JP2019066539A - Binder resin composition for electrophotographic toner - Google Patents

Abstract

To provide a binder resin composition for an electrophotographic toner that has excellent low-temperature fixability and charge stability, and a crystalline polyester resin.SOLUTION: The present invention provides: (1) a binder resin composition for an electrophotographic toner containing a crystalline polyester resin C and an amorphous resin A, where the crystalline polyester resin C is a polycondensate of an alcohol component containing aliphatic diol having 2 to 14 carbon atoms in an amount of 60 mol% or more and 95 mol% or less and aromatic alcohol in an amount of 5 mol% or more and 40 mol% or less and a carboxylic acid component containing an aliphatic dicarboxylic acid compound having 6 to 14 carbon atoms; (2) an electrophotographic toner containing the binder resin composition of (1); and (3) the crystalline polyester resin that is a polycondensate of an alcohol component containing aliphatic diol having 2 to 14 carbon atoms in an amount of 60 mol% or more and 95 mol% or less and aromatic alcohol in an amount of 5 mol% or more and 40 mol% or less and a carboxylic acid component containing an aliphatic dicarboxylic acid compound having 6 to 14 carbon atoms.SELECTED DRAWING: None

Description

  The present invention relates to a binder resin composition for toners for electrophotography, a toner for electrophotography and a crystalline polyester resin.

  In recent years, with the increase in speed and energy saving of printers and copiers, toners excellent in low-temperature fixability are increasingly required. In addition, charging stability is also required during high speed printing.

For example, Patent Document 1 includes a binder resin and a magnetic powder, and the binder resin includes an amorphous polyester resin and a crystalline polyester resin of 5% by mass or more with respect to the amorphous polyester resin, A magnetic toner is described which contains an aromatic compound in a crystalline polyester resin, and the aromatic compound is an aromatic polyvalent carboxylic acid and / or a styrene acrylic polymer block.
In patent document 2, the binder resin containing an amorphous polyester resin and a crystalline polyester resin, and the first mold release agent are contained at least, and the repetition derived from the alcohol component contained in the amorphous polyester resin is repeated. The ratio of the repeating unit derived from the ethylene oxide adduct of bisphenol A in the unit is more than 50 mol% and 100 mol% or less, and 1,4-butane occupied in the repeating unit derived from the alcohol component contained in the crystalline polyester resin The proportion of the total amount of repeating units derived from at least one selected from the group consisting of diol and 1,6-hexanediol is 95 mol% or more, and accounts for the repeating units derived from the carboxylic acid component contained in the crystalline polyester resin And the proportion of repeating units derived from terephthalic acid is 3 mol% or more and 20 mol% or less, and 1,10-decanedicarboxylic acid and 1,8-ok The toner for electrostatic image development is described in which the proportion of the total amount of repeating units derived from at least one selected from the group consisting of tandicarboxylic acid is 80 mol% or more and 97 mol% or less.

  Patent Document 3 describes a binder resin composition for toners for electrophotography comprising crystalline polyester C and amorphous resin A, wherein the crystalline polyester C is an aliphatic diol having 9 to 14 carbon atoms. Crystals having an acid value of 20 mg KOH / g or less obtained by polycondensation of an alcohol component containing 70 mol% 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 Binder Resin Composition for Toner for Electrophotography, which is a water-repellent polyester.

International Publication No. 2016/052620 JP, 2014-178626, A JP, 2016-099518, A

From the viewpoint of obtaining a toner excellent in low-temperature fixability, the use of a crystalline polyester resin containing an aliphatic monomer such as aliphatic alcohol and aliphatic carboxylic acid tends to deteriorate the charge stability.
As a means for improving charge stability, it is known to simultaneously polycondensate an aromatic carboxylic acid which tends to obtain a resin having a high glass transition temperature such as terephthalic acid (TPA) as a raw material for crystalline polyester resin. However, it is still insufficient (Patent Document 1).
The present invention provides a binder resin composition for toners for electrophotography, a toner for electrophotography, and a crystalline polyester resin, which have excellent low-temperature fixability and charge stability.

The present inventors have found that the above-mentioned problems can be solved by introducing an aromatic alcohol as a raw material of a crystalline polyester resin.
That is, the present invention relates to the following [1] to [3].
[1] A binder resin composition for toners for electrophotography comprising crystalline polyester resin C and amorphous resin A,
The alcohol component containing 60 mol% to 95 mol% of an aliphatic diol having 2 to 14 carbon atoms and 5 mol% to 40 mol% of an aromatic alcohol, and the carbon number of the crystalline polyester resin C is The binder resin composition for toners for electrophotography which is a polycondensation product with the carboxylic acid component containing the aliphatic dicarboxylic acid compound which is 6 or more and 14 or less.
[1] A toner for electrophotography comprising the binder resin composition of [1].
[3] An alcohol component containing 60 to 95 mol% of an aliphatic diol having 2 to 14 carbon atoms and 5 to 40 mol% of an aromatic alcohol, and having 6 to 14 carbon atoms A crystalline polyester resin which is a polycondensate with a carboxylic acid component containing an aliphatic dicarboxylic acid compound.

According to the present invention, it is possible to provide a binder resin composition for an electrophotographic toner, an electrophotographic toner, and a crystalline polyester resin, which have excellent low-temperature fixability and charge stability.
Further, in addition to the above effects, it is possible to provide a binder resin composition for toners for electrophotography, toners for electrophotography, and crystalline polyester resins having excellent storage stability and image density.

[Binder resin composition for toner for electrophotography]
The binder resin composition for toners for electrophotography of the present invention (hereinafter, also simply referred to as “binder resin composition”) contains a crystalline polyester resin C and an amorphous resin A.
The crystalline polyester resin C has an alcohol component containing 60 mol% to 95 mol% of an aliphatic diol having 2 to 14 carbon atoms and 5 mol% to 40 mol% of an aromatic alcohol, and 6 carbon atoms It is a polycondensate with the carboxylic acid component containing the aliphatic dicarboxylic acid compound which is 14 or less.
According to the present invention, the reason why a binder resin composition for toners for electrophotography having excellent low temperature fixability and charge stability is obtained is not clear but is considered as follows.

When a crystalline polyester resin containing an aliphatic monomer as an alcohol component is used in combination to improve low-temperature fixability, charging stability is deteriorated. It is considered that this is because the amorphous region of the crystalline polyester resin easily leaks the charge. As a means for improving charge stability, as a raw material of crystalline polyester resin, aliphatic alcohol, aliphatic carboxylic acid and polyester having high glass transition temperature such as terephthalic acid (hereinafter, also simply referred to as "TPA") Although it is described to simultaneously polycondense with an aromatic carboxylic acid (Patent Document 1), the effect of improving charge stability is still insufficient. On the other hand, by introducing an aromatic alcohol into the crystalline polyester resin, it is possible to prevent a decrease in the degree of crystallization while maintaining excellent low-temperature fixability, and to prevent a decrease in charge stability. It is thought that
Furthermore, the dispersibility of the crystalline polyester resin is improved by the surface energy lowering action by the introduction of the aromatic alcohol, so that excellent storage stability is exhibited, and further, since the pigment dispersibility is also improved, an excellent image density is exhibited. .

