Method for manufacturing binder resin for toner

Abstract

To provide a method for producing a binder resin for a toner which is excellent in hot offset resistance and low temperature fixability of a toner.SOLUTION: A method for producing a binder resin for a toner includes a step A of addition polymerizing an addition polymerizable monomer and an amphoteric reactive monomer in the presence of a polymer (A) having an unsaturated bond, and a step B of polycondensing a polycondensable monomer containing a carboxylic acid component and an alcohol component, in which the step A and the step B are carried out in the same reaction container, and a polycondensation-based resin segment and an addition polymerization-based resin segment are bonded to each other through the amphoteric reactive monomer, wherein a substance amount of a monomer having an unsaturated bond constituting the polymer (A) having the unsaturated bond is 5.0×10-5 mmol or more and 2.0×10-2 mmol or less with respect to 1 g of the total amount of the addition polymerizable monomer, the amphoteric reactive monomer and the polycondensable monomer.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for manufacturing a binder resin for toner used in developing latent images formed in electrophotography, electrostatic recording, electrostatic printing, etc., and a method for manufacturing toner for developing electrostatic images. [Background technology]

[0002] Patent Document 1 discloses an electrophotographic toner characterized by containing a binder resin having at least an unsaturated double bond, a reactive monomer, and a radical polymerization catalyst.

[0003] Patent Document 2 discloses a method for producing toner, which includes the steps of: dispersing a polyester resin formed by the condensation of a polyhydric alcohol and an unsaturated polycarboxylic acid in an aqueous medium to prepare a polyester resin particle dispersion; adding a vinyl polymerizable monomer and a radical polymerization initiator to the polyester resin particle dispersion, then carrying out a radical polymerization reaction to prepare a dispersion of resin particles consisting of a resin in which the vinyl polymerizable monomer has reacted with the polyester resin; and mixing a dispersion of colorant particles with at least the resin particles consisting of a resin in which the vinyl polymerizable monomer has reacted with the polyester resin, and agglomerating the resin particles and colorant particles to form toner particles.

[0004] Patent Document 3 discloses a method for producing a binder resin for toner, comprising the steps of (A) of carrying out an addition polymerization reaction of an addition polymerization resin monomer containing styrene, and (B) of mixing the reaction mixture produced in step (A) with fumaric acid and / or maleic acid during and / or after step (A), wherein the amount of fumaric acid and / or maleic acid mixed in step (B) is 0.05 to 10 parts by weight per 100 parts by weight of the addition polymerization resin monomer. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 8-30026 [Patent Document 2] Japanese Patent Publication No. 2011-95736 [Patent Document 3] Japanese Patent Publication No. 2005-350510 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] While high molecular weight amorphous polyester resins are effective as binders to ensure the toner's resistance to hot offset, there are concerns about deterioration of low-temperature fixation performance.

[0007] This invention relates to a method for producing a toner binder resin that exhibits excellent hot offset resistance and low-temperature fixing properties for toner. [Means for solving the problem]

[0008] The present invention [1] A method for producing a binder resin for toner in which a polycondensation resin segment and an addition polymerization resin segment are bonded via both reactive monomers, comprising step A of addition polymerization of an addition polymer (A) having an unsaturated bond and step B of polycondensation of a polycondensation monomer containing a carboxylic acid component and an alcohol component, wherein steps A and B are carried out in the same reaction vessel, and the amount of unsaturated monomers constituting the polymer (A) having an unsaturated bond is 5.0 × 10¹⁶ per 1 g of the total amount of the addition polymer, both reactive monomers and the polycondensation monomer. -5 ≥ mmol 2.0 × 10⁻¹ -2 A method for producing a binder resin for toner, which is less than or equal to mmol, and [2] A method for producing toner for electrostatic image developing, comprising the steps of (I) dispersing the toner binder resin obtained by the method described in (1) in an aqueous medium to obtain resin particles, and (II) agglomerating and fusing the resin particles to obtain toner particles. Regarding. [Effects of the Invention]

[0009] The binder resin for toner obtained by the method of the present invention has the effect of being excellent in both hot offset resistance and low-temperature fixing property of the toner.

Embodiments for Carrying Out the Invention

[0010] In the present invention, when producing a binder resin for toner in which a polycondensation resin segment and an addition polymerization resin segment are bonded via a bifunctional monomer, the step of addition-polymerizing an addition-polymerizable monomer and a bifunctional monomer is carried out in the presence of a polymer (A) having a predetermined amount of unsaturated bonds, which is a major feature. Although the details are unclear, it is presumed that the effects of the present invention are achieved by the following mechanism.

[0011] As described above, a high molecular weight amorphous polyester is effective for ensuring hot offset resistance, but there is a concern about deterioration of low-temperature fixing property. However, in the present invention, by addition-polymerizing an addition-polymerizable monomer and a bifunctional monomer in the presence of a polymer (A) having a predetermined amount of unsaturated bonds, a part of the polymer (A) having unsaturated bonds functions as a crosslinking element, and the unsaturated bond portion of the polymer (A) binds to the addition polymerization resin segment, thereby generating a high molecular weight crosslinked body having a resin component with an appropriate molecular weight that is excellent in low-temperature fixing property while avoiding gelation throughout. Thus, it is considered that a binder resin capable of achieving both low-temperature fixing property and hot offset resistance can be produced.

[0012] In the present invention, the polymer (A) having an unsaturated bond is not particularly limited as long as it has an unsaturated bond, and examples thereof include polyester resins, composite resins having polyester resin segments and styrene resin segments, polyamide resins, vinyl resins such as styrene resins, epoxy resins, polycarbonate resins, polyurethane resins, etc. In the present invention, from the viewpoints of ease of compounding and compatibility between low-temperature fixing property and hot offset resistance, a polyester resin or a composite resin having a polyester resin segment and a styrene resin segment is preferable, and a composite resin having a polyester resin segment and a styrene resin segment is more preferable.

[0013] The polyester resin is preferably a polycondensate of an alcohol component and a carboxylic acid component containing a monomer having an unsaturated bond in at least one of them.

[0014] As the monomer having an unsaturated bond, an unsaturated aliphatic dicarboxylic acid-based compound is preferable from the viewpoint of reactivity with an addition-polymerizable monomer.

[0015] Examples of the unsaturated aliphatic dicarboxylic acid-based compound include fumaric acid, maleic acid, citraconic acid, mesaconic acid, 2-pentenedioic acid, itaconic acid, anhydrides of these acids, alkyl esters of these acids having 1 to 3 carbon atoms, etc., and fumaric acid or maleic acid is preferable. Therefore, the polymer (A) having an unsaturated bond preferably has a structural unit derived from at least one of fumaric acid and maleic acid. <00001​​​​​The content of the unsaturated aliphatic dicarboxylic acid compound is preferably 2 mol% or more, more preferably 5 mol% or more, and preferably 80 mol% or less, more preferably 60 mol% or less, in the carboxylic acid component.

[0018] Other carboxylic acid components include saturated aliphatic dicarboxylic acid compounds, aromatic dicarboxylic acid compounds, and trivalent or higher carboxylic acid compounds.

[0019] Examples of saturated aliphatic dicarboxylic acid compounds include succinic acid, succinic acid derivatives substituted with hydrocarbon groups, adipic acid, sebacic acid, anhydrides of these acids, and alkyl esters of these acids with 1 to 3 carbon atoms.

[0020] Examples of aromatic dicarboxylic acid compounds include phthalic acid, isophthalic acid, terephthalic acid, anhydrides of these acids, and alkyl esters of these acids with 1 to 3 carbon atoms.

[0021] Examples of carboxylic acid compounds with a valency of 3 or higher include trimellitic acid, pyromellitic acid, anhydrides of these acids, and alkyl esters of these acids with 1 to 3 carbon atoms.

[0022] From the viewpoint of achieving a high softening point, when a trivalent or higher carboxylic acid compound is included, the content of the trivalent or higher carboxylic acid compound is preferably 10 mol% or more, more preferably 20 mol% or more, and preferably 50 mol% or less, and more preferably 40 mol% or less, in the carboxylic acid component.

[0023] The alcohol component preferably contains an alkylene oxide adduct of bisphenol A. The alkylene oxide adduct of bisphenol A is of formula (I):

[0024] [ka]

[0025] (In the formula, OR and RO are oxyalkylene groups, R is an ethylene group and / or a propylene group, x and y represent the average number of moles of alkylene oxide added, each being a positive number, and the sum of x and y is 1 or greater, preferably 1.5 or greater, and 16 or less, preferably 8 or less, more preferably 6 or less, and even more preferably 4 or less.) Compounds represented by are preferred.

[0026] From the viewpoint of low-temperature fixability, the content of the bisphenol A alkylene oxide adduct is preferably 70 mol% or more, more preferably 80 mol% or more, even more preferably 90 mol% or more, even more preferably 95 mol% or more, and even more preferably 100 mol% in the alcohol component.

[0027] Other alcohol components include aliphatic diols, bisphenol A, hydrogenated bisphenol A, sorbitol, pentaerythritol, glycerin, trivalent or higher alcohols such as trimethylolpropane, etc.

[0028] The alcohol component may contain a monohydric alcohol, and the carboxylic acid component may contain a monohydric carboxylic acid compound, as appropriate.

[0029] The equivalent ratio (COOH group / OH group) of the carboxyl group of the carboxylic acid component to the hydroxyl group of the alcohol component is preferably 0.6 or higher, more preferably 0.7 or higher, even more preferably 0.75 or higher, and preferably 1.2 or lower, more preferably 1.15 or lower.

