxylic acid component CII-ac, wherein the alcohol component CII-al comprises 20 mol% or more of an aliphatic monohydric alcohol having 10 or more and 30 or less carbon atoms, and the carboxylic acid component CII-ac comprises 90 mol% or more of a divalent aliphatic carboxylic acid compound having 2 or more and 14 or less carbon atoms.

2. The toner for electrostatic image development according to claim 1, wherein, The aliphatic monocarboxylic acid compound has 16 or more but less than 24 carbon atoms.

3. The toner for electrostatic image development according to claim 1 or 2, wherein, The aliphatic monohydric alcohol has 16 or more but less than 24 carbon atoms.

4. The toner for electrostatic image development according to claim 1 or 2, wherein, The aliphatic carboxylic acid compounds with more than 2 elements are saturated aliphatic dicarboxylic acid compounds.

5. The toner for electrostatic image development according to claim 1 or 2, wherein, The ester composition C is the same as the ester composition CI.

6. The toner for electrostatic image development according to claim 1 or 2, wherein, The ester composition C is the ester composition CII.

7. The toner for electrostatic image development according to claim 1 or 2, wherein, The content of the ester composition C, calculated as the content in the total amount of the resin component of the colorant, is more than 1% by mass and less than 20% by mass.

8. The toner for electrostatic image development according to claim 1 or 2, wherein, The amine compound comprises one or more selected from polyalkylene imines, polyallylamines, ethylene polyamines, polyethylene polyamines, and tertiary alkyl alcoholamines having 1 or more and 5 or fewer carbon atoms, which are alkylene compounds.

9. The toner for electrostatic image development according to claim 1 or 2, wherein, The amine compound comprises a polyalkylene imine having 1 or more but less than 5 carbon atoms in its alkylene group.

10. The toner for electrostatic image development according to claim 9, wherein, The total amount of polyalkylene imides in the amine compound having 1 or more and 5 or fewer carbon atoms in the alkylene group is 70% or more by mass.

11. The toner for electrostatic image development according to claim 1 or 2, wherein, The weight-average molecular weight of the amorphous polyester resin A is above 2000 and below 10000.

12. The toner for electrostatic image development according to claim 1 or 2, wherein, The softening point of the amorphous polyester resin A is above 80°C and below 120°C.

13. The toner for electrostatic image development according to claim 1 or 2, wherein, The amount of the amine compound is 0.05 parts by mass and 20 parts by mass or less relative to 100 parts by mass of the amorphous polyester resin A.

14. The toner for electrostatic image development according to claim 1 or 2, wherein, The softening point of the resin composition P is above 80°C and below 130°C.

15. The toner for electrostatic image development according to claim 1 or 2, wherein, The content of the resin composition P, calculated as the content in the total amount of the resin component of the colorant, is 20% by mass or more and 90% by mass or less.

16. The toner for electrostatic image development according to claim 1 or 2, wherein, The mass ratio of the content of the ester composition C in the colorant to the content of the resin composition P, i.e., the ratio of ester composition C to resin composition P, is 0.01 or more and 1 or less.

17. The toner for electrostatic image development according to claim 1 or 2, wherein, The total content of the resin composition P and the ester composition C, calculated as the total content of the resin components of the colorant, is 40% by mass or more and 90% by mass or less.

18. The toner for electrostatic image development according to claim 1 or 2, wherein, The release agent comprises one or more selected from polypropylene wax, polyethylene wax, polypropylene-polyethylene copolymer wax; microcrystalline wax, paraffin wax, Fischer-Tropsch wax, Sasol wax or their oxides; and carnauba wax, lignite wax or their deoxidized waxes.

19. The toner for electrostatic image development according to claim 1 or 2, wherein, The release agent has a melting point above 60°C and below 150°C.

20. The toner for electrostatic image development according to claim 1 or 2, wherein, The content of the release agent is 0.1 parts by mass or more and 10 parts by mass or less, relative to 100 parts by mass of the total resin component of the colorant.

