JP2016099518A - Binder resin composition for electrophotographic toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a binder resin composition for an electrophotographic toner excellent in low-temperature fixability, shelf stability, and excellent in image density in high temperature and high humidity; and an electrophotographic toner containing the binder resin composition.SOLUTION: Provided is a binder resin composition for an electrophotographic toner and an electrophotographic toner containing the binder resin composition. The composition contains a crystalline polyester C and an amorphous resin A. The crystallin polyester C is a crystalline polyester that is obtained by condensation polymerization of an alcohol component containing 70 mol% or more of an aliphatic diol having 9 or more and 14 or less carbon atoms with a carboxylic acid component containing an aromatic dicarboxylic acid compound and an aliphatic dicarboxylic acid compound having 4 or more and 6 or less carbon atoms, and has an acid value of 20 mgKOH/g or less.SELECTED DRAWING: None

Description

  The present invention relates to a binder resin composition for an electrophotographic toner used in an electrophotographic method, an electrostatic recording method, an electrostatic printing method, and the like, and an electrophotographic toner containing the binder resin composition.

  In recent years, as printers and copiers have become faster and more energy efficient, toners with excellent low-temperature fixability have become increasingly necessary.

  For example, Patent Document 1 discloses that an alcohol component and an aromatic dicarboxylic acid compound are contained in an amount of 50 to 97 mol% in order to provide a toner having excellent low-temperature fixability and chargeability and excellent grindability. A crystalline polyester obtained by condensation polymerization of a carboxylic acid component containing 3 to 50 mol% of an unsaturated aliphatic dicarboxylic acid compound, which is crosslinked by the unsaturated aliphatic dicarboxylic acid compound Is disclosed.

JP 2010-145633 A

  Although the crystalline polyester described in Patent Document 1 is excellent in grindability, it is still not sufficient in terms of low temperature fixability and image density under high temperature and high humidity.

  The present invention relates to a binder resin composition for an electrophotographic toner that is excellent in low-temperature fixability, storage stability, and image density under high temperature and high humidity, and an electrophotographic toner containing the binder resin composition.

The present invention
[1] A binder resin composition for an electrophotographic toner containing crystalline polyester C and amorphous resin A, wherein the crystalline polyester C contains 70 mol of aliphatic diol having 9 to 14 carbon atoms. % Crystalline polyester having an acid value of 20 mgKOH / g or less, obtained by polycondensation of an alcohol component containing 2% or more and a carboxylic acid component containing an aromatic dicarboxylic acid compound and an aliphatic dicarboxylic acid compound having 4 to 6 carbon atoms And a binder resin composition for electrophotographic toners, and [2] an electrophotographic toner containing the binder resin composition of [1].

  The electrophotographic toner containing the binder resin composition for toner of the present invention exhibits excellent effects in low-temperature fixability, durability, and image density under high temperature and high humidity.

  The reason why the toner containing the binder resin composition of the present invention is excellent in low-temperature fixability, storage stability, and image density stability under high temperature and high humidity is not clear, but is considered as follows.

A toner containing a crystalline polyester obtained by using an aliphatic diol having 9 to 14 carbon atoms and an aromatic dicarboxylic acid compound has high crystallinity and excellent low-temperature fixability. In the present invention, by using an aliphatic dicarboxylic acid compound having 4 or more and 6 or less carbon atoms as a carboxylic acid component, compatibility with an amorphous resin is increased, and by reducing the acid value, It is considered that the exposure of the conductive polyester to the toner surface can be suppressed, and the storage stability and the image density stability under high temperature and high humidity are also excellent.
The crystalline polyester described in Patent Document 1 has no description of an acid value, and improves pulverizability by crosslinking with an unsaturated aliphatic dicarboxylic acid compound. Since the compatibility is lowered, the effect of the present invention is considered to be low.

  The crystallinity of the resin is represented by the ratio between the softening point and the maximum endothermic peak temperature measured by a differential scanning calorimeter, that is, the crystallinity index defined by the value of [softening point / maximum endothermic peak temperature]. The crystalline resin has a crystallinity index of 0.6 to 1.4, preferably 0.7 to 1.2, more preferably 0.9 to 1.2, and the amorphous resin has a crystallinity index of more than 1.4 or less than 0.6, Preferably it is more than 1.5, 0.5 or less, more preferably 1.6 or more, or 0.5 or less. The crystallinity of the resin can be adjusted by the type and ratio of the raw material monomers, production conditions (for example, reaction temperature, reaction time, cooling rate) and the like. The highest endothermic peak temperature refers to the temperature of the peak on the highest temperature side among the observed endothermic peaks. In the crystalline resin, the highest endothermic peak temperature is the melting point.

  The crystalline polyester is obtained by polycondensation of an alcohol component containing an aliphatic diol having 9 to 14 carbon atoms and an aromatic dicarboxylic acid compound and a carboxylic acid component containing an aliphatic dicarboxylic acid compound having 4 to 6 carbon atoms. Crystalline polyester C obtained.

  Examples of the aliphatic diol having 9 to 14 carbon atoms contained in the alcohol component include 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, and the like. Even if it is 1 type, 2 or more types may be used together. Among these, 1,9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol are preferable, and 1,10-decanediol is more preferable from the viewpoint of improving toner fixing properties.

  The aliphatic diol having 9 to 14 carbon atoms is preferably an α, ω-aliphatic diol having a hydroxyl group at the end of the carbon chain from the viewpoint of improving the low-temperature fixability of the toner. -More preferably a linear alkanediol.

  The carbon number of the aliphatic diol is 9 or more, and preferably 10 or more, from the viewpoints of storage stability and low-temperature fixability. Further, from the viewpoint of image density and low temperature fixability under high temperature and high humidity, it is 14 or less, preferably 12 or less, and more preferably 10 or less.

  The content of the aliphatic diol having 9 to 14 carbon atoms is 70 mol% or more, 80 mol% or more in the alcohol component of the crystalline polyester C from the viewpoint of storage stability and image density under high temperature and high humidity. Is preferable, 90 mol% or more is more preferable, and 95 mol% or more is more preferable. Moreover, 100 mol% or less is preferable, substantially 100 mol% is more preferable, and 100 mol% is further more preferable.

  Other alcohol components include aliphatic diols having 2 to 8 carbon atoms, aliphatic diols having 15 or more carbon atoms, aromatic diols such as alkylene oxide adducts of bisphenol A, sorbitol, pentaerythritol, glycerin, trimethylolpropane, etc. And trihydric or higher alcohols.

  Examples of the aromatic dicarboxylic acid compound contained in the carboxylic acid component include phthalic acid, isophthalic acid, terephthalic acid; anhydrides of these acids and alkyl (C1-3) esters of these acids, etc. Of these, terephthalic acid is preferred. In the present invention, the carboxylic acid compound includes not only a free acid but also an anhydride that decomposes during the reaction to produce an acid and an alkyl ester having 1 to 3 carbon atoms.

  The content of the aromatic dicarboxylic acid compound is preferably 60 mol% or more, more preferably 70 mol% or more, from the viewpoint of storage stability and image density under high temperature and high humidity in the carboxylic acid component of the crystalline polyester C. 75 mol% or more is more preferable. Further, from the same viewpoint, 90 mol% or less is preferable, and 85 mol% or less is more preferable.

  As aliphatic dicarboxylic acid compounds having 4 to 6 carbon atoms, succinic acid (carbon number: 4), fumaric acid (carbon number: 4), glutaric acid (carbon number: 5), adipic acid (carbon number: 6) , Anhydrides of these acids, alkyl esters having 1 to 3 carbon atoms thereof, and the like.

  The chain hydrocarbon group in the aliphatic dicarboxylic acid compound may be linear or branched, and the carbon number of the aliphatic dicarboxylic acid compound is from the viewpoint of storage stability and image density under high temperature and high humidity. 4 or more. From the same viewpoint, it is 6 or less, preferably 5 or less, and more preferably 4. However, the carbon number of the alkyl group in the alkyl ester portion is not included in the carbon number of the aliphatic dicarboxylic acid compound.

  The content of the aliphatic dicarboxylic acid compound having 4 or more and 6 or less carbon atoms is 10 mol% in the carboxylic acid component of the crystalline polyester C from the viewpoint of low-temperature fixability, storage stability, and image density under high temperature and high humidity. The above is preferable, and 15 mol% or more is more preferable. Further, from the viewpoint of improving low-temperature fixability by increasing crystallinity, it is preferably 30 mol% or less, and more preferably 25 mol% or less.

  The molar ratio of the aromatic dicarboxylic acid compound and the aliphatic dicarboxylic acid compound having 4 to 6 carbon atoms (aromatic dicarboxylic acid compound / aliphatic dicarboxylic acid compound having 4 to 6 carbon atoms) is storability, high temperature and high humidity From the viewpoint of the image density under, preferably 1.0 or more, more preferably 1.5 or more, further preferably 2.0 or more, further preferably 3.3 or more, low-temperature fixability, storage stability, image under high temperature and high humidity. From the viewpoint of concentration and ease of production, it is preferably 20 or less, more preferably 15 or less, still more preferably 10 or less, and still more preferably 5 or less.