[0030] Polyester resins can be produced, for example, by polycondensing an alcohol component and a carboxylic acid component in an inert gas atmosphere, preferably in the presence of an esterification catalyst, and optionally in the presence of an esterification co-catalyst, polymerization inhibitor, etc., at a temperature preferably 130°C or higher, more preferably 170°C or higher, and preferably 250°C or lower, more preferably 240°C or lower.

[0031] Examples of esterification catalysts include tin compounds such as dibutyltin oxide and tin(II) 2-ethylhexanoate, and titanium compounds such as titanium diisopropylate bistriethanolamine. The amount of esterification catalyst used is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and preferably 1.5 parts by mass or less, and more preferably 1 part by mass or less, per 100 parts by mass of the total amount of alcohol and carboxylic acid components. Examples of esterification co-catalysts include gallic acid. The amount of esterification co-catalyst used is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and preferably 0.5 parts by mass or less, and more preferably 0.1 parts by mass or less, per 100 parts by mass of the total amount of alcohol and carboxylic acid components. Examples of polymerization inhibitors include tert-butylcatechol. The amount of polymerization inhibitor used is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and preferably 0.5 parts by mass or less, and more preferably 0.1 parts by mass or less, based on 100 parts by mass of the total amount of alcohol and carboxylic acid components.

[0032] In this invention, the polyester resin may be a polyester resin that has been modified to such an extent that its properties are not substantially impaired. Examples of modified polyester resins include polyester resins that have been grafted or blocked with phenol, urethane, epoxy, etc., by methods described in Japanese Patent Publication No. 11-133668, Japanese Patent Publication No. 10-239903, Japanese Patent Publication No. 8-20636, etc. Among modified polyester resins, urethane-modified polyester resins obtained by urethane elongation of polyester resin with a polyisocyanate compound are preferred.

[0033] In a composite resin containing the polyester resin segment and the styrene-based resin segment, the raw material monomer of the polyester resin constituting the polyester resin segment is the same as the raw material monomer of the polyester resin.

[0034] The styrene-based resin segment is an addition polymer of a raw material monomer containing at least styrene, or a styrene derivative such as α-methylstyrene or vinyltoluene (hereinafter, styrene and styrene derivatives are collectively referred to as "styrene compounds").

[0035] The styrene compound, preferably styrene, content in the raw material monomer of the styrene-based resin segment is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more, from the viewpoint of preservation, and preferably 95% by mass or less, more preferably 93% by mass or less, and even more preferably 90% by mass or less, from the viewpoint of low-temperature fixability.

[0036] Furthermore, the styrene-based resin segment may contain an alkyl (meth)acrylate ester with an alkyl group having 7 or more carbon atoms as a raw material monomer. Examples of alkyl (meth)acrylate esters include 2-ethylhexyl (meth)acrylate, (iso)octyl (meth)acrylate, (iso)decyl (meth)acrylate, and (iso)stearyl (meth)acrylate. It is preferable to use one or more of these. In this specification, "(iso)" means that this group may or may not be present, and when these groups are not present, it indicates that it is normal. Also, "(meth)acrylic acid" refers to acrylic acid, methacrylic acid, or both.

[0037] The number of carbon atoms in the alkyl group of the alkyl (meth)acrylate, used as a raw material monomer for the styrene-based resin segment, is preferably 7 or more, more preferably 8 or more, and preferably 12 or less, more preferably 10 or less, from the viewpoint of improving the low-temperature fixability of the toner. Note that the number of carbon atoms in the alkyl ester refers to the number of carbon atoms derived from the alcohol component constituting the ester.

[0038] The raw material monomers for the styrene-based resin segment may include raw material monomers other than styrene compounds and alkyl (meth)acrylates, such as ethylenically unsaturated monoolefins such as ethylene and propylene; diolefins such as butadiene; halovinyls such as vinyl chloride; vinyl esters such as vinyl acetate and vinyl propionate; ethylenically monocarboxylic acid esters such as dimethylaminoethyl (meth)acrylate; vinyl ethers such as methyl vinyl ether; vinylidene halides such as vinylidene chloride; and N-vinyl compounds such as N-vinylpyrrolidone.

[0039] The addition polymerization reaction of the raw material monomers for styrene resin segments can be carried out by conventional methods in the presence of polymerization initiators such as dibutyl peroxide and dicumyl peroxide, chain transfer agents, crosslinking agents, etc., in the presence of organic solvents or without solvents. The temperature conditions are preferably 110°C or higher, more preferably 140°C or higher, and preferably 200°C or lower, more preferably 170°C or lower.

[0040] When using an organic solvent during the addition polymerization reaction, xylene, toluene, methyl ethyl ketone, acetone, etc., can be used. The amount of organic solvent used is preferably 10 to 50 parts by mass per 100 parts by mass of the raw material monomer of the styrene resin segment.

[0041] It is more preferable that the composite resin is a resin in which a polyester resin segment and a styrene-based resin segment are chemically bonded via reactive monomers that can react with both the raw material monomers of the polyester resin segment and the raw material monomers of the styrene-based resin segment.

[0042] The reactive monomers are preferably compounds having at least one functional group selected from the group consisting of hydroxyl groups, carboxyl groups, epoxy groups, primary amino groups, and secondary amino groups, preferably a hydroxyl group and / or a carboxyl group, more preferably a carboxyl group, and an ethylenically unsaturated bond within the molecule. More preferably, at least one selected from the group consisting of acrylic acid, methacrylic acid, fumaric acid, maleic acid, and maleic anhydride is preferred, and even more preferably, at least one selected from the group consisting of acrylic acid, methacrylic acid, and fumaric acid is preferred from the viewpoint of reactivity in polycondensation and addition polymerization reactions. However, when used together with a polymerization inhibitor, polycarboxylic acid compounds having an ethylenically unsaturated bond, such as fumaric acid, function as raw material monomers for polyester resin segments. In this case, fumaric acid, etc., are not the reactive monomers, but raw material monomers for polyester resin segments.

[0043] From the viewpoint of improving the dispersibility between the styrene-based resin segment and the polyester resin segment and improving the durability of the toner, the amount of both reactive monomers used is preferably 1 mole or more, more preferably 2 moles or more, per 100 moles of the total alcohol component of the polyester resin segment, and from the viewpoint of low-temperature fixability, it is preferably 30 moles or less, more preferably 20 moles or less, and even more preferably 10 moles or less. Furthermore, the amount of both reactive monomers used is preferably 1 part by mass or more, more preferably 2 parts by mass or more, per 100 parts by mass of the total raw material monomers of the styrene resin segment, from the viewpoint of improving the dispersibility between the styrene resin segment and the polyester resin segment and improving the durability of the toner, and preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less, from the viewpoint of low-temperature fixation. Here, the polymerization initiator is included in the total raw material monomers of the styrene resin segment.

[0044] The composite resin is preferably manufactured by the following method. When both reactive monomers are used, both reactive monomers are preferably used in the addition polymerization reaction together with the raw material monomers of the styrene-based resin segment, from the viewpoint of improving the electrostatic stability and low-temperature fixability of the toner.

[0045] The composite resin can be produced, for example, by a method comprising a polycondensation reaction (X) of raw material monomers for a polyester resin segment and an addition polymerization reaction (Y) of raw material monomers for a styrene-based resin segment. (i) Step (Y) may be performed after step (X), (ii) Step (X) may be performed after step (Y), or (iii) Steps (X) and (Y) may be performed simultaneously.

[0046] In method (i), after step (Y), the reaction temperature may be raised again, and if necessary, raw material monomers of trivalent or higher polyester resin segments that act as crosslinking agents may be added to the reaction system to further advance the polycondensation reaction in step (X) and the reaction with both reactive monomers. Alternatively, instead of step (X) in which a polycondensation reaction is performed, a pre-polymerized polyester resin may be used. When steps (X) and (Y) are carried out in parallel, a mixture containing the raw material monomers for the styrene-based resin segment can be added dropwise to a mixture containing the raw material monomers for the polyester resin segment and reacted.

[0047] Methods (i) to (iii) described above are preferably carried out in the same container.

[0048] The mass ratio of the polyester resin segment to the styrene resin segment in the composite resin is preferably 98 / 2 or less, more preferably 95 / 5 or less, and even more preferably 90 / 10 or less, from the viewpoint of electrostatic stability, and preferably 60 / 40 or more, more preferably 70 / 30 or more, and even more preferably 75 / 25 or more, from the viewpoint of low-temperature fixability. Here, the mass of the polyester resin segment is the amount obtained by subtracting the amount of reaction water (calculated value) dehydrated by the polycondensation reaction from the amount of raw material monomers of the polyester resin segment used, and the amounts of both reactive monomers are included in the amount of raw material monomers of the polyester resin segment. The mass of the styrene resin segment is the total amount of raw material monomers and polymerization initiator of the styrene resin segment.

[0049] The amount of unsaturated monomer in polymer (A) having unsaturated bonds is preferably 0.01 mmol or more, more preferably 0.03 mmol or more, and even more preferably 0.05 mmol or more per 1 g of polymer (A) having unsaturated bonds, from the viewpoint of hot offset resistance, and preferably 3 mmol or less, more preferably 2 mmol or less, and even more preferably 1.5 mmol or less, from the viewpoint of low-temperature fixation.

[0050] The softening point of polymer (A) having unsaturated bonds is preferably 80°C or higher, more preferably 90°C or higher, and even more preferably 95°C or higher, from the viewpoint of storage stability, and preferably 160°C or lower, more preferably 150°C or lower, and even more preferably 140°C or lower, from the viewpoint of low-temperature fixation.