Definitions of various terms in the present specification are shown below.
Whether the 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.) / Endothermic maximum peak temperature (° C.)) in the measurement method described in the examples described later. The crystalline resin is a resin having a crystallinity index of 0.6 or more and less than 1.4, preferably 0.7 or more, more preferably 0.9 or more, and preferably 1.2 or less. An amorphous resin is a resin having a crystallinity index of 1.4 or more or less than 0.6. The crystallinity index can be appropriately adjusted according to the type and ratio of the raw material monomers, and the production conditions such as the reaction temperature, the reaction time, and the cooling rate.
The term "carboxylic acid compound" is a concept that includes not only the carboxylic acid but also an anhydride that is decomposed during the reaction to form an acid, and an alkyl ester of the carboxylic acid (the carbon number of the alkyl group is 1 or more and 3 or less). .
When the carboxylic acid compound is an alkyl ester of a carboxylic acid, the carbon number of the alkyl group which is an alcohol residue of the ester is not counted as the carbon number of the carboxylic acid compound.
“Binder resin” means a resin component contained in toner including crystalline polyester resin C and amorphous resin A.

<Crystalline polyester resin C>
The crystalline polyester resin C (hereinafter, also simply referred to as “resin C”) has 2 or more carbon atoms from the viewpoint of obtaining excellent low-temperature fixability and charge stability, and from the viewpoint of obtaining excellent storage stability and image density. Contains an alcohol component containing 60 to 95 mol% of an aliphatic diol having 14 or less and 5 to 40 mol% of an aromatic alcohol, and an aliphatic dicarboxylic acid compound having 6 to 14 carbon atoms. It is a polycondensate with a carboxylic acid component.

Each component of the resin C will be described below.
From the viewpoint of obtaining excellent low-temperature fixability and charge stability, and from the viewpoint of obtaining excellent storage stability and image density, the alcohol component has 60 mol% to 95 mol of aliphatic diol having 2 to 14 carbon atoms. % Or less and 5 mol or more and 40 mol% or less of aromatic alcohol.
The carbon number of the aliphatic diol is 2 or more, preferably 4 or more, more preferably 6 or more, and 14 or less, preferably, from the viewpoint of further improving low-temperature fixability, charge stability, storage stability and image density. Is 12 or less.
As aliphatic diols, α, ω-aliphatic diols are preferred.
Examples of α, ω-aliphatic diols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,7-heptanediol. 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol It can be mentioned. Among these, 1,6-hexanediol, 1,9-nonanediol and 1,12-dodecanediol are preferable from the viewpoint of further improving low-temperature fixing ability, charging stability, storage ability and image density, From the viewpoint of improvement, 1,12-dodecanediol is more preferable.
The amount of the aliphatic diol is at least 60 mol%, preferably at least 70 mol%, more preferably at least 80 mol%, based on the alcohol component, from the viewpoint of further improving low-temperature fixability, charge stability, storage stability and image density. And not more than 95 mol%, preferably not more than 90 mol%.

The aromatic alcohol is preferably an alkylene oxide adduct of bisphenol A, from the viewpoint of further improving low-temperature fixability and charge stability, and from the viewpoint of further improving storage stability and image density, more preferably a formula ( I):

(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, and x and y each represent the average addition mole number of alkylene oxide, and each is positive) And the value of the sum of x and y is 1 or more, preferably 1.5 or more, and 16 or less, preferably 8 or less, more preferably 4 or less). It is a thing.
Examples of the alkylene oxide adduct of bisphenol A include propylene side adduct of bisphenol A [2,2-bis (4-hydroxyphenyl) propane] (hereinafter also referred to as “BPA-PO”), ethylene side of bisphenol A An adduct (hereinafter also referred to as "BPA-EO") may be mentioned. Among these, ethylene side adducts of bisphenol A are more preferable. One or two or more of these alkylene oxide adducts of bisphenol A may be used.
The amount of the aromatic alcohol is at least 5 mol%, preferably at least 8 mol%, based on the alcohol component, from the viewpoint of obtaining excellent low temperature fixability and charge stability, and from the viewpoint of obtaining excellent storage stability and image density. , More preferably 10 mol% or more, and 40 mol% or less, preferably 35 mol% or less, more preferably 30 mol% or less, still more preferably 25 mol% or less, still more preferably 20 mol% or less .

The alcohol component may contain another alcohol component different from the α, ω-aliphatic diol and the alkylene oxide adduct of bisphenol A. Other alcohol components include, for example, aliphatic diols other than α, ω-aliphatic diols such as 1,2-propylene glycol, neopentyl glycol, etc .; trivalent or higher alcohols such as glycerin, pentaerythritol, trimethylolpropane, etc. Can be mentioned.
One or more of these alcohol components may be used.

The carboxylic acid component contains an aliphatic dicarboxylic acid compound having 6 to 14 carbon atoms.
The carbon number of the aliphatic dicarboxylic acid compound is 6 or more, preferably 8 or more, from the viewpoint of further improving low-temperature fixability, charge stability, storage stability and image density, and low-temperature fixability and charge stability From the viewpoint of further improving, it is 14 or less, preferably 12 or less, more preferably 10 or less.
Examples of aliphatic dicarboxylic acid compounds include adipic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, or anhydrides thereof, and alkyl esters thereof (having 1 to 3 carbon atoms in the alkyl group). Among these, linear aliphatic dicarboxylic acids are preferable, adipic acid, sebacic acid and dodecanedioic acid are more preferable, from the viewpoint of further improving low-temperature fixability, charge stability, storage stability and image density, adipic acid and sebacine are more preferable. Acids are more preferred and sebacic acid is even more preferred. These carboxylic acid components may be used alone or in combination of two or more.

  The amount of the aliphatic dicarboxylic acid compound is preferably 80 mol% or more, more preferably 85 mol% or more, and further preferably 85 mol% or more in the carboxylic acid component from the viewpoint of further improving the low temperature fixing property, charge stability, storage property and image density. It is preferably 90 mol% or more, more preferably 95 mol% or more, and preferably 100 mol% or less, more preferably 100 mol%.

