JP2023084006A - Toner binder resin composition - Google Patents

Abstract

To provide a toner binder resin composition used for electro-photographic toner and capable of improving the image quality of a printed matter, such as fine line reproducibility.SOLUTION: A toner binder resin composition includes a condensate (AT) of: a polyester resin segment being the condensation polymer of an alcohol component and a carboxylic acid component including an aromatic dicarboxylic acid of 80 mol% or more; a vinyl resin segment being the addition polymer of a raw material monomer including a styrene based compound; and a tertiary amine (T).SELECTED DRAWING: None

Description

The present invention relates to a toner binder resin composition used for developing latent images formed by electrophotography, electrostatic recording, electrostatic printing and the like, and an electronic device containing the toner binder resin composition. It relates to photographic toner.

In the field of electrophotography, along with the development of electrophotographic systems, there is a demand for the development of toners that are compatible with higher image quality and higher speed.
In Patent Document 1, a coloring agent, a resin composition obtained by condensing an amorphous polyester resin having an acid group and an amine compound, a carboxylic acid component containing 20 mol% or more of an aliphatic monocarboxylic acid compound, An ester composition (CI) containing a condensate with an alcohol component containing 90 mol% or more of a dihydric or higher aliphatic alcohol and an alcohol component containing 20 mol% or more of an aliphatic monoalcohol, and a dihydric or higher aliphatic carboxylic acid and an ester composition (CII) containing a condensate with a carboxylic acid component containing 90 mol % or more of an acid compound and an ester composition that is at least one selected from the ester composition (CII). . The toner is described as having excellent image density and gloss.
Patent Document 2 describes a dry toner using a polyester in which at least part of the COOH is replaced by N-containing functional groups such as amines, ammonium, betaine, pyridinium salts, and azines. It is described that the toner is a positively charged toner that develops a negative electrostatic latent image in the normal direction and exhibits stable developability against environmental changes and aging.

Japanese Patent Application Laid-Open No. 2021-47403 JP-A-61-14644

However, there is a demand for further improvement in image quality corresponding to higher image quality and higher speed.
TECHNICAL FIELD The present invention relates to a binder resin composition for toner that can improve the image quality of printed matter such as reproducibility of fine lines when used in an electrophotographic toner.

The present inventors have found that the above problems can be solved by a binder resin composition for toner containing a condensate of a polyester resin segment, a vinyl resin segment, and a tertiary amine. .

That is, the present invention relates to the following [1] to [3].
[1] A polyester resin segment that is a polycondensate of a carboxylic acid component containing 80 mol % or more of an alcohol component and an aromatic dicarboxylic acid, a vinyl resin segment that is an addition polymer of raw material monomers containing a styrene compound, and a third A binder resin composition for toner containing a condensate (AT) of a class amine (T) and a condensate (AT) thereof.
[2] An electrophotographic toner containing the binder resin composition for toner according to [1].
[3] A method for producing a binder resin composition for toner according to [1], including the following steps 1 and 2.
Step 1: Step of condensing a polyester resin segment, a vinyl resin segment, and a tertiary amine (T) to obtain a reaction mixture containing a condensate (AT) Step 2: The reaction mixture obtained in Step 1 the process of steaming

According to the present invention, it is possible to provide a binder resin composition for toner that can improve the image quality of printed matter, such as fine line reproducibility, by using it in an electrophotographic toner.

[Binder resin composition for toner]
The binder resin composition for toner of the present invention is an addition polymer of a polyester resin segment, which is a polycondensate of a carboxylic acid component containing 80 mol % or more of an alcohol component and an aromatic dicarboxylic acid, and a raw material monomer containing a styrene compound. It contains a condensation product (AT) of a certain vinyl resin segment and a tertiary amine (T).
With the above configuration, a binder resin composition for toner can be obtained that can improve the image quality of printed matter such as fine line reproducibility when used in an electrophotographic toner. Although the reason is not clear, it is considered as follows.

The binder resin composition for toner of the present invention is a condensation product (AT ). The condensate (AT) has a polyester resin segment with relatively easy molecular motion and a vinyl resin segment that is an addition polymer of a raw material monomer containing a styrene compound with a high concentration of aromatic rings that is relatively resistant to molecular motion. As a result, the polyester resin segment is easily polarized, and the vinyl resin segment is difficult to polarize. In addition, since the condensate (AT) contains the tertiary amine (T), the nitrogen atoms of the obtained condensate (AT) can be positively charged. Therefore, in the condensate (AT) contained in the binder resin composition for toner of the present invention, the easy-to-polarize segment and the hard-to-polarize segment coexist in the same molecule, so that the electric field in the condensate (AT) Since the positive and negative pairs are less likely to occur and the polarization is increased, the improvement of the dielectric constant and the increase of the positive chargeability due to the inclusion of the tertiary amine (T) are strongly exhibited. Further, 80 mol % or more of the carboxylic acid component constituting the polyester resin segment contained in the condensate (AT) is an aromatic dicarboxylic acid, and the polyester resin segment has a high aromatic ring concentration. Toners containing substances are capable of long-term charge maintenance. Furthermore, since the condensate (AT) contained in the binder resin composition for toner of the present invention has a high aromatic ring concentration and a high charge transfer speed, charging rises when the toner is charged by friction with a charging blade. is faster, and the charging stability of the toner can be improved. As a result, it is believed that the toner containing the binder resin composition for toner of the present invention has an improved dielectric constant, which makes it easier to maintain the positive chargeability, thereby improving the image quality of printed matter such as reproducibility of fine lines.

Definitions of various terms used in this specification are shown below.
Whether a resin is crystalline or amorphous is determined by the crystallinity index. The crystallinity index is defined as the ratio of the softening point of the resin to the maximum endothermic peak temperature (softening point (°C)/maximum endothermic peak temperature (°C)) in the measurement method described in the Examples below. A crystalline resin is a resin having a crystallinity index of 0.6 or more and 1.4 or less. An amorphous resin is a resin with a crystallinity index of more than 1.4 or less than 0.6 when no endothermic peak is observed or when it is observed. The crystallinity index can be appropriately adjusted depending on the type and ratio of raw material monomers, and production conditions such as reaction temperature, reaction time, and cooling rate. The maximum endothermic peak temperature refers to the temperature of the peak with the maximum peak area among the endothermic peaks observed under the conditions of the measurement method described in the Examples.
In the specification, the carboxylic acid component of the polyester resin includes not only the exemplified compounds, but also anhydrides that decompose during the reaction to generate acids, and alkyl esters of each carboxylic acid (wherein the alkyl group has 1 to 3 carbon atoms below) are also included.
In the specification, the "binder resin composition" means a resin component contained in the toner containing the condensate (AT).

<Condensate (AT)>
The condensate (AT) is a condensate of a polyester resin segment, a vinyl resin segment and a tertiary amine (T). The condensate (AT) is preferably amorphous.
The condensate (AT) is preferably a condensate (AT') obtained by a condensation reaction between the composite resin (A) containing the polyester resin segment and the vinyl resin segment and the tertiary amine (T). The condensate (AT) may contain, for example, an unreacted composite resin (A) to the extent that its properties are not substantially impaired, but the tertiary amine (T) when used as an electrophotographic toner It is preferable not to contain a tertiary amine (T) from the viewpoint of obtaining a printed matter with excellent fine line reproducibility and improved image quality by suppressing leakage of charge and deterioration of charging property of the toner.
The condensate (AT) is preferably an amorphous resin.

[Polyester resin segment]
Examples of the alcohol component of the polyester resin segment include alkylene oxide adducts of aromatic diols, linear or branched aliphatic diols, alicyclic diols, and trihydric or higher polyhydric alcohols. Among these, an alkylene oxide adduct of an aromatic diol is preferable from the viewpoint of improving the molecular mobility of the polyester resin segment in the condensate (AT) and improving the thin line reproducibility.

The alkylene oxide adduct of an aromatic diol is preferably an alkylene oxide adduct of bisphenol A, more preferably of formula (I):

（式中、ＯＲ^１及びＲ^２Ｏはオキシアルキレン基であり、Ｒ^１及びＲ^２はそれぞれ独立にエチレン基又はプロピレン基であり、ｘ及びｙはアルキレンオキシドの平均付加ｍｏｌ数を示し、それぞれ正の数であり、ｘとｙの和の値は１以上１６以下である）で表されるビスフェノールＡのアルキレンオキシド付加物である。

(Wherein, OR ¹ and R ² O are oxyalkylene groups, R ¹ and R ² are each independently an ethylene group or a propylene group, x and y represent the average number of added moles of alkylene oxide, each positive and the sum of x and y is 1 or more and 16 or less).