  The total content of the aromatic dicarboxylic acid compound and the aliphatic dicarboxylic acid compound having 4 to 6 carbon atoms is the carboxylic acid of the crystalline polyester C from the viewpoint of low-temperature fixability, image density under high temperature and high humidity, and storage stability. In the component, 70 mol% or more is preferable, 80 mol% or more is more preferable, 90 mol% or more is more preferable, and 95 mol% or more is more preferable. Moreover, 100 mol% or less is preferable, substantially 100 mol% is more preferable, and 100 mol% is further more preferable.

  Examples of other carboxylic acid compounds include aliphatic dicarboxylic acid compounds having 2 to 3 carbon atoms, aliphatic dicarboxylic acid compounds having 7 or more carbon atoms, trivalent or higher carboxylic acid compounds such as trimellitic acid and pyromellitic acid. It is done.

  The equivalent molar ratio (COOH group / OH group) of the carboxylic acid component and the alcohol component of the crystalline polyester C is preferably 0.8 or more and more preferably 0.9 or more from the viewpoint of ease of production. Further, from the viewpoint of image density under high temperature and high humidity, 1.2 or less is preferable, 1.1 or less is more preferable, and 1.0 or less is more preferable.

  The polycondensation reaction between the alcohol component and the carboxylic acid component is performed at a temperature of about 140 to 250 ° C. in an inert gas atmosphere, if necessary, in the presence of an esterification catalyst, an esterification promoter, a polymerization inhibitor, etc. Can be done. Examples of the esterification catalyst include tin compounds such as dibutyltin oxide and tin (II) 2-ethylhexanoate, and titanium compounds such as titanium diisopropylate bistriethanolamate. The amount of the esterification catalyst used is preferably 0.01 to 1.5 parts by mass, more preferably 0.1 to 1.0 part by mass with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. Examples of the esterification promoter include gallic acid. The amount of the esterification cocatalyst used is preferably 0.001 to 0.5 parts by mass, more preferably 0.01 to 0.1 parts by mass with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. Examples of the polymerization inhibitor include tert-butylcatechol. The amount of the polymerization inhibitor used is preferably 0.001 to 0.5 parts by mass and more preferably 0.01 to 0.1 parts by mass with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component.

  The acid value of the crystalline polyester C is 20 mgKOH / g or less, preferably 18 mgKOH / g or less, from the viewpoint of low-temperature fixability, storage stability, and image density under high temperature and high humidity. From the viewpoint of image density at 15 mgKOH / g or less, more preferably 13 mgKOH / g or less. Further, from the viewpoint of productivity, 5 mgKOH / g or more is preferable, and 7 mgKOH / g or more is more preferable.

  The softening point of the crystalline polyester C is preferably 60 ° C. or higher, more preferably 65 ° C. or higher, and further preferably 70 ° C. or higher from the viewpoint of storage stability. Further, from the viewpoint of low temperature fixability, 120 ° C. or lower is preferable, 110 ° C. or lower is more preferable, and 100 ° C. or lower is further preferable.

  The melting point of the crystalline polyester C is preferably 60 ° C. or higher, more preferably 65 ° C. or higher, from the viewpoint of storage stability. From the viewpoint of low-temperature fixability, 110 ° C. or lower is preferable, and 100 ° C. or lower is more preferable.

  The number average molecular weight of the crystalline polyester C is preferably 2000 or more, more preferably 3000 or more, and further preferably 4000 or more, from the viewpoint of storage stability. Further, from the viewpoint of low-temperature fixability, 8000 or less is preferable, 7000 or less is more preferable, and 5500 or less is more preferable.

  Amorphous resin A includes polyesters, vinyl resins, composite resins having a polycondensation resin component and an addition polymerization resin component, and the like. Low-temperature fixability, storage stability, and image density under high temperature and high humidity Therefore, a composite resin having an amorphous polyester and an amorphous polycondensation resin component and an addition polymerization resin component is preferable.

  The alcohol component of the amorphous polycondensation resin component of the amorphous polyester and the amorphous composite resin is represented by the formula (I):

(In the formula, RO and OR are oxyalkylene groups, R is an ethylene and / or propylene group, x and y are the average number of moles of alkylene oxide added, each being a positive number, The sum is preferably 1-16, more preferably 1-8, and even more preferably 1.5-4)
It is preferable to contain the alkylene oxide adduct of bisphenol A represented by these.

  The content of the alkylene oxide adduct of bisphenol A represented by the formula (I) is preferably 70 mol% or more, more preferably 80 mol% or more in the alcohol component from the viewpoint of low temperature fixability and storage stability. More preferably, mol% or more, more preferably 95 mol% or more. Moreover, 100 mol% or less is preferable, substantially 100 mol% is more preferable, and 100 mol% is further more preferable.

  Examples of alcohols other than aromatic diols include diols such as ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, neopentyl glycol, polyethylene glycol, polypropylene glycol, hydrogenated bisphenol A; sorbitol, pentaerythritol, glycerin And trihydric or higher alcohols such as trimethylolpropane.

  The carboxylic acid component of the amorphous polycondensation resin component of the amorphous polyester and the amorphous composite resin preferably contains an aromatic dicarboxylic acid compound from the viewpoint of storage stability and image density under high temperature and high humidity. .

  Examples of the aromatic dicarboxylic acid compound include phthalic acid, isophthalic acid, terephthalic acid; anhydrides of these acids and alkyl (carbon number 1 to 3) esters of these acids, among which terephthalic acid is preferable. . In the present invention, the carboxylic acid compound includes not only a free acid but also an anhydride that decomposes during the reaction to produce an acid and an alkyl ester having 1 to 3 carbon atoms.

  The content of the aromatic dicarboxylic acid compound is preferably 30 mol% or more, more preferably 50 mol% or more, and more preferably 65 mol% or more in the carboxylic acid component from the viewpoint of storage stability and image density under high temperature and high humidity. preferable. From the viewpoint of low-temperature fixability, 95 mol% or less is preferable, 90 mol% or less is more preferable, and 85 mol% or less is more preferable.

  The carboxylic acid component preferably contains a trivalent or higher carboxylic acid compound from the viewpoint of storage stability and durability.

  Examples of trivalent or higher carboxylic acid compounds include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, pyromellitic acid and acid anhydrides thereof, lower alkyl (carbon number) 1-3) Esters and the like, among which trimellitic acid compounds are preferred.

  The content of the trivalent or higher carboxylic acid compound, preferably the trimellitic acid compound content is preferably 1 mol% or more, more preferably 2 mol% or more, from the viewpoint of storage stability and durability in the carboxylic acid component. 3 mol% or more is more preferable. Further, from the viewpoint of low-temperature fixability, it is preferably 50 mol% or less, more preferably 40 mol% or less, and further preferably 30 mol% or less.

  Other carboxylic acid components include alkyl having 1 to 20 carbon atoms such as oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, dodecenyl succinic acid, octyl succinic acid, etc. And aliphatic dicarboxylic acid compounds such as succinic acid substituted with a group or an alkenyl group having 2 to 20 carbon atoms.

  From the viewpoint of low-temperature fixability, storage stability, and image density under high temperature and high humidity, the raw material monomer for amorphous polyester is a monohydric alcohol having 8 to 22 carbon atoms and 1 to 8 to 22 carbon atoms. It is preferable to contain at least one of valent carboxylic acid compounds, and it is more preferable to contain a monovalent carboxylic acid compound having 8 to 22 carbon atoms.

  The number of carbon atoms of the monovalent alcohol and the monovalent carboxylic acid compound is preferably 8 or more, more preferably 16 or more, and more preferably 18 or more from the viewpoints of low-temperature fixability, storage stability, and image density under high temperature and high humidity. Further preferred. Further, from the same viewpoint, it is preferably 22 or less, more preferably 20 or less, and further preferably 18 or less.

  The monovalent alcohol and the monovalent carboxylic acid compound are preferably aliphatic from the viewpoint of low-temperature fixability. However, in monovalent aliphatic alcohols and monovalent aliphatic carboxylic acid compounds, compounds having an ethylenically unsaturated group (reactive unsaturated group) used for both reactive monomers described later are excluded.

  Examples of the monovalent aliphatic alcohol having 8 to 22 carbon atoms include palmityl alcohol, stearyl alcohol, and behenyl alcohol. Among these, stearyl alcohol is preferable.

  Examples of the monovalent aliphatic carboxylic acid compound having 8 to 22 carbon atoms include palmitic acid, stearic acid, behenic acid and the like, and among these, stearic acid is preferable.

  The total content of monohydric alcohol having 8 to 22 carbon atoms and monovalent carboxylic acid compound having 8 to 22 carbon atoms is the total amount of alcohol component and carboxylic acid component, which is a raw material monomer of crystalline polyester, From the viewpoint of low-temperature fixability, storage stability, and image density under high temperature and high humidity, 2 mol% or more is preferable, 4 mol% or more is more preferable, 5 mol% or more is more preferable, and from the same viewpoint, 15 mol% or less is preferable, 12 mol% or less is more preferable, and 11 mol% or less is more preferable.