The aromatic carboxylic acid compound may be contained in the range which does not impair the effect of this invention.
Examples of the aromatic carboxylic acid compound include aromatic monocarboxylic acid compounds, aromatic dicarboxylic acid compounds, and trivalent or higher polyvalent aromatic carboxylic acid compounds.
As an aromatic monocarboxylic acid compound, benzoic acid, p-tertiary butyl benzoic acid, or its alkyl ester (C1 or more and 3 or less carbon number of an alkyl group) are mentioned, for example. These carboxylic acid components may be used alone or in combination of two or more.
As an aromatic dicarboxylic acid compound, phthalic acid, isophthalic acid, terephthalic acid, or these anhydrides, these alkyl esters (C1 or more and 3 or less carbon number of an alkyl group) are mentioned, for example.
Examples of trivalent or higher polyvalent aromatic carboxylic acid compounds include pyromellitic acid, trimellitic acid, or anhydrides thereof, and alkyl esters thereof (the carbon number of the alkyl group is 1 or more and 3 or less). Among these, trimellitic acid or trimellitic anhydride is preferable.
These carboxylic acid components may be used alone or in combination of two or more.

  The molar ratio of the carboxyl group of the carboxylic acid component to the hydroxyl group of the alcohol component [COOH group / OH group] is preferably 0.6 or more, more preferably 0.7 or more, still more preferably 0.8 or more, and preferably 1.3 or less. Preferably it is 1.2 or less, More preferably, it is 1.0 or less.

[Physical Properties of Crystalline Polyester Resin C]
The crystallinity of the resin C is preferably 40% or more, more preferably 50% or more, preferably 60% or more, from the viewpoint of further improving low-temperature fixability, charge stability, storage stability and image density. 100% or less, preferably 90% or less, more preferably 80% or less, still more preferably 70% or less.
For example, resin C is obtained by polycondensing an aliphatic alcohol and an aliphatic dicarboxylic acid compound at the time of production of resin C, adding an aromatic alcohol and polycondensation, and condensing the aromatic alcohol at the terminal of resin C, The degree of crystallization can be in the range of In addition, crystallinity degree is calculated | required by the method as described in an Example.

The softening point of the resin C is preferably 150 ° C. or less, more preferably 130 ° C. or less, still more preferably 110 ° C. or less, further preferably from the viewpoint of further improving low-temperature fixability, charge stability, storage stability and image density. The temperature is 100 ° C. or less, and preferably 40 ° C. or more, more preferably 50 ° C. or more, still more preferably 60 ° C. or more.
The melting point of the resin C is preferably 150 ° C. or less, more preferably 130 ° C. or less, still more preferably 110 ° C. or less, still more preferably 100, from the viewpoint of further improving low-temperature fixability, charge stability, storage stability and image density. C. or less, and preferably 40 ° C. or more, more preferably 50 ° C. or more.

  The acid value of the resin C is preferably 1 mg KOH / g or more, more preferably 5 mg KOH / g or more, and preferably 40 mg KOH / g or less, more preferably 30 mg KOH / g or less, from the viewpoint of improving storage stability. Preferably it is 20 mgKOH / g or less, More preferably, it is 15 mgKOH / g or less, More preferably, it is 10 mgKOH / g or less.

  The hydroxyl value of the resin C is preferably 1 mg KOH / g or more, more preferably 3 mg KOH / g or more, still more preferably 5 mg KOH / g or more, and preferably 30 mg KOH / g or less, from the viewpoint of improving storage stability. Preferably it is 20 mgKOH / g or less, More preferably, it is 10 mgKOH / g or less.

  The weight average molecular weight of the resin C is preferably 10,000 or more, more preferably 15,000 or more, and still more preferably 20,000 or more, from the viewpoint of further improving low-temperature fixability, charge stability, storage stability, and image density. Is 100,000 or less, more preferably 60,000 or less, still more preferably 40,000 or less.

[Method of producing crystalline polyester resin C]
The resin C is obtained, for example, by polycondensation of an alcohol component and a carboxylic acid component.
The method for producing the resin C preferably includes the following steps 1 and 2 from the viewpoint of further improving the low-temperature fixability, the charge stability, the storage stability, and the image density.
Step 1: Step of polycondensing alcohol component A-1 containing preferably 80 mol% or more of aliphatic diol having 2 to 14 carbon atoms and aliphatic dicarboxylic acid compound having 6 to 14 carbon atoms Step 2: Obtain A step of adding an alcohol component A-2 containing preferably 80 mol% or more of an aromatic alcohol after the hydroxyl value of the obtained polycondensate preferably becomes 10 mg KOH / g or less, and further polycondensation C is preferably obtained by the manufacturing method including the above-mentioned step 1 and step 2.

  As described in the above-mentioned production method, first, the alcohol component containing an aliphatic diol and the aliphatic carboxylic acid compound are polycondensed, and then the alcohol component containing an aromatic alcohol is polycondensed to end the aromatic alcohol at the molecular chain end Can be introduced preferentially, and a decrease in the degree of crystallinity of the resulting polyester resin can be prevented. For this reason, it is considered that the amorphous region is further reduced and the charging stability is further improved as compared with the resin in which the aromatic carboxylic acid is simultaneously polycondensed.

  The content of the aliphatic diol having 2 to 14 carbon atoms, which is the alcohol component A-1, is preferably 80% by mole or more, from the viewpoint of further improving the low-temperature fixability, charge stability, storage stability, and image density. It is preferably 90 mol% or more, more preferably 95 mol% or more, still more preferably 98 mol% or more, and preferably 100 mol% or less, and preferably 100 mol%.

  The addition amount of the aliphatic diol which is an alcohol component is preferably 60 mol parts or more, more preferably 100 mol parts or more with respect to 100 mol parts of the alcohol component, from the viewpoint of further improving the low temperature fixability, charge stability, storage stability and image density. The amount is preferably 65 parts by mol or more, more preferably 75 parts by mol or more, and preferably 95 parts by mol or less, more preferably 92 parts by mol or less, still more preferably 90 parts by mol or less.

In step 1, if necessary, an esterification catalyst such as di (2-ethylhexanoate) tin (II), dibutyltin oxide, titanium diisopropylate bistriethanolaminate, etc. is used as a total of 100 for the alcohol component and the carboxylic acid component. 0.01 parts by mass to 5 parts by mass with respect to parts by mass; an esterification promoter such as gallic acid (same as 3,4,5-trihydroxybenzoic acid) in a total amount of 100 parts by mass of an alcohol component and a carboxylic acid component It may carry out polycondensation using 0.001 mass part or more and 0.5 mass part or less with respect to it.
The temperature for polycondensation is preferably 120 ° C. or more, more preferably 160 ° C. or more, still more preferably 180 ° C. or more, and preferably 250 ° C. or less, more preferably 230 ° C. or less.
The polycondensation may be carried out in an inert gas atmosphere.