21. The toner for electrostatic image development according to claim 1 or 2, further comprising an amorphous polyester resin B, wherein the softening point of the amorphous polyester resin B is greater than 120°C and less than 170°C.

22. The toner for electrostatic image development according to claim 21, wherein, The content of the amorphous polyester resin B, calculated as the content in the total amount of resin components of the colorant, is 10% by mass or more and 60% by mass or less.

23. The toner for electrostatic image development according to claim 1 or 2, wherein, The content of the colorant is more than 1 part by mass and less than 40 parts by mass relative to 100 parts by mass of the total resin component of the colorant.

24. The toner for electrostatic image development according to claim 1 or 2, wherein, The toner used for electrostatic image development is a pulverized toner based on melt mixing.

25. A method for manufacturing a toner for electrostatic image development, comprising: Step 1: The step of condensing an amorphous polyester resin A with acid groups with an amine compound to obtain a resin composition P; as well as Step 2: A step of melt-blending the colorant raw material, which includes the resin composition P obtained in Step 1, the colorant, the release agent, and the ester composition C. The ester composition C is selected from one or more of the following ester compositions C1 and CII. Ester composition CI: An ester composition containing a condensate of a carboxylic acid component CI-ac and an alcohol component CI-al, wherein the carboxylic acid component CI-ac comprises 20 mol% or more of an aliphatic monocarboxylic acid compound having 10 or more and 30 or less carbon atoms, and the alcohol component CI-al comprises 90 mol% or more of a divalent aliphatic alcohol having 2 or more and 14 or less carbon atoms. Ester composition CII: An ester composition containing a condensate of an alcohol component CII-al and a carboxylic acid component CII-ac, wherein the alcohol component CII-al comprises 20 mol% or more of an aliphatic monohydric alcohol having 10 or more and 30 or less carbon atoms, and the carboxylic acid component CII-ac comprises 90 mol% or more of a divalent aliphatic carboxylic acid compound having 2 or more and 14 or less carbon atoms.

26. The method for manufacturing a toner for electrostatic image development according to claim 25, wherein, The ester composition C is ester composition CI.

27. The method for manufacturing a toner for electrostatic image development according to claim 25 or 26, wherein, The amine compound comprises one or more selected from polyalkylene imines, polyallylamines, ethylene polyamines, polyethylene polyamines, and tertiary alkyl alcoholamines having 1 or more and 5 or fewer carbon atoms, which are alkylene compounds.

28. The method for manufacturing a toner for electrostatic image development according to claim 25 or 26, wherein, The amine compound comprises a polyalkylene imine having 1 or more but less than 5 carbon atoms in its alkylene group.

29. The method for manufacturing a toner for electrostatic image development according to claim 28, wherein, The total amount of polyalkylene imides in the amine compound having 1 or more and 5 or fewer carbon atoms in the alkylene group is 70% or more by mass.

30. The method for manufacturing a toner for electrostatic image development according to claim 25 or 26, wherein, The weight-average molecular weight of the amorphous polyester resin A is above 2000 and below 10000.

31. The method for manufacturing a toner for electrostatic image development according to claim 25 or 26, wherein, The softening point of the amorphous polyester resin A is above 80°C and below 120°C.

32. The method for manufacturing a toner for electrostatic image development according to claim 25 or 26, wherein, The electrostatic image developing toner also contains amorphous polyester resin B, which has a softening point exceeding 120°C and below 170°C.

33. The method for manufacturing a toner for electrostatic image development according to claim 25 or 26, wherein, The release agent comprises one or more selected from polypropylene wax, polyethylene wax, polypropylene-polyethylene copolymer wax; microcrystalline wax, paraffin wax, Fischer-Tropsch wax, Sasol wax or their oxides; and carnauba wax, lignite wax or their deoxidized waxes.

34. The method for manufacturing a toner for electrostatic image development according to claim 25 or 26, wherein, The release agent has a melting point above 60°C and below 150°C.

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