JP5833409B2 - Binder resin for toner - Google Patents

Description

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

In recent years, as printers and copiers have become faster and more energy efficient, toners with excellent low-temperature fixability have become increasingly necessary. However, when the molecular weight is lowered in order to melt the binder resin of a normal toner at a low temperature, the glass transition point of the resin is lowered, the storage stability is lowered, and the durability is also lowered.
In order to solve this problem, a polyester obtained by using a carboxylic acid having an aromatic ring such as terephthalic acid or isophthalic acid as a raw material monomer as a binder resin for toner having a low molecular weight and a high glass transition point is widely used. However, it does not have sufficient durability.

On the other hand, Patent Document 1 has a furan structure and a reduced viscosity with the object of providing a thermoplastic resin having a sufficient molecular weight that is excellent in heat resistance, mechanical properties, and weather resistance using biomass as a raw material. A thermoplastic resin characterized by (ηsp / C) of 0.48 dL / g or more and a terminal acid value of less than 200 μeq / g is disclosed. Patent Document 2 discloses a method for producing a polyester resin containing a dicarboxylic acid unit having a furan structure.
However, the resins described in Patent Document 1 and Patent Document 2 are excellent in mechanical properties mainly used for film applications and injection molded products, and thus have high crystallinity and are not suitable as binder resins for toners. .

JP 2008-291243 A JP 2008-291244 A

  An object of the present invention is to provide a toner binder resin excellent in low-temperature fixability, storage stability and durability of the toner, and an electrophotographic toner containing the binder resin.

The present invention
[1] A binder resin for toner containing an amorphous polyester having a furan ring, wherein the amorphous polyester is obtained by condensation polymerization of a carboxylic acid component and an alcohol component, and the carboxylic acid component And a binder resin for toner, wherein at least one of the alcohol components is a carboxylic acid component containing an aliphatic carboxylic acid compound having 6 to 40 carbon atoms and / or an alcohol component containing an aliphatic alcohol having 6 to 40 carbon atoms And [2] An electrophotographic toner comprising the toner binder resin described in [1].

  The binder resin for toner of the present invention can achieve both the low-temperature fixability and the storage stability of the toner, and further has an excellent effect of improving the durability.

  The binder resin of the present invention has a furan ring and is an amorphous polyester obtained by using an aliphatic carboxylic acid compound having 6 to 40 carbon atoms and / or an aliphatic alcohol having 6 to 40 carbon atoms as a raw material monomer It has the feature in that it contains. By using a compound having a furan ring as a raw material monomer for an amorphous polyester, the present inventors have achieved a glass transition with a low softening point, in other words, a resin having a high glass transition point, in other words, a low number average molecular weight. Since a resin with a high point is obtained, the toner has excellent low-temperature fixability and storage stability, and an aliphatic carboxylic acid compound having 6 to 40 carbon atoms and / or an aliphatic alcohol having 6 to 40 carbon atoms is used as a raw material monomer. Thus, the inventors have found that the durability of the toner is remarkably improved. The reason for this is unclear, but aliphatic carboxylic acid compounds having 6 to 40 carbon atoms and aliphatic alcohols having 6 to 40 carbon atoms are thought to improve the dispersibility of the wax and, as a result, improve the durability of the toner. However, at the same time, the glass transition point is lowered and the storage stability of the toner is lowered. However, since the amorphous polyester having a furan ring has a rigid structure, an effective amount of an aliphatic carboxylic acid compound having 6 to 40 carbon atoms and / or an aliphatic alcohol having 6 to 40 carbon atoms is used. However, it is considered that the decrease in the glass transition point is suppressed and both the storage stability and the durability of the toner are compatible.

  In the present invention, the crystallinity of the resin is determined by the ratio between the softening point and the maximum endothermic peak temperature measured by a differential scanning calorimeter (DSC), that is, the crystallinity index defined by “softening point / maximum endothermic peak temperature”. expressed. Generally, when the crystallinity index exceeds 1.4, the resin is amorphous, and when it is less than 0.6, the crystallinity is low and there are many amorphous portions. In the present invention, the “amorphous” resin refers to a resin having a crystallinity index exceeding 1.4 or less than 0.6.

  The crystallinity of the resin can be easily adjusted depending on the type and combination of raw material monomers used. Specifically, a carboxylic acid component or alcohol component having a branched chain structure, a trivalent or higher carboxylic acid component or alcohol component, for example, an alkyl or alkenyl succinic acid or a hydroxyl group bonded to a secondary carbon atom as described later. Amorphization can be promoted by using an appropriate amount of aliphatic diol, trimellitic acid, trimellitic anhydride, or the like.

  The “maximum endothermic peak temperature” refers to the temperature of the peak on the highest temperature side among the endothermic peaks observed under the conditions of the measurement methods described in the examples. If the maximum peak temperature is within 20 ° C of the softening point, the maximum peak temperature is the melting point of the crystalline resin (crystalline polyester). The peak is attributed to the transition.

  In the present invention, the amorphous polyester having a furan ring is a resin obtained by condensation polymerization of a carboxylic acid component and an alcohol component as raw material monomers, as described above, and comprising a carboxylic acid component and an alcohol. At least one of the components is a carboxylic acid component containing an aliphatic carboxylic acid compound having 6 to 40 carbon atoms and / or an alcohol component containing an aliphatic alcohol having 6 to 40 carbon atoms.

  The aliphatic carboxylic acid compound having 6 to 40 carbon atoms is preferably a linear or branched mono- or dicarboxylic acid compound from the viewpoints of durability and storage stability of the toner. When the number of carbon atoms is less than 6, the durability of the toner decreases. When the number of carbon atoms exceeds 40, the storage stability of the toner decreases. Further, the number of carbon atoms is preferably 6 or more from the viewpoint of toner durability, more preferably 8 or more, further preferably 12 or more, from the viewpoint of storage stability, preferably 40 or less, more preferably 36 or less, and further preferably 26 or less. Preferably, 22 or less is more preferable, and 16 or less is more preferable. Therefore, from the viewpoints of storage stability and durability of the toner, the carbon number is 6 to 40, preferably 8 to 36, more preferably 12 to 26, still more preferably 12 to 22, and still more preferably 12 to 16. In the present invention, the carbon number of the carboxylic acid compound is the carbon number including the carbon number of the carboxyl group, but does not include the carbon number of the alkyl group of the alkyl ester. Further, in the present invention, including carboxylic acids, acid anhydrides, alkyl (C1-3) ester derivatives and the like are collectively referred to as carboxylic acid compounds.

  Specific examples of linear or branched monocarboxylic acid compounds include hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, lauric acid, stearic acid, myristic acid, palmitic acid, arachidic acid, behenic acid. Examples thereof include acids, lignoceric acid, linolenic acid, linoleic acid, oleic acid, acid anhydrides thereof, and alkyl (carbon number 1 to 3) esters.

  Specific examples of linear or branched dicarboxylic acid compounds include alkyl (the alkyl group preferably has 8 to 22 carbon atoms, more preferably 8 to 18 carbon atoms, and still more preferably 8 to 14 carbon atoms). Or alkenyl (the alkenyl group preferably has 8 to 22 carbon atoms, more preferably 8 to 18 carbon atoms, still more preferably 8 to 14 carbon atoms) succinic acid (hereinafter simply referred to as succinic acid derivative), adipic acid , Pentanedicarboxylic acid, hexanedicarboxylic acid, heptanedicarboxylic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, dimer acid dimerized from unsaturated fatty acids having 8 to 18 carbon atoms, acid anhydrides thereof, Alkyl (C1-C3) ester etc. are mentioned.

  Among the aliphatic carboxylic acid compounds having 6 to 40 carbon atoms, succinic acid derivatives, sebacic acid and dimer acid are preferable from the viewpoint of low-temperature fixability and durability of the toner, and low-temperature fixability, durability and storage of the toner are preferred. From the viewpoint of properties, succinic acid derivatives are more preferable. The content of the aliphatic carboxylic acid compound having 6 to 40 carbon atoms, preferably the content of the succinic acid derivative is preferably 2 mol% or more in the carboxylic acid component from the viewpoint of low-temperature fixability and durability of the toner. More preferably 6 mol% or more, more preferably 10 mol% or more, more preferably 75 mol% or less, more preferably 60 mol% or less, from the viewpoint of low-temperature fixability and storage stability of the toner, 50 mol% or less is more preferable, 40 mol% or less is more preferable, and 30 mol% or less is more preferable. Therefore, from the viewpoint of low-temperature fixability, storage stability and durability of the toner, 2 to 75 mol% is preferable, 4 to 60 mol% is preferable, 6 to 50 mol% is more preferable, and 6 to 40 mol% is more preferable. 10-30 mol% is more preferable.