The alkylene oxide adducts of bisphenol A include, for example, propylene oxide adducts of bisphenol A [2,2-bis(4-hydroxyphenyl)propane] and ethylene oxide adducts of bisphenol A. These may use 1 type(s) or 2 or more types.
The content of the alkylene oxide adduct of bisphenol A is preferably 70 mol% or more in the alcohol component from the viewpoint of improving the molecular mobility of the polyester resin segment in the condensate (AT) and improving the fine line reproducibility. More preferably 90 mol % or more, still more preferably 95 mol % or more, and 100 mol % or less, still more preferably 100 mol %.

Examples of linear or branched aliphatic diols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol and 1,4-butanediol. , 2,3-butanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1 , 12-dodecanediol.
Examples of alicyclic diols include hydrogenated bisphenol A [2,2-bis(4-hydroxycyclohexyl)propane], alkylene oxide adducts having 2 to 4 carbon atoms of hydrogenated bisphenol A (average addition mol number 2 above and below 12).
Examples of trihydric or higher polyhydric alcohols include glycerin, pentaerythritol, trimethylolpropane, and sorbitol.
One or more of these alcohol components may be used.

The carboxylic acid component of the polyester resin segment contains 80 mol % or more of an aromatic dicarboxylic acid from the viewpoint of improving the molecular mobility of the polyester resin segment in the condensate (AT) and improving the fine line reproducibility. The carboxylic acid component may contain a dicarboxylic acid other than the aromatic dicarboxylic acid and a polycarboxylic acid having a valence of 3 or more. Hereinafter, a dicarboxylic acid and/or a polycarboxylic acid having a valence of 3 or more is also simply referred to as a "polycarboxylic acid".
Examples of aromatic dicarboxylic acids include phthalic acid, isophthalic acid, and terephthalic acid. Among these, isophthalic acid and terephthalic acid are preferred, and terephthalic acid is more preferred.
The amount of the aromatic dicarboxylic acid is 80 mol % or more, preferably 82 mol, in the carboxylic acid component from the viewpoint of improving the molecular mobility of the polyester resin segment in the condensate (AT) and improving the thin line reproducibility. % or more, more preferably 85 mol % or more, and preferably 95 mol % or less, more preferably 93 mol % or less, still more preferably 90 mol % or less.

Examples of dicarboxylic acids other than aromatic dicarboxylic acids include linear or branched aliphatic dicarboxylic acids and alicyclic dicarboxylic acids.
The number of carbon atoms in the linear or branched aliphatic dicarboxylic acid is preferably 2 or more, more preferably 3 or more, and preferably 30 or less, more preferably 20 or less.
Linear or branched aliphatic dicarboxylic acids include, for example, oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, dodecanedioic acid, and azelaic acid. , and succinic acid substituted with an aliphatic hydrocarbon group having 1 to 20 carbon atoms. Examples of the succinic acid substituted with an aliphatic hydrocarbon group having 1 to 20 carbon atoms include dodecylsuccinic acid, dodecenylsuccinic acid, and octenylsuccinic acid.
Alicyclic dicarboxylic acids include, for example, cyclohexanedicarboxylic acid.
Among these, linear or branched aliphatic dicarboxylic acids are preferred, fumaric acid, sebacic acid, and succinic acid substituted with an aliphatic hydrocarbon group having 1 to 20 carbon atoms are more preferred, and fumaric acid is even more preferred.
The amount of linear or branched aliphatic dicarboxylic acid in the carboxylic acid component is preferably 5 mol% or more, more preferably 7 mol% or more, still more preferably 10 mol% or more, and preferably 20 mol% or less, more preferably is 18 mol % or less, more preferably 15 mol % or less.

The trivalent or higher polyvalent carboxylic acid is preferably a trivalent carboxylic acid, such as trimellitic acid. Preferred is trimellitic acid or its anhydride.
When a trivalent or higher polycarboxylic acid is contained, the amount of the trivalent or higher polycarboxylic acid is preferably 3 mol% or more, more preferably 5 mol% or more, and still more preferably 8 mol% or more in the carboxylic acid component. , and preferably 20 mol % or less, more preferably 17 mol % or less, still more preferably 15 mol % or less.
One or more of these carboxylic acid components may be used.

The equivalent ratio of the carboxy group of the carboxylic acid component to the hydroxyl group of the alcohol component [COOH group/OH group] is preferably 0.7 or more, more preferably 0.8 or more, and preferably 1.3 or less, or more. It is preferably 1.2 or less.

[Vinyl resin segment]
The vinyl resin segment is an addition polymer of raw material monomers containing styrene compounds.
Styrenic compounds include, for example, unsubstituted or substituted styrene. Examples of substituents for styrene include alkyl groups having 1 to 5 carbon atoms, halogen atoms, alkoxy groups having 1 to 5 carbon atoms, sulfonic acid groups, and salts thereof.
Styrenic compounds include, for example, styrene, methylstyrene, α-methylstyrene, β-methylstyrene, tert-butylstyrene, chlorostyrene, chloromethylstyrene, methoxystyrene, styrenesulfonic acid and salts thereof. Among these, styrene is preferred.
From the viewpoint of suppressing the polarization of the vinyl resin segment in the condensate (AT) and improving the thin line reproducibility, the content of the styrene compound in the raw material monomer of the vinyl resin segment is preferably 70% by mass or more, or more. It is preferably 80% by mass or more, more preferably 90% by mass or more, and is 100% by mass or less, more preferably 100% by mass.

When raw material monomers constituting the vinyl resin segment contain raw material monomers other than styrene compounds, examples of raw material monomers include alkyl (meth)acrylate, benzyl (meth)acrylate, and dimethylaminoethyl (meth)acrylate. Olefins such as ethylene, propylene and butadiene; Halovinyls such as vinyl chloride; Vinyl esters such as vinyl acetate and vinyl propionate; Vinyl ethers such as methyl vinyl ether; Halogens such as vinylidene chloride vinylidene; and N-vinyl compounds such as N-vinylpyrrolidone. Among these, (meth)acrylic acid esters are preferred, and alkyl (meth)acrylates are more preferred.
The number of carbon atoms in the alkyl group in the alkyl (meth)acrylate is preferably 1 or more, more preferably 4 or more, still more preferably 6 or more, and is preferably 24 or less, more preferably 22 or less, and still more preferably 20. It is below.
Examples of alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, (iso)propyl (meth)acrylate, (iso- or tertiary) butyl (meth)acrylate, (meth)acrylate, ) (iso)amyl acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (iso)octyl (meth)acrylate, (iso)decyl (meth)acrylate, (meth)acrylic acid ( iso) dodecyl, (iso) palmityl (meth) acrylate, (iso) stearyl (meth) acrylate, (iso) behenyl (meth) acrylate and the like, preferably 2-ethylhexyl (meth) acrylate or ( Meth)stearyl acrylate, more preferably 2-ethylhexyl acrylate, stearyl methacrylate, and still more preferably 2-ethylhexyl acrylate.
In addition, "(iso or tertiary)" and "(iso)" mean both when these prefixes exist and when they do not exist, and when these prefixes do not exist, normal is indicated. Moreover, "(meth)acrylic acid" indicates acrylic acid or methacrylic acid.

When the raw material monomer constituting the vinyl resin segment contains a (meth)acrylic acid ester, the content of the (meth)acrylic acid ester in the raw material monomer of the vinyl resin segment is preferably 1% by mass or more, more preferably It is 3% by mass or more, more preferably 5% by mass or more, and preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less.
The total amount of the styrenic compound and the (meth)acrylic acid ester in the raw material monomers of the vinyl resin segment is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and even more preferably. is 100% by mass.

[Structural Unit Derived from Both Reactive Monomers]
The condensate (AT) preferably has structural units derived from bi-reactive monomers that are covalently bonded to the polyester resin segment and the vinyl resin segment.
The “structural unit derived from a bireactive monomer” means a unit obtained by reacting a functional group and an addition polymerizable group of a bireactive monomer.
Examples of addition polymerizable groups include carbon-carbon unsaturated bonds (ethylenically unsaturated bonds).
Examples of bi-reactive monomers include addition polymerizable monomers having at least one functional group selected from a hydroxyl group, a carboxyl group, an epoxy group, a primary amino group and a secondary amino group in the molecule. . Among these, from the viewpoint of reactivity, addition polymerizable monomers having at least one functional group selected from hydroxyl groups and carboxy groups are preferred, and addition polymerizable monomers having a carboxy group are more preferred.
Addition-polymerizable monomers having a carboxy group include, for example, acrylic acid, methacrylic acid, fumaric acid, and maleic acid. Among these, acrylic acid and methacrylic acid are preferred, and acrylic acid is more preferred, from the viewpoint of reactivity in both polycondensation reaction and addition polymerization reaction.
When the bireactive monomer is an addition-polymerizable monomer having a carboxy group, the amount of structural units derived from the bireactive monomer is preferably 0 per 100 mol parts of the alcohol component of the polyester resin segment of the condensate (AT). .5 mol parts or more, more preferably 1 mol parts or more, still more preferably 2 mol parts or more, and preferably 15 mol parts or less, more preferably 10 mol parts or less, still more preferably 7 mol parts or less.