In the step 2, after the hydroxyl value of the obtained polycondensate becomes 10 mg KOH / g or less, more preferably 6 mg KOH / g or less, still more preferably 3 mg KOH / g or less, the aromatic alcohol is added.
The content of the aromatic alcohol which is the alcohol component A-2 is preferably 80 mol% or more, more preferably 90 mol%, from the viewpoint of further improving the low temperature fixing property, the charging stability, the storage property and the image density. The content is more preferably 95% by mass or more, further preferably 98% by mass or more, and preferably 100% by mass or less, and preferably 100% by mass.

The amount of the aromatic alcohol added is preferably 5 parts by mole or more, more preferably 8 parts by mole, with respect to 100 parts by mole of the alcohol component, from the viewpoint of further improving low-temperature fixability, charge stability, storage stability and image density. The amount is more preferably 10 parts by mol or more, and preferably 35 parts by mol or less, more preferably 30 parts by mol or less, still more preferably 25 parts by mol or less, still more preferably 20 parts by mol or less.
After addition of the aromatic alcohol, polycondensation is further performed, but the polymerization conditions are as shown in step 1.

  In the binder resin composition, the content of the resin C is preferably 1% by mass or more, more preferably 3 in the binder resin, from the viewpoint of further improving low-temperature fixability, charge stability, storage stability and image density. % By mass, more preferably 5% by mass or more, further preferably 8% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, still more preferably It is 15% by mass or less.

<Amorphous resin A>
Examples of the amorphous resin A (hereinafter, also simply referred to as “resin A”) include amorphous polyester resins and modified amorphous polyester resins. As a modified amorphous polyester resin, for example, a urethane modified product of an amorphous polyester resin, an epoxy modified product of an amorphous polyester resin, a composite resin containing an amorphous polyester resin segment and a vinyl resin segment Can be mentioned. Among these, an amorphous polyester resin, that is, an amorphous polyester resin which is not modified is preferable.

The amorphous polyester resin is, for example, a polycondensation product of an alcohol component and a carboxylic acid component.
Examples of the alcohol component include aromatic diols, linear or branched aliphatic diols, alicyclic diols, and trivalent or higher polyhydric alcohols. Among these, aromatic diols are preferable.
The aromatic diol is preferably an alkylene oxide adduct of bisphenol A, more preferably an alkylene oxide adduct of bisphenol A represented by the formula (I).
Examples of the alkylene oxide adduct of bisphenol A include polyoxypropylene adduct of bisphenol A [2,2-bis (4-hydroxyphenyl) propane] and polyoxyethylene adduct of bisphenol A. One or more of these may be used.
The amount of the alkylene oxide adduct of bisphenol A is preferably 80 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, and 100 mol% or less in the alcohol component. Preferably it is 100 mol%.

In addition to the aromatic diol, a linear or branched aliphatic diol, an alicyclic diol, or a trivalent or higher polyhydric alcohol may be contained as an alcohol component.
As a linear or branched aliphatic diol, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 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], and alkylene oxides having 2 or more and 4 or less carbon atoms of hydrogenated bisphenol A (average addition mole number 2 or more 12) The following may be mentioned: adducts.
Examples of trivalent or higher polyhydric alcohols include glycerin, pentaerythritol, trimethylolpropane and sorbitol.
One or more of these alcohol components may be used.

As a carboxylic acid component, a dicarboxylic acid compound and a trivalent or more polyvalent carboxylic acid compound are mentioned, for example. As a dicarboxylic acid compound, an aromatic dicarboxylic acid compound, a linear or branched aliphatic dicarboxylic acid compound, and an alicyclic dicarboxylic acid compound are mentioned, for example. Among these, aromatic dicarboxylic acid compounds are preferable.
As an aromatic dicarboxylic acid compound, for example, isophthalic acid, terephthalic acid, or anhydrides thereof, alkyl esters thereof (for example, carbon number of 1 or more and 3 or less of alkyl group) can be mentioned. Among these, terephthalic acid is preferred.
The amount of the aromatic dicarboxylic acid compound is preferably 20 mol% or more, more preferably 30 mol% or more, still more preferably 40 mol% or more, and 100 mol% or less in the carboxylic acid component.

Examples of linear or branched aliphatic dicarboxylic acid compounds include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, dodecanedioic acid, tetradecane A diacid, dodecyl succinic acid, dodecenyl succinic acid, octenyl succinic acid, or these anhydrides, these alkyl esters (for example, carbon number 1 or more and 3 or less of an alkyl group) are mentioned. Among these, adipic acid is preferred.
These carboxylic acid components may be used alone or in combination of two or more.
The amount of the linear or branched aliphatic dicarboxylic acid compound is preferably 10 mol% or more, more preferably 15 mol% or more, still more preferably 20 mol% or more, and 50 mol% or less in the carboxylic acid component. It is.

The carboxylic acid component preferably contains a trivalent or higher polyvalent carboxylic acid compound, and preferably contains trimellitic acid or an anhydride thereof.
The amount of the trivalent or higher polyvalent carboxylic acid compound in the carboxylic acid component is preferably 3 mol% or more, more preferably 10 mol% or more, still more preferably 15 mol% or more, and preferably 40 mol% The following content is more preferably 30 mol% or less, still more preferably 25 mol% or less.

  The molar ratio of the carboxyl group of the carboxylic acid component to the hydroxyl group of the alcohol component (COOH group / OH group) is preferably 0.7 or more, more preferably 0.8 or more, and preferably 1.3 or less, more preferably 1.2 or less .

  The method for producing the resin A is obtained, for example, by polycondensation of an alcohol component and a carboxylic acid component. The conditions of the polycondensation are preferably in the same range as the conditions of the polycondensation shown in the above-mentioned step 1.

[Physical Properties of Amorphous Resin A]
The acid value of the resin A is preferably 1 mg KOH / g or more, more preferably 2.5 mg KOH / g or more, still more preferably 4 mg KOH / g or more, and preferably 40 mg KOH / g or less, more preferably 30 mg KOH / g or less More preferably, it is 20 mg KOH / g or less.

  The hydroxyl value of the resin A is preferably 1 mg KOH / g or more, more preferably 10 mg KOH / g or more, still more preferably 15 mg KOH / g or more, and preferably 60 mg KOH / g or less, more preferably 45 mg KOH / g or less, further Preferably it is 30 mgKOH / g or less.

  The softening point of the resin A is preferably 70 ° C. or more, more preferably 90 ° C. or more, still more preferably 100 ° C. or more, still more preferably 110 ° C. or more, and preferably 150 ° C. or less, more preferably 140 ° C. or less More preferably, the temperature is 135 ° C. or less.

  The glass transition temperature of the resin A is preferably 50 ° C. or more, more preferably 55 ° C. or more, and preferably 80 ° C. or less, more preferably 75 ° C. or less, still more preferably 70 ° C. or less.