  The aliphatic alcohol having 6 to 40 carbon atoms is preferably a linear or branched mono- or dialcohol from the viewpoints of storage stability and durability of the toner. When the number of carbon atoms is less than 6, the durability of the toner decreases. When the number of carbon atoms exceeds 40, the storage stability of the toner decreases. Further, the number of carbon atoms is preferably 6 or more from the viewpoint of toner durability, more preferably 8 or more, further preferably 12 or more, from the viewpoint of storage stability, preferably 40 or less, more preferably 36 or less, and further preferably 26 or less. Preferably, 22 or less is more preferable, and 16 or less is more preferable. Therefore, from the viewpoints of storage stability and durability of the toner, the carbon number is 6 to 40, preferably 8 to 36, more preferably 12 to 26, still more preferably 12 to 22, and still more preferably 12 to 16.

  Specific examples of the linear or branched monoalcohol include hexanol, heptanol, octanol, nonanol, decanol, dodecanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, linoleyl alcohol and the like.

  Specific examples of the linear or branched dialcohol include hexanediol, heptanediol, octanediol, nonanediol, decanediol, dodecanediol, dimer diol and the like.

  The content of the aliphatic alcohol having 6 to 40 carbon atoms is preferably 2 mol% or more, more preferably 4 mol% or more, and more preferably 6 mol% or more from the viewpoint of low-temperature fixability and durability of the toner in the alcohol component. Preferably, it is more preferably 10 mol% or more, from the viewpoint of low-temperature fixability and storage stability of the toner, preferably 75 mol% or less, more preferably 60 mol% or less, further preferably 50 mol% or less, and 40 mol% or less. Even more preferred is 30 mol% or less. Therefore, from the viewpoint of low-temperature fixability, storage stability and durability of the toner, 2 to 75 mol% is preferable, 4 to 60 mol% is more preferable, 6 to 50 mol% is further preferable, and 6 to 40 mol% is more preferable. More preferably, 10-30 mol% is still more preferable.

  The total amount of the aliphatic carboxylic acid compound having 6 to 40 carbon atoms and the aliphatic alcohol having 6 to 40 carbon atoms is the total amount of the carboxylic acid component and the alcohol component, from the viewpoint of low-temperature fixability and durability of the toner. 1 mol% or more is preferable, 2 mol% or more is more preferable, 3 mol% or more is more preferable, 5 mol% or more is more preferable, and 35 mol% or less is preferable from the viewpoint of low-temperature fixability and storage stability of the toner. 30 mol% or less is more preferable, 20 mol% or less is more preferable, and 15 mol% or less is more preferable. Therefore, from the viewpoint of low-temperature fixability and storage stability and durability of the toner, 1 to 35 mol% is preferable, 2 to 30 mol% is more preferable, 3 to 20 mol% is further preferable, and 5 to 15 mol% is more preferable. Further preferred.

  [Total amount of aliphatic carboxylic acid compound having 6 to 40 carbon atoms and aliphatic alcohol having 6 to 40 carbon atoms] / [Total amount of carboxylic acid compound having furan ring and alcohol having furan ring described later] The molar ratio is preferably 0.03 or more, more preferably 0.05 or more, further preferably 0.1 or more, still more preferably 0.2 or more, from the viewpoint of low-temperature fixability and durability of the toner, and from the viewpoint of low-temperature fixability and storage stability of the toner. Is preferably 5 or less, more preferably 3 or less, further preferably 2 or less, and even more preferably 1 or less. Therefore, from the viewpoint of low-temperature fixability and storage stability and durability of the toner, 0.03 to 5 is preferable, 0.05 to 5 is more preferable, 0.1 to 3 is further preferable, 0.1 to 2 is still more preferable, and 0.2 to 1 is more preferable Further preferred.

  The molar ratio of the succinic acid derivative / the carboxylic acid compound having a furan ring described later is preferably 0.03 or more, more preferably 0.05 or more, still more preferably 0.1 or more, from the viewpoint of low-temperature fixability and durability of the toner. The above is more preferable, and from the viewpoint of low-temperature fixability and storage stability of the toner, 5 or less is preferable, 3 or less is more preferable, 2 or less is more preferable, and 1 or less is more preferable. Therefore, from the viewpoint of low-temperature fixability, storage stability and durability of the toner, 0.03 to 5 is preferable, 0.05 to 5 is more preferable, 0.1 to 3 is further preferable, 0.1 to 2 is still more preferable, and 0.2 to 1 is more preferable Further preferred.

  In the present invention, the amorphous polyester having a furan ring is an alcohol component containing a carboxylic acid component having a furan ring and / or an alcohol having a furan ring in at least one of the carboxylic acid component and the alcohol component. It is preferable that is used. As a furan ring, the formula (Ia) or (Ib):

The structure represented by these is preferable.

  As the carboxylic acid compound having a furan ring, furan carboxylic acid such as furan-2,5-dicarboxylic acid, furan-2,4-dicarboxylic acid, furan-2,3-dicarboxylic acid, furan-3,4-dicarboxylic acid, etc. A compound (in this specification, a carboxylic acid compound includes an ester of a carboxylic acid and an alcohol having 1 to 6 carbon atoms, preferably an alcohol having 1 to 3 carbon atoms and an acid anhydride); furan-2-carboxylic acid; Furan carboxylic acid compounds such as furan-3-carboxylic acid; Hydroxyfuran carboxylic acid compounds such as 5-hydroxymethyl-furan-2-carboxylic acid; Furfuryl acetic acid compounds, 3-carboxy-4-methyl-5-propyl-2- Carboxylic acid compounds such as furan propionate (in the present specification, hydroxycarboxylic acid compounds are included in the carboxylic acid compound) and the like. Among these, from the viewpoint of low-temperature fixability and storage stability of the toner, Njikarubon acid compound is preferably at least one selected from the group consisting of furan carboxylic acid compound and a hydroxy-furancarboxylic acid compounds, in particular the flange carboxylic acid compound in terms of the storage stability of the toner is more preferable.

  Examples of the alcohol having a furan ring include furan alcohol such as dihydroxyfuran; hydroxymethylfurfuryl alcohol such as 5-hydroxymethylfurfuryl alcohol; furfuryl alcohol; 5-hydroxymethylfurfural. From the viewpoint of low-temperature fixability and storage stability of the toner, at least one selected from the group consisting of furan alcohol, hydroxymethylfurfuryl alcohol and furfuryl alcohol is preferred, and particularly from the viewpoint of toner preservability, furan alcohol and hydroxymethyl. Furfuryl alcohol is more preferred.

  As the carboxylic acid compound having a furan ring represented by the formula (Ia), furan-2,5-dicarboxylic acid, furan-2,4-dicarboxylic acid, furan-2,3-dicarboxylic acid, furan-3,4-dicarboxylic acid Examples thereof include furandicarboxylic acid compounds such as acids; carboxylic acid compounds such as hydroxyfurancarboxylic acid compounds such as 5-hydroxymethyl-furan-2-carboxylic acid.

  Examples of the alcohol having a furan ring represented by the formula (Ia) include hydroxymethylfurfuryl alcohol such as 5-hydroxymethylfurfuryl alcohol; flanged alcohol such as dihydroxyfuran; 5-hydroxymethylfurfural.

  Examples of the carboxylic acid compound having a furan ring represented by the formula (Ib) include furan carboxylic acid compounds such as furan-2-carboxylic acid and furan-3-carboxylic acid; and furfuryl acetic acid compounds.

  Examples of the alcohol having a furan ring represented by the formula (Ib) include furfuryl alcohol.

  Among the above carboxylic acid compounds and alcohols, from the viewpoints of low-temperature fixability and storage stability of the toner, a carboxylic acid compound and an alcohol having a furan ring represented by the formula (Ia) are preferable. Methylfurfuryl alcohol is more preferable, and furancarboxylic acid compound is more preferable.

  The total amount of the carboxylic acid compound having a furan ring and the alcohol having a furan ring is preferably 10 to 10 in the total amount of the carboxylic acid component and the alcohol component, from the viewpoint of toner storage stability, low-temperature fixability, and durability. It is 95 mol%, More preferably, it is 15-75 mol%, More preferably, it is 20-50 mol%, More preferably, it is 25-40 mol%.

