JP5954866B2 - 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 temperature of the resin is lowered and the storage stability is 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 temperature is widely used. Yes.

  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.

  Patent Document 3 has a specific furan ring structural unit for the purpose of providing a novel polyester resin that can be used to produce a molded article having excellent impact resistance. A polyester resin is disclosed.

JP 2008-291243 A JP 2008-291244 A JP 2009-197110 A

  However, the resins described in Patent Document 1 and Patent Document 2 are mainly used for film applications and injection molded products, and the resin described in Patent Document 3 is also a molded product composition. It has high crystallinity and is not suitable as a binder resin for toner.

  Amorphous polyester having a furan ring has a relatively hard molecular structure, can have a high glass transition temperature while having a low softening point, and can be a toner with good low-temperature fixability and storage stability of the toner. However, in order to achieve a high glass transition temperature at a low softening point, it is necessary to lower the molecular weight due to the specificity of the molecular structure of the amorphous polyester having a furan ring. On the other hand, it is considered that the filming characteristic of the toner is determined by a thermal factor depending on the glass transition temperature and the like and a mechanical factor depending on the molecular weight of the binder resin and the like. Therefore, in order to use an amorphous polyester resin having a furan ring for a toner, if the molecular weight is set low, there is a problem that it becomes weak against mechanical factors and filming resistance deteriorates.

  An object of the present invention is to provide a binder resin for toner that can achieve both low-temperature fixability and storage stability of the toner, and also has good filming resistance, and an electrophotographic toner containing the binder resin. There is to do.

The present invention
[1] Amorphous polyester A having a furan ring obtained by polycondensation of an alcohol component containing an aliphatic diol and a carboxylic acid component, and a formula (I):

(In the formula, RO and OR are oxyalkylene groups, R is an ethylene and / or propylene group, x and y represent the number of added moles of alkylene oxide, and each is a positive number)
An alcohol component containing an alkylene oxide adduct of bisphenol A and a carboxylic acid component containing one or more carboxylic acid compounds selected from aromatic dicarboxylic acid compounds and fumaric acid. And a toner binder resin containing the amorphous polyester B obtained as described above, 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 that the filming resistance is good.

  The toner binder resin of the present invention is an amorphous polyester A obtained by using an aliphatic diol as an alcohol component and an amorphous polyester A having a furan ring and an alkylene oxide adduct of bisphenol A as an alcohol component. Containing polyester B. As described above, the amorphous polyester having a furan ring has both a low temperature fixing property and a storage stability, but has a problem in filming resistance. For this problem, it is conceivable to use a polymer having a high molecular weight and a good mechanical factor. In particular, amorphous polyester B using an alkylene oxide adduct of bisphenol A has a molecular skeleton as a bulky, In addition, since the compatibility with the amorphous polyester A having a low molecular weight furan ring is particularly good, the molecular motion of the amorphous polyester A is restricted, so that an amorphous polyester having a furan ring can be obtained. It is presumed that the filming resistance is remarkably improved by preventing fusion of the film. However, the present invention is not limited to the above expression mechanism.

  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 A having a furan ring is an amorphous polyester obtained by condensation polymerization of an alcohol component containing an aliphatic diol and a carboxylic acid component, and at least of the carboxylic acid component and the alcohol component. The resin is preferably a resin in which a carboxylic acid component containing a carboxylic acid compound having a furan ring and / or an alcohol component containing an alcohol having a furan ring is used. As a furan ring, the formula (a) or (b):

The structure represented by these is preferable.

  Examples of the carboxylic acid compound having a furan ring include furan carboxylic acid compounds such as 2,5-furandicarboxylic acid, 2,4-furandicarboxylic acid, 2,3-furandicarboxylic acid, and 3,4-furandicarboxylic acid (this specification) In the description, the carboxylic acid compound includes a carboxylic acid, 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); 2-furancarboxylic acid, 3-furancarboxylic acid Such as 5-hydroxymethyl-furan-2-carboxylic acid; furfuryl acetic acid compound, 3-carboxy-4-methyl-5-propyl-2-furanpropionate, etc. Carboxylic acid compounds (in this specification, hydroxycarboxylic acid compounds are included in the carboxylic acid compounds) and the like.

  Among these, at least one selected from the group consisting of furandicarboxylic acid compounds, furancarboxylic acid compounds and hydroxyfurancarboxylic acid compounds is preferable from the viewpoint of low-temperature fixability and storage stability of the toner. From the viewpoint of properties, furandicarboxylic acid compounds are 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.