  The acid value, hydroxyl value, softening point, and glass transition temperature of the resin A can be appropriately adjusted according to the type of raw material monomer and the amount thereof used, and the production conditions such as the reaction temperature, reaction time, cooling rate, etc. Those values are determined by the method described in the examples.

  In the binder resin composition, the content of the resin A is preferably 60% by mass or more in the binder resin from the viewpoint of further improving low-temperature fixability and charging stability and from the viewpoint of further improving storage stability. More preferably, it is 70% by mass or more, more preferably 80% by mass or more, further preferably 85% by mass or more, and preferably 99% by mass or less, more preferably 97% by mass or less, still more preferably 95% by mass or less More preferably, it is 92% by mass or less.

  In the binder resin composition, the mass ratio of resin C to resin A [resin C / resin A] is preferably from the viewpoint of further improving low-temperature fixability and charge stability, and from the viewpoint of further improving storage stability. 1/99 or more, more preferably 3/97 or more, still more preferably 5/95 or more, still more preferably 8/92 or more, and preferably 40/60 or less, more preferably 30/70 or less, more preferably Is 20/80 or less, more preferably 15/85 or less.

[Resin H, L]
Among the amorphous resins A described above, it is preferable that two or more resins having different softening points by 10 ° C. or more are included from the viewpoint of improving low-temperature fixability. A resin having a higher softening point is an amorphous resin H (hereinafter, also simply referred to as “resin H”), and a resin of a lower softening point is an amorphous resin L (hereinafter, also simply referred to as “resin L”) Do.

  The softening point of the resin H is preferably 170 ° C. or less, more preferably 160 ° C. or less, and preferably 110 ° C. or more, more preferably 120 ° C. or more, more preferably from the viewpoint of improving the hot offset resistance. It is 130 ° C. or higher.

  The softening point of the resin L is preferably 80 ° C. or more, more preferably 95 ° C. or more, and preferably 125 ° C. or less, more preferably 115 ° C. or less, from the viewpoint of improving low-temperature fixability.

  The difference between the softening points of the resin H and the resin L is preferably 10 ° C. or more, more preferably 15 ° C. or more, still more preferably 20 ° C. or more, and preferably 60 ° C. or less, more preferably 50 ° C. or less, further Preferably it is 40 degrees C or less.

  The mass ratio (H / L) of resin H to resin L is preferably 20/80 or more, more preferably 25/75 or more, still more preferably 30/70 or more, and preferably 60/40 or less, more preferably Preferably it is 50/50 or less, More preferably, it is 40/60 or less.

<Charge control agent>
The binder resin composition may contain a charge control agent.
The charge control agent may contain any of a positively chargeable charge control agent and a negatively chargeable charge control agent.
As positively chargeable charge control agents, 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” (all, manufactured by Orient Chemical Industries Ltd.), etc .; Triphenylmethane dyes containing tertiary amines as side chains, quaternary ammonium salt compounds, eg “ Bontron P-51 "(Orient Chemical Industry Co., Ltd.), cetyltrimethyl ammonium bromide," COPY CHARGE PX VP 435 "(Clariant Co., Ltd.), etc .; Polyamine resin, such as" AFP-B "(Orient Chemical Co., Ltd.) etc. Imidazole derivatives, such as “PLZ-2001”, “PLZ-8001” (all manufactured by Shikoku Kasei Kogyo Co., Ltd.), etc. Styrene-acrylic resins, such as “FCA-701PT” (Fujikura Kasei Etc., Ltd.) Co., Ltd., and the like.

Examples of negatively chargeable charge control agents include metal-containing azo dyes such as, for example, "Varifast black 3804", "Bontron S-31", "Bontron S-32", "Bontron S-34", "Bontron S-36" ( As described above, Orient Chemical Industry Co., Ltd.), “Aisenspirone Black TRH”, “T-77” (Hodogaya Chemical Co., Ltd.), etc .; metal compounds of benzylic acid compounds, for example, “LR-147”, LR-297 "(above, manufactured by Nippon Carlit Co., Ltd.), etc .; Metal compounds of salicylic acid compounds, for example," Bontron E-81 "," Bontron E-84 "," Bontron E-88 "," Bontron E-304 " (The above, made by Orient Chemical Industry Co., Ltd.), "TN-105" (made by Hodogaya Chemical Co., Ltd.), etc .; Copper phthalocyanine dye; quaternary ammonium salt, such as "COPY CHARGE NX VP434" (made by Clariant), nitro Imidazole derivatives, etc .; Organic metal compounds and the like.
One or more of these may be used.
Among charge control agents, a negatively chargeable charge control agent is preferable, and a metal compound of a benzylic acid compound or a metal compound of a salicylic acid compound is more preferable.

  The content of the charge control agent is preferably 0.01 parts by mass or more, more preferably 0.2 parts by mass or more, and preferably 10 parts by mass or less, more preferably 5 parts by mass, with respect to 100 parts by mass of the binder resin. The content is more preferably 3 parts by mass or less, still more preferably 2 parts by mass or less.

<Colorant>
The binder resin composition may contain a colorant.
The colorant may be either a dye or a pigment, preferably a pigment. Specifically, for example, 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 azo, etc. are listed. Be One or more of these may be used.

  The content of the colorant is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and preferably 40 parts by mass with respect to 100 parts by mass of the binder resin from the viewpoint of improving the image density of the toner. It is preferably at most 20 parts by mass, more preferably at most 10 parts by mass.

<Release agent>
The binder resin composition may contain a release agent.
The release agent is preferably a wax. As a mold release agent, for example, polypropylene wax, polyethylene wax, polypropylene polyethylene copolymer wax; hydrocarbon wax such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax, Sazol wax or their oxides; carnauba wax Montan wax or ester-based waxes such as deacidified waxes or fatty acid ester waxes; fatty acid amides, fatty acids, higher alcohols, fatty acid metal salts. One or more of these may be used.

The melting point of the release agent is preferably 60 ° C. or more, more preferably 70 ° C. or more, and preferably 160 ° C. or less, more preferably 140 ° C. or less.
The melting point of the release agent is according to the method described in the examples.

  The content of the releasing agent is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, still more preferably 1.5 parts by mass or more, and preferably 10 parts by mass with respect to 100 parts by mass of the binder resin. The content is more preferably 8 parts by mass or less, still more preferably 7 parts by mass or less.

  The binder resin composition contains, for example, additives such as a magnetic powder, a fluidity improver, a conductivity adjustor, a reinforcing filler such as a fibrous substance, an antioxidant, an antiaging agent, and a cleanability improver. It may be

[toner]
The toner contains the above-mentioned binder resin composition, and preferably contains toner particles containing the above-mentioned binder resin composition. The preferred content of each component is the same as the preferred content in the above-mentioned binder resin composition.
The volume median particle diameter (D ₅₀ ) of the toner particles is preferably 2 μm or more, more preferably 3 μm or more, still more preferably 4 μm or more, and preferably 10 μm or less, from the viewpoint of obtaining a high quality image. Preferably it is 9 micrometers or less, More preferably, it is 8 micrometers or less.