  Further, the content of the carboxylic acid compound having a furan ring is preferably 10 to 100 mol%, more preferably 20 to 96 mol% in the carboxylic acid component, from the viewpoint of low-temperature fixability, storage stability and durability of the toner. More preferably, it is 20 to 90 mol%, more preferably 30 to 90 mol%, still more preferably 30 to 80 mol%, still more preferably 60 to 80 mol%, and the content of the furandicarboxylic acid compound is From the viewpoint of low-temperature fixability, storage stability and durability of the toner, the carboxylic acid component is preferably 10 to 100 mol%, more preferably 20 to 96 mol%, still more preferably 20 to 90 mol%, and still more preferably Is 30 to 90 mol%, more preferably 30 to 80 mol%, still more preferably 60 to 80 mol%.

  The content of the alcohol having a furan ring is preferably 10 to 100% by mole, more preferably 20 to 96% by mole, and still more preferably 20% in the alcohol component from the viewpoints of low-temperature fixability, storage stability and durability of the toner. It is -90 mol%, More preferably, it is 30-80 mol%.

  Further, from the viewpoint of low-temperature fixability, storage stability and durability of the toner, the content of the carboxylic acid compound having one type of furan ring in the carboxylic acid component is preferably 10 to 100 mol%, more preferably 20 to 20%. 96 mol%, more preferably 20 to 90 mol%, still more preferably 30 to 80 mol%, still more preferably 60 to 80 mol%, and the content of alcohol having one type of furan ring in the alcohol component Is preferably 10 to 100 mol%, more preferably 20 to 96 mol%, more preferably 20 to 90 mol%, still more preferably 30 to 80 mol%. Note that one type is a structural type, and even if the composition formula is the same, different structural formulas are regarded as different types.

  As the alcohol component other than the alcohol having a furan ring and the aliphatic alcohol having 6 to 40 carbon atoms, an aliphatic diol having 2 to 5 carbon atoms is preferable from the viewpoint of low-temperature fixability of the toner, and the fatty acid having 3 to 4 carbon atoms. Group diols are more preferred.

  Examples of the aliphatic diol having 2 to 5 carbon atoms include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 1,4-butenediol, 2,3-butanediol, 2,3-pentanediol, 2 , 4-pentanediol and the like.

  Of these, secondary carbon is used from the viewpoint of further improving the storage stability of the toner and promoting the amorphousness of the resin by improving the low temperature fixability by further reducing the mobility of the resin together with the furan ring. An aliphatic diol having 3 to 5 carbon atoms and having a hydroxyl group bonded to an atom is preferred. The aliphatic diol preferably has 3 to 4 carbon atoms from the viewpoint of low-temperature fixability and storage stability. Specific examples include 1,2-propanediol, 1,2-butanediol, and 1,3-butane. 1,2-propanediol and 2,3-butanediol are preferred from the viewpoint of low-temperature fixability, storage stability and durability of the toner, and 1,2-propanediol. Is more preferable.

  The content of the aliphatic diol having 2 to 5 carbon atoms is preferably 10 to 100 mol in alcohol components other than the alcohol having a furan ring and the aliphatic alcohol having 6 to 40 carbon atoms from the viewpoint of low-temperature fixability of the toner. %, More preferably 20-100 mol%, more preferably 30-100 mol%, even more preferably 50-100 mol%, even more preferably 90-100 mol%, even more preferably substantially 100 mol% The content of the aliphatic diol having 3 to 5 carbon atoms having a hydroxyl group bonded to a secondary carbon atom is preferably 10 to 100 mol in the alcohol component from the viewpoint of low temperature fixability and storage stability of the toner. %, More preferably 20-100 mol%, more preferably 30-100 mol%, even more preferably 50-100 mol%, even more preferably 90-100 mol%, even more preferably substantially 100 mol% It is.

  When the alcohol component includes an alcohol having a furan ring, the alcohol (molar ratio) having an aliphatic diol having 2 to 5 carbon atoms / furan ring (molar ratio) is preferably 0 to 10 from the viewpoint of low-temperature fixability and storage stability of the toner. 0.1 to 8 is more preferable, and 0.2 to 5 is more preferable.

  As alcohol components other than these, aromatic alcohols are preferable from the viewpoint of storage stability of the toner.

  As the aromatic alcohol, the formula (II):

(In the formula, R ¹ O and OR ¹ are oxyalkylene groups, R ¹ is an ethylene and / or propylene group, x and y indicate the number of added moles of alkylene oxide, and each is a positive number; The average value of the sum of y and y is preferably 1 to 16, more preferably 1 to 8, and even more preferably 1.5 to 4)
An alkylene oxide adduct of bisphenol A represented by

  Specific examples of the alkylene oxide adduct of bisphenol A represented by the formula (II) include 2,2-bis (4-hydroxyphenyl) propane polyoxypropylene adduct and 2,2-bis (4-hydroxy). And an alkylene oxide adduct of bisphenol A such as a polyoxyethylene adduct of phenyl) propane.

  The content of the alkylene oxide adduct of bisphenol A is preferably 10 to 100 mol% in the alcohol component other than the alcohol having a furan ring and the aliphatic alcohol having 6 to 40 carbon atoms from the viewpoint of storage stability of the toner. Preferably it is 20-100 mol%, More preferably, it is 30-100 mol%, More preferably, it is 50-100 mol%, More preferably, it is 90-100 mol%, More preferably, it is substantially 100 mol%.

  In the present invention, the alcohol component may contain a trihydric or higher polyhydric alcohol having 3 to 5 carbon atoms from the viewpoint of promoting the amorphization of the resin and improving the low-temperature fixability and durability of the toner. . As the trihydric or higher polyhydric alcohol having 3 to 5 carbon atoms, glycerin, pentaerythritol and the like are preferable, and glycerin is more preferable. The content of the trihydric or higher polyhydric alcohol having 3 to 5 carbon atoms is preferably 0.1 to 30 mol%, more preferably 1 to 25 mol% in the alcohol component from the viewpoint of improving the low-temperature fixability and durability of the toner. Preferably, 5 to 25 mol% is more preferable.

  As the carboxylic acid component other than the carboxylic acid compound having a furan ring and the aliphatic carboxylic acid compound having 6 to 40 carbon atoms, an aromatic dicarboxylic acid compound or an aliphatic dicarboxylic acid compound having 2 to 5 carbon atoms is preferable.

  The aromatic dicarboxylic acid compound is preferable from the viewpoints of chargeability and storage stability of the toner.

  Examples of the aromatic dicarboxylic acid compound include phthalic acid, isophthalic acid, terephthalic acid, acid anhydrides thereof, and alkyl (carbon number 1 to 5) esters.

  Among the carboxylic acid components other than the carboxylic acid compound having a furan ring and the aliphatic carboxylic acid compound having 6 to 40 carbon atoms, the aromatic dicarboxylic acid compound is preferably 10 to 100 mol% from the viewpoint of chargeability of the toner. Preferably it is 20-100 mol%, More preferably, it is 50-100 mol%, More preferably, it is 90-100 mol%, More preferably, it is substantially 100 mol%.

  When the carboxylic acid component contains a carboxylic acid compound having a furan ring, the aromatic dicarboxylic acid compound / the carboxylic acid compound having a furan ring (molar ratio) is preferably 0 to 10 from the viewpoints of chargeability and storage stability of the toner. 0.1 to 8 is more preferable, and 0.2 to 5 is more preferable.

  The aliphatic dicarboxylic acid compound having 2 to 5 carbon atoms is preferable from the viewpoint of low-temperature fixability, and 2 to 4 carbon atoms are more preferable.

  Examples of the aliphatic dicarboxylic acid compound having 2 to 5 carbon atoms include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, succinic acid, their acid anhydrides, and alkyl (1 to 3 carbon atoms) esters. Etc.

  From the viewpoint of low-temperature fixability of the toner, the content of the aliphatic dicarboxylic acid compound having 2 to 5 carbon atoms is selected from the carboxylic acid components other than the carboxylic acid compound having a furan ring and the aliphatic carboxylic acid compound having 6 to 40 carbon atoms. Preferably, it is 10-100 mol%, More preferably, it is 20-100 mol%, More preferably, it is 50-100 mol%, More preferably, it is 90-100 mol%, More preferably, it is substantially 100 mol%.