[0051] The glass transition temperature of polymer (A) having unsaturated bonds is preferably 40°C or higher, more preferably 50°C or higher, from the viewpoint of storage stability, and preferably 80°C or lower, more preferably 70°C or lower, and even more preferably 65°C or lower, from the viewpoint of low-temperature fixation.

[0052] The acid value of polymer (A) having unsaturated bonds is preferably 2 mg KOH / g or more, more preferably 5 mg KOH / g or more, from the viewpoint of low-temperature fixability, and preferably 40 mg KOH / g or less, more preferably 30 mg KOH / g or less, from the viewpoint of hygroscopicity.

[0053] The weight-average molecular weight of polymer (A) having unsaturated bonds is preferably 1,000 or more, more preferably 5,000 or more, and even more preferably 10,000 or more, from the viewpoint of storage properties, and preferably 1,000,000 or less, more preferably 750,000 or less, and even more preferably 500,000 or less, from the viewpoint of low-temperature fixability.

[0054] From a similar viewpoint, the number-average molecular weight of the polymer (A) having unsaturated bonds is preferably 500 or more, more preferably 1,500 or more, even more preferably 2,000 or more, and preferably 10,000 or less, more preferably 7,500 or less, and even more preferably 5,000 or less.

[0055] The physical properties of polymer (A) having unsaturated bonds are measured using the same method as for the binder resin.

[0056] As the addition polymerization resin segment, a styrene-based resin segment is preferred, and the addition polymerization monomer preferably includes raw material monomers for styrene-based resins such as styrene, α-methylstyrene, vinyltoluene, and other styrene derivatives (hereinafter, styrene and styrene derivatives are collectively referred to as "styrene compounds").

[0057] The styrene compound, preferably styrene, content in the addition polymerizable monomer is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more, from the viewpoint of storage under high humidity, and preferably 95% by mass or less, more preferably 93% by mass or less, and even more preferably 90% by mass or less, from the viewpoint of low-temperature fixability.

[0058] Furthermore, the addition polymerizable monomer may include an alkyl (meth)acrylate ester with an alkyl group having 7 or more carbon atoms. Examples of alkyl (meth)acrylate esters include 2-ethylhexyl (meth)acrylate, (iso)octyl (meth)acrylate, (iso)decyl (meth)acrylate, and (iso)stearyl (meth)acrylate. It is preferable to use one or more of these. In this specification, "(iso)" means that this group may or may not be present, and when these groups are not present, it indicates that it is normal. Also, "(meth)acrylic acid" refers to acrylic acid, methacrylic acid, or both.

[0059] In alkyl (meth)acrylate esters as addition polymerizable monomers, the number of carbon atoms in the alkyl group is preferably 7 or more, more preferably 8 or more, and preferably 12 or less, more preferably 10 or less, from the viewpoint of improving the low-temperature fixing properties of the toner. Note that the number of carbon atoms in the alkyl ester refers to the number of carbon atoms derived from the alcohol component constituting the ester.

[0060] The addition polymerizable monomers may include monomers other than styrene compounds and alkyl (meth)acrylates, such as ethylenically unsaturated monoolefins like ethylene and propylene; diolefins like butadiene; halovinyls like vinyl chloride; vinyl esters like vinyl acetate and vinyl propionate; ethylenically monocarboxylic acid esters like dimethylaminoethyl (meth)acrylate; vinyl ethers like methyl vinyl ether; vinylidene halides like vinylidene chloride; and N-vinyl compounds like N-vinylpyrrolidone.

[0061] Both reactive monomers are monomers that can react with either polycondensable monomers or addition polymerizable monomers. The reactive monomers are preferably compounds having at least one functional group selected from the group consisting of hydroxyl groups, carboxyl groups, epoxy groups, primary amino groups, and secondary amino groups, preferably a hydroxyl group and / or a carboxyl group, more preferably a carboxyl group, and an ethylenically unsaturated bond. More preferably, at least one selected from the group consisting of acrylic acid, methacrylic acid, fumaric acid, maleic acid, and maleic anhydride is preferred, and even more preferably, at least one selected from the group consisting of acrylic acid, methacrylic acid, and fumaric acid is preferred from the viewpoint of reactivity in polycondensation and addition polymerization reactions. However, when used with a polymerization inhibitor, polycarboxylic acid compounds having an ethylenically unsaturated bond, such as fumaric acid, function as raw material monomers for polyester resin segments. In this case, fumaric acid, etc., are not both reactive monomers, but raw material monomers for polyester resin segments.

[0062] From the viewpoint of improving the dispersibility between the styrene-based resin segment and the polyester resin segment and improving the durability of the toner, the amount of both reactive monomers used is preferably 1 mole or more, more preferably 2 moles or more, per 100 moles of the total alcohol component of the polyester resin segment, and from the viewpoint of low-temperature fixability, it is preferably 30 moles or less, more preferably 20 moles or less, and even more preferably 10 moles or less. Furthermore, the amount of both reactive monomers used is preferably 1 part by mass or more, more preferably 2 parts by mass or more, per 100 parts by mass of the total raw material monomers of the styrene resin segment, from the viewpoint of improving the dispersibility between the styrene resin segment and the polyester resin segment and improving the durability of the toner, and preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less, from the viewpoint of low-temperature fixation. Here, the polymerization initiator is included in the total raw material monomers of the styrene resin segment.

[0063] Polycondensable resin segments are preferred, and the polycondensable monomer contains an alcohol component and a carboxylic acid component.

[0064] The alcohol component preferably includes an alkylene oxide adduct of bisphenol A. The compound represented by formula (I) is preferred as the alkylene oxide adduct of bisphenol A.

[0065] From the viewpoint of low-temperature fixability, the content of the bisphenol A alkylene oxide adduct is preferably 70 mol% or more, more preferably 80 mol% or more, even more preferably 90 mol% or more, even more preferably 95 mol% or more, and even more preferably 100 mol% in the alcohol component.

[0066] Other alcohol components include aliphatic diols, bisphenol A, hydrogenated bisphenol A, sorbitol, pentaerythritol, glycerin, trivalent or higher alcohols such as trimethylolpropane, etc.

[0067] The carboxylic acid component preferably includes an aromatic dicarboxylic acid compound.

[0068] Examples of aromatic dicarboxylic acid compounds include phthalic acid, isophthalic acid, terephthalic acid, anhydrides of these acids, and alkyl esters of these acids with 1 to 3 carbon atoms.

[0069] From the viewpoint of low-temperature fixability, the content of aromatic dicarboxylic acid compounds is preferably 40 mol% or more, more preferably 50 mol% or more, and 100 mol% or less, preferably 90 mol% or less, in the carboxylic acid component.

[0070] Other carboxylic acid components besides aromatic dicarboxylic acid compounds include aliphatic dicarboxylic acid compounds and trivalent or higher carboxylic acid compounds.

[0071] Examples of aliphatic dicarboxylic acid compounds include aliphatic dicarboxylic acids such as oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid optionally substituted with a hydrocarbon group having 1 to 20 carbon atoms, adipic acid, anhydrides of these acids, and alkyl esters having 1 to 3 carbon atoms in the alkyl group, and the like.

[0072] Examples of carboxylic acid compounds having a trivalent or higher valence include trimellitic acid, pyromellitic acid, anhydrides of these acids, alkyl esters having 1 to 3 carbon atoms in these acids, and the like.

[0073] The equivalent ratio of the carboxy group of the carboxylic acid component to the hydroxy group of the alcohol component (COOH group / OH group) is preferably 0.6 or more, more preferably 0.7 or more, still more preferably 0.75 or more, and preferably 1.2 or less, more preferably 1.15 or less.

[0074] The binder resin for toner in the present invention includes a step A of addition-polymerizing an addition-polymerizable monomer and a bifunctional monomer in the presence of a polymer (A) having an unsaturated bond, and a step B of polycondensing a polycondensable monomer containing a carboxylic acid component and an alcohol component, and is produced by a method in which steps A and B are carried out in the same reaction vessel.

[0075] In step A, from the viewpoint of hot offset resistance, the amount of substance of the monomer having an unsaturated bond constituting the polymer (A) having an unsaturated bond is 5.0×10 -5 mmol or more, preferably 1.0×10 -4 mmol or more, more preferably 3.0×10 -4 mmol or more, still more preferably 5.0×10 -4 mmol or more, and from the viewpoint of low-temperature fixing property, it is 2.0×10 -2 mmol or less, preferably 1.9×10 -2 mmol or less, more preferably 1.8×10 -2 mmol or less, still more preferably 1.75×10-2 It is less than a millimeter.

[0076] Furthermore, the amount of polymer (A) having unsaturated bonds used in step A is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, even more preferably 0.08 parts by mass or more, and preferably 2.8 parts by mass or less, more preferably 2.6 parts by mass or less, and even more preferably 2.4 parts by mass or less, based on 100 parts by mass of the total amount of polycondensation resin segment and addition polymerization resin segment. The amount of polycondensation resin segment is the theoretical yield calculated by subtracting the amount of reaction water from the total amount of polycondensable monomers, and the amount of addition polymerization resin segment is the total amount of addition polymerizable monomers and polymerization initiators.

[0077] In step A, the addition polymerization reaction can be carried out by conventional methods in the presence of polymerization initiators such as dibutyl peroxide and dicumyl peroxide, chain transfer agents, crosslinking agents, etc., in the presence of an organic solvent or without a solvent. The temperature conditions are preferably 110°C or higher, more preferably 140°C or higher, and preferably 200°C or lower, more preferably 170°C or lower.