The surface of the toner particles may be treated with an external additive.
Examples of the external additive include fine particles of inorganic material such as hydrophobic silica, titanium oxide, alumina, cerium oxide and carbon black, and fine particles of polymer such as polycarbonate, polymethyl methacrylate, and silicone resin. Among these, hydrophobic silica is preferred.
When an external additive is used, the addition amount of the external additive is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, still more preferably 1 part by mass or more, with respect to 100 parts by mass of toner particles. Preferably it is 5 mass parts or less, More preferably, it is 4 mass parts or less.

[Method of producing toner]
The toner may be a toner obtained by any known method such as a melt-kneading method, an emulsion phase inversion method, a polymerization method, an emulsion aggregation method, but from the viewpoint of productivity and dispersibility of the colorant, the toner is melted. A pulverized toner by a kneading method is preferred.

When the toner is a pulverized toner, for example, the method of producing the toner includes, for example, a step of melting and kneading a toner raw material containing the resin C and the resin A, and a step 2: grinding and classifying the molten mixture obtained in the step 1 To obtain

In step 1, the toner raw material may contain other additives such as a charge control agent, a colorant, and a release agent. These toner raw materials are preferably mixed in advance with a mixer such as a Henschel mixer or a ball mill and then supplied to a kneader.
The temperature for melt-kneading is preferably 80 ° C. or more, more preferably 90 ° C. or more, still more preferably 100 ° C. or more, and preferably 160 ° C. or less, preferably 140 ° C. or less.
The melt-kneading in step 1 can be performed using a known kneader such as a closed kneader, a single screw extruder, a twin screw extruder, or an open roll kneader. From the viewpoint of melt-mixing crystals, a twin-screw extruder which can be set to high temperature conditions is preferable.
The molten mixture obtained in step 1 is subjected to the subsequent step 2 after being cooled to such an extent that grinding is possible.

The grinding in step 2 may be performed in multiple stages. For example, the resin kneaded material obtained by curing the molten mixture may be roughly pulverized to 1 mm or more and 5 mm or less, and then finely pulverized to a desired particle size.
As a grinder suitably used for coarse grinding, a hammer mill, an atomizer, Rotoplex is mentioned, for example. As a grinder suitably used for pulverization, for example, a fluidized bed jet mill, a collision plate jet mill, and a rotary mechanical mill can be mentioned. From the viewpoint of grinding efficiency, it is preferable to use a fluidized bed jet mill and a collision plate jet mill, and it is more preferable to use a collision plate jet mill.

Examples of classifiers used for classification include rotor classifiers, pneumatic classifiers, inertial classifiers, and sieve classifiers. In the classification step, the pulverized material which has been insufficiently ground and removed may be subjected to the grinding step again, and the grinding step and the classification step may be repeated as necessary.
The toner is added to the surface of the toner particles, as necessary, using a fluidizing agent or the like as an external additive.

  The toner is used to develop a latent image formed in electrophotography, electrostatic recording, electrostatic printing, and the like. The toner can be used as a one-component developer or as a two-component developer mixed with a carrier.

  Hereinafter, although a specific embodiment is mentioned and described as an example, the present invention is not limited to these.

[Measuring method]
Each physical property value of resin etc. was measured by the following method.

[Acid value and hydroxyl value of resin]
The acid value and hydroxyl value of the resin are measured based on the method of JIS K 0070: 1992. However, only the measurement solvent is changed to a mixed solvent of acetone and toluene (acetone: toluene = 1: 1 (volume ratio)) from a mixed solvent of ethanol and ether specified in JIS K 0070: 1992.

[Softening point and glass transition temperature of resin]
(1) Softening point While using a flow tester "CFT-500D" (manufactured by Shimadzu Corporation) to heat a 1 g sample at a heating rate of 6 ° C./min, a load of 1.96 MPa is applied by a plunger to obtain a diameter of 1 mm , Pushed out of a 1 mm long nozzle. The plunger drop amount of the flow tester is plotted against the temperature, and the temperature at which half of the sample flowed out is taken as the softening point.
(2) Maximum peak temperature of heat absorption Sample cooled from 20 ° C. to 0 ° C. at a temperature decrease rate of 10 ° C./min using a differential scanning calorimeter “Q-100” (manufactured by TA Instruments Japan Ltd.) as it is The temperature is maintained for 1 minute and then measured while raising the temperature to 180.degree. C. at a heating rate of 10.degree. C./min. Of the observed endothermic peaks, the temperature of the peak located on the highest temperature side is taken as the maximum endothermic peak temperature.
(3) Glass transition temperature 0.01 to 0.02 g of a sample is weighed in an aluminum pan using a differential scanning calorimeter "Q-100" (manufactured by TEA Instruments Japan Co., Ltd.), and heated to 200 ° C. The temperature is cooled to 0 ° C. at a temperature decrease rate of 10 ° C./min. Next, measurement is performed while raising the temperature to 150 ° C. at a heating rate of 10 ° C./min. The temperature at the intersection of the extension of the baseline below the maximum endothermic peak temperature and the tangent showing the maximum slope from the rising portion of the peak to the peak of the peak is taken as the glass transition temperature.

[Number average molecular weight of resin, weight average molecular weight]
The molecular weight distribution is measured by gel permeation chromatography (GPC) according to the following method to determine the weight average molecular weight Mw of the resin.
(1) Preparation of sample solution The resin is dissolved in chloroform so that the concentration becomes 0.5 g / 100 mL. Next, this solution is filtered using a fluororesin filter “FP-200” (manufactured by Sumitomo Electric Industries, Ltd.) with a pore size of 2 μm to remove insoluble components, and this is used as a sample solution.
(2) Molecular Weight Measurement Using the following apparatus, chloroform is flowed at a flow rate of 1 mL per minute as an eluent to stabilize the column in a 40 ° C. thermostat. 100 μL of a sample solution is injected into it and measured. The molecular weight of the sample is calculated based on a previously prepared calibration curve. In this calibration curve, monodispersed polystyrenes having known molecular weights of several kinds (Tosoh Corp .; 2.63 × 10 ³ , 2.06 × 10 ⁴ , 1.02 × 10 ⁵ , GL Science Inc .; 2.10 × 10 ³ , 7.00) are known. A sample prepared by using × 10 ³ and 5.04 × 10 ⁴ ) as a standard sample is used.
Measuring device: "CO-8010" (made by Tosoh Corporation)
Analysis column: "GMH _XL " + "G3000H _XL " (all are manufactured by Tosoh Corporation)

Melting point of mold release agent
A sample of 0.02 g is weighed in an aluminum pan using a differential scanning calorimeter “Q100” (manufactured by TEA Instruments Japan Co., Ltd.), heated to 200 ° C., and then cooled from 200 ° C. at a temperature decrease rate of 10 ° C./min. Cool to 0 ° C. Next, the sample is heated at a temperature rising rate of 10 ° C./min, the heat quantity is measured, and the maximum endothermic peak temperature is taken as the melting point.