  In the present invention, the carboxylic acid component is a trivalent or higher polyvalent carboxylic acid compound having 3 to 5 carbon atoms from the viewpoint of promoting the amorphization of the resin and improving the low-temperature fixability, durability and storage stability of the toner. It is preferable to contain. The trivalent or higher polyvalent carboxylic acid compound having 3 to 5 carbon atoms is preferably trimellitic acid or pyromellitic acid, more preferably trimellitic acid compound, and more preferably trimellitic anhydride. The content of the trivalent or higher polyvalent carboxylic acid compound having 3 to 5 carbon atoms is preferably 0.1 to 40 mol%, preferably 1 to 30 mol% in the carboxylic acid component from the viewpoint of durability and storage stability of the toner. More preferably, 5-28 mol% is more preferable, 20-28 mol% is further more preferable, and 23-28 mol% is further more preferable.

  Examples of other carboxylic acid compounds include alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; rosin; rosin modified with fumaric acid, succinic acid, maleic acid, acrylic acid, and the like.

  The alcohol component contains a monovalent alcohol having 5 or less carbon atoms, and the carboxylic acid component contains a monovalent carbon atom having 5 or less carbon atoms, from the viewpoint of adjusting the molecular weight and improving offset resistance. It may be.

  The molar ratio of the carboxylic acid component to the alcohol component (carboxylic acid component / alcohol component) is preferably 0.5 to 1.3, more preferably 0.6 to 1.3, and more preferably 0.7 to 1.1.

  In the production of the amorphous polyester of the present invention, the condensation polymerization of the alcohol component and the carboxylic acid component is preferably performed in an inert gas atmosphere, from the viewpoint of reactivity and thermal decomposability of the compound having a furan ring. The reaction temperature is preferably 160 to 230 ° C, more preferably 180 to 220 ° C.

  The amorphous polyester of the present invention can be produced with or without a catalyst depending on the type and combination of raw material monomers used. For example, when no catalyst is used, a resin excellent in hue can be obtained as a binder resin for toner.

  Examples of the catalyst include esterification catalysts such as tin compounds and titanium compounds.

  As the tin compound, for example, dibutyltin oxide is known, but in the present invention, a tin (II) compound having no Sn—C bond is preferable from the viewpoint of good dispersibility in the polyester. .

  Examples of the tin (II) compound having no Sn—C bond include a tin (II) compound having a Sn—O bond, a tin (II) compound having a Sn—X (X represents a halogen atom) bond, and the like. Preferably, a tin (II) compound having a Sn—O bond is more preferable.

Examples of tin (II) compounds having Sn-O bonds include tin (II) oxalate, tin (II) acetate, tin (II) octoate, tin (II) 2-ethylhexanoate, and tin (II) laurate. , Tin (II) carboxylate having a carboxylic acid group having 2 to 28 carbon atoms such as tin (II) stearate, tin (II) oleate; octyloxy tin (II), lauroxy tin (II), stearoxy tin (II) ), Alkoxytin (II) having an alkoxy group having 2 to 28 carbon atoms such as oleyloxytin (II); tin (II) oxide; tin (II) sulfate, Sn—X (X represents a halogen atom) Examples of the tin (II) compound having a bond include tin (II) halides such as tin (II) chloride and tin (II) bromide, and among these, from the standpoint of charge rising effect and catalytic ability , (R ² COO) ₂ Sn (wherein R ² represents an alkyl group or alkenyl group having 5 to 19 carbon atoms), (R ³ O) ₂ Sn (where R ³ Is C 6-20 alk Alkoxy tin (II) and tin oxide represented by SnO (II) is preferably represented by a group or an alkenyl group), (R ² COO) fatty tin represented by ₂ Sn (II) and tin oxide ( II) is more preferable, and tin (II) octoate, tin (II) 2-ethylhexanoate, tin (II) stearate and tin (II) oxide are more preferable.

Specific examples of titanium compounds include titanium diisopropylate bistriethanolamate [Ti (C ₆ H ₁₄ O ₃ N) ₂ (C ₃ H ₇ O) ₂ ], titanium diisopropylate bisdiethanolamate [Ti (C ₄ H ₁₀ O ₂ N) ₂ (C ₃ H ₇ O) ₂ ], titanium dipentylate bistriethanolamate [Ti (C ₆ H ₁₄ O ₃ N) ₂ (C ₅ H ₁₁ O) ₂ ], titanium diety rate bis triethanolaminate _{[Ti (C 6 H 14 O 3} N) 2 (C 2 H 5 O) 2 ], titanium dihydroxy octylate bis triethanolaminate _{[Ti (C 6 H 14 O 3} N) 2 (OHC 8 H ₁₆ O) ₂ ], titanium distearate bistriethanolamate [Ti (C ₆ H ₁₄ O ₃ N) ₂ (C ₁₈ H ₃₇ O) ₂ ], titanium triisopropylate triethanolamate [Ti (C ₆ H ₁₄ O ₃ N) (C ₃ H ₇ O) ₃ ], titanium monopropylate tris (triethanolaminate) [Ti (C ₆ H ₁₄ O ₃ N) ₃ (C ₃ H ₇ O)] and the like, among these, titanium diisopropylate bistri Ethanolaminate, titanium diisopropylate bisdiethanolamate and titanium dipentylate bistriethanolamate are preferred, and these are also available as commercial products of Matsumoto Trading Co., Ltd., for example.

Specific examples of other preferable titanium compounds include tetra-n-butyl titanate [Ti (C ₄ H ₉ O) ₄ ], tetrapropyl titanate [Ti (C ₃ H ₇ O) ₄ ], tetrastearyl titanate [Ti ( C ₁₈ H ₃₇ O) ₄ ], tetramyristyl titanate [Ti (C ₁₄ H ₂₉ O) ₄ ], tetraoctyl titanate [Ti (C ₈ H ₁₇ O) ₄ ], dioctyl dihydroxyoctyl titanate [Ti (C ₈ H ₁₇ O) ₂ (OHC ₈ H ₁₆ O) ₂ ], dimyristyl dioctyl titanate [Ti (C ₁₄ H ₂₉ O) ₂ (C ₈ H ₁₇ O) ₂ ] and the like. Among these, tetrastearyl titanate, tetra Myristyl titanate, tetraoctyl titanate and dioctyl dihydroxy octyl titanate are preferred. These can be obtained, for example, by reacting a titanium halide with a corresponding alcohol, or can be obtained as a commercial product such as Nisso.

  The amount of the esterification catalyst present is preferably 0.01 to 2.0 parts by weight, more preferably 0.1 to 1.5 parts by weight, and still more preferably 0.2 to 1.0 parts by weight with respect to 100 parts by weight of the total amount of the alcohol component and the carboxylic acid component.

  In the present invention, it is preferable to use a pyrogallol compound having a benzene ring in which hydrogen atoms bonded to three adjacent carbon atoms are substituted with a hydroxyl group, together with an esterification catalyst, from the viewpoint of improving the storage stability of the toner.

  Examples of pyrogallol compounds include pyrogallol, gallic acid, gallic acid esters, 2,3,4-trihydroxybenzophenone, benzophenone derivatives such as 2,2 ', 3,4-tetrahydroxybenzophenone, epigallocatechin, epigallocatechin gallate, etc. Catechin derivatives and the like.

  The amount of the pyrogallol compound in the condensation polymerization reaction is preferably 0.001 to 1.0 part by weight, more preferably 0.005 to 0.4 part by weight, from the viewpoint of storage stability of the toner with respect to 100 parts by weight of the total amount of the alcohol component and the carboxylic acid component. Preferably, 0.01 to 0.2 parts by weight is more preferable. Here, the abundance of the pyrogallol compound means the total amount of the pyrogallol compound subjected to the condensation polymerization reaction.

  The pyrogallol compound is considered to function as a promoter for the esterification catalyst. The esterification catalyst used together with the pyrogallol compound is preferably at least one metal catalyst selected from the group consisting of tin compounds, titanium compounds, antimony trioxide, zinc acetate, and germanium dioxide.

  The weight ratio of the pyrogallol compound to the esterification catalyst (pyrogallol compound / esterification catalyst) is preferably from 0.01 to 0.5, more preferably from 0.03 to 0.3, and even more preferably from 0.05 to 0.2, from the viewpoint of storage stability of the toner.