[0078] When using an organic solvent during the addition polymerization reaction, xylene, toluene, methyl ethyl ketone, acetone, etc., can be used. The amount of organic solvent used is preferably 10 to 50 parts by mass per 100 parts by mass of the raw material monomer of the styrene resin segment.

[0079] In step B, the polycondensation reaction can be carried out, for example, when an alcohol component and a carboxylic acid component are used as polycondensable monomers, in an inert gas atmosphere, preferably in the presence of an esterification catalyst, and optionally in the presence of an esterification co-catalyst, polymerization inhibitor, etc., at a temperature preferably 130°C or higher, more preferably 170°C or higher, and preferably 250°C or lower, more preferably 240°C or lower.

[0080] Examples of esterification catalysts include tin compounds such as dibutyltin oxide and tin(II) 2-ethylhexanoate, and titanium compounds such as titanium diisopropylate bistriethanolamine. The amount of esterification catalyst used is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and preferably 1.5 parts by mass or less, and more preferably 1 part by mass or less, per 100 parts by mass of the total amount of alcohol and carboxylic acid components. Examples of esterification co-catalysts include gallic acid. The amount of esterification co-catalyst used is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and preferably 0.5 parts by mass or less, and more preferably 0.1 parts by mass or less, per 100 parts by mass of the total amount of alcohol and carboxylic acid components. Examples of polymerization inhibitors include t-butylcatechol. The amount of polymerization inhibitor used is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and preferably 0.5 parts by mass or less, and more preferably 0.1 parts by mass or less, based on 100 parts by mass of the total amount of alcohol and carboxylic acid components.

[0081] The order of steps A and B is not particularly limited as long as step A is carried out in the presence of a polymer (A) having unsaturated bonds. (i) step B may be carried out after step A, (ii) step A may be carried out after step B, or (iii) steps A and B may be carried out simultaneously. However, in the present invention, from the viewpoint of the reactivity of polymer (A) and addition polymerizable monomer, method (i), in which step B is carried out after step A, is preferred.

[0082] In method (i), step A may be carried out in the presence of a polycondensable monomer and polymer (A). In this case, it is preferable to add an esterification catalyst, an esterification co-catalyst, etc., to the reaction system after step A and carry out step B under temperature conditions suitable for the polycondensation reaction. In method (ii), step B may be carried out in the presence of polymer (A), followed by step A.

[0083] The mass ratio of the polycondensation resin segment to the addition polymerization resin segment in the binder resin is preferably 98 / 2 or less, more preferably 95 / 5 or less, and even more preferably 90 / 10 or less, from the viewpoint of electrostatic stability, and preferably 60 / 40 or more, more preferably 70 / 30 or more, and even more preferably 75 / 25 or more, from the viewpoint of low-temperature fixation. Here, the mass of the polycondensation resin segment is the total amount of the polycondensation monomer and both reactive monomers used minus the amount of reaction water (calculated value) dehydrated by the polycondensation reaction. The mass of the addition polymerization resin segment is the total amount of the addition polymerizable monomer and polymerization initiator.

[0084] The softening point of the binder resin is preferably 80°C or higher, more preferably 90°C or higher, from the viewpoint of storage stability, and preferably 150°C or lower, more preferably 130°C or lower, from the viewpoint of low-temperature fixation.

[0085] The glass transition temperature of the binder resin is preferably 50°C or higher, more preferably 53°C or higher, from the viewpoint of storage stability, and preferably 70°C or lower, more preferably 65°C or lower, from the viewpoint of low-temperature fixation.

[0086] The acid value of the binder resin is preferably 2 mg KOH / g or more, more preferably 5 mg KOH / g or more, from the viewpoint of low-temperature fixation, and preferably 40 mg KOH / g or less, more preferably 30 mg KOH / g or less, from the viewpoint of hygroscopicity.

[0087] The weight-average molecular weight of the binder resin is preferably 5,000 or more, more preferably 10,000 or more, and even more preferably 15,000 or more, from the viewpoint of storage properties, and preferably 200,000 or less, more preferably 150,000 or less, and even more preferably 100,000 or less, from the viewpoint of low-temperature fixation properties.

[0088] The number-average molecular weight of the binder resin is similarly preferably 1,000 or more, more preferably 1,500 or more, and even more preferably 2,000 or more, and from the viewpoint of low-temperature fixation, it is preferably 10,000 or less, more preferably 5,000 or less, and even more preferably 3,000 or less.

[0089] A toner for electrostatic image development can be obtained using the binder resin obtained by the method of the present invention. The binder resin content is preferably 60% by mass or more, more preferably 70% by mass or more, and preferably less than 100% by mass, more preferably 98% by mass or less, and even more preferably 95% by mass or less, in the toner. The binder resin may contain resins other than the binder resin obtained by the method of the present invention, but the content of such binder resins is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more, in the total amount of binder resin.

[0090] The toner may contain additives such as colorants, release agents, charge control agents, magnetic powders, flow improvers, conductivity modifiers, reinforcing fillers such as fibrous materials, antioxidants, and cleaning properties improvers in the binder resin.

[0091] As colorants, dyes, pigments, magnetic materials, etc., used as colorants for toners can be used. Examples include carbon black, phthalocyanine blue, permanent brown FG, brilliant first scarlet, pigment red 122, pigment green B, rhodamine-B base, solvent red 49, solvent red 146, solvent blue 35, quinacridone, carmine 6B, isoindoline, pigment yellow, disazo yellow, etc. In this invention, the toner may be either black toner or color toner.

[0092] From the viewpoint of improving the toner's image density and low-temperature fixability, the colorant content is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and preferably 40 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less, per 100 parts by mass of the binder resin.

[0093] Examples of mold release agents include hydrocarbon waxes and their oxides, such as polypropylene wax, polyethylene wax, polypropylene-polyethylene copolymer wax, microcrystalline wax, paraffin wax, and Fischer-Tropsch wax; ester waxes such as carnauba wax, montane wax and their deoxidizing waxes, and fatty acid ester waxes; and fatty acid amides, fatty acids, higher alcohols, fatty acid metal salts, etc., which can be used individually or in combination of two or more.

[0094] The melting point of the release agent is preferably 60°C or higher, more preferably 70°C or higher, from the viewpoint of toner transferability, and preferably 160°C or lower, more preferably 140°C or lower, even more preferably 120°C or lower, and even more preferably 110°C or lower, from the viewpoint of low-temperature fixation.

[0095] The release agent content is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 1.5 parts by mass or more, and preferably 20 parts by mass or less, and more preferably 15 parts by mass or less, per 100 parts by mass of binder resin, from the viewpoint of low-temperature fixation and offset resistance of the toner and dispersibility in the binder resin.

[0096] The charge control agent is not particularly limited and may contain either a positively charged charge control agent or a negatively charged charge control agent.

[0097] Positively charged charge control agents include nigrosine dyes, such as "Nigrosine Base EX," "Oil Black BS," "Oil Black SO," "Bontron N-01," "Bontron N-04," "Bontron N-07," "Bontron N-09," and "Bontron N-11" (all manufactured by Orient Chemical Industries, Ltd.); triphenylmethane-based dyes containing tertiary amines as side chains; quaternary ammonium salt compounds, such as "Bontron P-51" (manufactured by Orient Chemical Industries, Ltd.), cetyltrimethylammonium bromide, and "COPY CHARGE PX." Examples include VP435 (manufactured by Clariant), polyamine resins such as AFP-B (manufactured by Orient Chemical Industries, Ltd.), imidazole derivatives such as PLZ-2001 and PLZ-8001 (both manufactured by Shikoku Chemicals, Ltd.), and styrene-acrylic resins such as FCA-701PT and FCA-201-PS (manufactured by Fujikura Chemicals, Ltd.).

[0098] Furthermore, as negative charge control agents, metal-containing azo dyes, such as "Barifast Black 3804," "Bontron S-31," "Bontron S-32," "Bontron S-34," and "Bontron S-36" (all manufactured by Orient Chemical Industries, Ltd.), "Eisenspiron Black TRH," and "T-77" (manufactured by Hodogaya Chemical Co., Ltd.); metal compounds of benzyl acid compounds, such as "LR-147" and "LR-297" (both manufactured by Nippon Carlit Co., Ltd.); metal compounds of salicylic acid compounds, such as "Bontron E-81," "Bontron E-84," "Bontron E-88," and "Bontron E-304" (all manufactured by Orient Chemical Industries, Ltd.), and "TN-105" (manufactured by Hodogaya Chemical Co., Ltd.); copper phthalocyanine dyes; and quaternary ammonium salts, such as "COPY CHARGE NX" Examples include VP434 (manufactured by Clariant), nitroimidazole derivatives, organometallic compounds, etc.

[0099] From the viewpoint of the charge stability of the toner, the content of the charge control agent is preferably 0.01 parts by mass or more, more preferably 0.2 parts by mass or more, and preferably 10 parts by mass or less, more preferably 5 parts by mass or less, even more preferably 3 parts by mass or less, and even more preferably 2 parts by mass or less, per 100 parts by mass of the binder resin.

[0100] Toner can be manufactured by any of the conventionally known methods, such as the melt-kneading method, the emulsification-phase inversion method, or the polymerization method. However, in the present invention, from the viewpoint of low-temperature fixation, it is preferable to manufacture toner by a method that includes the steps of (I) dispersing the toner binder resin obtained by the method of the present invention in an aqueous medium to obtain resin particles, and (II) agglomerating and fusing the resin particles to obtain toner particles.