[Volume median particle diameter (D ₅₀ ) of toner particles]
The volume median particle size (D ₅₀ ) of the toner particles is measured by the following method.
Measuring machine: "Coulter Multisizer II" (made by Beckman Coulter)
Aperture diameter: 50μm
Analysis software: Coulter multisizer Accucomp version 1.19 (manufactured by Beckman Coulter)
Electrolyte: Isoton II (manufactured by Beckman Coulter)
Dispersion: Emulgen 109 P (manufactured by Kao Corporation, polyoxyethylene lauryl ether, HLB: 13.6) 5% by mass Electrolytic solution Dispersion conditions: 10 mg of the measurement sample is added to 5 mL of the dispersion, and dispersed for 1 minute with an ultrasonic dispersion machine Then, add 25 mL of electrolyte solution, and further disperse for 1 minute with an ultrasonic disperser.
Measurement conditions: 100 mL of the electrolyte and the dispersion are added to a beaker, and 30,000 particles are measured at a concentration that can measure the particle diameter of 30,000 particles in 20 seconds, and the volume median particle diameter Find D ₅₀ ).

[Degree of crystallinity of crystalline polyester resin]
X-ray source: Cu / Kα-radiation, tube voltage: 40 kV, tube current: 120 mA, measurement range using a powder X-ray diffraction (XRD) measuring apparatus “Rigaku RINT 2500VC X-RAY diffractometer” (manufactured by Rigaku Corporation) : The peak intensity is measured by a continuous scan method at a diffraction angle (2θ) of 5 to 40 ° and a scanning speed of 5.0 ° / min. The sample is measured immediately after the crystalline polyester resin in a molten state is air-cooled at 25 ° C. and pulverized. From the obtained X-ray diffraction, the value calculated from the following formula is taken as the degree of crystallization of the crystalline polyester resin.

[Production of resin]
Preparation Examples C1 to C8, C53, C54, C55 [Resins C-1 to C-8, C-53, C-54, C-55]
A raw material monomer other than BPA-EO or BPA-PO shown in Table 1 was added to a 10 liter four-necked flask equipped with a thermometer, a stainless steel stirring rod, a fractionation column, a dehydration pipe, a cooling pipe, and a nitrogen introduction pipe. Put in and keep at 140 ° C for 2 hours in a mantle heater in a nitrogen atmosphere, then raise the temperature from 140 ° C to 200 ° C at 10 ° C / hr, then make a polycondensation reaction at 200 ° C for 2 hours, and then add an esterification catalyst The reaction was carried out until the hydroxyl value reached 3 mg KOH / g or less at 200 ° C. and 8.0 kPa. Thereafter, BPA-EO or BPA-PO is added, reacted at normal pressure for 1 hour, and reacted to a desired softening point at 8 kPa to obtain crystalline polyester resins C-1 to C-8, C-53. , C-54, C-55.

Production Example C51, C52 [Resins C-51, C-52]
A raw material monomer shown in Table 1 and an esterification catalyst are placed in a 10 liter four-necked flask equipped with a thermometer, a stainless steel stirring rod, a fractionation column, a dehydration pipe, a cooling pipe, and a nitrogen introduction pipe, and a nitrogen atmosphere In the heating mantle at 140 ° C for 2 hours in a mantle heater, the temperature is raised from 140 ° C to 200 ° C at 10 ° C / hr. The reaction was carried out to the softening point of to give crystalline polyester resins C-51 and C-52.

Production Example A1 (Resin A-1)
Raw material monomers and esterification catalysts other than adipic acid shown in Table 2 are placed in a 10 liter four-necked flask equipped with a thermometer, a stainless steel stirring rod, a fractionation column, a dehydration pipe, a cooling pipe, and a nitrogen introduction pipe. After keeping the temperature at 210 ° C for 1 hour in a mantle heater in a nitrogen atmosphere, the temperature is raised from 210 ° C to 235 ° C at 10 ° C / hr, and then the polycondensation reaction is carried out at 235 ° C for 5 hours. The reaction was carried out for 1 hour. After cooling to 180 ° C., adipic acid was added. After the addition, the reaction is carried out for 1 hour while maintaining the temperature at 180 ° C, then the temperature is raised from 180 ° C to 210 ° C at 10 ° C / hr, and the reaction is carried out at 210 ° C and 10 kPa until the desired softening point is reached. , Resin A-1 was obtained.

Production Example A2 (Resin A-2)
Put the raw material monomer and esterification catalyst shown in Table 2 into a 10-liter four-necked flask equipped with a thermometer, a stainless steel stirring rod, a fractionation column, a dehydration pipe, a cooling pipe, and a nitrogen introduction pipe, Heat at 10 ° C / hr from 210 ° C to 235 ° C, then carry out a condensation polymerization reaction at 235 ° C for 5 hours, and further desired at 235 ° C and 8.0 kPa The reaction was carried out until the softening point was reached to obtain a resin A-2.

[Manufacture of toner]
Examples 1 to 12 and Comparative Examples 1 to 5
100 parts by mass of resin having the compounding ratio shown in Table 3 as binder resin, 1 part by mass of negatively chargeable charge control agent "Bontron E-81" (manufactured by Orient Chemical Industry Co., Ltd.), coloring agent "Pigment Blue 15: 3 (Dainichi Seika Kogyo Co., Ltd.) 5 parts by mass, and mold release agent “HNP-9” (Nippon Seiwa Co., Ltd., paraffin wax, melting point: 80 ° C.) 2 parts by mass after thoroughly mixing with a Henschel mixer A melt kneading was carried out using a co-rotating twin-screw extruder having a total length of 1560 mm of a kneading portion, a screw diameter of 42 mm and a barrel inner diameter of 43 mm, a roll rotational speed of 200 r / min and a heating temperature of 100 ° C. in the roll. The feed rate of the mixture was 20 kg / h and the average residence time was about 18 seconds. The obtained melt-kneaded product was cooled, roughly pulverized, pulverized by a jet mill, and classified to obtain toner particles having a volume median particle size (D ₅₀ ) of 8 μm.