The content of the vinyl resin segment in the condensate (AT) is preferably 5% by mass or more, more preferably 7% by mass or more, still more preferably 8% by mass, based on the total amount of the polyester resin segment and the vinyl resin segment. % by mass or more, more preferably 13% by mass or more, still more preferably 17% by mass or more, and preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 23% by mass or less. The content of the polyester resin segment in the condensate (AT) is preferably 70% by mass or more, more preferably 75% by mass or more, and still more preferably 77% by mass, based on the total amount of the polyester resin segment and the vinyl resin segment. % or more, and preferably 95% by mass or less, more preferably 93% by mass or less, even more preferably 92% by mass or less, even more preferably 87% by mass or less, and even more preferably 83% by mass or less. In addition, the structural unit derived from the bi-reactive monomer is included in the polyester resin segment in the calculation.

The content of structural units derived from both reactive monomers in the condensate (AT) is preferably 0.1% by mass or more, more preferably 0.2, based on the total amount of the polyester resin segment and the vinyl resin segment. % by mass or more, more preferably 0.3% by mass or more, and preferably 10% by mass or less, more preferably 7% by mass or less, and even more preferably 4% by mass or less.

The above amount is calculated based on the ratio of the amounts of the polyester resin segment, the raw material monomer of the vinyl resin segment, the bi-reactive monomer, and the radical polymerization initiator, and the mass of the polyester resin segment, etc. is the mass of water generated by polycondensation. Based on the mass excluding When a radical polymerization initiator is used, the mass of the radical polymerization initiator is included in the vinyl resin segment and calculated.

(Tertiary amine (T))
Examples of the tertiary amine (T) include a tertiary amine (T1) having a hydroxyalkyl group, a tertiary amine (T2) having a carboxyalkyl group, and a tertiary amine having an addition-polymerizable functional group ( T3).
Tertiary amines (T1) having a hydroxyalkyl group include triethanolamine, triisopropanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, N , N-dipropylethanolamine, N,N-diisopropylethanolamine, N,N-dibutylethanolamine, 3-dimethylamino-1-propanol, 3-diethylamino-1-propanol, 3-dipropylamino-1-propanol , 3-diisopropylamino-1-propanol, 3-dibutylamino-1-propanol, 4-dimethylamino-1-butanol, 4-diethylamino-1-butanol, 4-dipropylamino-1-butanol, 4-diisopropylamino -1-butanol, 4-dibutylamino-1-butanol, 3-dimethylamino-1,2-propanediol, 3-diethylamino-1,2-propanediol, 3-dipropylamino-1,2-propanediol, and 3-diisopropylamino-1,2-propanediol.
Tertiary amines (T2) having a carboxyalkyl group include N,N-dimethylglycine, N,N-diethylglycine, N,N-dipropylglycine, N,N-diisopropylglycine, N,N-dibutylglycine , N-methyliminodiacetic acid, N-ethyliminodiacetic acid, N-propyliminodiacetic acid, N-isopropyliminodiacetic acid, N-butyliminodiacetic acid, 1-pyrrolidineacetic acid, 1-piperidineacetic acid, nitrotriacetic acid, N-(2-carboxyethyl ) iminodiacetic acid, 3-dimethylaminopropionic acid, 3-diethylaminopropionic acid, 3-dipropylaminopropionic acid, 3-diisopropylaminopropionic acid, 3-dibutylaminopropionic acid, N-methyl-3,3'-iminodi Propionic acid, N-ethyl-3,3'-iminodipropionic acid, N-propyl-3,3'-iminodipropionic acid, N-isopropyl-3,3'-iminodipropionic acid, N-butyl-3 , 3′-iminodipropionic acid, 3-(1-pyrrolidine)propionic acid, 3-(1-piperidine)propionic acid, 3,3′,3″-nitrotripropionic acid and the like.
Examples of the tertiary amine (T3) having an addition-polymerizable functional group include N,N-dimethylallylamine, N,N-diethylallylamine, N,N-dipropylallylamine, N,N-diisopropylallylamine, N,N- dibutylallylamine, 1-allylpyrrolidine, 1-allylpiperidine, triallylamine and the like.
In addition, a monoester obtained by condensation reaction of a tertiary amine (T1) having a hydroxyalkyl group and dicarboxylic acid, and a condensation reaction of a tertiary amine (T1) having a hydroxyalkyl group and (meth)acrylic acid ( A meth)acrylic acid ester may be used as the tertiary amine (T). As the dicarboxylic acid, the dicarboxylic acids exemplified as the carboxylic acid component of the polyester resin segment can be used, and aliphatic dicarboxylic acids are preferred.
Among these, the tertiary amine (T) is preferably a tertiary amine (T1) having a hydroxyalkyl group for introduction into the condensate (AT).

The boiling point of the tertiary amine (T) at 1 atm is preferably 130°C or higher, more preferably 140°C or higher, and still more preferably 150°C or higher, from the viewpoint of productivity of the condensate (AT), and , preferably 300° C. or lower, more preferably 270° C. or lower, and still more preferably 250° C. or lower.
In addition, when using 2 or more types as a tertiary amine (T), the boiling point of a tertiary amine is calculated as a weighted average value.
The molecular weight of the tertiary amine (T) is preferably 230 or less, more preferably 210 or less, still more preferably 200 or less, and preferably 100 or more, from the viewpoint of increasing the positive charging property of the condensate (AT). is.

The tertiary amine (T) is preferably a tertiary amine (T1) having a hydroxyalkyl group, more preferably a hydroxyalkyl group having 2 or 3 carbon atoms and a direct amine having 1 to 4 carbon atoms. Tertiary amines having chain or branched alkyl groups, more preferably 3-dimethylamino-1-propanol, N-methyldiethanolamine, and N,N-dibutylethanolamine. These tertiary amines can be used singly or in combination of two or more.

The content of the structural unit derived from the tertiary amine (T) in the condensate (AT) improves the dielectric constant of the condensate (AT), increases the positive chargeability, and improves the fine line reproducibility. From the viewpoint of Preferably, it is 3% by mass or less.

(Composite resin (A))
The composite resin (A) includes a polyester resin segment that is a polycondensate of an alcohol component and a carboxylic acid component, and a vinyl resin segment that is an addition polymer of raw material monomers containing a styrene compound. Also, the composite resin (A) is preferably amorphous.
In the composite resin (A), it is preferable that the polyester resin segment and the vinyl resin segment are bonded to both reactive monomers via covalent bonds. The alcohol component and carboxylic acid component of the polyester resin segment, the raw material monomer of the vinyl resin segment, and the bi-reactive monomer include the alcohol component and carboxylic acid component of the polyester resin segment shown in the condensate (AT), and the vinyl resin segment. Examples thereof include those similar to those of the raw material monomer and the bi-reactive monomer, and the preferred ranges are also the same.

[Method for producing condensate (AT)]
A method for producing the condensate (AT) includes step 1 of condensing a polyester resin segment, a vinyl resin segment, and a tertiary amine (T) to obtain a reaction mixture containing the condensate (AT). .
The condensate (AT) is produced by a polycondensation step of polycondensing an alcohol component and a carboxylic acid component in the presence of a tertiary amine (T), and an addition polymerization of a raw material monomer for the vinyl resin segment and a bi-reactive monomer. You may manufacture by the method containing a polymerization process. In addition, the condensate (AT) is obtained by the polycondensation step of polycondensing the alcohol component and the carboxylic acid component, and the addition polymerization of the raw material monomer of the vinyl resin segment and the bi-reactive monomer in the presence of the tertiary amine (T). It may be produced by a method including an addition polymerization step of causing.
The addition polymerization step may be performed after the polycondensation step, the polycondensation step may be performed after the addition polymerization step, or the polycondensation step and the addition polymerization step may be performed simultaneously.
The condensate (AT) can be produced by condensing a composite resin (A) containing a polyester resin segment and a vinyl resin segment with a tertiary amine (T) to produce a condensate (AT'). preferable.