[0101] In step (I), methods for obtaining resin particles include adding resin components to an aqueous medium and performing dispersion treatment using a disperser, and gradually adding an aqueous medium to a molten or organic solvent solution of resin components to perform phase inversion emulsification (phase inversion emulsification). Among these, the phase inversion emulsification method is preferred from the viewpoint of improving the low-temperature fixability and durability of the toner.

[0102] Examples of phase inversion emulsification methods include (A) a method in which resin components are dissolved in an organic solvent to obtain an organic solvent solution of the resin components, and then an aqueous medium is added to the obtained solution to perform phase inversion emulsification; and (B) a method in which resin components are melted and mixed to obtain a resin mixture, and then an aqueous medium is added to the mixture to perform phase inversion emulsification. From the viewpoint of obtaining a homogeneous aqueous dispersion of resin particles for cores, method (A) is preferred.

[0103] The organic solvent used for phase inversion emulsification is not particularly limited as long as it can dissolve the resin, but an example is methyl ethyl ketone.

[0104] The amount of organic solvent used is preferably 30 parts by mass or more and 1000 parts by mass or less per 100 parts by mass of the binder resin.

[0105] The amount of aqueous medium used is preferably 100 parts by mass or more and 3000 parts by mass or less per 100 parts by mass of the organic solvent. The aqueous medium used in step (I) may contain an alcohol-based solvent with 1 to 3 carbon atoms, such as ethanol, but preferably contains 50% by mass or more, more preferably 70% by mass or more, even more preferably 90% by mass or more, and even more preferably 99% by mass or more of water.

[0106] When stirring the mixture, commonly used mixing and stirring devices such as anchor blades can be used.

[0107] In the phase inversion emulsification method, it is preferable to treat the resin with a neutralizing agent. Examples of neutralizing agents include alkali metals such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; and organic bases such as ammonia, trimethylamine, ethylamine, diethylamine, triethylamine, triethanolamine, and tributylamine. The amount of neutralizing agent added is preferably such that the degree of neutralization is about 50-100% of the acid value of the polyester after the reaction.

[0108] A surfactant or the like may be used as a dispersant to reduce the melt viscosity and melting point of the binder resin, and to improve the dispersibility of the resulting resin particles.

[0109] The solid content concentration of the dispersion of resin particles containing the binder resin obtained in step (I) is preferably 5% by mass or more, more preferably 10% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less, from the viewpoint of the stability of the dispersion and the ease of handling the dispersion in the flocculation step. The solid content includes non-volatile components such as resin and surfactant.

[0110] The average particle size of the resin particles is preferably 0.05 μm or more, more preferably 0.10 μm or more, even more preferably 0.15 μm or more, and preferably 0.80 μm or less, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less, from the viewpoint of uniform aggregation in subsequent steps. In the present invention, the average particle size of the resin particles is the median particle size (D 50 This refers to the particle size that can be measured using a laser diffraction particle size analyzer or similar device.

[0111] Next, the resin particles obtained in step (I) are aggregated and fused together (step (II)).

[0112] In step (II), flocculation is performed, for example, by adding a flocculant to a mixed dispersion containing resin particles at a temperature of 0°C to 40°C, causing the resin particles to flocce in an aqueous medium to obtain flocculated particles. Furthermore, from the viewpoint of promoting flocculation, it is preferable to raise the temperature of the dispersion after adding the flocculant.

[0113] The temperature maintained during aggregation is preferably 45°C or higher, more preferably 50°C or higher, and preferably 80°C or lower, more preferably 70°C or lower, and even more preferably 65°C or lower.

[0114] Furthermore, additives such as colorants, release agents, and charge control agents may be pre-mixed with the binder resin when preparing the resin particles, or each additive may be mixed separately with a resin, surfactant, etc. as appropriate, and dispersed in a dispersion medium such as water to prepare a dispersion solution which may be mixed with the resin particles and subjected to the flocculation process. The resin mixed with the additives may be the same as or different from the binder resin.

[0115] As flocculants, organic flocculants include quaternary ammonium salt cationic surfactants and polyethyleneimines, while inorganic flocculants include inorganic metal salts, inorganic ammonium salts, and metal complexes with two or more valent progenitors. Examples of inorganic metal salts include metal salts such as sodium sulfate, sodium chloride, calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, and aluminum sulfate, as well as inorganic metal salt polymers such as polyaluminum chloride, polyaluminum hydroxide, and calcium polysulfide. Examples of inorganic ammonium salts include ammonium sulfate, ammonium chloride, and ammonium nitrate.

[0116] From the viewpoint of controlling aggregation and obtaining the desired particle size, the amount of flocculant used is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, even more preferably 20 parts by mass or more, preferably 60 parts by mass or less, and more preferably 50 parts by mass or less, per 100 parts by mass of the binder resin.

[0117] Next, the aggregated particles containing at least a binder resin obtained in the aggregation step are heated and fused together to obtain toner particles (fusion step).

[0118] The aggregation of fused particles may be stopped by adding an anti-aggregation agent once the particles have grown to a suitable particle size for use as toner.

[0119] The temperature within the system during the fusion process is preferably 2°C higher, more preferably 4°C higher, and even more preferably 6°C higher than the maximum glass transition temperature of the binder resin, and preferably 30°C higher or lower, and more preferably 20°C higher or lower, from the viewpoint of the desired toner particle size, particle size distribution, shape control, and particle fusion properties. Furthermore, the stirring speed is preferably such that aggregated particles do not settle. In this invention, if two or more types of resins are used as the binder resin, the glass transition temperature of the resin with the highest glass transition temperature is used as the reference.

[0120] Toner particles can be obtained by subjecting the fused particles obtained in step (II) to a solid-liquid separation step such as filtration, a washing step, and a drying step as appropriate.

[0121] Toner is preferably used with external additives to improve its transferability. Examples of external additives include inorganic fine particles such as silica, alumina, titania, zirconia, tin oxide, and zinc oxide, and organic fine particles such as melamine resin fine particles and polytetrafluoroethylene resin fine particles. Two or more types may be used in combination. Among these, silica is preferred, and from the viewpoint of toner transferability, hydrophobic silica that has been hydrophobicized is more preferred.

[0122] Examples of hydrophobic agents used to hydrophobize the surface of silica particles include hexamethyldisilazane (HMDS), dimethyldichlorosilane (DMDS), dimethylsiloxane, silicone oil, octyltriethoxysilane (OTES), and methyltriethoxysilane.

[0123] The average particle size of the external additive is preferably 10 nm or larger, more preferably 15 nm or larger, and more preferably 250 nm or smaller, more preferably 200 nm or smaller, and even more preferably 90 nm or smaller, from the viewpoint of the toner's chargeability, fluidity, and transferability.

[0124] From the viewpoint of the toner's electrostatic properties, fluidity, and transferability, the content of the external additive is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, even more preferably 0.3 parts by mass or more, and preferably 5 parts by mass or less, and more preferably 4 parts by mass or less, per 100 parts by mass of toner particles before treatment with the external additive.

[0125] The volume-intermediate particle size (D) of the toner of the present invention 50 The volume median particle size (D) is preferably 3 μm or more, more preferably 4 μm or more, and preferably 15 μm or less, more preferably 10 μm or less. 50) refers to the particle size at which the cumulative volume frequency, calculated using volume fractions, accounts for 50% of the total volume frequency, starting from the smallest particle size. Furthermore, if the toner is treated with an external additive, the volume median particle size of the toner particles before treatment with the external additive is considered the volume median particle size of the toner.

[0126] The toner of the present invention can be used as is as a one-component developing toner, or as a two-component developing toner mixed with a carrier, in image forming apparatuses using either a one-component developing method or a two-component developing method, respectively. [Examples]

[0127] The present invention will be specifically described below with reference to examples, but the present invention is not limited in any way by these examples. The physical properties of resins, etc., can be measured by the following methods.

[0128] [Softening point of resin] Using a flow tester "CFT-500EX" (manufactured by Shimadzu Corporation), 1 g of sample is heated at a heating rate of 6°C / min while a load of 1.96 MPa is applied by a plunger, and the sample is extruded from a nozzle with a diameter of 1 mm and a length of 1 mm. The amount of plunger descent of the flow tester is plotted against temperature, and the temperature at which half of the sample has flowed out is defined as the softening point.

[0129] [Glass transition temperature of resins] Using a differential scanning calorimeter "Q-100" (manufactured by T.A. Instruments Japan), 0.01 to 0.02 g of the sample is weighed into an aluminum pan and heated from room temperature (20°C) to 200°C at a heating rate of 10°C / min, and then cooled to 0°C at a cooling rate of 10°C / min. Next, the sample is heated at a heating rate of 10°C / min and the endothermic peak is measured. The temperature at the intersection of the extension of the baseline below the maximum endothermic peak temperature and the tangent line showing the maximum slope from the rising part of the peak to the peak apex is defined as the glass transition temperature.

[0130] [Acid value of resins] The measurement will be performed according to the method of JIS K0070:1992. However, the measurement solvent will be changed from the ethanol and ether mixture specified in JIS K0070:1992 to an acetone and toluene mixture (acetone:toluene = 1:1 (volume ratio)).