  The amorphous polyester of the present invention refers to a resin including a polyester unit obtained by condensation polymerization of an alcohol component and a carboxylic acid component, and includes not only polyester but also polyester / polyamide. From the viewpoint of charging stability, polyester is preferred.

  In addition, polyester modified | denatured to such an extent that the characteristic is not impaired substantially may be sufficient.

  Examples of the polyester-modified resin include a urethane-modified polyester obtained by modifying a polyester with a urethane bond, an epoxy-modified polyester obtained by modifying a polyester with an epoxy bond, and two or more resin components including a polyester component and a vinyl resin component. Examples include composite resins.

  A composite resin having a polyester component and a vinyl resin component is prepared by a method of melt-kneading each resin in the presence of an initiator or the like, a method of dissolving and mixing each resin in a solvent, It may be produced by any method such as a method of polymerizing the raw material monomer mixture. A resin obtained by a method of performing a condensation polymerization reaction and an addition polymerization reaction using a raw material monomer for the polyester component and a raw material monomer for the vinyl resin component is preferable (Japanese Patent Laid-Open No. 7-98518). Specifically, in addition to the raw material monomer of the condensation polymerization resin and the raw material monomer of the addition polymerization resin, a compound capable of reacting with both the raw material monomer of the condensation polymerization resin and the raw material monomer of the addition polymerization resin (both reactions) It is preferable that the resin be a hybrid resin (resin in which a condensation polymerization resin and an addition polymerization resin are partially bonded via an both-reactive monomer). As the both reactive monomers, in the molecule, at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an epoxy group, a primary amino group and a secondary amino group, preferably a hydroxyl group and / or A compound having a carboxyl group, more preferably a carboxyl group and an ethylenically unsaturated bond is preferred, and acrylic acid, methacrylic acid and fumaric acid are more preferred.

  Raw material monomers for vinyl resin components include styrene compounds such as styrene and α-methylstyrene; ethylenically unsaturated monoolefins such as ethylene and propylene; diolefins such as butadiene; halovinyls such as vinyl chloride; vinyl acetate Vinyl esters such as vinyl propionate; alkyl (1 to 18 carbon atoms) esters of (meth) acrylic acid; esters of ethylenic monocarboxylic acids such as dimethylaminoethyl (meth) acrylate; vinyl ethers such as vinyl methyl ether And vinylidene halides such as vinylidene chloride; N-vinyl compounds such as N-vinylpyrrolidone and the like. Styrene, butyl acrylate, 2-ethylhexyl acrylate, and methyl methacrylate are preferable from the viewpoints of reactivity, grindability, and charge stability, and an alkyl ester of styrene and / or (meth) acrylic acid is a vinyl resin component. The content is preferably 50% by weight or more, more preferably 80 to 100% by weight.

  In addition, when polymerizing the raw material monomer of a vinyl-type resin component, you may use a polymerization initiator, a crosslinking agent, etc. as needed.

  The weight ratio of the raw material monomer of the polyester component to the raw material monomer of the vinyl resin component (the raw material monomer of the polyester component / the raw material monomer of the vinyl resin component) is preferably 55/45 to from the viewpoint of forming a continuous phase with the polyester component. It is 95/5, More preferably, it is 60 / 40-95 / 5, More preferably, it is 70 / 30-90 / 10. The bireactive monomer is a raw material monomer for the polyester component.

  The amorphous polyester of the present invention can be adjusted to a high glass transition point even at a low molecular weight. The glass transition point is 40 to 100 ° C. from the viewpoint of low-temperature fixability and storage stability of the toner. Is preferable, 45-85 degreeC is more preferable, 45-80 degreeC is further more preferable.

  The softening point of the amorphous polyester of the present invention is preferably 180 ° C. or lower from the viewpoint of low-temperature fixability of the toner, and preferably 80 ° C. or higher from the viewpoint of storage stability and durability of the toner. And from a viewpoint of durability, 80-180 degreeC is preferable, 90-160 degreeC is more preferable, 95-150 degreeC is further more preferable.

  Since the amorphous polyester of the present invention can be adjusted to a high glass transition point even if the softening point is low, the softening point is 80 ° C. from the viewpoint of low-temperature fixability, storage stability and durability of the toner. When the temperature is lower than 115 ° C, the glass transition point is preferably 40 to 70 ° C, more preferably 50 to 65 ° C. When the softening point is 115 to 180 ° C, the glass transition point is preferably 55 to 90 ° C, more preferably 60 to 85 ° C.

  The acid value of the amorphous polyester of the present invention is preferably from 1 to 80 mgKOH / g, more preferably from 2 to 70 mgKOH / g, further preferably from 3 to 60 mgKOH / g, and from 3 to 20 mgKOH from the viewpoint of charging stability of the toner. / g is more preferable, and the hydroxyl value is preferably 5 to 80 mgKOH / g, more preferably 5 to 75 mgKOH / g, further preferably 10 to 70 mgKOH / g, and further preferably 40 to 70 mgKOH / g.

  The softening point, glass transition point, acid value, and hydroxyl value of the amorphous polyester can be easily adjusted by adjusting the raw material monomer composition, the polymerization initiator, the molecular weight, the catalyst amount, etc., or by selecting the reaction conditions. For example, by increasing the reaction temperature of the condensation polymerization, increasing the reaction time, increasing the amount of catalyst, or using a cocatalyst together, the condensation polymerization reaction can be promoted to increase the softening point and glass transition point. Can do. In addition, the glass transition point may be increased by increasing the total amount of the carboxylic acid compound having a furan ring and the alcohol having a furan ring in the total amount of the carboxylic acid component and the alcohol component used in the condensation polymerization reaction. it can.

  The binder resin of the present invention comprises a resin having a high softening point (high softening point resin) and a resin having a low softening point (low softening point resin) from the viewpoint of low-temperature fixability, storage stability, durability, and charging stability of the toner. Preferably, both the high softening point resin and the low softening point resin are resins containing a furan ring.

  The difference in softening point between the high softening point resin and the low softening point resin is preferably 10 ° C. or more, more preferably 20 to 60 ° C., from the viewpoint of low temperature fixability and storage stability of the toner.

  The softening point of the high softening point resin is preferably 115 to 180 ° C., more preferably 120 to 160 ° C., and the softening point of the low softening point resin is preferably 80 ° C. or more and less than 115 ° C., more preferably 90 to 110 ° C. The weight ratio of the high softening point resin to the low softening point resin (high softening point resin / low softening point resin) is preferably 1/4 to 4/1, more preferably 1/3 to 3/1, and more preferably 1/3 to 1/1 is more preferable.

  By using the amorphous polyester of the present invention as a binder resin, it is possible to obtain an electrophotographic toner excellent in durability while maintaining low-temperature fixability and storage stability of the toner.

  In the toner of the present invention, a known binder resin other than the amorphous polyester, for example, a vinyl resin such as styrene-acrylic resin, an epoxy resin, a polycarbonate, a polyurethane, or the like, as long as the effects of the present invention are not impaired. Although other resins may be used in combination, the content of the amorphous polyester of the present invention is preferably 70% by weight or more, more preferably 80% by weight or more, and more preferably 90% by weight or more in the binder resin. Preferably, substantially 100% by weight is even more preferred.

  The toner of the present invention further includes a colorant, a release agent, a charge control agent, a charge control resin, a magnetic powder, a fluidity improver, a conductivity modifier, an extender pigment, a reinforcing filler such as a fibrous substance, an oxidation Additives such as an inhibitor, an anti-aging agent, and a cleaning property improver may be appropriately contained.

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

  Release agents include polyolefin wax, paraffin wax, silicones; fatty acid amides such as oleic acid amide, erucic acid amide, ricinoleic acid amide, stearic acid amide; carnauba wax, rice wax, candelilla wax, wood wax, jojoba Plant waxes such as oils; animal waxes such as beeswax; waxes such as mineral and petroleum waxes such as montan wax, ozokerite, ceresin, microcrystalline wax, and Fischer-Tropsch wax, which are used alone or in combination of two or more Can be mixed and used.

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

  The content of the release agent is preferably 0.5 to 10 parts by weight, more preferably 1 to 8 parts by weight, and more preferably 1.5 to 7 parts by weight from the viewpoint of dispersibility in the binder resin with respect to 100 parts by weight of the binder resin. Part by weight is more preferred.