Condensation of the composite resin (A) and the tertiary amine (T) may be carried out by directly condensing the acid group of the composite resin (A) and the hydroxyalkyl group of the tertiary amine (T1) having a hydroxyalkyl group. It is often produced by condensing the hydroxyl group of the composite resin (A) and the hydroxyalkyl group of the tertiary amine (T1) having a hydroxyalkyl group via a dicarboxylic acid and/or a polyvalent carboxylic acid having a valence of 3 or more. Alternatively, it may be produced by direct condensation of the hydroxyl group of the composite resin (A) and the carboxyalkyl group of the tertiary amine (T2) having a carboxyalkyl group. As the polyvalent carboxylic acid, the carboxylic acid mentioned as the carboxylic acid component of the polyester resin segment can be used, preferably linear or branched aliphatic dicarboxylic acid, more preferably succinic acid, fumaric acid, and sebacic acid. One or more selected, more preferably fumaric acid.
As a method for producing the condensate (AT'), preferably, the acid group of the composite resin (A) and the hydroxyalkyl group of the tertiary amine (T) having a hydroxyalkyl group are directly condensed. is.

[Method for producing composite resin (A)]
The composite resin (A) may be produced, for example, by a method comprising a step A of polycondensing an alcohol component and a carboxylic acid component, and a step B of addition-polymerizing a raw material monomer of a vinyl-based resin segment and a bi-reactive monomer. good.
Process B may be performed after process A, process A may be performed after process B, or process A and process B may be performed simultaneously.
In step A, a part of the carboxylic acid component is subjected to a polycondensation reaction, and then step B is carried out. A method of further advancing the polycondensation reaction with the carboxy group of the constituent site derived from the reactive monomer is preferred.

In step A, if necessary, an esterification catalyst such as di(2-ethylhexanoic acid) tin (II), dibutyltin oxide, titanium diisopropoxybis(triethanolamine) is added to the alcohol component and the carboxylic acid component. 0.001 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the total amount of; Polycondensation may be carried out using 0.0001 parts by mass or more and 0.5 parts by mass or less per 100 parts by mass of the total amount.
Further, when a monomer having an unsaturated bond such as fumaric acid is used for polycondensation, it is preferably 0.0001 part by mass or more with respect to 100 parts by mass as the total amount of the alcohol component and the carboxylic acid component, if necessary. A radical polymerization inhibitor of 0.5 parts by mass or less may be used. Examples of radical polymerization inhibitors include 4-tert-butylcatechol.
The temperature of the polycondensation reaction is preferably 120° C. or higher, more preferably 130° C. or higher, still more preferably 140° C. or higher, and preferably 250° C. or lower, more preferably 240° C. or lower. In addition, you may perform polycondensation in an inert gas atmosphere.

Examples of the radical polymerization initiator for addition polymerization in step B include peroxides such as dibutyl peroxide, persulfates such as sodium persulfate, and 2,2′-azobis(2,4-dimethylvaleronitrile) such as azo compounds.
The amount of the radical polymerization initiator to be used is preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the raw material monomer for the vinyl resin segment.
The addition polymerization temperature is preferably 110° C. or higher, more preferably 130° C. or higher, and preferably 230° C. or lower, more preferably 220° C. or lower, still more preferably 210° C. or lower.

Condensation of the acid group of the composite resin (A) with the tertiary amine (T1) having a hydroxyalkyl group can be carried out by heating them and removing water generated by the dehydration reaction from the system by reducing pressure or the like. .
Further, when a monomer having an unsaturated bond such as fumaric acid is used, it is preferably 0.0001 part by mass or more and 0.5 part by mass with respect to 100 parts by mass as the total amount of the alcohol component and the carboxylic acid component, if necessary. Part by mass or less of a radical polymerization inhibitor may be used. Examples of radical polymerization inhibitors include 4-tert-butylcatechol.
The condensation reaction temperature is preferably 120° C. or higher, more preferably 130° C. or higher, still more preferably 140° C. or higher, and preferably 250° C. or lower, more preferably 230° C. or lower, further preferably 210° C. or lower. be. Note that the condensation may be performed in an inert gas atmosphere.

After obtaining the condensate (AT), it is preferred to include step 2 of steaming the reaction mixture containing the condensate (AT). By steaming the reaction mixture, unreacted tertiary amine (T) contained in the condensate can be efficiently removed.
Steaming may be performed by introducing water vapor into the reaction system, or may be performed by dropping ion-exchanged water into the reaction system to generate water vapor in the reaction system. From the viewpoint of simplicity of operation, it is preferable to drop ion-exchanged water into the reaction system to generate water vapor in the reaction system. In order to efficiently separate the tertiary amine (T) from the reaction mixture, the amount of steam or ion-exchanged water supplied is preferably 1 part by mass or more, or more than 100 parts by mass of the total amount of the condensate (AT). It is preferably 2 parts by mass or more, more preferably 3 parts by mass or more. In addition, from the viewpoint of simplifying the removal of moisture after steaming, the amount of water vapor or ion-exchanged water supplied is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, more preferably 6 parts by mass or less.

[Physical properties of condensate (AT)]
The dielectric constant of the condensate (AT) is preferably 2.50 × 10 ^-13 /cm or more, more preferably 2.70 × 10 ^-13 /cm or more, from the viewpoint of increasing positive chargeability and improving thin line reproducibility. cm or more, more preferably 2.80×10 ⁻¹³ /cm or more, still more preferably 2.85×10 ⁻¹³ /cm or more, and preferably 3.40×10 ⁻¹³ /cm or less, more preferably is 3.20×10 ⁻¹³ /cm or less, more preferably 3.10×10 ⁻¹³ /cm or less, further preferably 3.05×10 ⁻¹³ /cm or less.

The charge transfer speed in the condensate (AT) is preferably 0.020 or more, more preferably 0.025 or more, and still more preferably 0.027 or more from the viewpoint of improving charging stability and fine line reproducibility. Yes, and preferably 0.110 or less, more preferably 0.080 or less, still more preferably 0.050 or less.

The glass transition temperature of the condensate (AT) is preferably 30° C. or higher, more preferably 35° C. or higher, and still more preferably 40° C. or higher, and is preferably 80° C. or lower from the viewpoint of further improving low-temperature fixability. , more preferably 70° C. or lower, still more preferably 60° C. or lower.
The softening point of the condensate (AT) is preferably 70° C. or higher, more preferably 80° C. or higher, and still more preferably 90° C. or higher. It is more preferably 140° C. or lower, still more preferably 125° C. or lower.

The acid value of the condensate (AT) is preferably 2 mgKOH/g or more, more preferably 3 mgKOH/g or more, still more preferably 5 mgKOH/g or more, and preferably 20 mgKOH/g or less, more preferably 15 mgKOH/g. 13 mgKOH/g or less, more preferably 13 mgKOH/g or less.
The hydroxyl value of the condensate (AT) is preferably 20 mgKOH/g or more, more preferably 30 mgKOH/g or more, still more preferably 35 mgKOH/g or more, and preferably 60 mgKOH/g or less, more preferably 55 mgKOH/g. Below, more preferably 50 mgKOH/g or less.
The amine value of the condensate (AT) is preferably 2 mgKOH/g or more, more preferably 4 mgKOH/g or more, still more preferably 6 mgKOH/g or more, and preferably 20 mgKOH/g or less, more preferably 15 mgKOH/g. Below, more preferably 10 mgKOH/g or less.

The dielectric constant, charge transfer rate, glass transition temperature, softening point, acid value, hydroxyl value, and amine value of the condensate (AT) are determined by the type and amount of raw material monomers used, reaction temperature, reaction time, cooling rate, etc. can be adjusted as appropriate depending on the production conditions, and these values are determined by the method described in Examples.
When two or more condensates (AT) are used in combination, the dielectric constant, charge transfer rate, glass transition temperature, softening point, acid value, hydroxyl value, and amine value obtained as a mixture thereof are It is preferably within the aforementioned range.

The binder resin composition for toner of the present invention further contains other resins such as the composite resin (A) described above and the amorphous polyester resin (B) described later within a range that does not impair the effects of the present invention. may
The content of the condensate (AT) is preferably 25% by mass or more, more preferably 30% by mass or more, and more preferably 30% by mass or more in the binder resin composition, from the viewpoint of increasing the positive chargeability and improving the fine line reproducibility. It is preferably 35% by mass or more, and preferably 55% by mass or less, more preferably 50% by mass or less, and even more preferably 45% by mass or less.

(Amorphous polyester resin (B))
The binder resin composition for toner of the present invention contains an amorphous polyester resin (B) (hereinafter also simply referred to as "resin (B)") from the viewpoint of improving low-temperature fixability and hot offset resistance. It may be contained further.