  The polycondensation reaction between the alcohol component and the carboxylic acid component is, for example, in the presence of an esterification catalyst, an esterification co-catalyst, a polymerization inhibitor, etc. in an inert gas atmosphere, if necessary, at about 160 to 250 ° C. At a temperature of Examples of the esterification catalyst include tin compounds such as dibutyltin oxide and tin (II) 2-ethylhexanoate, and titanium compounds such as titanium diisopropylate bistriethanolamate. The amount of the esterification catalyst used is preferably 0.01 to 1.5 parts by mass, more preferably 0.1 to 1.0 part by mass with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. Examples of the esterification promoter include gallic acid. The amount of the esterification cocatalyst used is preferably 0.001 to 0.5 parts by mass, more preferably 0.01 to 0.1 parts by mass with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. Examples of the polymerization inhibitor include tert-butylcatechol. The amount of the polymerization inhibitor used is preferably 0.001 to 0.5 parts by mass and more preferably 0.01 to 0.1 parts by mass with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component.

  From the viewpoint of durability, the equivalent molar ratio of the carboxylic acid component and the alcohol component (COOH group / OH group) is preferably 0.80 or more, and more preferably 0.88 or more. Further, from the viewpoint of charging stability under high temperature and high humidity, 1.00 or less is preferable, and 0.93 or less is more preferable.

  In the present invention, the polyester resin obtained by polycondensation of the alcohol component and the carboxylic acid component includes a resin-modified resin.

  Examples of the resin-modified resin include urethane-modified polyester in which the resin is modified with a urethane bond, and epoxy-modified polyester in which the polyester is modified with an epoxy bond.

  The addition polymerization resin component of the amorphous composite resin is preferably a styrene resin from the viewpoint of improving the scratch resistance of the fixed image and reducing the amount of toner scattering.

  Therefore, it is preferable to use a known radical polymerizable monomer including a styrene compound and an alkyl (meth) acrylate as a raw material monomer for the addition polymerization resin component.

  Examples of the styrene compound include styrene, α-methyl styrene, 2-methyl styrene, vinyl toluene, chlorostyrene, and the like, and styrene is preferable.

  The content of the styrene compound is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, and 75% by mass in the raw material monomer of the addition polymerization resin component from the viewpoint of heat-resistant storage stability. The above is more preferable. Further, from the viewpoint of low-temperature fixability, it is preferably 95% by mass or less, more preferably 90% by mass or less, and further preferably 88% by mass or less.

  Alkyl (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, normal or isopropyl (meth) acrylate, normal, iso or tertiary butyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl ( Examples include meth) acrylate, decyl (meth) acrylate, and dodecyl (meth) acrylate. The alkyl (meth) acrylate means an alkyl ester of acrylic acid, methacrylic acid, and a mixture thereof.

  The number of carbon atoms of the alkyl group of the alkyl (meth) acrylate is preferably 1 or more, more preferably 2 or more, further preferably 3 or more, and further preferably 4 or more, from the viewpoint of low-temperature fixability. Further, from the viewpoint of heat resistant storage stability, 12 or less is preferable, and 8 or less is more preferable. From these viewpoints, 2-ethylhexyl acrylate is preferable as the alkyl (meth) acrylate.

  The content of the alkyl (meth) acrylate is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 12% by mass or more, from the viewpoint of low-temperature fixability in the raw material monomer of the addition polymerization resin component. From the viewpoint of heat-resistant storage stability, it is preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, and further preferably 25% by mass or less.

  Examples of other radical polymerizable monomers include vinyl esters such as vinyl acetate; vinyl ethers such as vinyl methyl ether.

  Moreover, the raw material monomer of the addition polymerization resin component may contain a small amount of a polyfunctional monomer for the purpose of improving high temperature offset resistance. Examples of the polyfunctional monomer include compounds having two or more polymerizable double bonds. Examples of the compound having two or more polymerizable double bonds include aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; carboxylic acid esters having two double bonds such as ethylene glycol diacrylate; divinylaniline and divinyl ether And divinyl compounds such as divinyl sulfide and divinyl sulfone; and compounds having three or more vinyl groups.

  The addition polymerization reaction of the raw material monomer of the addition polymerization resin component can be carried out in the usual manner, for example, in the presence of a polymerization initiator, a crosslinking agent, etc., in the presence or absence of an organic solvent. 110 to 200 ° C is preferable, and 140 to 170 ° C is more preferable.

  Moreover, you may perform addition polymerization reaction in presence of a polymerization initiator etc. as needed. Examples of the polymerization initiator include peroxides such as dibutyl peroxide and dicumyl peroxide. The amount of the polymerization initiator used is preferably 4 to 12 parts by mass with respect to 100 parts by mass of the raw material monomer of the addition polymerization resin component.

  When an organic solvent is used in the addition polymerization reaction, xylene, toluene, methyl ethyl ketone, acetone or the like can be used. The amount of the organic solvent used is preferably about 10 to 50 parts by mass with respect to 100 parts by mass of the raw material monomer of the addition polymerization resin component.

  The amorphous composite resin is, for example, (1) a method of polycondensing a raw material monomer of an amorphous polycondensation resin component in the presence of an addition polymerization resin having a carboxy group or a hydroxyl group (carboxy groups and hydroxyl groups are described later) (2) A method of subjecting a raw material monomer of an addition polymerization resin component to addition polymerization in the presence of a polyester resin having a reactive unsaturated bond. Etc. can be obtained.

  From the viewpoint of low-temperature fixability of the toner, the amorphous composite resin is further added to the amorphous polycondensation resin component raw material monomer and the addition polymerization resin component raw material monomer, in addition to the amorphous polycondensation resin component. It is preferable that the resin (hybrid resin) is obtained by using both reactive monomers capable of reacting with both the raw material monomer and the raw material monomer of the addition polymerization resin component. Therefore, when the composite monomer is obtained by polymerizing the raw material monomer of the amorphous polycondensation resin component and the raw material monomer of the addition polymerization resin component, the polycondensation reaction and / or the addition polymerization reaction is carried out by the presence of both reactive monomers. It is preferable to carry out below. As a result, the amorphous composite resin becomes a resin (hybrid resin) in which the amorphous polycondensation resin component and the addition polymerization resin component are bonded via the structural unit derived from both reactive monomers. The condensation resin component and the addition polymerization resin component are more finely and uniformly dispersed.

  From these, the composite resin comprises (a) a raw material monomer of an amorphous polycondensation resin component containing an alcohol component and a carboxylic acid component, (b) a raw material monomer of an addition polymerization resin component, and (c) an amorphous material. A hybrid resin obtained by polymerizing a bireactive monomer capable of reacting with both the raw material monomer of the polycondensation resin component and the raw material monomer of the addition polymerization resin component is preferable.

  As the both reactive monomers, in the molecule, at least one functional group selected from the group consisting of a hydroxyl group, a carboxy group, an epoxy group, a primary amino group, and a secondary amino group, preferably a hydroxyl group and / or A compound having a carboxy group, more preferably a carboxy group, and an ethylenically unsaturated bond is preferred. By using such a bireactive monomer, the dispersibility of the resin to be a dispersed phase can be further improved. The both reactive monomers are preferably at least one selected from the group consisting of acrylic acid, methacrylic acid, fumaric acid, maleic acid and maleic anhydride, but from the viewpoint of reactivity of polycondensation reaction and addition polymerization reaction Therefore, acrylic acid, methacrylic acid and fumaric acid are more preferable. However, when used together with a polymerization inhibitor, a polyvalent carboxylic acid such as fumaric acid may function as a polycondensation monomer.

  The amount of both reactive monomers used is such that the dispersibility of the addition polymerization resin component and the amorphous polycondensation resin component is increased, and the amorphous polycondensation resin component of the amorphous polycondensation resin component is improved from the viewpoint of improving the low-temperature fixability of the toner. 1 to 20 mol [(mole of both reactive monomers / total mol of alcohol component of amorphous polycondensation resin component) × 100] is preferable with respect to 100 mol of the alcohol component in total, and 2 to 15 mol is more preferable. Preferably, 2 to 10 mol is more preferable, and 2 to 25 mol [(mol of both reactive monomers / total mol of raw material monomer of addition polymerization resin component) with respect to 100 mol of the total amount of raw material monomers of addition polymerization resin component. ) × 100] is preferable, and 3 to 15 mol is more preferable.

  Specifically, the composite resin is preferably produced by the following method. Both reactive monomers are preferably used in the addition polymerization reaction together with the raw material monomer of the addition polymerization resin component from the viewpoint of improving the low-temperature fixability of the toner.

(i) After the step (A) of the polycondensation reaction with the raw material monomer of the amorphous polycondensation resin component, the step (B) of the addition polymerization reaction with the raw material monomer of the addition polymerization resin component and the both reactive monomers is performed. Method In this method, step (A) is carried out under reaction temperature conditions suitable for polycondensation reaction, the reaction temperature is lowered, and step (B) is carried out under temperature conditions suitable for addition polymerization reaction. The raw material monomer and both reactive monomers of the addition polymerization resin component are preferably added to the reaction system at a temperature suitable for the addition polymerization reaction. Both reactive monomers react with the amorphous polycondensation resin component together with the addition polymerization reaction.
A part of the raw material monomer of the amorphous polycondensation resin component is used in the first step (A), and after the step (B), the remaining raw material monomer is added to the reaction system, and the reaction temperature is increased again. The polycondensation reaction (A) and the reaction with both reactive monomers can be further advanced.