[0131] [Number-average molecular weight and weight-average molecular weight of resins] The number-average molecular weight and weight-average molecular weight are determined by gel permeation chromatography (GPC) using the following method. (1) Preparation of sample solution The sample is dissolved in tetrahydrofuran at 40°C to a concentration of 0.5 g / 100 mL. Then, this solution is filtered using a PTFE type membrane filter "DISMIC-25JP" (manufactured by Toyo Roshi Co., Ltd.) with a pore size of 0.20 μm to remove insoluble components and obtain the sample solution. (2) Molecular weight measurement Using the measuring apparatus and analytical column described below, tetrahydrofuran is flowed as the eluent at a flow rate of 1 mL / min, and the column is stabilized in a constant temperature bath at 40°C. 100 μL of the sample solution is then injected and the measurement is performed. The molecular weight of the sample is calculated based on a calibration curve prepared in advance. The calibration curve used in this case includes several types of monodisperse polystyrene (A-500 (5.0 × 10) manufactured by Tosoh Corporation). 2 ), A-1000 (1.01 x 10 3 ), A-2500 (2.63 x 10 3 ), A-5000 (5.97 x 10 3 ), F-1 (1.02×10 4 ), F-2 (1.81×10 4 ), F-4 (3.97×10 4 ), F-10 (9.64×10 4 ), F-20 (1.90×10 5 ), F-40 (4.27×10 5 ), F-80 (7.06×10 5 ), F-128 (1.09×10 6 The sample prepared using )) as a standard sample is used. The value in parentheses indicates the molecular weight. Measuring device: HLC-8220GPC (manufactured by Tosoh Corporation) Analysis column: TSKgel GMH XL +TSKgel G3000H XL (Manufactured by Tosoh Corporation)

[0132] [Melting point of release agent] Using a differential scanning calorimeter "DSC Q20" (manufactured by T.A. Instruments Japan Co., Ltd.), 0.01 to 0.02 g of the sample is weighed into an aluminum pan, heated to 200°C at a heating rate of 10°C / min, and then cooled to -10°C at a cooling rate of 5°C / min. Next, the sample is heated to 180°C at a heating rate of 10°C / min and measured. The maximum endothermic peak temperature observed from the resulting melting endothermic curve is defined as the melting point of the release agent.

[0133] [Average particle size of external additives] The average particle diameter refers to the number-average particle diameter, which is calculated by measuring the particle size (average of the major and minor axes) of 500 particles from scanning electron microscope (SEM) images and using the number-average value of these measurements.

[0134] [Volume median particle size and CV value of resin particles, colorant particles, and mold release agent particles] (1) Measuring device: Laser diffraction particle size analyzer "LA-920" (manufactured by Horiba, Ltd.) (2) Measurement conditions: Take the sample dispersion into a measuring cell, add distilled water, and adjust the concentration to the appropriate range for absorbance, using the medium particle size (D 50 The volume-average particle size (Dv) is measured. The coefficient of variation (CV) is calculated according to the following formula. CV value (%) = (Standard deviation of particle size distribution / Volume-average particle size (Dv)) × 100

[0135] [Solid content concentration of resin particle dispersion, colorant particle dispersion, and mold release agent particle dispersion] Using the infrared moisture meter "FD-230" (manufactured by Kett Scientific Research Institute Co., Ltd.), the moisture content (mass%) of a 5g sample is measured at a drying temperature of 150°C and measurement mode 96 (monitoring time 2.5 minutes, moisture content fluctuation range 0.05%). The solid content concentration is calculated according to the following formula. Solid concentration (mass%) = 100-moisture (mass%)

[0136] [Volume median particle size (D) of aggregated particles and toner particles] 50 ) and CV value] Measuring instrument: Coulter Multisizer II (manufactured by Beckman Coulter, Inc.) Aperture diameter: 100 μm Analysis software: Coulter Multisizer AccuComp version 1.19 (manufactured by Beckman Coulter, Inc.) Electrolyte: Isoton II (manufactured by Beckman Coulter, Inc.) Dispersion: Prepared by dissolving Emulgen 109P (manufactured by Kao Corporation, polyoxyethylene lauryl ether, HLB (Griffin): 13.6) in the electrolyte and adjusting to 5% by mass (the dispersion is used as is for aggregated particles). Dispersion conditions: 10 mg of the sample to be measured is added to 5 mL of the dispersion, and dispersed for 1 minute using an ultrasonic disperser (machine name: US-1 manufactured by SND Corporation, output: 80W). Then, 25 mL of the electrolyte is added, and dispersed for another minute using the ultrasonic disperser to prepare the sample dispersion. Measurement conditions: Add the sample dispersion to 100 mL of the electrolyte solution to a concentration that allows for the measurement of the particle size of 30,000 particles in 20 seconds. Measure the 30,000 particles and determine the median particle size (D) from their particle size distribution. 50 The particle size and volume-average particle size (Dv) are determined. The coefficient of variation (CV) is calculated from the obtained particle size distribution according to the following formula. CV value (%) = (Standard deviation of particle size distribution / Volume-average particle size (Dv)) × 100

[0137] [Circularity of fused particles] The circularity of the fused particles is measured under the following conditions. Measurement device: Flow-type particle image analyzer "FPIA-3000" (manufactured by Sysmex Corporation) Preparation of dispersion: The dispersion of fused particles is diluted with deionized water to a solid content concentration of 0.001 to 0.05% by mass. Measurement mode: HPF measurement mode

[0138] Example 1 of the production of polymers containing unsaturated bonds As shown in Table 1, the alcohol component and terephthalic acid were placed in a 10 L four-necked flask equipped with a nitrogen inlet tube, stirrer, and thermocouple. Under a nitrogen atmosphere, the temperature was raised to 160°C, and a monomer mixture consisting of styrene resin raw material monomers, both reactive monomers, and polymerization initiator was added dropwise over 1 hour. After aging at 160°C for 30 minutes, the temperature was raised to 200°C, and after reaching 200°C, unreacted monomers were removed under reduced pressure of 8 kPa for 1 hour. After cooling to 150°C, the esterification catalyst and esterification co-catalyst were added, and the temperature was raised to 235°C for 8 hours to carry out the esterification reaction. After that, the reaction was carried out under reduced pressure of 8 kPa for 1 hour, then the temperature was lowered to 160°C, fumaric acid and polymerization inhibitor were added, and the temperature was raised again to 190°C. After reaching 190°C, it was held for 30 minutes, and then the temperature was raised to 210°C at a rate of 10°C / h, and after reaching 210°C it was held for 2 hours. Subsequently, the reaction was carried out at 66.7 kPa while maintaining a temperature of 210°C until the softening point shown in Table 1 was reached, yielding a composite resin (resin A1) containing unsaturated bonds. The physical properties of the obtained resin are shown in Table 1.

[0139] Example 2 of the production of polymers containing unsaturated bonds As shown in Table 1, the alcohol component and terephthalic acid were placed in a 10 L four-necked flask equipped with a nitrogen inlet tube, stirrer, and thermocouple. Under a nitrogen atmosphere, the temperature was raised to 160°C, and a monomer mixture consisting of styrene resin raw material monomers, both reactive monomers, and polymerization initiator was added dropwise over 1 hour. After aging at 160°C for 30 minutes, the temperature was raised to 200°C, and after reaching 200°C, unreacted monomers were removed under reduced pressure of 8 kPa for 1 hour. After cooling to 150°C, an esterification catalyst and esterification co-catalyst were added, and the temperature was raised to 235°C for 8 hours to carry out the esterification reaction. After that, the reaction was carried out under reduced pressure of 8 kPa for 1 hour, then the temperature was lowered to 160°C, fumaric acid, trimellitic anhydride, and polymerization inhibitor were added, and the temperature was raised again to 190°C. After reaching 190°C, the temperature was maintained for 30 minutes, then increased to 210°C at a rate of 10°C / h, and maintained for 2 hours after reaching 210°C. Subsequently, the reaction was carried out at 66.7 kPa while maintaining 210°C until the softening point shown in Table 1 was reached, yielding composite resins (resins A2 and A3) containing unsaturated bonds. The physical properties of the obtained resins are shown in Table 1.

[0140] Example 3 of the production of polymers containing unsaturated bonds The alcohol component, terephthalic acid, esterification catalyst, and esterification co-catalyst shown in Table 1 were placed in a 10 L four-necked flask equipped with a nitrogen inlet tube, stirrer, and thermocouple. The esterification reaction was carried out under a nitrogen atmosphere, heated to 235°C for 8 hours. After that, the reaction was carried out under reduced pressure of 8 kPa for 1 hour, then the temperature was lowered to 160°C, fumaric acid or maleic acid and a polymerization inhibitor were added, and the temperature was raised again to 190°C. After reaching 190°C, the temperature was held for 30 minutes, then the temperature was raised to 210°C at a rate of 10°C / h, and the temperature was held for 2 hours after reaching 210°C. After that, the reaction was carried out at 210°C at 66.7 kPa until the softening point shown in Table 1 was reached, yielding polyester resins with unsaturated bonds (resins A4, A5). The physical properties of the obtained resins are shown in Table 1.

[0141] [Table 1]

[0142] Examples A1, A3-A9 and Comparative Examples A2, A3 As shown in Tables 2 and 3, polycondensable monomers other than succinic acid or fumaric acid and polymers (A) having unsaturated bonds were placed in a 10 L four-necked flask equipped with a nitrogen inlet tube, stirrer, and thermocouple. The mixture was heated to 160°C under a nitrogen atmosphere, and a monomer mixture consisting of addition polymerizable monomers, both reactive monomers, and polymerization initiators was added dropwise over 1 hour. After aging at 160°C for 30 minutes, the temperature was raised to 200°C, and after reaching 200°C, it was maintained under reduced pressure of 8 kPa for 1 hour. After cooling to 150°C, an esterification catalyst and esterification co-catalyst were added, and the temperature was raised to 235°C for 8 hours to carry out the esterification reaction. After reacting under reduced pressure of 8 kPa for 1 hour, the temperature was cooled to 160°C, succinic acid or fumaric acid was added, and the temperature was raised again to 190°C. After reaching 190°C, the mixture was held for 30 minutes, and then reacted at 40 kPa until the softening points listed in Tables 2 and 3 were reached, yielding composite resins (resins B2, B4-B12). The physical properties of the obtained resins are shown in Tables 2 and 3.