The resin (B) is preferably, for example, an amorphous polyester resin containing a polycondensate of an alcohol component and a carboxylic acid component.
Polyester resins include polyester resins and modified polyester resins. Examples of modified polyester resins include urethane-modified polyester resins and epoxy-modified polyester resins. Among these, amorphous polyester resins, which are polycondensates of alcohol components and carboxylic acid components, are preferred.

The alcohol component is an alkylene oxide adduct of an aromatic diol similar to the alcohol component of the polyester resin segment of the composite resin (A) described above, a linear or branched aliphatic diol, an alicyclic diol, or a trivalent or higher polyvalent Among them, alkylene oxide adducts of aromatic diols are preferred, more preferably alkylene oxide adducts of bisphenol A, still more preferably bisphenol A [2, 2-bis(4-hydroxyphenyl)propane] and ethylene oxide adducts of bisphenol A. These may use 1 type(s) or 2 or more types.

Examples of carboxylic acid components include dicarboxylic acids and polycarboxylic acids having a valence of 3 or more.
The dicarboxylic acid includes the same dicarboxylic acid as the carboxylic acid component of the polyester resin segment described above, such as aromatic dicarboxylic acid, linear or branched aliphatic dicarboxylic acid, and alicyclic dicarboxylic acid. Among these, at least one selected from aromatic dicarboxylic acids and linear or branched aliphatic dicarboxylic acids is preferable.
The amount of the aromatic dicarboxylic acid in the carboxylic acid component is preferably 40 mol% or more, more preferably 50 mol% or more, still more preferably 60 mol% or more, and preferably 95 mol% or less, more preferably 85 mol% or less, More preferably, it is 75 mol % or less.
Examples of the polycarboxylic acid having a valence of 3 or more include the same polycarboxylic acid having a valence of 3 or more as the carboxylic acid component of the polyester resin segment described above.

The amount of linear or branched aliphatic dicarboxylic acid is preferably 1 mol% or more, more preferably 3 mol% or more, still more preferably 5 mol% or more, and preferably 60 mol% or less, more preferably 60 mol% or less, in the carboxylic acid component. is 30 mol % or less, more preferably 20 mol % or less.

When a trivalent or higher polycarboxylic acid is contained, the amount of the trivalent or higher polycarboxylic acid is preferably 3 mol% or more, more preferably 5 mol% or more, and still more preferably 8 mol% or more in the carboxylic acid component. , and preferably 30 mol % or less, more preferably 25 mol % or less, and still more preferably 20 mol % or less.
One or more of these carboxylic acid components may be used.

The equivalent ratio of the carboxy group of the carboxylic acid component to the hydroxyl group of the alcohol component [COOH group/OH group] is preferably 0.7 or more, more preferably 0.8 or more, and preferably 1.3 or less, or more. It is preferably 1.2 or less.

Resin (B) may be produced, for example, by step A of polycondensing an alcohol component and a carboxylic acid component.
Step A is the same as Step A described in the method for producing composite resin (A), and the preferred range is also the same.

[Physical properties of amorphous polyester resin (B)]
The glass transition temperature of the resin (B) is preferably 30° C. or higher, more preferably 40° C. or higher, and still more preferably 50° C. or higher. It is more preferably 80° C. or lower, still more preferably 70° C. or lower.
The softening point of the resin (B) is preferably 70° C. or higher, more preferably 90° C. or higher, and still more preferably 100° C. or higher. It is preferably 150° C. or lower, more preferably 145° C. or lower.

The acid value of the resin (B) is preferably 1 mgKOH/g or more, more preferably 2 mgKOH/g or more, still more preferably 3 mgKOH/g or more, and preferably 20 mgKOH/g or less, more preferably 15 mgKOH/g or less. and more preferably 10 mgKOH/g or less.
The hydroxyl value of the resin (B) is preferably 20 mgKOH/g or more, more preferably 25 mgKOH/g or more, still more preferably 30 mgKOH/g or more, and preferably 50 mgKOH/g or less, more preferably 45 mgKOH/g or less. and more preferably 40 mgKOH/g or less.
The glass transition temperature, softening point, acid value, and hydroxyl value of the resin (B) can be appropriately adjusted depending on the type and amount of raw material monomer used, and production conditions such as reaction temperature, reaction time, and cooling rate. Moreover, those values are determined by the method described in Examples.
When two or more resins (B) are used in combination, the glass transition temperature, softening point, acid value, and hydroxyl value obtained as a mixture thereof are preferably within the ranges described above. .

The content of the resin (B) in the binder resin composition is preferably 35% by mass or more, more preferably 40% by mass or more, still more preferably 45% by mass or more, and preferably 65% by mass or less. More preferably 60 mass % or less, still more preferably 55 mass % or less.

(Crystalline polyester resin (C))
The binder resin composition for toner of the present invention preferably contains a crystalline polyester resin (C) (hereinafter also simply referred to as “resin (C)”) from the viewpoint of improving low-temperature fixability.

Resin (C) is, for example, a crystalline polyester resin that is a polycondensate of an alcohol component and a carboxylic acid component.
As the alcohol component, α,ω-aliphatic diols are preferred.
The number of carbon atoms in the α,ω-aliphatic diol is preferably 2 or more, more preferably 4 or more, still more preferably 6 or more, and preferably 16 or less, more preferably 14 or less, still more preferably 12 or less. be.
Examples of α,ω-aliphatic diols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, and 1,14-tetradecanediol mentioned. Among these, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol and 1,12-dodecanediol are preferred, and 1,6-hexanediol is more preferred. .

The amount of the α,ω-aliphatic diol in the alcohol component is preferably 80 mol% or more, more preferably 85 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% or more, and 100 mol% or less. , more preferably 100 mol %.

The alcohol component may contain other alcohol components different from the α,ω-aliphatic diol. Examples of other alcohol components include aliphatic diols other than α,ω-aliphatic diols such as 1,2-propanediol and neopentyl glycol; aromatic diols such as alkylene oxide adducts of bisphenol A; Trihydric or higher alcohols such as erythritol and trimethylolpropane are included. One or more of these alcohol components may be used.

As the carboxylic acid component, aliphatic dicarboxylic acids are preferable, and linear aliphatic dicarboxylic acids are more preferable.
The number of carbon atoms in the aliphatic dicarboxylic acid is preferably 4 or more, and preferably 14 or less, more preferably 12 or less.
Aliphatic dicarboxylic acids include, for example, fumaric acid, sebacic acid, dodecanedioic acid, and tetradecanedioic acid. Among these, fumaric acid, sebacic acid and tetradecanedioic acid are preferred, and fumaric acid is more preferred. One or more of these carboxylic acid components may be used.

The amount of the aliphatic dicarboxylic acid in the carboxylic acid component is preferably 80 mol% or more, more preferably 85 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% or more, and 100 mol% or less, More preferably, it is 100 mol %.

The carboxylic acid component may contain other carboxylic acid components different from the aliphatic dicarboxylic acid. Other carboxylic acid components include, for example, aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid; and trivalent or higher polyvalent carboxylic acids. One or more of these carboxylic acid components may be used.

The equivalent ratio of the carboxy group of the carboxylic acid component to the hydroxyl group of the alcohol component [COOH group/OH group] is preferably 0.7 or more, more preferably 0.8 or more, and preferably 1.3 or less, or more. It is preferably 1.2 or less.

Resin (C) may be produced, for example, by step A of polycondensing an alcohol component and a carboxylic acid component.
Step A is the same as Step A described in the method for producing the composite resin (A), and the preferred range is also the same except for the temperature of the polycondensation reaction.
The temperature of the polycondensation reaction in the method for producing the resin (C) is preferably 110°C or higher, more preferably 120°C or higher, still more preferably 130°C or higher, and preferably 250°C or lower, more preferably 240°C. 230° C. or less, more preferably 230° C. or less. In addition, you may perform polycondensation in an inert gas atmosphere.

[Physical properties of crystalline polyester resin (C)]
The softening point of the resin (C) is preferably 60° C. or higher, more preferably 70° C. or higher, and still more preferably 80° C. or higher from the viewpoint of toner storage stability, and from the viewpoint of further improving low-temperature fixability. , preferably 150° C. or lower, more preferably 140° C. or lower, and still more preferably 130° C. or lower.
The melting point of the resin (C) is preferably 60° C. or higher, more preferably 70° C. or higher, and even more preferably 80° C. or higher from the viewpoint of toner storage stability. It is preferably 150° C. or lower, more preferably 140° C. or lower, and still more preferably 130° C. or lower.