  Among these, at least one selected from the group consisting of furan alcohol, hydroxymethylfurfuryl alcohol and furfuryl alcohol is preferable from the viewpoint of low-temperature fixability and storage stability of the toner, and in particular, the storage stability of the toner. From the viewpoint, furan alcohol and hydroxymethylfurfuryl alcohol are more preferable.

  Examples of carboxylic acid compounds having a furan ring represented by the formula (a) include 2,5-furan-dicarboxylic acid, 2,4-furandicarboxylic acid, 2,3-furandicarboxylic acid, and 3,4-furandicarboxylic acid. Flange carboxylic acid compounds; carboxylic acid compounds such as hydroxyfuran carboxylic acid compounds such as 5-hydroxymethyl-furan-2-carboxylic acid, and the like. From the viewpoint of low-temperature fixability and storage stability of the toner, 2,5- Flange carboxylic acid and 2,5-furandicarboxylic acid ethyl ester are preferred.

  Examples of the alcohol having a furan ring represented by the formula (a) include hydroxymethylfurfuryl alcohol such as 5-hydroxymethylfurfuryl alcohol; flange alcohol such as dihydroxyfuran; 5-hydroxymethylfurfural and the like. From the viewpoint of stability and storage stability, 5-hydroxymethylfurfuryl alcohol is preferred.

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

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

  Among the carboxylic acid compounds and alcohols described above, from the viewpoint 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 (a) are preferable. Hydroxymethylfurfuryl alcohol is more preferable, and furandicarboxylic 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 95 mol from the viewpoint of storage stability and low-temperature fixability of the toner in the total amount of the carboxylic acid component and the alcohol component. %, More preferably 15 to 75 mol%, still more preferably 20 to 70 mol%, still more preferably 30 to 65 mol%, still more preferably 40 to 60 mol%.

  The alcohol component contains an aliphatic diol. Since aliphatic diol has a flexible structure, it is excellent in low temperature fixability.

  As the aliphatic diol, an aliphatic diol having 2 to 5 carbon atoms is preferable.

  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.

  Among these, from the viewpoint of further improving the storage stability of the toner and promoting the amorphization of the resin by improving the low temperature fixability by further reducing the mobility of the resin together with the furan ring. C3-C5 aliphatic diols having a hydroxyl group bonded to a secondary carbon atom are preferred. Such aliphatic diols preferably have 3 to 4 carbon atoms from the viewpoint of low-temperature fixability and storage stability of the toner. Specific examples include 1,2-propanediol, 1,2-butanediol, 1, Examples include 3-butanediol and 2,3-butanediol. From the viewpoint of low-temperature fixability and storage stability of the toner, 1,2-propanediol and 2,3-butanediol are preferable. From the viewpoint, 1,2-propanediol is more preferable.

  The content of the aliphatic diol is preferably 50 to 100 mol%, more preferably 70 to 100 mol%, still more preferably 80 to 100 mol% in the alcohol component, from the viewpoint of low-temperature fixability and storage stability of the toner. .

  When the alcohol component contains an alcohol having a furan ring, the alcohol / aliphatic diol (molar ratio) having a furan ring is preferably 2/98 to 50/50 from the viewpoint of low-temperature fixability and storage stability of the toner. 5 / 95-40 / 60 are preferable, 10 / 90-30 / 70 are preferable, and 15 / 85-25 / 75 are preferable.

  The alcohol component of the amorphous polyester A preferably does not contain an alkylene oxide adduct of bisphenol A represented by the following formula (I). Even if it is contained, 20 mol% in the alcohol component The following is preferable, 10 mol% or less is more preferable, and 5 mol% or less is more preferable.

  The alcohol component of the amorphous polyester A promotes the amorphization of the resin, and may contain a trihydric or higher polyhydric alcohol having 3 to 5 carbon atoms from the viewpoint of low-temperature fixability of the toner.

  The content of the carboxylic acid compound having a furan ring is preferably 20 to 100 mol%, more preferably 50 to 100 mol%, and still more preferably 70 to 100 mol%, from the viewpoint of low-temperature fixability and storage stability of the toner. .

  Carboxylic acid components other than carboxylic acid compounds having a furan ring include aromatic dicarboxylic acid compounds such as phthalic acid, isophthalic acid, and terephthalic acid; oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, succinic acid Examples thereof include aliphatic dicarboxylic acids such as acids; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; polyvalent carboxylic acids having 3 or more valences, acid anhydrides thereof, and alkyl (C1 to C3) esters.

  The carboxylic acid component of the amorphous polyester A contains 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 storage stability of the toner. Preferably it is. 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 3 to 30 mol%, more preferably 5 to 20 mol% in the carboxylic acid component, from the viewpoint of storage stability of the toner. 5 to 10 mol% is more preferable.