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

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

  In addition, as a negatively chargeable charge control agent, metal-containing azo dyes such as “Varifirst Black 3804”, “Bontron S-31” (above, manufactured by Orient Chemical Industries), “T-77” (Hodogaya Chemical) Manufactured by Kogyo Co., Ltd.), Bontron S-32, Bontron S-34, Bontron S-36 (above, Orient Chemical Co., Ltd.), Eisenspiron Black TRH (Hodogaya Chemical Co., Ltd.) A metal compound of a benzylic acid compound, such as “LR-147”, “LR-297” (manufactured by Nippon Carlit Co., Ltd.); a metal compound of a salicylic acid compound, such as “Bontron E-81”, “Bontron E- 84, “Bontron E-88”, “E-304” (manufactured by Orient Chemical Co., Ltd.), “TN-105” (manufactured by Hodogaya Chemical Co., Ltd.); copper phthalocyanine dye; quaternary ammonium salt such as “ COPY CHARGE NX VP434 "(manufactured by Clariant), nitroimidazole derivative; organometallic Compounds, for example "TN105" (Hodogaya Chemical Co., Ltd.).

  The content of the charge control agent is preferably 0.01 to 10 parts by weight, more preferably 0.01 to 5 parts by weight, and more preferably 0.3 to 3 parts by weight with respect to 100 parts by weight of the binder resin from the viewpoint of charging stability of the toner. More preferably, 0.5 to 3 parts by weight is even more preferable, and 1 to 2 parts by weight is even more preferable.

  The present invention preferably contains a charge control resin in order to improve chargeability. As the charge control resin, a styrene resin is preferable, and from the viewpoint of developing positive chargeability of the toner, a quaternary ammonium base-containing styrene resin is preferable, and from the viewpoint of developing negative chargeability of the toner, a sulfonic acid group-containing styrene. Based resins are preferred.

  The amount of the styrenic resin contained as the charge control resin is preferably 3 to 40 parts by weight, more preferably 4 to 30 parts by weight with respect to 100 parts by weight of the binder resin, from the viewpoint of improving the chargeability of the toner. 5 to 20 parts by weight is more preferable.

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

  The toner for electrophotography of the present invention may be obtained by a method including a step of granulating a raw material containing the binder resin of the present invention in an aqueous medium. The production method is not particularly limited. For example, (A) a method in which primary particles containing a binder resin are formed in advance in an aqueous medium, and then the primary particles are aggregated and coalesced; (B) in an aqueous medium. Examples thereof include a method in which primary particles containing a binder resin are formed in advance and then the primary particles are fused, and a method (C) in which a raw material containing the binder resin is dispersed in an aqueous medium to form particles.

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

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

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

  The amount of the aqueous medium used is preferably 100 to 1000 parts by weight with respect to 100 parts by weight of the organic solvent. The aqueous medium used in the method (1) may contain a solvent such as an organic solvent, but water is preferably 50% by weight or more, preferably 70% by weight or more, more preferably 90% by weight or more. More preferably, it contains 99% by weight or more.

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

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

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

  The average primary particle diameter is preferably 0.05 to 3 μm, more preferably 0.05 to 1 μm, and even more preferably 0.05 to 0.8 μm from the viewpoint of uniformly agglomerating in the subsequent step. In the present invention, the average particle size of primary particles refers to the volume median particle size (D50) and can be measured by a laser diffraction type particle size measuring instrument or the like.

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

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

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

  From the same viewpoint, the temperature in the system in the aggregation process is preferably a softening point of the binder resin of −70 ° C. or more and a softening point or less.

  In addition, additives such as a colorant and a charge control agent may be premixed in the binder resin when preparing the primary particles, or a dispersion liquid in which each additive is separately dispersed in a dispersion medium such as water. It may be prepared, mixed with primary particles, and subjected to an aggregation process. When the additive is previously mixed with the binder resin when preparing the primary particles, it is preferable to melt and knead the binder resin and the additive in advance. For melt kneading, it is preferable to use an open roll type biaxial kneader. The open roll type twin-screw kneader is a kneader in which two rolls are arranged close to each other in parallel, and a heating function or a cooling function can be imparted by passing a heat medium through each roll. Therefore, the open roll type twin screw kneader is an open type part to be melt kneaded and is provided with a heating roll and a cooling roll. The heat of kneading generated can be easily dissipated.

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

  The amount of the flocculant used is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, and even more preferably 10 parts by weight or less with respect to 100 parts by weight of the binder resin from the viewpoint of environmental resistance characteristics of the toner.

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

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

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

  In the washing step, it is preferable to use an acid in order to remove metal ions on the toner surface in order to ensure sufficient charging characteristics and reliability as the toner. Further, when a nonionic surfactant is used in a dispersion such as a colorant, it is preferably completely removed by washing, and washing with an aqueous solution below the cloud point of the nonionic surfactant is preferred. . The washing is preferably performed a plurality of times.

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

The volume median particle size (D ₅₀ ) of the toner of the present invention is preferably 3 to 15 μm, more preferably 3 to 10 μm. In the present specification, the volume-median particle size (D ₅₀ ) means a particle size at which the cumulative volume frequency calculated by the volume fraction is 50% when calculated from the smaller particle size.

  In the toner of the present invention, it is preferable to use inorganic fine particles as an external additive in order to improve transferability. Specifically, at least one selected from the group consisting of silica, alumina, titania, zirconia, tin oxide, and zinc oxide is preferable. Among these, silica is preferable, and from the viewpoint of preventing embedding, the specific gravity is More preferably, small silica is contained.

  Silica is preferably hydrophobic silica that has been subjected to a hydrophobic treatment, from the viewpoint of toner transferability.

  Examples of the hydrophobizing agent for hydrophobizing the surface of silica particles include organochlorosilane, organoalkoxysilane, organodisilazane, cyclic organopolysilazane, linear organopolysiloxane, and the like. Examples thereof include silazane (HMDS), dimethyldichlorosilane (DMDS), silicone oil, octyltriethoxysilane (OTES), methyltriethoxysilane, and the like. Among these, hexamethyldisilazane is preferable.

  The average particle diameter of the external additive is preferably from 10 to 250 nm, more preferably from 10 to 200 nm, and even more preferably from 15 to 150 nm, from the viewpoints of the chargeability, fluidity and transferability of the toner.

  The content of the external additive is preferably 0.05 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, and further preferably 0.3 to 0.3 parts by weight with respect to 100 parts by weight of the toner before being processed with the external additive. 3 parts by weight.

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

[Softening point of resin]
Using a flow tester (Shimadzu Corporation, CFT-500D), a 1 g sample is heated at a heating rate of 6 ° C / min, and a 1.96 MPa load is applied by a plunger and extruded from a nozzle with a diameter of 1 mm and a length of 1 mm. . Plot the plunger drop amount of the flow tester against the temperature, and let the softening point be the temperature at which half of the sample flowed out.

[Maximum peak temperature of resin endotherm]
Using a differential scanning calorimeter (Q-100 Japan, Q-100), weigh 0.01 to 0.02 g of the sample into an aluminum pan and cool it from room temperature to 0 ° C at a rate of 10 ° C / min. Then, it was left still for 1 minute. Thereafter, the measurement was carried out at a heating rate of 50 ° C./min. Of the endothermic peaks observed, the peak temperature on the highest temperature side was defined as the highest endothermic peak temperature.

[Glass transition point of resin]
Using a differential scanning calorimeter (Seiko Denshi Kogyo Co., Ltd., DSC210), 0.01 to 0.02 g of sample was weighed into an aluminum pan, heated to 200 ° C, and cooled to 0 ° C at a rate of 10 ° C / min. The sample is heated at a heating rate of 10 ° C / min, and the temperature is the intersection of the base line extension below the maximum endothermic peak temperature and the tangent that indicates the maximum slope from the peak rise to the peak apex. .

[Hydroxyl value of the resin]
Measured according to the method of JIS K0070.

[Melting point of release agent]
Using a differential scanning calorimeter (Seiko Denshi Kogyo Co., Ltd., DSC210), the temperature was raised to 200 ° C, and the sample was cooled to 0 ° C at a temperature drop rate of 10 ° C / min. The maximum peak temperature of heat of fusion is taken as the melting point.