The acid value of resin (C) is preferably 1 mgKOH/g or more, more preferably 2 mgKOH/g or more, still more preferably 3 mgKOH/g or more, and preferably 20 mgKOH/g or less, more preferably 15 mgKOH/g or less. and more preferably 10 mgKOH/g or less.

The softening point, melting point, and acid value of the resin (C) can be appropriately adjusted depending on the type and amount of raw material monomer used, and production conditions such as reaction temperature, reaction time, and cooling rate. Obtained by the method described. When two or more resins (C) are used in combination, the softening point, melting point, and acid value obtained as a mixture thereof are preferably within the above ranges.

The content of the resin (C) in the binder resin composition is preferably 3% by mass or more, more preferably 5% by mass or more, still more preferably 8% by mass or more, and preferably 20% by mass or less. It is more preferably 18% by mass or less, still more preferably 15% by mass or less.

[Electrophotographic toner]
The electrophotographic toner of the present invention (hereinafter also referred to as "the toner of the present invention") contains the binder resin composition for toner, and preferably contains a colorant and the binder resin composition for toner. contains.
The toner of the present invention contains, for example, toner base particles and an external additive.
The toner base particles contain the binder resin composition for toner, and preferably contain a colorant and the binder resin composition for toner.
The toner base particles may contain, for example, a colorant derivative, a charge control agent, a release agent such as wax, and other additives.
The content of the binder resin composition for toner is preferably 60% by mass or more, more preferably 65% by mass or more in the toner base particles, from the viewpoint of increasing the positive chargeability of the toner and improving the reproducibility of fine lines. , more preferably 70% by mass or more, and preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less.

[Coloring agent]
In the present invention, the toner base particles preferably contain a colorant.
As the colorant, all dyes, pigments, etc. used as colorants for toners can be used.
Examples of colorants include carbon black, phthalocyanine blue (eg, pigment blue 15:3), permanent brown FG, brilliant first scarlet, pigment green B, rhodamine-B base, solvent red 49, solvent red 146, and solvent blue 35. , quinacridone, carmine 6B, disazo yellow. The toner may be black toner or color toner other than black.
The content of the colorant in the toner base particles is preferably 1% by mass or more, more preferably 3% by mass or more, and is preferably 25% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass. % by mass or less.

〔Release agent〕
In the present invention, the toner base particles preferably contain a release agent.
Release agents include, for example, polypropylene wax, polyethylene wax, polypropylene polyethylene copolymer wax; hydrocarbon waxes such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax, and Sasol wax; and oxides thereof; carnauba wax. , montan waxes or their deoxidized waxes, ester waxes such as fatty acid ester waxes; fatty acid amides, fatty acids, higher alcohols, and fatty acid metal salts. These may use 1 type(s) or 2 or more types.

The melting point of the release agent is preferably 60° C. or higher, more preferably 70° C. or higher, and is preferably 160° C. or lower, more preferably 140° C. or lower, still more preferably 120° C. or lower, and still more preferably 100° C. or lower. is.
The content of the release agent in the toner base particles is preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 2% by mass or more, and still more preferably 3% by mass or more, and It is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less.

[Charge control agent]
The toner of the present invention may contain a charge control agent. The charge control agent may contain either a positive charge control agent or a negative charge control agent. Among these, positive charge control agents are preferred.
Examples of positive charge control agents include nigrosine dyes such as "Nigrosine Base EX", "Oil Black BS", "Oil Black SO", "Bontron (registered trademark) N-01", "Bontron (registered trademark) N- 04", "Bontron (registered trademark) N-07", "Bontron (registered trademark) N-09", "Bontron (registered trademark) N-11" (manufactured by Orient Chemical Industry Co., Ltd.), etc.; tertiary amines as a side chain, a quaternary ammonium salt compound, such as "Bontron (registered trademark) P-51" (manufactured by Orient Chemical Industry Co., Ltd.), cetyltrimethylammonium bromide, "COPY CHARGE PX VP435" ( Clariant Co., Ltd.), etc.; polyamine resins, such as "AFP-B" (Orient Chemical Industry Co., Ltd.); imidazole derivatives, such as "PLZ-2001" and "PLZ-8001" (manufactured by Shikoku Kasei Kogyo Co., Ltd.) etc.; styrene-acrylic resins such as “FCA-701PT” and “FCA-201-PS” (manufactured by Fujikura Kasei Co., Ltd.).

Examples of negatively chargeable charge control agents include metallized azo dyes such as "Varifast (registered trademark) Black 3804", "Bontron (registered trademark) S-31", "Bontron (registered trademark) S-32", "Bontron (registered trademark) S-34”, “Bontron (registered trademark) S-36” (manufactured by Orient Chemical Industry Co., Ltd.), “Izenspiron Black TRH”, “T-77” (Hodogaya Chemical Industry Co., Ltd. manufactured by), etc.; metal compounds of benzylic acid compounds, such as “LR-147” and “LR-297” (manufactured by Nihon Carlit Co., Ltd.), etc.; metal compounds of salicylic acid compounds, such as “Bontron (registered trademark) E -81”, “Bontron (registered trademark) E-84”, “Bontron (registered trademark) E-88”, “Bontron E-304” (manufactured by Orient Chemical Industry Co., Ltd.), “TN-105” (maintenance copper phthalocyanine dyes; quaternary ammonium salts such as "COPY CHARGE PX VP434" (manufactured by Clariant), nitroimidazole derivatives and the like; organometallic compounds and the like. One or more of these charge control agents may be used.

The content of the charge control agent is preferably 1 part by mass or more, more preferably 5 parts by mass or more, still more preferably 10 parts by mass or more with respect to 100 parts by mass of the total binder resin component of the toner. is 25 parts by mass or less, more preferably 20 parts by mass or less, and still more preferably 18 parts by mass or less.

[Other additives]
The toner base particles contain other additives such as magnetic powder, fluidity improver, conductivity modifier, reinforcing filler such as fibrous substance, antioxidant, anti-aging agent, and cleaning improver. may be contained as appropriate.

The content of the toner base particles in the toner of the present invention is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and is 100% by mass or less, preferably 99% by mass. % or less.

The volume median particle size ( _D50 ) of the toner base particles is preferably 2 μm or more, more preferably 3 μm or more, still more preferably 4 μm or more, and is preferably 20 μm or less, more preferably 15 μm or less, and still more preferably 10 μm or less. As used herein, the volume-median particle size (D ₅₀ ) means a particle size at which the cumulative volume frequency calculated as a volume fraction is 50%, calculated from the smaller particle size.

[External additive]
The toner of the present invention may further contain an external additive in order to improve fluidity. Examples of external additives include fine particles of inorganic materials 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. be done. These may be used alone or in combination of two or more. Among these external additives, silica is preferred, and hydrophobic silica treated with a hydrophobizing agent is more preferred.

Hydrophobizing agents include, for example, hexamethyldisilazane (HMDS), dimethyldichlorosilane (DMDS), silicone oil, octyltriethoxysilane (OTES), and methyltriethoxysilane. Among these, hexamethyldisilazane is preferred.

When surface treatment of the toner base particles is performed using an external additive, the content of the external additive in the toner of the present invention is set to 100 parts by mass of the toner base particles, from the viewpoint of the chargeability and fluidity of the toner. On the other hand, it is preferably 0.5 parts by mass or more, more preferably 0.8 parts by mass or more, still more preferably 1 part by mass or more, and preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and further Preferably, it is 4 parts by mass or less.

The toner of the present invention may be a toner obtained by any known method such as a melt-kneading method, an emulsion phase inversion method, a suspension polymerization method, an emulsion aggregation method, etc. However, the productivity and the dispersibility of the colorant may be improved. From this point of view, a pulverized toner obtained by a melt-kneading method is preferable.
In the melt-kneading method, after uniformly dispersing the binder resin composition for toner, the colorant, and, if necessary, a property improving agent such as a release agent, the mixture is melt-kneaded, cooled, pulverized, and melted by a known method. By classifying, a toner having a volume median particle size (D ₅₀ ) of 2 μm or more and 20 μm or less can be obtained.

The toner of the present invention is used for developing latent images formed in electrophotography, electrostatic recording, electrostatic printing, and the like. The toner can be used as a one-component developer, or mixed with a carrier and used as a two-component developer.

EXAMPLES The present invention will be specifically described below with reference to Examples, but the present invention is not limited to these Examples. Physical properties such as resins were measured by the following methods.

[measurement]
[Resin softening point, crystallinity index, melting point, glass transition temperature]
(1) Softening point Using a flow tester "CFT-500D" (manufactured by Shimadzu Corporation), while heating a 1 g sample at a temperature increase rate of 6 ° C./min, a load of 1.96 MPa is applied with a plunger, and the diameter It was extruded through a 1 mm, 1 mm long nozzle. The amount of plunger depression of the flow tester was plotted against the temperature, and the softening point was defined as the temperature at which half of the sample flowed out.