(ii) The step (A) of the polycondensation reaction using the raw material monomer of the amorphous polycondensation resin component is performed after the step (B) of the addition polymerization reaction using the raw material monomer of the addition polymerization resin component and the both reactive monomers. Method In this method, the step (B) is performed under a reaction temperature condition suitable for the addition polymerization reaction, the reaction temperature is increased, and the polycondensation reaction of the step (A) is performed under a temperature condition suitable for the polycondensation reaction. . Both reactive monomers are involved in the polycondensation reaction as well as the addition polymerization reaction.
The raw material monomer of the amorphous polycondensation resin component may be present in the reaction system during the addition polymerization reaction, or may be added to the reaction system under temperature conditions suitable for the polycondensation reaction. In the former case, it can be adjusted by adding an esterification catalyst at a temperature suitable for the polycondensation reaction.

(iii) The step (A) of the polycondensation reaction using the raw material monomer of the amorphous polycondensation resin component and the step (B) of the addition polymerization reaction using the raw material monomer and both reactive monomers of the addition polymerization resin component are performed in parallel. In this method, the step (A) and the step (B) are performed simultaneously under the reaction temperature conditions suitable for the addition polymerization reaction, the reaction temperature is increased, and suitable for the polycondensation reaction. It is preferable to add a raw material monomer of a trivalent or higher-valent amorphous polycondensation resin component that becomes a cross-linking agent to the polymerization system under the above temperature conditions, and further perform the polycondensation reaction in step (A). . At that time, under a temperature condition suitable for the polycondensation reaction, a radical polymerization inhibitor can be added to advance only the polycondensation reaction. Both reactive monomers are involved in the polycondensation reaction as well as the addition polymerization reaction.

  In the method (i), a prepolymerized polyester resin may be used instead of the step (A) in which the polycondensation reaction is performed. In the method (iii), when the step (A) and the step (B) are performed in parallel, the addition polymerization resin component of the mixture containing the raw material monomer of the amorphous polycondensation resin component is added. A mixture containing raw material monomers can also be dropped and reacted.

  The methods (i) to (iii) are preferably performed in the same container.

In the composite resin, the mass ratio between the amorphous polycondensation resin component and the addition polymerization resin component (amorphous polycondensation resin component / addition polymerization resin component) is low temperature fixability, storage stability, and high temperature high humidity. From the viewpoint of the image density below, 60/40 or more is preferable, 65/35 or more is more preferable, 70/30 or more is more preferable, and 75/25 or more is more preferable. From the same viewpoint, 95/5 or less is preferable, 90/10 or less is more preferable, and 85/15 or less is more preferable.
The mass ratio of the amorphous polycondensation resin component and the addition polymerization resin component is calculated from the ratio of the total amount. The amorphous polycondensation resin component uses a value obtained by removing the amount of dehydration during the condensation reaction from the total amount of raw material monomers of the amorphous polycondensation resin component. Moreover, the mass of an addition polymerization type resin component uses the total amount of the raw material monomer and polymerization initiator of an addition polymerization type resin component. The mass of the both reactive monomers described later is included in the mass of the amorphous polycondensation resin component.

From the above viewpoint, the amorphous resin A is
Raw material monomer of amorphous polycondensation resin containing alcohol component containing alkylene oxide adduct of bisphenol and carboxylic acid component containing aromatic dicarboxylic acid compound, raw material monomer of addition polymerization resin and amorphous polycondensation system Amorphous hybrid resin A1 comprising an amorphous polycondensation resin component and an addition polymerization resin component obtained by polymerizing a compound capable of reacting with either a resin raw material monomer or an addition polymerization resin raw material monomer And a raw material monomer of an amorphous polycondensation resin comprising an alcohol component containing an alkylene oxide adduct of bisphenol and a carboxylic acid component containing an aromatic dicarboxylic acid compound, and the raw material monomer having 8 to 22 carbon atoms Selected from the group consisting of monovalent aliphatic alcohols and monovalent aliphatic carboxylic acid compounds having 8 to 22 carbon atoms At least one monovalent long chain monomer, amorphous obtain a raw material monomer containing 0.1 to 10 mol% by polycondensation polyester A2
It is preferable that 1 type, or 2 or more types of amorphous resin chosen from these are included.

  In the amorphous resin A, when the content of the amorphous hybrid resin A1 or the amorphous polyester A2 or both are used together, the total content is preferably 70% by mass or more, more preferably 80% by mass or more. Preferably, 90% by mass or more is more preferable, and 95% by mass or more is more preferable. Moreover, 100 mass% or less is preferable, substantially 100 mass% is more preferable, and 100 mass% is further more preferable.

  The softening point of the amorphous resin A is preferably 70 ° C. or higher, and more preferably 90 ° C. or higher, from the viewpoint of print storage stability and development stability. Further, from the viewpoint of low-temperature fixability, it is preferably 160 ° C. or lower, and more preferably 150 ° C. or lower.

  From the viewpoint of durability, the glass transition temperature of the amorphous resin A is preferably 40 ° C. or higher, more preferably 45 ° C. or higher, and further preferably 50 ° C. or higher. Further, from the viewpoint of low-temperature fixability, 75 ° C. or lower is preferable, 70 ° C. or lower is more preferable, and 65 ° C. or lower is further preferable. The glass transition temperature is a physical property peculiar to an amorphous resin.

  The acid value of the amorphous resin A is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, from the viewpoint of low-temperature fixability. Further, from the viewpoint of image density under high temperature and high humidity, 40 mgKOH / g or less is preferable, and 30 mgKOH / g or less is more preferable.

  The number average molecular weight of the amorphous resin A is preferably 1500 or more, more preferably 2000 or more, and further preferably 2500 or more, from the viewpoint of storage stability. Further, from the viewpoint of low temperature fixability, 6000 or less is preferable, 5000 or less is more preferable, and 4000 or less is more preferable.

  The mass ratio of the crystalline polyester C to the amorphous resin A (crystalline polyester C / amorphous resin A) is preferably 30/70 or less from the viewpoint of storage stability and image density under high temperature and high humidity. / 80 or less is more preferable, 18/82 or less is more preferable, and 15/85 or less is more preferable. Further, from the viewpoint of low-temperature fixability and image density under high temperature and high humidity, 3/97 or more is preferable, 5/95 or more is more preferable, and 7/93 or more is more preferable. When the binder resin composition contains an amorphous resin other than the amorphous resin A and a crystalline polyester other than the crystalline polyester C, the mass ratio of the amorphous resin including them and the crystalline polyester is also the above. It is preferable to be within the range.

  The total content of the amorphous resin A and the crystalline polyester C is preferably 80% by mass or more, more preferably 90% by mass or more, and further preferably 95% by mass or more in the binder resin composition. Moreover, 100 mass% or less is preferable, substantially 100 mass% is more preferable, and 100 mass% is further more preferable.

  The binder resin composition of the present invention preferably contains two kinds of amorphous resins having different softening points from the viewpoint of low-temperature fixability and hot offset resistance, at least one of which is the amorphous resin A. It is more preferable that both are the amorphous resin A.

  Of the two types of amorphous resins having different softening points, the softening point of the amorphous resin AH having a higher softening point is preferably 110 ° C. or higher, more preferably 115 ° C. or higher, from the viewpoint of hot offset resistance. 118 ° C. or higher is more preferable. Further, from the viewpoint of low-temperature fixability, 150 ° C. or lower is preferable, and 130 ° C. or lower is more preferable.

  On the other hand, the softening point of the amorphous resin AL having a lower softening point is preferably 75 ° C. or higher, more preferably 80 ° C. or higher, and further preferably 85 ° C. or higher from the viewpoint of storage stability. From the viewpoint of low-temperature fixability, it is preferably less than 110 ° C, more preferably 105 ° C or less, and further preferably 100 ° C or less.

  From the viewpoint of hot offset resistance, the mass ratio of the amorphous resin AH to the amorphous resin AL (amorphous resin AH / amorphous resin AL) is preferably 0.2 or more, more preferably 0.5 or more, and 0.7 or more. More preferably, 0.9 or more is more preferable, and 1.2 or more is more preferable. Further, from the viewpoint of low-temperature fixability, it is preferably 10 or less, more preferably 7 or less, further preferably 5 or less, further preferably 3 or less, and further preferably 1.3 or less.

  The toner for electrophotography containing the binder resin composition of the present invention is excellent in low-temperature fixability, storage stability, and image density under high temperature and high humidity. The binder resin composition of the present invention may be obtained by mixing the crystalline polyester C and the amorphous resin A. When the toner is produced, each resin is directly used as a raw material. You may use for mixing.

  In the toner of the present invention, a known resin other than the binder resin composition of the present invention may be used in combination as long as the effects of the present invention are not impaired, but the content of the binder resin composition of the present invention is not limited. Is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more in the binder resin. Moreover, 100 mass% or less is preferable, substantially 100 mass% is more preferable, and 100 mass% is further more preferable.

  The toner of the present invention includes a colorant, a release agent, a charge control agent, magnetic powder, a fluidity improver, a conductivity modifier, a reinforcing filler such as a fibrous substance, an antioxidant, and a cleaning property improver. Additives may be contained, and it is preferable that a colorant, a release agent and a charge control agent are contained.