[Volume-median particle diameter of toner (D ₅₀ )]
Measuring machine: Coulter Multisizer II (Beckman Coulter, Inc.)
Aperture diameter: 50μm
Analysis software: Coulter Multisizer AccuComp version 1.19 (Beckman Coulter)
Electrolyte: Isoton II (Beckman Coulter, Inc.)
Dispersion: Emulgen 109P (manufactured by Kao Corporation, polyoxyethylene lauryl ether, HLB: 13.6) 5% electrolyte dispersion condition: 10 mg of measurement sample is added to 5 ml of dispersion, and dispersed for 1 minute with an ultrasonic disperser. Then, 25 ml of the electrolytic solution is added, and further dispersed with an ultrasonic disperser for 1 minute.
Measurement conditions: Add 100 ml of electrolyte and dispersion in a beaker, measure 30,000 particles at a concentration that can measure the particle size of 30,000 particles in 20 seconds, and determine the volume-median particle size ( determine the D _50).

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

Resin Production Example 1 [Resin 1, 2, 4-7, 9-17]
Predetermined amounts of raw material monomer and esterification catalyst shown in Tables 1 to 4 are placed in a 5-liter four-necked flask equipped with a thermometer, a stainless steel stirring rod, a flow-down condenser and a nitrogen inlet tube, and the mantle is placed in a nitrogen atmosphere. After heating up to 180 ° C. in a heater, the temperature was raised to 210 ° C. over 5 hours. Thereafter, it was confirmed that the reaction rate reached 95% or higher at 210 ° C., and the reaction was carried out at 40 kPa until the softening point shown in Tables 1 to 4 was reached. 7, 9-17). The reaction rate means a value of the amount of produced reaction water / theoretical product water amount × 100.

Resin Production Example 2 [Resin 3, 19]
Predetermined amounts of raw material monomer and esterification catalyst shown in Tables 1 and 4 are placed in a 5-liter four-necked flask equipped with a thermometer, a stainless steel stirring rod, a flow-down condenser and a nitrogen inlet tube, and the mantle is placed in a nitrogen atmosphere. The temperature was raised to 235 ° C in a heater, and the reaction was carried out at 235 ° C for 10 hours. Then, after reacting at 235 ° C. and 8 kPa for 1 hour, cooling to 210 ° C. and reacting at 20 kPa until reaching the softening point shown in Tables 1 and 4, amorphous polyester (resins 3 and 19) Got.

Resin Production Example 3 [Resin 8, 18]
The raw material monomer and esterification catalyst excluding the prescribed amount of trimellitic anhydride shown in Tables 2 and 4 are placed in a 5-liter four-necked flask equipped with a thermometer, a stainless stir bar, a flow-down condenser and a nitrogen inlet tube. After heating up to 180 ° C. in a mantle heater in a nitrogen atmosphere, the temperature was raised to 210 ° C. over 5 hours. Thereafter, it was confirmed that the reaction rate reached 95% or higher at 210 ° C., and a predetermined amount of trimellitic anhydride shown in Tables 2 and 4 was added. After reacting at normal pressure for 1 hour, the reaction was performed at 40 kPa until the softening points shown in Tables 2 and 4 were reached, and amorphous polyesters (resins 8 and 18) were obtained.

Examples 1 to 16 and Comparative Examples 1 and 2
100 parts by weight of binder resin shown in Table 5, 5 parts by weight of colorant “Regal 330R” (Cabot, carbon black), release agent “Mitsui High Wax NP055” (Mitsui Chemicals, polypropylene wax, melting point: 125 (° C) 2 parts by weight and 1 part by weight of the negatively chargeable charge control agent “Bontron E-81” (Orient Chemical Industries, Ltd.) were thoroughly mixed with a Henschel mixer, and then rotated using a co-rotating twin screw extruder. Melt kneading was performed at a speed of 200 r / min and a heating temperature of 80 ° C. in the roll. The obtained melt-kneaded product was cooled and coarsely pulverized, then pulverized with a jet mill and classified to obtain toner particles having a volume median particle size (D ₅₀ ) of 8 μm.

  To 100 parts by weight of the obtained toner particles, 1.0 part by weight of hydrophobic silica “NAX-50” (manufactured by Nippon Aerosil Co., Ltd., hydrophobizing agent: HMDS, average particle size: about 30 nm) is added and mixed with a Henschel mixer. As a result, a toner was obtained.

Example 17
Charge binder resin, coloring agent, etc., and charge control resin `` FCA-701PT '' (Fujikura Kasei Co., Ltd., quaternary ammonium base-containing styrene acrylic resin, softening point: 123 ° C) 5 parts by weight Instead of the control agent, 1 part by weight of the positively chargeable charge control agent “Bontron P-51” (manufactured by Orient Chemical Co., Ltd.) is used, and hydrophobic silica “TG” is used instead of “NAX-50” as an external additive. -C243 "(manufactured by Cabot, average particle size 100 nm, hydrophobizing agent: hexamethyldisilazane + octyltriethoxysilane) was used in the same manner as in Example 1 except that 1.0 part by weight was used.

Examples 18 and 20
As a colorant, instead of carbon black “Regal 330R”, in Example 18, cyan pigment “Toner Cyan BG” (manufactured by Clariant, PB15: 3) 5 parts by weight, in Example 20, yellow pigment “Paliotol Yellow D1155 ”(BASF, PY185) 6 parts by weight, instead of“ Mitsui High Wax NP055 ”as a release agent,“ HNP-9 ”(Nihon Seiki Co., Ltd., paraffin wax, melting point: 80 ° C.) 2 1 part by weight of LR-147 (Nippon Carlit Co., Ltd.) instead of Bontron E-81 (Orient Chemical Co., Ltd.) Example except that 1.0 part by weight of hydrophobic silica “R-972” (manufactured by Nippon Aerosil Co., Ltd., average particle size of 16 nm, hydrophobizing agent: dimethyldichlorosilane) was used instead of “NAX-50” as the agent. In the same manner as in Example 1, a toner was obtained.

Example 19
Instead of carbon black “Regal 330R”, 5 parts by weight of magenta pigment “Super Magenta R” (manufactured by Dainippon Ink and Chemicals, PR122) is used as a colorant, and as a release agent, “Mitsui High Wax NP055” Instead, 2 parts by weight of “HNP-9” (manufactured by Nippon Seiki Co., Ltd., paraffin wax, melting point: 80 ° C.) is used, and “Bontron E-81” (manufactured by Orient Chemical Co., Ltd.) is used as a negatively chargeable charge control agent. 1 part by weight of LR-297 '' (manufactured by Nippon Carlit Co., Ltd.) and hydrophobic silica `` R-972 '' (manufactured by Nippon Aerosil Co., Ltd., average particle size of 16 nm) instead of `` NAX-50 '' as an external additive , Hydrophobic treatment agent: dimethyldichlorosilane) A toner was obtained in the same manner as in Example 1 except that 1.0 part by weight was used.

Example 21
(Preparation of resin dispersion)
600 g of methyl ethyl ketone was put into a 5 L container equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen introduction tube, and 140 g of resin 1 and 860 g of resin shown in Table 5 were added and dissolved at room temperature. . The resulting solution was neutralized by adding 3.9 g of triethylamine (1 equivalent with respect to the binder resin acid value), and then 2000 g of ion-exchanged water was added, followed by stirring at 250 r / min under reduced pressure. Then, methyl ethyl ketone was distilled off at a temperature of 50 ° C. or lower to obtain a self-dispersing aqueous resin particle dispersion (resin content: 9.6% by weight (in terms of solid content)). The average particle diameter of the polyester particles (primary particles) dispersed in the obtained resin dispersion was 0.3 μm.

(Preparation of colorant dispersion)
Cyan pigment “Toner Cyan BG” (Clariant, PB15: 3) 50 g, nonionic surfactant (Emulgen 150, Kao Corporation, polyoxyethylene lauryl ether, HLB: 18.4, cloud point: 100 ° C. or higher ) 5 g and ion-exchanged water 200 g were mixed to dissolve copper phthalocyanine, and dispersed for 10 minutes using a homogenizer to obtain a colorant dispersion.

(Preparation of release agent dispersion)
"HNP-9" (Nippon Seiki Co., Ltd., paraffin wax, melting point: 80 ° C) 50g, cationic surfactant (Sanisol B50, Kao Corporation) 5g and ion-exchanged water 200g were heated to 95 ° C. Then, the paraffin wax was dispersed using a homogenizer, and then dispersed with a pressure discharge type homogenizer to obtain a release agent dispersion liquid in which the paraffin wax was dispersed with an average particle size of 550 nm.