(2) Crystallinity index Using a differential scanning calorimeter "Q100" (manufactured by TA Instruments Japan Co., Ltd.), 0.02 g of the sample was weighed into an aluminum pan, and the temperature was lowered to 0 at a cooling rate of 10 ° C./min. Cooled to °C. Next, the sample was allowed to stand still for 1 minute, then heated to 180°C at a heating rate of 10°C/min, and the calorific value was measured. Among the observed endothermic peaks, the temperature of the peak with the maximum peak area is defined as the maximum endothermic peak temperature (1), and (softening point (°C)) / (maximum endothermic peak temperature (1) (°C)) A crystallinity index was determined.

(3) Melting point and glass transition temperature Using a differential scanning calorimeter "Q100" (manufactured by TA Instruments Japan Co., Ltd.), 0.02 g of a sample was weighed in an aluminum pan and heated to 200 ° C. , and then cooled to 0° C. at a cooling rate of 10° C./min. Then, the temperature of the sample was increased at a temperature increase rate of 10°C/min, and the calorie was measured. Among the observed endothermic peaks, the temperature of the peak with the maximum peak area was defined as the maximum endothermic peak temperature (2). In the case of a crystalline resin, the peak temperature was taken as the melting point.
In the case of an amorphous resin, when a peak is observed, the temperature of the peak is measured. The temperature at the point of intersection with the extended line of the baseline on the low temperature side was defined as the glass transition temperature.

[Acid value and hydroxyl value of resin]
Measured according to JIS K0070:1992. However, chloroform was used as the measurement solvent.

[Amine value of resin]
1.0 to 1.5 g of the sample was correctly weighed in a 150 mL beaker, and about 70 mL of ethyl alcohol was added to dissolve the sample to obtain a sample solution. 2 to 3 drops of phenolphthalein indicator solution was added to the sample solution, and 10 mass % sodium hydroxide solution was added to make it weakly alkaline. Using a potentiometric titrator, titration was performed with a 0.2 mol/L alcoholic hydrochloric acid standard solution until the first and second equivalence points were passed. After that, the amine value was calculated by the following formula 1.

In Formula 1, A, B, and f are as follows.
A: Amount (mL) of 0.2 mol/L alcoholic hydrochloric acid standard solution required for titration up to the first equivalence point
B: Amount (mL) of 0.2 mol/L alcoholic hydrochloric acid standard solution required for titration up to the second equivalence point
f: factor of 0.2 mol/L alcoholic hydrochloric acid standard solution

[Dielectric constant]
A resin sample of 3 g was weighed and melt-pressed with a hot press under the conditions of 75° C. and 20 MPa to prepare disk-shaped resin pellets. After that, the dielectric constant was measured with an electrode for dielectric measurement "Agilent 16451B" (manufactured by Agilent Technologies).

[Charge transfer speed]
A resin sample of 0.1 g was weighed and dissolved in 5 mL of chloroform. Drop 0.2 mL of a resin chloroform solution into an aluminum disk-shaped container with a diameter of 13 mm (manufactured by Nanoseeds Co., Ltd.: NS-D series sample pan for electrostatic diffusivity measurement), and dry at room temperature under a nitrogen stream to obtain a measurement sample. and The surface of the measurement sample was measured with a surface potential meter (manufactured by Nanoseeds Co., Ltd.: electrostatic diffusivity measuring device NS-D100) to obtain the charge transfer rate.

[Volume Median Particle Diameter _D50 of Toner Base Particles]
The volume-median particle diameter _D50 of the toner base particles was measured as follows.
・Measuring machine: “Coulter Multisizer (registered trademark) III” (manufactured by Beckman Coulter, Inc.)
・Aperture diameter: 50 μm
・ Analysis software: “Multisizer (registered trademark) III version 3.51” (manufactured by Beckman Coulter, Inc.)
・ Electrolyte: “Isoton (registered trademark) II” (manufactured by Beckman Coulter, Inc.)
- Dispersion: Polyoxyethylene lauryl ether "Emulgen (registered trademark) 109P" (manufactured by Kao Corporation, HLB: 13.6) was dissolved in the electrolytic solution to obtain a dispersion having a concentration of 5% by mass.
Dispersion conditions: 10 mg of a toner measurement sample was added to 5 mL of the dispersion liquid, dispersed for 1 minute with an ultrasonic disperser, then 25 mL of an electrolytic solution was added, and dispersed for 1 minute with an ultrasonic disperser. , to prepare a sample dispersion.
Measurement conditions: By adding the sample dispersion to 100 mL of the electrolytic solution, the particle size of 30,000 particles is adjusted to a concentration that can be measured in 20 seconds, and then 30,000 particles are measured. The volume median particle size _D50 was determined from the distribution.

[Resin production]
Production Example A1 (condensate AT'-1)
3535 g of the propylene oxide (2.2) adduct of bisphenol A and 1407 g of the ethylene oxide (2.2) adduct of bisphenol A were placed in a 10-liter four-way flask equipped with a dehydration tube equipped with a nitrogen inlet, a stirrer and a thermocouple. It was placed in a three-necked flask and heated to 100°C, then 1880 g of terephthalic acid was added and the temperature was raised to 160°C. A mixture of 1,592 g of styrene, 42 g of acrylic acid, and 64 g of dibutyl peroxide was added dropwise over 1 hour while the temperature was kept at 160° C., reacted for 60 minutes, the temperature was raised to 200° C., and the pressure in the flask was further lowered. , and 8 kPa for 1 hour. After that, 35 g of di(2-ethylhexanoic acid) tin (II) and 3.5 g of gallic acid were added, the temperature was raised to 235° C., and reaction was carried out at 235° C. for 8 hours. After that, the mixture was cooled to 150° C., 193 g of fumaric acid, 3.5 g of 4-tert-butylcatechol and 169 g of 3-dimethylamino-1-propanol were added, the temperature was raised to 160° C., and the mixture was reacted for 1 hour. After that, the temperature was raised to 200° C. at 10° C./h, and 350 g of deionized water was added dropwise over 1 hour to perform steaming. After that, the pressure in the flask was lowered, and reaction was carried out under reduced pressure at 8 kPa for 1 hour to obtain condensate AT'-1.

Production Examples A2 and A3 (condensates AT'-2 and AT'-3)
Condensates AT'-2 and AT'-3 were obtained in the same manner as in Production Example A1, except that 3-dimethylamino-1-propanol was changed to a tertiary amine shown in Table 1. .

Production Example A4 (condensate AT'-4)
Condensate AT'-4 was obtained in the same manner as in Production Example A1, except that steaming was not carried out in Production Example A1.

Production Example A5 (Resin A-1)
3607 g of the propylene oxide (2.2) adduct of bisphenol A and 1436 g of the ethylene oxide (2.2) adduct of bisphenol A were placed in a 10-liter four-way flask equipped with a dehydration tube equipped with a nitrogen inlet, a stirrer and a thermocouple. The mixture was placed in a one-necked flask and heated to 100°C, then 1919 g of terephthalic acid was added and the temperature was raised to 160°C. A mixture of 1,624 g of styrene, 42 g of acrylic acid, and 65 g of dibutyl peroxide was added dropwise over 1 hour while the temperature was maintained at 160° C., reacted for 60 minutes, the temperature was raised to 200° C., and the pressure in the flask was further lowered. , and 8 kPa for 1 hour. After that, 36 g of di(2-ethylhexanoic acid) tin (II) and 3.6 g of gallic acid were added, the temperature was raised to 235° C., and the mixture was reacted at 235° C. for 8 hours. After that, the mixture was cooled to 150° C., 196 g of fumaric acid and 3.6 g of 4-tert-butylcatechol were added, the temperature was raised to 160° C., and the mixture was reacted for 1 hour. After that, the temperature was raised to 200°C at 10°C/h. After that, the pressure in the flask was lowered, and reaction was carried out under reduced pressure for 1 hour at 8 kPa to obtain composite resin A-1.

Production Example A6 (Resin A-2)
Composite resin A-2 was obtained in the same manner as in Production Example A5, except that 350 g of deionized water was added dropwise over 1 hour to perform steaming.