  To 100 parts by mass of the obtained toner particles, 1.0 part by mass of hydrophobic silica “AEROSIL NAX 50” (manufactured by Nippon Aerosil Co., Ltd., hydrophobizing agent: HMDS, average particle diameter: about 30 nm) is added as an external additive, The toner was obtained by mixing with a Henschel mixer.

[Evaluation]
Low temperature fixability
The toner is mounted on a non-magnetic one-component developing device "OKI MICROLINE 5400" (manufactured by Oki Data Corporation), the toner adhesion amount is adjusted to 0.45 ± 0.03 mg / cm ² , and a solid image of 4.1 cm × 13.0 cm is obtained. It printed on "J paper" (made by Fuji Xerox Co., Ltd.). Before passing through the fixing device, the solid image was taken out to obtain an unfixed image. The obtained unfixed image is fixed at a fixing speed of 240 mm / sec by setting the temperature of the fixing roll to 100 ° C. with an external fixing machine obtained by modifying the fixing machine of “Microline 3010” (manufactured by Oki Data Co., Ltd.) The Thereafter, the fixing roll temperature was set to 105 ° C., and the same operation was performed. While raising the temperature to 200 ° C. by 5 ° C., fixing processing of the unfixed image was performed at each temperature to obtain a fixed image. A mending tape (made by Sumitomo 3M Ltd.) is attached to the image fixed at each temperature, and then a 500 g cylindrical weight (contact area 4 cm ² ) is placed on the image to sufficiently adhere the tape to the fixed image. The Thereafter, the mending tape was slowly peeled off from the fixed image, and the optical reflection density of the image after tape peeling was measured using a reflection densitometer “RD-915” (manufactured by Macbeth). The optical reflection density is also measured for the image before pasting the tape in advance, and the ratio ([Reflection density after tape peeling / reflection density before tape pasting] x 100) first exceeds 90% fixation The temperature of the roll was taken as the minimum fixing temperature, and was used as an index of low temperature fixing ability. The results are shown in Table 3.

[Normal temperature normal humidity charging stability]
The toner was left for 72 hours under an environment of temperature 25 ° C. and relative humidity 50%.
0.6 g of toner and 19.4 g of silicone ferrite carrier (manufactured by Kanto Denka Kogyo Co., Ltd., average particle diameter: 90 μm) are placed in a 50 mL polyethylene container and mixed at 250 r / min using a ball mill for 60 seconds, 3600 The charge amount of the toner after second mixing was measured using a Q / M meter (manufactured by EPPING) according to the following method.
After the specified mixing time, charge the specified amount of toner and carrier mixture into the cell attached to the Q / M meter, and suction only the toner for 90 seconds through a 32 μm mesh sieve (stainless, twill, wire diameter: 0.0035 mm) did. The voltage change on the carrier generated at that time was monitored, and the value of [total electric quantity (μC) after 90 seconds / suctioned toner quantity (g)] was taken as the charge quantity (μC / g).
The ratio of the charge amount after 60 seconds of mixing time to the charge amount after 3600 seconds of mixing time (charge amount after 3600 seconds of mixing time / charge amount after 60 seconds of mixing time) was calculated. As the ratio of the charge amount is closer to 1, the charge stability is more excellent.

[Conservability]
In a 20 mL container (about 3 cm in diameter), 4 g of the toner was placed and left for 72 hours under the environment of a temperature of 55 ° C. and a relative humidity of 60%. After standing, the degree of toner aggregation was visually observed, and the storage stability was evaluated according to the following evaluation criteria. The results are shown in Table 3.
(Evaluation criteria)
A: No aggregation was observed after 48 hours and 72 hours.
B: No aggregation was observed after 48 hours, but slight aggregation was observed after 72 hours.
C: No aggregation was observed after 48 hours, but aggregation was clearly observed after 72 hours.
D: Aggregation is observed within 48 hours.

[Image density]
Using a commercially available printer "Microline (registered trademark) 5400" (Oki Data Co., Ltd.) on a high quality paper "J paper A4 size" (manufactured by Fuji Xerox Co., Ltd.), the adhesion amount of toner on the paper is 0.42 to 0.48 mg / paper. A solid image of cm ² was output to obtain a printed matter.
Next, the temperature of the fixing device was set to 130 ° C., and the toner was fixed at a speed of 1.5 seconds per sheet in the longitudinal direction of A4 to obtain a printed matter.
The reflection image density of the fixed image portion of the output printed matter was measured using a colorimeter “SpectroEye” (GretagMacbeth Co., Ltd., light emitting condition: standard light source D50, observation field of view 2 °, density reference DINNB, absolute white reference) . The larger the value of the reflection image density, the better the image density.

  As described above, from the results of Examples and Comparative Examples, it is understood that the toners of Examples exhibit excellent low-temperature fixability and charging stability. Furthermore, according to the toner of the example, it is understood that the storage stability and the image density are also excellent.

Claims (7)

A binder resin composition for toners for electrophotography comprising a crystalline polyester resin C and an amorphous resin A,
The alcohol component containing 60 mol% to 95 mol% of an aliphatic diol having 2 to 14 carbon atoms and 5 mol% to 40 mol% of an aromatic alcohol, and the carbon number of the crystalline polyester resin C is The binder resin composition for toners for electrophotography which is a polycondensation product with the carboxylic acid component containing the aliphatic dicarboxylic acid compound which is 6 or more and 14 or less. The binder resin composition for a toner for electrophotography according to claim 1, wherein the crystalline polyester resin C is obtained by a production method including the following steps 1 and 2.
Step 1: Step of polycondensing alcohol component A-1 containing 80 mol% or more of aliphatic diol having 2 to 14 carbon atoms with aliphatic dicarboxylic acid compound having 6 to 14 carbon atoms Step 2: Obtained A step of adding an alcohol component A-2 containing 80 mol% or more of an aromatic alcohol after the time when the hydroxyl value of the polycondensate becomes 10 mg KOH / g or less, and further polycondensation   The binder resin composition for toners for electrophotography according to claim 1 or 2 whose crystallinity degree of said crystalline polyester resin C is 40% or more and 100% or less.   The binder resin composition for a toner for electrophotography according to any one of claims 1 to 3, wherein the aromatic alcohol is an alkylene oxide adduct of bisphenol A.   The binder resin composition for a toner for electrophotography according to any one of claims 1 to 4, wherein the aliphatic dicarboxylic acid compound is a linear aliphatic dicarboxylic acid compound.   An electrophotographic toner comprising the binder resin composition according to any one of claims 1 to 5.   An alcohol component containing 60 mol% to 95 mol% of an aliphatic diol having 2 to 14 carbon atoms and 5 mol% to 40 mol% of an aromatic alcohol, and an aliphatic having 6 to 14 carbon atoms A crystalline polyester resin which is a polycondensate with a carboxylic acid component containing a dicarboxylic acid compound.