[0143] Example A2 As shown in Table 2, polycondensable monomers other than succinic acid, resin A1, esterification catalyst, and esterification co-catalyst were placed in a 10 L four-necked flask equipped with a nitrogen inlet tube, stirrer, and thermocouple, and the esterification reaction was carried out under a nitrogen atmosphere at 235°C for 8 hours. After that, the reaction was carried out under reduced pressure of 8 kPa for 1 hour, then the temperature was lowered to 160°C, and a monomer mixture consisting of addition polymerizable monomer, bireactive monomer, and polymerization initiator was added dropwise over 1 hour. After aging at 160°C for 30 minutes, the temperature was raised to 200°C, and after reaching 200°C, it was held under reduced pressure of 8 kPa for 1 hour. After lowering the temperature to 160°C, succinic acid was added and the temperature was raised again to 190°C. After reaching 190°C, it was held for 30 minutes, and then the reaction was carried out at 40 kPa until the softening point shown in Table 2 was reached to obtain the composite resin (resin B3). The physical properties of the obtained resin are shown in Table 2.

[0144] Comparative Example A1 As shown in Table 2, polycondensable monomers other than succinic acid and resin A1 were placed in a 10 L four-necked flask equipped with a nitrogen inlet tube, stirrer, and thermocouple. The mixture was heated to 160°C under a nitrogen atmosphere, and a monomer mixture consisting of addition polymerizable monomer, bireactive monomer, and polymerization initiator was added dropwise over 1 hour. After aging at 160°C for 30 minutes, the temperature was raised to 200°C, and after reaching 200°C, it was held under reduced pressure of 8 kPa for 1 hour. After cooling to 150°C, an esterification catalyst and esterification co-catalyst were added, and the temperature was raised to 235°C for 8 hours to carry out the esterification reaction. After reacting under reduced pressure of 8 kPa for 1 hour, the temperature was cooled to 160°C, succinic acid was added, and the temperature was raised again to 190°C. After reaching 190°C, it was held for 30 minutes, and then the reaction was carried out at 40 kPa until the softening point shown in Table 2 was reached to obtain the composite resin (resin B1). The physical properties of the obtained resin are shown in Table 2.

[0145] Comparative examples A4, A5 As shown in Table 3, polycondensable monomers other than succinic acid, resin A4 (only for Comparative Example A5), esterification catalyst, and esterification co-catalyst were placed in a 10 L four-necked flask equipped with a nitrogen inlet tube, stirrer, and thermocouple. The esterification reaction was carried out under a nitrogen atmosphere at 235°C for 8 hours. After that, the reaction was carried out under reduced pressure of 8 kPa for 1 hour, then the temperature was lowered to 160°C, succinic acid was added, and the temperature was raised again to 190°C. After reaching 190°C, the temperature was held for 30 minutes, and then the reaction was carried out at 40 kPa until the softening point shown in Table 3 was reached to obtain polyester resins (resins B13, B14). The physical properties of the obtained resins are shown in Table 3.

[0146] [Table 2]

[0147] [Table 3]

[0148] The following shows examples of toner production using the obtained resins. However, resin B7 in Comparative Example A3 was obtained in a gelled state and therefore could not be used as a binder resin, and was not used.

[0149] Examples of resin particle dispersion manufacturing In a 3L container equipped with a stirrer, reflux condenser, dropping funnel, thermometer, and nitrogen inlet tube, 200g of the resin shown in Table 4 and 200g of methyl ethyl ketone were placed and dissolved at 73°C for 2 hours. To the obtained solution, a 5% by mass aqueous sodium hydroxide solution was added to achieve a degree of neutralization of 60 mol% relative to the acid value of the resin, and the mixture was stirred for 30 minutes. Next, while maintaining the temperature at 73°C, 700g of deionized water was added over 50 minutes while stirring at 200 r / min to induce phase inversion emulsification. The obtained solution was maintained at 73°C, and the methyl ethyl ketone was removed under reduced pressure to obtain a dispersion. After that, the dispersion was cooled to 30°C while continuing to stir, and then deionized water was added to achieve a solid content concentration of 20% by mass to obtain resin particle dispersions X1 to X13. The physical properties of the resin particles in the dispersions are shown in Table 4.

[0150] [Table 4]

[0151] Examples of resin manufacturing for mold release agent dispersions A 10L four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer, and thermocouple was purged with nitrogen. The raw material monomers for the polyester resin segment (excluding succinic acid), esterification catalyst, and esterification co-catalyst, as shown in Table 5, were added. Under a nitrogen atmosphere, the reaction system was stirred and heated to 235°C, where it was maintained for 5 hours. After that, the pressure inside the flask was reduced and maintained at 8 kPa for 1 hour. After returning to atmospheric pressure, it was cooled to 160°C and maintained at 160°C. A mixture of the raw material monomers for the styrene resin segment, both reactive monomers, and polymerization initiator was added dropwise to the reaction system over 1 hour. After maintaining the reaction system at 160°C for 30 minutes, it was heated to 200°C, and the pressure inside the flask was further reduced and maintained at 8 kPa for 1 hour. After returning to atmospheric pressure, it was cooled to 190°C and succinic acid was added. After heating to 210°C at 10°C / h, the reaction was carried out at 4 kPa until the desired softening point was reached to obtain resin D1. The physical properties of the obtained resin are shown in Table 5.

[0152] [Table 5]

[0153] Manufacturing example of a mold release agent particle dispersion. 200 g of resin D1 and 200 g of methyl ethyl ketone were placed in a 3 L container equipped with a stirrer, reflux condenser, dropping funnel, thermometer, and nitrogen inlet tube, and dissolved at 73°C for 2 hours. To the resulting solution, a 5% by mass aqueous sodium hydroxide solution was added to achieve a degree of neutralization of 60 mol% relative to the acid value of resin D1, and the mixture was stirred for 30 minutes. Next, while maintaining the temperature at 73°C, 700 g of deionized water was added over 50 minutes while stirring at 280 r / min to induce phase inversion emulsification. The resulting solution was maintained at 73°C, and the methyl ethyl ketone was removed under reduced pressure to obtain an aqueous dispersion. Subsequently, the aqueous dispersion was cooled to 30°C while stirring at 280 r / min, and then deionized water was added to obtain resin particle dispersion S1 by reducing the solid content concentration to 20% by mass. The median particle size of the resin particles was 0.9 μm, and the CV value was 23%.

[0154] In a 1L beaker, 120g of deionized water, 86g of resin particle dispersion S1, and 40g of the release agent shown in Table 6 were added. The mixture was melted and stirred while maintaining a temperature of 90-95°C to obtain a molten mixture. The obtained molten mixture was dispersed for 20 minutes using an ultrasonic homogenizer "US-600T" (manufactured by Nippon Seiki Seisakusho Co., Ltd.) while maintaining a temperature of 90-95°C, and then cooled to room temperature (20°C). Deionized water was added to the obtained dispersion to adjust the solid content concentration to 20% by mass to obtain release agent particle dispersions W1 and W2. The physical properties of the release agent particles in the dispersions are shown in Table 6.

[0155] [Table 6]

[0156] Examples of resin manufacturing for colorant dispersion 16 g of methacrylic acid, 44 g of styrene, 30 g of styrene macromonomer "AS-6S" (manufactured by Toagosei Co., Ltd., number average molecular weight 6,000, solid content concentration 50% by mass), and 25 g of methoxypolyethylene methacrylate "Bremmer PME-200" (manufactured by NOF Corporation) were mixed to prepare 115 g of monomer mixture with a total monomer content of 100 g. The inside of a four-necked flask equipped with a nitrogen inlet tube, dropping funnel, stirrer, and thermocouple was purged with nitrogen, and 18 g of methyl ethyl ketone, 0.03 g of 2-mercaptoethanol, and 10% of the monomer mixture were added, and the mixture was heated to 75°C while stirring. With the reaction system maintained at 75°C, the remaining 90% of the monomer mixture—0.27 g of 2-mercaptoethanol, 42 g of methyl ethyl ketone, and 3 g of 2,2'-azobis(2,4-dimethylvaleronitrile) "V-65" (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)—was added dropwise to the reaction system over 3 hours using a dropping funnel. After the addition was complete, the reaction system was maintained at 75°C for 2 hours, then a solution of 3 g of "V-65" dissolved in 5 g of methyl ethyl ketone was added, and the system was further maintained at 75°C for 2 hours and then at 80°C for 2 hours. Subsequently, the methyl ethyl ketone was removed by distillation under reduced pressure to obtain resin E1. The weight-average molecular weight of the obtained resin was 50,000.

[0157] Example of manufacturing a dispersion of colorant particles In a 5L container equipped with a stirrer with a disperser blade, reflux condenser, dropping funnel, thermometer, and nitrogen inlet tube, 75g of resin E1 and 630g of methyl ethyl ketone were added and the resin was dissolved at 20°C. To the resulting solution, 101g of 5% by mass sodium hydroxide aqueous solution (enough to neutralize resin E1 to 91 moles) was added, followed by 955g of deionized water, and the mixture was stirred with a disperser blade at 2000 r / min at 20°C for 10 minutes. Next, 300g of pigment yellow 155 (Toner Yellow 3GP-CT, molecular weight 717, manufactured by Clariant Chemicals Co., Ltd.) was added, and the mixture was stirred with a disperser blade at 6400 r / min at 20°C for 2 hours. After that, the mixture was passed through a 200-mesh filter and subjected to 15 passes at a pressure of 150 MPa using a homogenizer "Microfluidizer M-110EH" (manufactured by Microfluidics). The obtained dispersion was stirred and the methyl ethyl ketone and some water were removed under reduced pressure at 70°C. After cooling, the dispersion was passed through a 200-mesh filter, and deionized water was added to obtain a colorant particle dispersion Z1 with a solid content concentration of 20% by mass. The median volume particle size of the colorant particles in the dispersion was 0.10 μm, and the CV value was 28%.