＊１：ＢＰＡ－ＰＯはビスフェノールＡのポリオキシプロピレン（２，２）付加物を意味する。ＢＰＡ－ＥＯはビスフェノールＡのポリオキシエチレン（２，２）付加物を意味する。
＊２：ポリエステル樹脂セグメントの原料モノマーのアルコール成分を１００モル部としたときの原料モノマー及び両反応性モノマーを構成する各モノマーのモル部を意味する。
＊３：ビニル系樹脂セグントの総量中における、原料モノマーを構成する各モノマーの含有量（質量％）を意味する。
＊４：ビニル系樹脂セグメントの総量を１００質量部としたときの、重合開始剤の添加量（質量部）を意味する。
＊５：縮合物（ＡＴ’）の総量中における、第三級アミン（Ｔ）の含有量（質量％）を意味する。
＊６：縮合物（ＡＴ’）の総量を１００質量部としたときの、イオン交換水の添加量（質量部）を意味する。
＊７：ポリエステル樹脂セグメント及びビニル系樹脂セグメントの合計量に対する、ビニル系樹脂セグメントの含有量（質量％）を意味する。

*1: BPA-PO means polyoxypropylene (2,2) adduct of bisphenol A. BPA-EO means polyoxyethylene (2,2) adduct of bisphenol A.
*2: Refers to the mole parts of each monomer constituting the raw material monomer and the bi-reactive monomer when the alcohol component of the raw material monomer of the polyester resin segment is taken as 100 mole parts.
*3: Indicates the content (% by mass) of each monomer constituting the raw material monomer in the total amount of the vinyl resin segment.
*4: Indicates the amount (parts by mass) of the polymerization initiator added when the total amount of the vinyl resin segment is 100 parts by mass.
*5: Indicates the content (% by mass) of the tertiary amine (T) in the total amount of the condensate (AT').
*6: Means the added amount (parts by mass) of ion-exchanged water when the total amount of condensate (AT') is 100 parts by mass.
*7: Indicates the content (% by mass) of the vinyl resin segment with respect to the total amount of the polyester resin segment and the vinyl resin segment.

Production Example B (Resin B-1)
4477 g of the propylene oxide (2.2) adduct of bisphenol A and 1782 g of the ethylene oxide (2.2) adduct of bisphenol A were added to a 10 liter 4-liter flask equipped with a dehydration tube equipped with a nitrogen inlet, a stirrer and a thermocouple. After the temperature was raised to 160° C., 1699 g of terephthalic acid, 481 g of trimellitic acid, 561 g of 2-dodecen-1-ylsuccinic anhydride, and 45 g of di(2-ethylhexanoic acid)tin(II) were added. was added, the temperature was raised to 235° C., and the reaction was carried out at 235° C. for 7 hours. After that, the pressure in the flask was lowered, and reaction was carried out under reduced pressure at 8 kPa for 1 hour to obtain Resin B-1 as an amorphous polyester resin.

Production Example C (Resin C-1)
4539 g of 1,6-hexanediol was placed in a 10-liter four-necked flask equipped with a dehydration tube equipped with a nitrogen inlet tube, a stirrer and a thermocouple, heated to 100° C., 4462 g of fumaric acid, 18 g of di(2-ethylhexanoic acid) tin (II) and 4.5 g of 4-tert-butylcatechol were added, and the temperature was raised to 140°C. After reacting for 1 hour, the temperature was raised to 150° C. and the reaction was continued for 1 hour. The temperature was raised to 200° C. at a rate of 10° C./h, and the mixture was reacted at 8.0 kPa for 3 hours to obtain Resin C-1 as a crystalline polyester resin.

[Toner manufacturing]
Examples 1-4 and Comparative Examples 1-2
40 parts by mass of condensates AT'-1 to 4, resin A-1, or resin A-2 shown in Table 4, 50 parts by mass of resin B-1 as an amorphous polyester resin, and resin C as a crystalline polyester resin -1 10 parts by mass, colorant "ECB-301" (manufactured by Dainichiseika Kogyo Co., Ltd.) 6 parts by mass, mold release agent "HNP-9" (manufactured by Nippon Seiro Co., Ltd.) 7 parts by mass, positive chargeability 15 parts by mass of the charge control agent "FCA-201-PS" (manufactured by Fujikura Kasei Co., Ltd.) was stirred for 3 minutes at a rotation speed of 1500 r/min (peripheral speed of 21.6 m/sec) using a Henschel mixer, and then mixed in the same direction. Melt-kneading was performed using a rotating twin-screw extruder (manufactured by Ikegai Co., Ltd., trade name: PCM-30, shaft diameter 2.9 cm, shaft cross-sectional area 7.06 cm ² ). The rotation speed of the rolls was 200 r/min (peripheral speed of 0.30 m/sec), the set barrel temperature was 1000°C, and the kneaded product was supplied at a rate of 10 kg/h (amount of mixture supplied per unit cross-sectional area of the shaft: 1.42 kg). /h·cm ² ).

The resulting kneaded product was rolled and cooled with cooling rolls, and then coarsely pulverized to about 1 mm using a hammer mill. The obtained coarsely pulverized material is finely pulverized and classified by an air jet mill (manufactured by Nippon Pneumatic Co., Ltd., trade name: IDS) to obtain toner base particles having a volume median particle diameter (D ₅₀ ) of 7.0 μm. rice field.
100 parts by mass of the obtained toner base particles, and 0.5 parts by mass of hydrophobic silica "TG-820F" (manufactured by Cabot Specialty Chemicals, Inc., number average particle diameter: 8 nm) as an external additive, hydrophobic Silica “NA-50Y” (manufactured by Nippon Aerosil Co., Ltd., number average particle diameter: 30 nm) 2.0 parts by mass, and polytetrafluoroethylene fine particles “KTL-500F” (manufactured by Kitamura Co., Ltd., number average particle diameter: 500 nm) ) were mixed for 3 minutes at 2100 r/min (peripheral speed 29 m/sec) in a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) to obtain a toner.

[Evaluation of image quality]
[Fine line reproducibility]
The toner obtained above was mounted in a non-magnetic one-component developing device (manufactured by Brother Industries, Ltd., trade name: HL-2040), and a 1 dot/3 space/horizontal line pattern was printed under an environment of 25° C. and a relative humidity of 50%. , Confirm the reproducibility of 1 dot line with a digital microscope (manufactured by Olympus Co., Ltd., product name: DSX510, using a 50x lens, observation conditions: 693x), and evaluate the fine line reproducibility with the following criteria A to D. bottom. If the quality is equal to or higher than the standard B, the image quality is excellent. Table 4 shows the results.
A: There are 5 or less discontinuities in a 1-dot line (1 line/cm).
B: 6 or more and 12 or less discontinuities exist in 1 dot line (1 line/cm).
C: 13 or more and 20 or less discontinuities exist in 1 dot line (1 line/cm).
D: 21 or more discontinuities exist in 1 dot line (1 line/cm).

From the results of Examples and Comparative Examples, it was found that the toner using the binder resin composition for toner of the present invention is excellent in fine line reproducibility and improves the image quality of printed matter. It is believed that this is because the condensate (AT) contained in the binder resin composition for toner of the present invention has improved dielectric constant and charge transfer speed, resulting in increased positive chargeability.

Claims (9)

A polyester resin segment that is a polycondensate of a carboxylic acid component containing 80 mol % or more of an alcohol component and an aromatic dicarboxylic acid, a vinyl resin segment that is an addition polymer of a raw material monomer containing a styrene compound, and a tertiary amine ( T) and a binder resin composition for toner containing a condensate (AT) of T). Claim 1, wherein the condensate (AT) is a condensate (AT') of a composite resin (A) containing the polyester resin segment and the vinyl resin segment, and the tertiary amine (T). 3. The binder resin composition for toner according to . 3. The binder resin composition for toner according to claim 1, wherein the tertiary amine (T) is a tertiary amine (T1) having a hydroxyalkyl group. 4. The binder resin composition for toner according to any one of claims 1 to 3, wherein the content of the styrene compound in the raw material monomers of said vinyl resin segment is 70% by mass or more. 5. The binder resin composition for toner according to claim 1, wherein the content of said vinyl resin segment in said condensate (AT) is 5% by mass or more and 30% by mass or less. 6. The binder resin composition for toner according to claim 1, wherein the condensate (AT) contains 0.5% by mass or more and 5% by mass or less of structural units derived from the tertiary amine (T). . 7. The binder resin composition for toner according to claim 1, wherein the condensate (AT) has an amine value of 2 mgKOH/g or more and 20 mgKOH/g or less. An electrophotographic toner containing the binder resin composition for toner according to any one of claims 1 to 7. 8. The method for producing a binder resin composition for toner according to any one of claims 1 to 7, comprising the following steps 1 and 2.
Step 1: Step of condensing a polyester resin segment, a vinyl resin segment, and a tertiary amine (T) to obtain a reaction mixture containing a condensate (AT) Step 2: The reaction mixture obtained in Step 1 the process of steaming