  As the colorant, all of dyes and pigments used as toner colorants can be used, such as carbon black, phthalocyanine blue, permanent brown FG, brilliant first scarlet, pigment green B, rhodamine-B base, Solvent Red 49, Solvent Red 146, Solvent Blue 35, Quinacridone, Carmine 6B, Disazo Yellow and the like can be used, and the toner of the present invention may be either a black toner or a color toner. The content of the colorant is preferably 1 part by mass or more and more preferably 2 parts by mass or more with respect to 100 parts by mass of the binder resin from the viewpoint of improving the toner image density and low-temperature fixability. Moreover, 40 mass parts or less are preferable, and 10 mass parts or less are more preferable.

  Examples of mold release agents include polypropylene wax, polyethylene wax, polypropylene polyethylene copolymer wax, aliphatic hydrocarbon wax such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax, and oxides thereof, carnauba wax, montan wax, Sazol wax and ester waxes such as those deoxidized waxes, fatty acid ester waxes, fatty acid amides, fatty acids, higher alcohols, fatty acid metal salts, etc. may be mentioned, and these may be used alone or in combination of two or more. Can be used.

  The melting point of the release agent is preferably 60 to 160 ° C., more preferably 60 to 150 ° C., from the viewpoints of low-temperature fixability and offset resistance of the toner.

  The content of the release agent is preferably 0.5 parts by mass or more with respect to 100 parts by mass of the binder resin from the viewpoint of low-temperature fixability and offset resistance of the toner and dispersibility in the binder resin. More preferably, it is more preferably 1.5 parts by mass or more. Further, from the same viewpoint, it is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and further preferably 7 parts by mass or less.

  The charge control agent is not particularly limited, and may contain either a positively chargeable charge control agent or a negatively chargeable charge control agent.

  Examples of positively chargeable charge control agents include nigrosine dyes such as “Nigrosine Base EX”, “Oil Black BS”, “Oil Black SO”, “Bontron N-01”, “Bontron N-04”, “Bontron N-07 ”,“ Bontron N-09 ”,“ Bontron N-11 ”(manufactured by Orient Chemical Co., Ltd.) and the like; triphenylmethane dyes containing tertiary amines as side chains, quaternary ammonium salt compounds such as“ Bontron P-51 "(manufactured by Orient Chemical Co., Ltd.), cetyltrimethylammonium bromide," COPY CHARGE PX VP435 "(manufactured by Clariant), etc .; polyamine resins such as" AFP-B "(manufactured by Orient Chemical Industries, Ltd.), etc. Imidazole derivatives such as “PLZ-2001” and “PLZ-8001” (manufactured by Shikoku Kasei Kogyo Co., Ltd.); styrene-acrylic resins such as “FCA-701PT” (Fujikura Chemical) Etc., Ltd.) Co., Ltd., and the like.

  In addition, as the negatively chargeable charge control agent, metal-containing azo dyes such as “Varifast Black 3804”, “Bontron S-31”, “Bontron S-32”, “Bontron S-34”, “Bontron S-36” (Above, manufactured by Orient Chemical Co., Ltd.), “Eisenspiron Black TRH”, “T-77” (manufactured by Hodogaya Chemical Co., Ltd.), etc .; metal compounds of benzylic acid compounds such as “LR-147” , “LR-297” (manufactured by Nippon Carlit Co., Ltd.), etc .; metal compounds of salicylic acid compounds such as “Bontron E-81”, “Bontron E-84”, “Bontron E-88”, “Bontron E-” 304 "(manufactured by Orient Chemical Co., Ltd.)," TN-105 "(manufactured by Hodogaya Chemical Co., Ltd.), etc .; copper phthalocyanine dyes; quaternary ammonium salts such as" COPY CHARGE NX VP434 "(manufactured by Clariant) Nitroimidazole derivatives And the like; organometallic compounds such as “TN105” (manufactured by Hodogaya Chemical Co., Ltd.) and the like.

  The content of the charge control agent is preferably 0.01 parts by mass or more and more preferably 0.2 parts by mass or more with respect to 100 parts by mass of the binder resin from the viewpoint of the charging stability of the toner. Further, from the same viewpoint, it is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, further preferably 3 parts by mass or less, and further preferably 2 parts by mass or less.

  The toner of the present invention may be a toner obtained by any conventionally known method such as a melt-kneading method, an emulsion phase inversion method, or a polymerization method, but from the viewpoint of productivity and dispersibility of the colorant, A pulverized toner obtained by a melt kneading method is preferred. In the case of pulverized toner by the melt-kneading method, for example, a raw material such as a binder resin, a colorant, and a charge control agent is uniformly mixed with a mixer such as a Henschel mixer, and then a hermetically sealed kneader, a single or twin screw extruder It can be produced by melt-kneading with an open roll kneader or the like, cooling, pulverizing and classifying. On the other hand, from the viewpoint of reducing the particle size of the toner, a toner by a polymerization method is preferable.

Further, the toner of the present invention may be obtained by a method including a step of forming a raw material containing the binder resin of the present invention into an aqueous medium. The production method is not particularly limited, for example,
(A) A method of aggregating and coalescing primary particles after previously forming primary particles containing a binder resin in an aqueous medium.
(B) A method in which primary particles containing a binder resin are formed in advance in an aqueous medium, and then the primary particles are fused.
(C) The raw material containing binder resin is disperse | distributed in an aqueous medium, and the method of granulating etc. is mentioned.

  In the present invention, the method (A) is preferable, and after introducing an aqueous medium into a mixed solution or dispersion prepared by dissolving or dispersing a raw material containing a binder resin in an organic solvent, the organic solvent is removed. A method including a step (1) of obtaining an aqueous dispersion of primary particles containing a binder resin and a step (2) of aggregating and coalescing the primary particles is preferable. As a specific example of the method (B), a radical polymerizable monomer solution in which a binder resin is dissolved is emulsion-polymerized to obtain resin fine particles, and the resin fine particles are fused in an aqueous medium (Japanese Patent Laid-Open No. 2001-2001). As a specific example of the method (C), the raw material containing the binder resin is heated and melted and dispersed in an aqueous medium containing no organic solvent while maintaining the molten state of the binder resin. Then, a method of drying (see JP 2001-235904 A) and the like are included.

  In the step (1), an aqueous medium is introduced into a mixed solution or dispersion prepared by dissolving or dispersing a raw material containing a binder resin in an organic solvent, and then the organic solvent is removed to remove the binder resin. It is a step of obtaining a primary particle aqueous dispersion containing.

  The amount of the organic solvent used is preferably 100 to 1000 parts by mass with respect to 100 parts by mass of the binder resin. Water and, if necessary, a neutralizing agent are mixed in the mixed solution and stirred, and then the organic solvent is removed from the obtained dispersion to obtain a primary particle aqueous dispersion of self-dispersing resin. Examples of the organic solvent include those described above.

  The amount of the aqueous medium used is preferably 100 to 3000 parts by mass with respect to 100 parts by mass of the organic solvent. The aqueous medium used in the method (1) may contain a solvent such as an organic solvent, but water is preferably 50% by mass or more, preferably 70% by mass or more, more preferably 90% by mass or more. More preferably, it contains 99% by mass or more.

  When stirring the mixture, a commonly used mixing and stirring device such as an anchor blade can be used. Examples of the neutralizing agent include alkali metals such as lithium hydroxide, sodium hydroxide and potassium hydroxide; organic bases such as ammonia, trimethylamine, ethylamine, diethylamine, triethylamine, triethanolamine and tributylamine. The addition amount of the neutralizing agent is preferably 0.5 to 1.5 equivalents, more preferably 0.7 to 1.3 equivalents, and even more preferably 0.8 to 1.2 equivalents with respect to the acid value of the polyester after the reaction to be neutralized.

  A dispersant can be used for the purpose of lowering the melt viscosity and melting point of the binder resin and improving the dispersibility of the primary particles produced. Examples of the dispersant include water-soluble polymers such as polyvinyl alcohol, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, sodium polyacrylate, and sodium polymethacrylate; sodium dodecylbenzenesulfonate, sodium octadecylsulfate, sodium oleate, Anionic surfactants such as sodium laurate and potassium stearate; Cationic surfactants such as laurylamine acetate, stearylamine acetate and lauryltrimethylammonium chloride; Amphoteric surfactants such as lauryldimethylamine oxide; Tricalcium phosphate, water Examples thereof include inorganic salts such as aluminum oxide, calcium sulfate, calcium carbonate, and barium carbonate. The amount of the dispersant used is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and still more preferably 10 parts by mass or less with respect to 100 parts by mass of the binder resin from the viewpoint of emulsion stability and detergency.

  The solid content concentration of the primary particles (hereinafter also simply referred to as primary particles) containing the binder resin obtained in step (1) depends on the stability of the dispersion and the handling of the dispersion in the aggregation step. From this viewpoint, 7 to 50% by mass is preferable, and 7 to 40% by mass is more preferable. In addition, non-volatile components, such as resin, are contained in solid content.

The average primary particle diameter is preferably 0.05 to 3 μm, more preferably 0.05 to 1 μm, and even more preferably 0.05 to 0.8 μm from the viewpoint of uniformly agglomerating in the subsequent step. In the present invention, the average particle size of primary particles refers to the volume median particle size (D ₅₀ ), and can be measured by a laser diffraction type particle size measuring instrument or the like.

  Then, the process (process (2)) which aggregates and unites the primary particle obtained at the process (1) is demonstrated.