(Preparation of charge control agent dispersion)
Charge control agent “LR-147” (manufactured by Nippon Carlit Co., Ltd.) 50 g, nonionic surfactant (Emulgen 150, manufactured by Kao Corporation, polyoxyethylene lauryl ether, HLB: 18.4, cloud point: 100 ° C. or higher) 5 g And 200 g of ion-exchanged water were mixed, and glass beads were used and dispersed for 10 minutes using a sand grinder to prepare a charge control agent dispersion in which the charge control agent was dispersed with an average particle size of 500 nm.

[Aggregation process]
490 g of the obtained resin particle dispersion, 20 g of the colorant dispersion, 15 g of the release agent dispersion, 7 g of the charge control agent dispersion and 2 g of the cationic surfactant (Sanisol B50, manufactured by Kao Corporation) After mixing and dispersing in a stainless steel flask using a homogenizer, the flask was heated to 48 ° C. while stirring in the oil bath for heating. Furthermore, after maintaining at 48 ° C. for 1 hour, it was confirmed that aggregated particles having a weight average particle diameter of 6.0 μm were formed. At this time, the solid content concentration was 8.8% by weight and the pH was 6.8.

[Joint process]
After adding 3 g of an anionic surfactant (Perex SS-L, manufactured by Kao Corporation) to the aggregated particle dispersion, a reflux tube was attached to the stainless steel flask, and the stirring was continued at 5 ° C / min. At a rate of 80 ° C. and held for 5 hours to coalesce and fuse the agglomerated particles. Thereafter, the mixture was cooled, the fused particles were filtered, thoroughly washed with ion exchange water, and then dried. The volume fine particle size (D ₅₀ ) of the obtained colored resin fine particle powder was 6.3 μm.

[Surface treatment process]
1.0 part by weight of hydrophobic silica “R-972” (manufactured by Nippon Aerosil Co., Ltd., average particle diameter: 16 nm, hydrophobizing agent: dimethyldichlorosilane) is added to 100 parts by weight of the obtained colored resin fine particle powder, and Henschel is added. Using a mixer, the mixture was added and externally added to obtain a cyan toner.

Example 22
A cyan toner was obtained in the same manner as in Example 21 except that the binder resin was changed to 70 g of resin and 830 g of resin. Aggregated particles having a weight average particle diameter of 0.2 μm were confirmed to be formed. At this time, the solid content concentration was 9.8% by weight and the pH was 6.7.

Test Example 1 [low temperature fixability]
An apparatus in which a fixing machine of a copying machine “AR-505” (manufactured by Sharp Corporation) is improved so that fixing can be performed outside the apparatus (however, for evaluation of Example 17, a non-magnetic one-component developing system printer “ The toner was mounted on “HL-2040” (manufactured by Brother Industries, Ltd.), and an unfixed image was obtained on a paper [CopyBond SF-70NA (75 g / m ² )] manufactured by Sharp Corporation. Using a fixing machine (fixing speed 390mm / sec) adjusted so that the total fixing pressure becomes 40kgf, gradually increase the temperature of the fixing roller from 100 ° C to 240 ° C by 10 ° C until the minimum fixing temperature is reached. The unfixed image was fixed on the fixing paper at each temperature. “UNICEF Cellophane” (Mitsubishi Pencil Co., Ltd., width: 18 mm, JISZ-1522) was pasted on the fixed image, passed through a fixing roller set at 30 ° C., and then the tape was peeled off. The optical reflection density of the image before and after the tape was peeled was measured using a reflection densitometer “RD-915” (manufactured by Macbeth), and the ratio between the two (after peeling / before sticking × 100) was initially 90 The fixing roller temperature exceeding 100% was set as the minimum fixing temperature, and the low-temperature fixing property was evaluated according to the following evaluation criteria. The results are shown in Table 5. The numerical value in parentheses in the table indicates the measured value of the minimum fixing temperature.

〔Evaluation criteria〕
A: The minimum fixing temperature is less than 140 ° C.
B: The minimum fixing temperature is 140 ° C. or higher and lower than 170 ° C.
C: The minimum fixing temperature is 170 ° C. or higher.

Test Example 2 [Preservation]
4 g of toner was placed in a cylindrical container having a radius of 12 mm and left for 72 hours in an environment of 55 ° C. and 60% humidity. After being left, the toner was taken out of the container, the degree of toner aggregation was visually observed, and storage stability was evaluated according to the following evaluation criteria. The results are shown in Table 5.

〔Evaluation criteria〕
A: No aggregation is observed even after 72 hours.
B: Aggregation is not observed after 48 hours, but aggregation is observed after 72 hours.
C: Aggregation is observed after 48 hours.

Test Example 3 [Durability]
“Page Presto N-4” (manufactured by Casio Computer Co., Ltd., fixing: contact fixing method, development: non-magnetic one-component development method, developing roll diameter: 2.3 cm) with toner mounted, temperature 32 ° C, humidity 85% Underneath, an oblique stripe pattern with a blackening rate of 5.5% was continuously printed. In the middle, a black solid image was printed every 500 sheets, and the presence or absence of streaks on the image was confirmed. Printing was stopped when streaks occurred on the image, and printing was performed up to 5000 sheets. The number of prints up to the time when the streak was visually observed on the image was defined as the number of streaks due to the fusion and fixing of the toner on the developing roll, and the durability was evaluated according to the following evaluation criteria. In other words, it can be determined that the greater the number of sheets where no streaking occurs, the higher the durability of the toner. The results are shown in Table 5. The numbers in parentheses in the table indicate the number of printed sheets up to the point where the durability streak was observed.

〔Evaluation criteria〕
A: Lines do not occur when printing 5000 sheets B: Lines occur when printing 2000 to 5000 sheets C: Lines occur when printing less than 2000 sheets

  From the above results, in comparison with Comparative Examples 1 and 2 containing an amorphous polyester having no furan ring as a binder resin, in Examples 1 to 22, the low temperature fixability, storage stability and durability were It turns out that all are good.

  The toner binder resin of the present invention is suitably used as a toner binder resin used for developing a latent image formed in, for example, electrophotography, electrostatic recording method, electrostatic printing method and the like.

Claims (9)

A electrophotographic toner comprising a binder resin for toner comprising an amorphous polyester having a furan ring, wherein the amorphous polyester is a condensation polymer of a carboxylic acid component and an alcohol component, the carboxylic At least one of the acid component and the alcohol component, alcohol component der belt toner containing aliphatic alcohols of the carboxylic acid component and / or a C 6-40 aliphatic carboxylic acid compound having 6 to 40 carbon atoms An electrophotographic toner comprising a binder resin. At least one of the carboxylic acid component and alcohol component is an alcohol component containing an alcohol having a carboxylic acid component and / or a furan ring containing a carboxylic acid compound having at least furan ring, toner over for electrophotography of claim 1, wherein . The toner for electrophotography according to claim 1 or 2, wherein the total amount of the carboxylic acid compound having a furan ring and the alcohol having a furan ring is 10 to 95 mol% in the total amount of the carboxylic acid component and the alcohol component. -. Alcohol component comprises an aliphatic diol having 3 to 5 carbon atoms having a hydroxyl group bonded to a secondary carbon atom, claims 1-3 electrophotographic toner over according any. 2. The total amount of the aliphatic carboxylic acid compound having 6 to 40 carbon atoms and the aliphatic alcohol having 6 to 40 carbon atoms is 1 to 35 mol% in the total amount of the carboxylic acid component and the alcohol component. to 4 electrophotographic toner over according to any one. The electrophotography according to any one of claims 1 to 5, wherein the aliphatic carboxylic acid compound having 6 to 40 carbon atoms is alkyl (8 to 22 carbon atoms) succinic acid and / or alkenyl (8 to 22 carbon atoms) succinic acid. use toner over. The toner for electrophotography according to any one of claims 2 to 6, wherein the carboxylic acid compound having a furan ring is at least one selected from the group consisting of furandicarboxylic acid compounds, furancarboxylic acid compounds and hydroxyfurancarboxylic acid compounds. -. Alcohols having furan ring, flange alcohol is at least one selected from the group consisting of hydroxymethyl furfuryl alcohol and furfuryl alcohol, according to claim 2-7 electrophotographic toner over according any. Molar ratio of [total amount of aliphatic carboxylic acid compound having 6 to 40 carbon atoms and aliphatic alcohol having 6 to 40 carbon atoms] / [total amount of carboxylic acid compound having furan ring and alcohol having furan ring] There is a 0.03 to 5, claim 2-8 electrophotographic toner over according any.