[0158] Examples B1-B9, Comparative Examples B1-B4 In a 3L four-necked flask equipped with a dehydration tube, a stirrer, and a thermocouple, 500g of the resin particle dispersion shown in Table 7, 49g of release agent particle dispersion W1, 49g of release agent particle dispersion W2, 63g of coloring agent particle dispersion Z1, and 3.3g of 15% by mass sodium dodecylbenzenesulfonate aqueous solution "Neoperex G-15" (manufactured by Kao Corporation, anionic surfactant) were added and mixed at a temperature of 25°C. Next, while stirring the mixture, a solution prepared by dissolving 43g of ammonium sulfate in 980g of deionized water and adding a 4.8% by mass potassium hydroxide aqueous solution to adjust the pH to 8.2 was added dropwise over 10 minutes at 25°C, and the temperature was raised to 58°C over 2 hours to determine the volume median particle size (D) of the aggregated particles. 50The mixture was kept at 58°C until the particle size reached 5.0 μm to obtain a dispersion of aggregated particles. To the obtained dispersion of aggregated particles, 22 g of polyoxyethylene lauryl ether sulfate sodium "Emal E-27C" (manufactured by Kao Corporation, anionic surfactant, effective concentration 27% by mass) and 1100 g of deionized water were added. The mixture was then heated to 78°C over 1 hour and kept at 78°C until the circularity reached 0.970 to obtain a dispersion of fused particles in which the aggregated particles had fused together. The resulting dispersion of fused particles was cooled to 30°C, and the dispersion was filtered by suction to separate the solid components. The mixture was then washed with deionized water at 25°C and filtered by suction at 25°C for 2 hours. Subsequently, toner particles were obtained by vacuum drying at 33°C for 24 hours using a vacuum constant temperature dryer "DRV622DA" (manufactured by ADVANTEC). 100 parts by mass of toner particles, 2.5 parts by mass of hydrophobic silica "RY-50" (manufactured by Nippon Aerosil Co., Ltd., hydrophobic treatment agent: silicone oil, average particle size: 40 nm), and 1.0 part by mass of hydrophobic silica "Cabosil® TS720" (manufactured by Cabot Japan Co., Ltd., hydrophobic treatment agent: dimethylsiloxane, average particle size: 12 μm) were placed in a Henschel mixer and stirred, and the mixture was passed through a 150-mesh sieve to obtain toner. The physical properties of the toner particles are shown in Table 7.

[0159] Examples B10, B11 and Comparative Examples B5, B6 100 parts by mass of binder resin, 4 parts by mass of coloring agent "Mogul-L" (manufactured by Cabot Corporation), 0.2 parts by mass of cyanine blue 4927 (manufactured by Dainichi Seika Kogyo Co., Ltd.), 1 part by mass of charge control agent "T-77" (manufactured by Hodogaya Chemical Industry Co., Ltd.), and 3 parts by mass of release agent "Carnauba Wax C1" (manufactured by Kato Yoko Co., Ltd., melting point: 80℃) were thoroughly mixed in a Henschel mixer, and then melt-kneaded using a co-rotating twin-screw extruder with a total length of the kneading section of 1560 mm, a screw diameter of 42 mm, and a barrel inner diameter of 43 mm. The roll rotation speed was 200 r / min, the heating setting temperature inside the roll was 90℃, the temperature of the kneaded material was 140℃, the supply rate of the kneaded material was 10 kg / h, and the average residence time was approximately 18 seconds. The resulting mixture was cooled from 140°C to 50°C in 1.5 hours, then rolled and cooled at 50°C using cooling rollers, followed by standing at 45°C for 4 hours. After that, it was crushed and classified using a jet mill to obtain the medium volume particle size (D) shown in Table 8. 50 Toner particles were obtained.

[0160] To 100 parts by mass of the obtained toner particles, 1.2 parts by mass of "Aerosil R-972" (hydrophobic silica, manufactured by Nippon Aerosil Co., Ltd., hydrophobic treatment agent: DMDS, average particle size: 16 nm) and 1.4 parts by mass of "RY-50" (hydrophobic silica, manufactured by Nippon Aerosil Co., Ltd., hydrophobic treatment agent: silicone oil, average particle size: 40 nm) were added as external additives, and the mixture was heated in a Henschel mixer at 3600 r / min for 5 minutes to obtain the toner.

[0161] Test Example 1 [Low Temperature Fixation] A modified fuser unit of the "AR-505" copier (manufactured by Sharp Corporation) was modified to allow for external fixing, and toner was installed in this modified unit. A printed document was obtained in an unfixed state (print area: 2cm x 12cm, adhesion amount: 0.5mg / cm²). 2Subsequently, using a fuser (fixing speed 300 mm / sec) adjusted to a total fixing pressure of 40 kgf, fixing tests were performed on unfixed printed materials at each temperature while sequentially increasing the temperature of the fixing roll from 100°C to 240°C in 5°C increments. Cellophane adhesive tape "UNICEF Cellophane" (manufactured by Mitsubishi Pencil Co., Ltd., width: 18 mm, JIS Z1522:2009) was attached to the image portion of the obtained printed material, and after passing it through a fixing roller set to 30°C, separate from the fixing roll of the fuser, the tape was peeled off. The optical reflectance density before and after the tape was applied was measured using a reflectance densitometer "RD-915" (manufactured by Gretag Macbeth Co., Ltd.), and the temperature of the fixing roll at which the ratio of the two (after peeling / before application × 100) first exceeded 90% was defined as the minimum fixing temperature. The results are shown in Tables 7 and 8. The lower the minimum fixing temperature, the better the low-temperature fixing performance. The fuser paper used is "CopyBond SF-70NA" (manufactured by Sharp Corporation, 75g / m²). 2 ) was used.

[0162] Test Example 2 [Hot Offset Resistance] In Test Example 1, the occurrence of hot offset at each fixing temperature was observed visually, and the lowest temperature at which hot offset occurred (hot offset occurrence temperature) was used as an indicator of hot offset resistance. The results are shown in Tables 7 and 8. The higher the lowest temperature at which hot offset occurs, the better the hot offset resistance.

[0163] In comparative example B5, hot offset occurred before reaching the minimum fixing temperature, resulting in improper fixing across the entire temperature range.

[0164] [Table 7]

[0165] [Table 8]

[0166] From the above results, it can be seen that the toners of Examples B1 to B11, which contain the binder resin obtained by the method of the present invention, are superior in both low-temperature fixation and hot offset resistance compared to Comparative Examples B1 to B6. In contrast, Comparative Example B1, which used a binder resin with too little polymer (A), lacked resistance to hot offset, and Comparative Example B5 failed to achieve proper fixation across the entire temperature range. Furthermore, Comparative Examples B2 and B6, which used binder resins with too much polymer (A), lacked low-temperature fixation. Furthermore, a comparison of Comparative Examples B3 and B4 reveals that polyester resins that do not use addition polymerizable monomers and are not compounded exhibit insufficient hot offset resistance, regardless of the presence or absence of polymer (A). [Industrial applicability]

[0167] The toner binder resin obtained by the method of the present invention is suitably used as a binder resin for electrostatic image developing toner, which is suitable for developing latent images formed in electrophotography, electrostatic recording, electrostatic printing, etc.

Claims

1. A method for producing a binder resin for toner in which a polycondensable resin segment and an addition polymer segment are bonded via both reactive monomers, comprising: step A, in which an addition polymerizable monomer and both reactive monomers are added polymerized in the presence of a polymer (A) having an unsaturated bond; and step B, in which a polycondensable monomer containing a carboxylic acid component and an alcohol component is polycondensed, wherein steps A and B are carried out in the same reaction vessel, wherein the polymer (A) having an unsaturated bond is a polyester resin or a composite resin having a polyester resin segment and a styrene resin segment, and the amount of unsaturated monomer constituting the polymer (A) having an unsaturated bond is 5.0 × 10¹⁶ per 1 g of the total amount of the addition polymerizable monomer, both reactive monomers and the polycondensable monomer. -5 ≥ mmol 2.0 × 10⁻¹ -2 A method for producing a binder resin for toner, with a quantity of 1 / 4 mmol or less.

2. The manufacturing method according to claim 1, wherein the weight-average molecular weight of the polymer (A) having unsaturated bonds is 1,000 or more and 1,000,000 or less.

3. The manufacturing method according to claim 1, wherein the amount of polymer (A) having an unsaturated bond used in step A is 0.01 parts by mass or more and 2.8 parts by mass or less, based on 100 parts by mass of the total amount of polycondensation resin segment and addition polymerization resin segment.

4. The method for producing according to claim 1, wherein the polymer (A) having an unsaturated bond has constituent units derived from at least one of fumaric acid and maleic acid.

5. A method for producing toner for electrostatic image developing, comprising the steps of (I) dispersing a toner binder resin obtained by any one of claims 1 to 4 in an aqueous medium to obtain resin particles, and (II) agglomerating and fusing the resin particles to obtain toner particles.

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