  In the step (2), the solid content concentration in the system in the aggregating step for aggregating the primary particles obtained in the step (1) can be adjusted by adding water to the binder resin dispersion. In order to cause aggregation, 5 to 50% by mass is preferable, 5 to 30% by mass is more preferable, and 5 to 20% by mass is further preferable.

  The pH in the system in the aggregation step is preferably 2 to 10, more preferably 2 to 9, more preferably 3 to 8, from the viewpoint of achieving both the dispersion stability of the mixed solution and the aggregation properties of fine particles such as a binder resin. Further preferred.

  From the same viewpoint, the temperature in the system in the aggregation process is preferably a softening point of the binder resin of −80 ° C. or more and a softening point or less.

  In addition, additives such as a colorant and a charge control agent may be premixed in the binder resin when preparing the primary particles, or a dispersion liquid in which each additive is separately dispersed in a dispersion medium such as water. It may be prepared, mixed with primary particles, and subjected to an aggregation process. When the additive is previously mixed with the binder resin when preparing the primary particles, it is preferable to melt and knead the binder resin and the additive in advance.

  In the aggregation process, an aggregating agent can be added in order to effectively perform aggregation. As an aggregating agent, a quaternary salt cationic surfactant, polyethyleneimine, or the like is used in an organic system, and an inorganic metal salt, a divalent or higher metal complex, or the like is used in an inorganic system. 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, aluminum sulfate, polyaluminum chloride, polyaluminum hydroxide, Examples thereof include inorganic metal salt polymers such as calcium sulfide.

  The amount of the flocculant used is preferably 50 parts by mass or less and more preferably 40 parts by mass or less with respect to 100 parts by mass of the binder resin from the viewpoint of environmental resistance characteristics of the toner.

  Subsequently, the agglomerated particles containing at least the binder resin obtained in the aggregating step are heated and united (a uniting step).

  The temperature in the system in the coalescence process is from the viewpoint of the target toner particle size, particle size distribution, shape control, and particle fusing property, the softening point of the binder resin is −50 ° C. or higher, and the softening point is + 10 ° C. or lower. The softening point is -45 ° C or higher and the softening point + 10 ° C or lower is more preferable, and the softening point is -40 ° C or higher and the softening point + 10 ° C or lower is more preferable. The stirring speed is preferably a speed at which the aggregated particles do not settle. In the present invention, when two or more kinds of resins are used as the binder resin, the softening point of the mixed resin is set as the softening point of the binder resin.

  A toner can be obtained by subjecting the coalesced particles obtained in the step (2) to a solid-liquid separation step such as filtration, a washing step, and a drying step as appropriate.

  In the drying step, any method such as a vibration type fluidized drying method, a spray drying method, a freeze drying method, a flash jet method, or the like can be employed.

  In the toner of the present invention, it is preferable to use an external additive in order to improve transferability. Examples of the external additive include inorganic fine particles such as silica, alumina, titania, zirconia, tin oxide and zinc oxide, and organic fine particles such as resin particles such as melamine resin fine particles and polytetrafluoroethylene resin fine particles. The above may be used in combination. Among these, silica is preferable, and hydrophobic silica that has been subjected to a hydrophobic treatment is more preferable from the viewpoint of toner transferability.

  Examples of the hydrophobizing agent for hydrophobizing the surface of silica particles include hexamethyldisilazane (HMDS), dimethyldichlorosilane (DMDS), silicone oil, octyltriethoxysilane (OTES), and methyltriethoxysilane. It is done.

  The average particle diameter of the external additive is preferably 10 nm or more, and more preferably 15 nm or more, from the viewpoint of the chargeability, fluidity, and transferability of the toner. From the same viewpoint, 250 nm or less is preferable, 200 nm or less is more preferable, and 90 nm or less is more preferable.

  The content of the external additive is preferably 0.05 parts by mass or more, and 0.1 parts by mass or more with respect to 100 parts by mass of the toner before being processed with the external additive, from the viewpoint of chargeability, fluidity, and transferability of the toner. More preferred is 0.3 part by mass or more. Further, from the same viewpoint, it is preferably 5 parts by mass or less, and more preferably 4 parts by mass or less.

The volume median particle size (D ₅₀ ) of the toner of the present invention is preferably from 3 to 15 μm, more preferably from 4 to 10 μm. In the present specification, the volume-median particle size (D ₅₀ ) means a particle size at which the cumulative volume frequency calculated by the volume fraction is 50% when calculated from the smaller particle size. When the toner is treated with an external additive, the volume median particle size of the toner particles before being treated with the external additive is defined as the volume median particle size of the toner.

  The toner of the present invention can be used as a one-component developing toner or as a two-component developer mixed with a carrier.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The physical properties of the resin and the like were measured by the following method.

[Softening point of resin]
Using a flow tester “CFT-500D” (manufactured by Shimadzu Corporation), a 1 g sample was heated at a heating rate of 6 ° C./min, and a load of 1.96 MPa was applied by a plunger, 1 mm in diameter and 1 mm in length. Extrude from the nozzle. The amount of plunger drop of the flow tester is plotted against the temperature, and the temperature at which half of the sample flows out is taken as the softening point.

[Maximum peak temperature of resin endotherm]
Using a differential scanning calorimeter “Q-20” (manufactured by TA Instruments Japan Co., Ltd.), 0.01 to 0.02 g of sample is weighed into an aluminum pan, and the temperature falls from room temperature to 10 ° C./min at 0 ° C. Cool to 0 ° C and hold at 0 ° C for 1 minute. Thereafter, the measurement is performed at a heating rate of 10 ° C./min. Among the observed endothermic peaks, the temperature of the peak on the highest temperature side is defined as the highest endothermic peak temperature.

[Glass transition temperature of resin]
Using a differential scanning calorimeter “Q-20” (manufactured by TA Instruments Japan), 0.01 to 0.02 g of sample is weighed into an aluminum pan, heated to 200 ° C., and the temperature drop rate from that temperature Cool to 0 ° C at 10 ° C / min. Next, the sample is heated and measured at a heating rate of 10 ° C./min. The glass transition temperature is defined as the temperature at the intersection of the base line extension below the maximum peak temperature of endotherm and the tangent line indicating the maximum slope from the peak rising portion to the peak apex.

[Resin acid value]
Measured according to the method of JIS K0070. However, only the measurement solvent is changed from the mixed solvent of ethanol and ether specified in JIS K0070 to the mixed solvent of acetone and toluene (acetone: toluene = 1: 1 (volume ratio)).

[Number average molecular weight of resin (Mn)]
The number average molecular weight is determined by gel permeation chromatography (GPC) by the following method. As the solvent and eluent, chloroform is used for crystalline polyester, and tetrahydrofuran is used for amorphous resin.
(1) Preparation of sample solution Dissolve the sample in a solvent at 40 ° C so that the concentration is 0.5 g / 100 ml. Subsequently, this solution is filtered using a PTFE type membrane filter “DISMIC-25JP” (manufactured by Toyo Roshi Kaisha, Ltd.) having a pore size of 0.20 μm to remove insoluble components to obtain a sample solution.
(2) Molecular weight measurement Using the following measuring device and analytical column, flow the eluent at a flow rate of 1 ml per minute and stabilize the column in a constant temperature bath at 40 ° C. Measurement is performed by injecting 100 μl of the sample solution. The molecular weight of the sample is calculated based on a calibration curve prepared in advance. The calibration curve at this time includes several types of monodisperse polystyrene (A-500 (5.0 × 10 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 )) prepared as standard samples are used.
Measuring device: HLC-8220GPC (manufactured by Tosoh Corporation)
Analytical column: TSKgel GMH _XL + TSKgel G3000H _XL (manufactured by Tosoh Corporation)

[Melting point of release agent]
Using a differential scanning calorimeter “DSC Q20” (manufactured by TA Instruments Japan Co., Ltd.), 0.01 to 0.02 g of sample is weighed into an aluminum pan and heated to 200 ° C. at a heating rate of 10 ° C./min. Then, cool to -10 ° C at a 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 peak temperature of the endotherm observed from the melting endotherm curve thus obtained is taken as the melting point of the release agent.

[Volume Median Particle Size (D ₅₀ ) of Resin Particles, Colorant Particles, Release Agent Particles, and Charge Control Agent Particles]
(1) Measuring device: Laser diffraction particle size measuring instrument “LA-920” (manufactured by HORIBA, Ltd.)
(2) Measurement conditions: Distilled water is added to the measurement cell, and the volume-median particle diameter is measured at a temperature at which the absorbance falls within an appropriate range.

[Solid content concentration of aqueous dispersion of resin]
Using an infrared moisture meter “FD-230” (manufactured by Kett Science Laboratory Co., Ltd.), measure the moisture content of a 5 g measurement sample at a drying temperature of 150 ° C. and a measurement mode of 96 (monitoring time 2.5 min / variation width 0.05%). To do. The solid content concentration is calculated according to the following formula.
Solid content concentration (% by mass) = 100-M
M: Water content (% by mass)

[Average particle diameter of external additive]
The average particle diameter refers to the number average particle diameter and refers to the number average value of the particle diameters of 500 particles measured from a scanning electron microscope (SEM) photograph of the external additive. When there is a major axis and a minor axis, the major axis is indicated.

[Volume-median particle size of toner]
Measuring machine: Coulter Multisizer II (Beckman Coulter, Inc.)
Aperture diameter: 100μm
Analysis software: Coulter Multisizer AccuComp version 1.19 (Beckman Coulter, Inc.)
Electrolyte: Isoton II (Beckman Coulter, Inc.)
Dispersion: Emulgen 109P (manufactured by Kao Corporation, polyoxyethylene lauryl ether, HLB (Griffin): 13.6) is dissolved in the electrolyte so as to have a concentration of 5% by mass.
Dispersion conditions: 10 mg of a measurement sample was added to 5 ml of the dispersion, and dispersed for 1 minute with an ultrasonic disperser, then 25 ml of the electrolyte was added, and further dispersed for 1 minute with an ultrasonic disperser. Prepare sample dispersion.
Measurement conditions: The sample dispersion is added to 100 ml of the electrolytic solution so that the particle size of 30,000 particles can be measured in 20 seconds, and 30,000 particles are measured. Determine the median particle size (D ₅₀ ).

[Production of resin]
Resin Production Example 1 [Resin C1 to C5, C7 to C9, C11, C12]
5 liters equipped with carboxylic acid components other than the alcohol components and fumaric acid shown in Tables 1 and 2, esterification catalyst, and promoter, equipped with thermometer, stainless steel stirring rod, dehydration tube, cooling tube, and nitrogen introduction tube Was heated to 180 ° C in a mantle heater in a nitrogen atmosphere, reacted for 5 hours, and then gradually heated to 210 ° C at a rate of 5 ° C / h. . After confirming that the reaction rate reached 80% or higher at 210 ° C, fumaric acid and t-butylcatechol were added, reacted at 190 ° C for 1 hour at normal pressure, and then heated to 200 ° C. After reacting at normal pressure for 1 hour, the reaction was carried out to a desired softening point at 8 kPa to obtain a crystalline polyester. The reaction rate means a value of the amount of produced reaction water / theoretical product water amount × 100.

Resin Production Example 2 [Resin C6]
Four 5 liters equipped with a carboxylic acid component other than the alcohol component and adipic acid shown in Table 1, an esterification catalyst and a cocatalyst equipped with a thermometer, a stainless steel stirring bar, a dehydrating tube, a cooling tube, and a nitrogen introducing tube The flask was placed in a neck flask, heated to 180 ° C. in a mantle heater in a nitrogen atmosphere, reacted for 5 hours, and then gradually heated to 210 ° C. at a rate of 5 ° C./h. After confirming that the reaction rate reached 80% or higher at 210 ° C, adipic acid was added and reacted at 190 ° C for 1 hour at normal pressure, then heated to 200 ° C and heated for 1 hour at normal pressure. Then, the reaction was carried out at 8 kPa to the desired softening point to obtain a crystalline polyester. The reaction rate means a value of the amount of produced reaction water / theoretical product water amount × 100.

Resin Production Example 3 [Resin C10]
Place the alcohol and carboxylic acid components shown in Table 2 and the esterification catalyst and cocatalyst into a 5-liter four-necked flask equipped with a thermometer, stainless steel stirring rod, dehydration tube, cooling tube, and nitrogen introduction tube. Then, the temperature was raised to 140 ° C. in a mantle heater in a nitrogen atmosphere, and the reaction was performed for 5 hours. Thereafter, it was confirmed that the reaction rate reached 80% or more at 200 ° C., and the reaction was carried out to a desired softening point at 8 kPa to obtain a crystalline polyester. The reaction rate means a value of the amount of produced reaction water / theoretical product water amount × 100.

Resin Production Example 4 [Resin C13]
Place the alcohol and carboxylic acid components shown in Table 2 and the esterification catalyst and cocatalyst into a 5-liter four-necked flask equipped with a thermometer, stainless steel stirring rod, dehydration tube, cooling tube, and nitrogen introduction tube. Then, the temperature was raised to 180 ° C. in a mantle heater in a nitrogen atmosphere, and after 7 hours of reaction, the temperature was raised stepwise to 210 ° C. at a rate of 10 ° C./h. Thereafter, it was confirmed that the reaction rate reached 80% or more at 210 ° C., and the reaction was carried out to a desired softening point at 8 kPa to obtain a crystalline polyester. The reaction rate means a value of the amount of produced reaction water / theoretical product water amount × 100.

Resin Production Example 4 [Resin A1, A2]
5 liters equipped with a carboxylic acid component other than the alcohol component and trimellitic anhydride shown in Table 3, an esterification catalyst and a cocatalyst, equipped with a thermometer, a stainless steel stirring bar, a dehydration tube, a cooling tube, and a nitrogen introduction tube Place in a four-necked flask, raise the temperature to 235 ° C in a mantle heater in a nitrogen atmosphere, react at normal pressure until the reaction rate reaches 80%, and then perform a vacuum reaction at 8 kPa for 1 hour It was.
Next, after cooling to 160 ° C., a mixture of the raw material monomer of the addition polymerization resin shown in Table 3, the both reactive monomers, and the polymerization initiator was added dropwise over 1 hour using a dropping funnel. After the dropwise addition, aging the addition polymerization reaction for 1 hour while maintaining the temperature at 160 ° C, the temperature was raised to 210 ° C, then trimellitic anhydride was added, the reaction was performed at 210 ° C for 1 hour, 210 ° C, Reaction was performed to a desired softening point at 10 kPa to obtain an amorphous hybrid resin.

Resin Production Example 5 [Resin A3 to A6]
5 liters equipped with a carboxylic acid component other than the alcohol component and trimellitic anhydride shown in Table 3, an esterification catalyst and a cocatalyst, equipped with a thermometer, a stainless steel stirring bar, a dehydration tube, a cooling tube, and a nitrogen introduction tube Place in a four-necked flask, raise the temperature to 235 ° C in a mantle heater in a nitrogen atmosphere, react at normal pressure until the reaction rate reaches 80%, and then perform a vacuum reaction at 8 kPa for 1 hour It was.
Thereafter, the mixture was cooled to 210 ° C., trimellitic anhydride was added, the reaction was carried out at 210 ° C. for 1 hour, and the reaction was carried out at 210 ° C. and 10 kPa to the desired softening point to obtain an amorphous polyester.

[Production of toner]
Examples 1-12 and Comparative Examples 1-6
(Preparation of resin dispersion)
Into a 5 liter container equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen introduction tube, 600 g of methyl ethyl ketone and 100 g of the amorphous resin shown in Table 4 were added at 50 ° C. The resin was dissolved.
To the obtained solution, 5% aqueous potassium hydroxide solution was added to neutralize the solution to a degree of neutralization of 80 mol%, and then 900 g of ion-exchanged water was added, followed by a stirring speed of 250 r / min. Under reduced pressure, methyl ethyl ketone was distilled off at a temperature of 50 ° C. or lower until it became 30 ppm or lower. The solid content concentration of the obtained resin dispersion was measured, and ion-exchanged water was added so that the solid content concentration was 10% by mass to obtain an aqueous dispersion of amorphous resin. The volume median particle size (D ₅₀ ) of the resin particles was 150 nm.

(Preparation of aqueous dispersion of crystalline polyester)
Into a 5 liter container equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen introduction tube, 600 g of methyl ethyl ketone and 200 g of the crystalline polyester shown in Table 4 were charged at 70 ° C., respectively. Was dissolved.
To the resulting solution, a 5% aqueous potassium hydroxide solution was added to neutralize to a degree of neutralization of 80 mol%, followed by the addition of 1800 g of ion-exchanged water, followed by a stirring speed of 250 r / min. Under reduced pressure, methyl ethyl ketone was distilled off at 70 ° C. until it became 30 ppm or less. The solid content concentration of the obtained resin dispersion was measured, and ion-exchanged water was added so that the solid content concentration was 10% by mass to obtain an aqueous dispersion of crystalline polyester. The volume median particle size (D ₅₀ ) of the resin particles was 180 nm.

(Preparation of colorant dispersion)
Mixing 50 g of copper phthalocyanine (manufactured by Dainichi Seika Kogyo Co., Ltd., model number: ECB-301), 5 g of nonionic surfactant (trade name: Emulgen (registered trademark) 150) manufactured by Kao Corporation and 200 g of ion-exchanged water Then, a colorant dispersion containing colorant particles was obtained by dispersing for 10 minutes using a homogenizer. The volume median particle size (D ₅₀ ) of the colorant particles was 120 nm.

(Preparation of release agent dispersion)
Paraffin wax (manufactured by Nippon Seiwa Co., Ltd., trade name: HNP9, melting point: 85 ° C.) 50 g, cationic surfactant (manufactured by Kao Corporation, trade name: Sanisol (registered trademark) B50) 5 g and ion-exchanged water 200 g was heated to 95 ° C., and the paraffin wax was dispersed using a homogenizer, followed by dispersion treatment using a pressure discharge homogenizer to obtain a release agent dispersion containing release agent particles. The volume median particle size (D ₅₀ ) of the release agent particles was 550 nm.

(Preparation of charge control agent dispersion)
Charge control agent (Orient Chemical Industry Co., Ltd., trade name: Bontron E-84) 50 g, Nonionic surfactant (Kao Co., Ltd., trade name: Emulgen (registered trademark) 150) 5 g and ion-exchanged water 200 g Were mixed using a glass bead and a sand grinder for 10 minutes to obtain a charge control agent dispersion containing charge control agent particles. The volume median particle size (D ₅₀ ) of the charge control agent particles was 500 nm.

(Manufacture of toner)
300 g of resin dispersion, 8 g of colorant dispersion, 6 g of release agent dispersion, charge control, so that the mass ratio of amorphous resin to crystalline polyester is the ratio shown in Table 4. 2 g of the agent dispersion and 52 g of deionized water were placed in a 2 liter container.
Next, 146 g of a 6.2 mass% ammonium sulfate aqueous solution was added dropwise over 30 minutes at room temperature with stirring at 100 r / min with a chi-type stirrer. Thereafter, the temperature was raised while stirring, and when the temperature reached 50 ° C., the temperature was fixed at 50 ° C. and held for 3 hours. After forming aggregated particles in this manner, a dilute solution obtained by diluting 4.2 g of a polyoxyethylene dodecyl ether sodium sulfate aqueous solution (solid content: 28% by mass) with 37 g of deionized water was added as an aggregation terminator.
Next, the temperature was raised to 80 ° C. at 0.16 ° C./min. After the temperature reached 80 ° C., the temperature was maintained at 80 ° C. for 1 hour, and then the heating was terminated. As a result, coalesced particles were formed, and then slowly cooled to room temperature, and toner particles having a volume median particle size (D ₅₀ ) of 6.2 μm were obtained through a suction filtration step, a washing step, and a drying step.

  Furthermore, 100 parts by mass of toner particles were mixed with hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., trade name: NAX-50, hydrophobizing agent: HMDS, average particle size 40 nm), and hydrophobic silica (Nippon Aerosil). Product name: R972, Hydrophobic treatment agent: DMDS, average particle size 16 nm) 1.5 parts by mass was added, and ST (upper blade) was added to a 10 liter Henschel mixer (Mitsui Mine Co., Ltd.). -Ao (lower blade) type stirring blade was attached, and the mixture was stirred at 3000 r / min for 2 minutes for external addition to obtain a toner.

Test Example 1 [Low-temperature fixability of toner]
Toner was installed in a machine that improved the fixing machine of the copier “AR-505” (manufactured by Sharp Corporation) so that it can be fixed outside the machine, and paper manufactured by Sharp Corporation [CopyBond SF-70NA ( 75 g / m ² )] was obtained in an unfixed state. Using a fixing machine (fixing speed 390mm / sec) adjusted so that the total fixing pressure is 40kgf, the fixing roller temperature is increased from 100 ° C to 240 ° C in 10 ° C increments, and the unfixed state at each temperature. The fixing test of the printed material was conducted. “Scotch Mending Tape” (Sumitomo 3M, width: 18 m) was applied to the fixed image, passed through a fixing roller set at 30 ° C., and then the tape was peeled off. The optical reflection density before and after the tape was peeled off was measured using a reflection densitometer “RD-915” (manufactured by Macbeth), and the ratio between the two (after peeling / before sticking × 100) was initially 90%. The temperature of the fixing roller that exceeded the minimum fixing temperature. The results are shown in Table 4. The lower the minimum fixing temperature, the better the low-temperature fixing property, and the temperature is preferably 160 ° C. or lower, more preferably 150 ° C. or lower, and further preferably 140 ° C. or lower.

Test Example 2 [Toner storability]
4 g of toner was placed in a 20 mL container (diameter: about 3 cm) and left for 72 hours in an environment of 55 ° C. and 60% humidity. The degree of toner aggregation was visually observed every 12 hours up to 72 hours. Table 4 shows the time when the occurrence of aggregation was observed. The slower the occurrence of aggregation, the better the storage stability under high temperature and high humidity, and the time when the occurrence of aggregation is observed is preferably 48 hours or more, more preferably 60 hours or more, and even more preferably 72 hours or more. In the table, “> 72” indicates that aggregation is not observed even after 72 hours.

Test Example 3 [Image density stability under high temperature and high humidity]
Mounts toner on "MICROLINE 3010" (Oki Data Corporation, fixing: contact fixing method, development: non-magnetic one-component developing method), and 500 images in a high-temperature, high-humidity (HH) environment at 35 ° C and 85% Got. Measure the image density of the 50th and 500th images using a transmission-type Macbeth densitometer “TR-927”, and the ratio of the image density (500th image density value / 50th image) Density), the stability of the image density in an HH environment was evaluated. The results are shown in Table 4. The larger the ratio value, the better the image density stability in the HH environment. The ratio value is preferably 0.75 or more, more preferably 0.85 or more, and further preferably 0.95 or more.

From comparison between Example 1 and Comparative Example 1, it can be seen that the toner of Example 1 containing crystalline polyester is excellent in low-temperature fixability.
In comparison between Examples 1 to 3 and Comparative Example 2, the toner of Example 1 using an aliphatic diol having 10 carbon atoms as the alcohol component of the crystalline polyester is low temperature fixability, storage stability, high temperature and high humidity. It can be seen that the image density is superior.
In comparison between Examples 1 and 4 and Comparative Example 3, the toner of Example 1 in which the content of the aromatic dicarboxylic acid compound in the carboxylic acid component of the crystalline polyester is 79 mol% is storable, and has high temperature and high humidity. It can be seen that the image density at is excellent.
In comparison between Examples 1 and 5 and Comparative Example 4, the toner of Example 1 in which the content of the aliphatic diol having 9 to 14 carbon atoms in the alcohol component of the crystalline polyester is 100 mol% is low temperature fixability and storage. It can be seen that the image quality is excellent and the image density under high temperature and high humidity.
In comparison with Examples 1 and 6, it can be seen that the toner of Example 1 using an aliphatic dicarboxylic acid compound having 4 carbon atoms as the carboxylic acid component of the crystalline polyester is superior in storage stability.
In contrast to Examples 1 and 7 and Comparative Example 5, the toner of Example 1 having the lowest acid value of crystalline polyester of 11 mg KOH / g is low temperature fixability, storage stability, and image density under high temperature and high humidity. It turns out that it is superior.
In contrast to Examples 1, 9, and 10, the toner of Example 1 in which the mass ratio of crystalline polyester / amorphous resin is 10/90 is low temperature fixability, storage stability, and high temperature and high humidity. It turns out that it is excellent by the balance of image density.
From the viewpoint of comparison between Examples 1, 11, and 12, from the viewpoint of low-temperature fixability, storage stability, and image density under high temperature and high humidity, the amorphous resin is preferably amorphous hybrid resin A1 and amorphous polyester A2. It can be seen that the amorphous hybrid resin A1 is more preferable from the viewpoints of storage stability and image density under high temperature and high humidity.
From the comparison between Example 1 and Comparative Example 6, when the aliphatic dicarboxylic acid compound having 4 to 6 carbon atoms of the crystalline polyester is not used as the carboxylic acid component, the low temperature fixability, the storage stability, and the high temperature and high humidity It can be seen that the image density decreases.

  The binder resin composition for an electrophotographic toner of the present invention is suitable as a binder resin composition for a toner used for developing a latent image formed in an electrophotographic method, an electrostatic recording method, an electrostatic printing method, or the like. It is used for.

Claims (6)

  A binder resin composition for an electrophotographic toner containing a crystalline polyester C and an amorphous resin A, wherein the crystalline polyester C contains 70 mol% or more of an aliphatic diol having 9 to 14 carbon atoms. A crystalline polyester having an acid value of 20 mgKOH / g or less, obtained by polycondensation of an alcohol component and a carboxylic acid component containing an aromatic dicarboxylic acid compound and an aliphatic dicarboxylic acid compound having 4 to 6 carbon atoms, Binder resin composition for electrophotographic toner.   The binder resin composition according to claim 1, wherein the content of the aliphatic dicarboxylic acid compound having 4 to 6 carbon atoms is 10 mol% or more and 30 mol% or less in the carboxylic acid component of the crystalline polyester C.   The binder resin composition according to claim 1 or 2, wherein the content of the aromatic dicarboxylic acid compound is 60 mol% or more and 90 mol% or less in the carboxylic acid component of the crystalline polyester C. Amorphous resin A is
Raw material monomer of amorphous polycondensation resin containing alcohol component containing alkylene oxide adduct of bisphenol and carboxylic acid component containing aromatic dicarboxylic acid compound, raw material monomer of addition polymerization resin and amorphous polycondensation system Amorphous hybrid resin A1 comprising an amorphous polycondensation resin component and an addition polymerization resin component obtained by polymerizing a compound capable of reacting with either a resin raw material monomer or an addition polymerization resin raw material monomer And a raw material monomer of an amorphous polycondensation resin comprising an alcohol component containing an alkylene oxide adduct of bisphenol and a carboxylic acid component containing an aromatic dicarboxylic acid compound, and the raw material monomer having 8 to 22 carbon atoms Selected from the group consisting of monovalent aliphatic alcohols and monovalent aliphatic carboxylic acid compounds having 8 to 22 carbon atoms At least one monovalent long chain monomer, amorphous polyesters obtained raw material monomer containing 0.1 mol% to 10 mol% or less by polycondensing the A2
The binder resin composition according to claim 1, comprising one or more amorphous resins selected from the group consisting of:   The binder resin according to any one of claims 1 to 4, wherein a mass ratio of the crystalline polyester C and the amorphous resin A (crystalline polyester C / amorphous resin A) is 3/97 or more and 30/70 or less. Composition.   An electrophotographic toner containing the binder resin composition according to claim 1.