  Amorphous polyester B has the formula (I):

(In the formula, RO and OR are oxyalkylene groups, R is an ethylene and / or propylene group, x and y indicate the number of added moles of alkylene oxide, each being a positive number, and the sum of x and y. 1 to 16 is preferable, 1 to 8 is more preferable, and 1.5 to 4 is more preferable)
Is an amorphous polyester obtained by polycondensation of an alcohol component containing an alkylene oxide adduct of bisphenol A and a carboxylic acid component.

  Specific examples of the alkylene oxide adduct of bisphenol A represented by the formula (I) include a polyoxypropylene adduct of 2,2-bis (4-hydroxyphenyl) propane and 2,2-bis (4-hydroxy). And an alkylene oxide adduct of bisphenol A such as a polyoxyethylene adduct of phenyl) propane. From the viewpoint of filming resistance, a polyoxypropylene adduct of 2,2-bis (4-hydroxyphenyl) propane is preferred, and from the viewpoint of low-temperature fixability, 2,2-bis (4-hydroxyphenyl) propane polyoxypropylene adduct is preferred. Oxyethylene adducts are preferred.

  The content of the alkylene oxide adduct of bisphenol A represented by the formula (I) is preferably 20 mol% or more in the alcohol component from the viewpoint of low-temperature fixability, storage stability, and filming resistance of the toner. Mole% or more is more preferable, 80 to 100 mol% is more preferable, and substantially 100 mol% is still more preferable.

  Examples of the alcohol component other than the alkylene oxide adduct of bisphenol A represented by the formula (I) include aliphatic alcohols.

  The carboxylic acid component of the amorphous polyester B contains one or more carboxylic acid compounds selected from an aromatic dicarboxylic acid compound and fumaric acid from the viewpoint of low-temperature fixability and storage stability of the toner.

  The carboxylic acid component of the amorphous polyester B preferably contains an aromatic dicarboxylic acid compound from the viewpoint of low-temperature fixability 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 3) esters.

  The content of the aromatic dicarboxylic acid compound is preferably 20 to 100 mol%, more preferably 50 to 100 mol% in the carboxylic acid component from the viewpoint of low-temperature fixability, storage stability and filming resistance of the toner. 70-100 mol% is more preferable.

  Further, the carboxylic acid component of the amorphous polyester B preferably contains fumaric acid from the viewpoint of low-temperature fixability of the toner.

  The content of fumaric acid is preferably 20 to 100 mol%, more preferably 50 to 100 mol%, and still more preferably 80 to 100 mol% in the carboxylic acid component from the viewpoint of low-temperature fixability of the toner.

  The aromatic dicarboxylic acid compound and fumaric acid may be used in combination. In that case, the molar ratio of the two (aromatic dicarboxylic acid compound / fumaric acid) is preferably 30/70 to 90/10, and preferably 50/50 to 70/30, from the viewpoint of low-temperature fixability and storage stability of the toner. More preferred.

  The carboxylic acid component of the amorphous polyester B preferably contains alkyl succinic acid and / or alkenyl succinic acid, more preferably alkenyl succinic acid, from the viewpoint of low-temperature fixability of the toner.

  The alkyl succinic acid and / or alkenyl succinic acid is preferably obtained from a compound having an alkylene group (alkylene compound) and at least one selected from maleic acid, fumaric acid and acid anhydrides thereof. More preferably, the compound is obtained from a compound and maleic acid, and the alkylene compound is preferably one having 9 to 14 carbon atoms, specifically, one obtained from ethylene, propylene, isobutylene, normal butylene or the like. For example, these trimers and tetramers are preferably used.

  Alkyl succinic acid and / or alkenyl succinic acid uses ene reaction by mixing and heating the known alkylene compound and at least one selected from maleic acid, fumaric acid and acid anhydrides thereof. However, from the viewpoint of ease of production, a method obtained by utilizing the ene reaction by mixing the known alkylene compound and maleic acid and heating is preferable.

  The content of the alkyl succinic acid and / or alkenyl succinic acid is preferably 5 to 40 mol%, more preferably 10 to 30 mol%, and more preferably 20 to 30 mol% in the carboxylic acid component from the viewpoint of low-temperature fixability of the toner. Is more preferable.

  Examples of carboxylic acid components other than the aromatic dicarboxylic acid compound and fumaric acid include oxalic acid, malonic acid, maleic acid, citraconic acid, itaconic acid, succinic acid, and other aliphatic dicarboxylic acids; cyclohexanedicarboxylic acid and other alicyclic dicarboxylic acids. Acids: Trivalent or higher polyvalent carboxylic acids, acid anhydrides thereof, alkyl (C1-3) esters and the like.

  In addition, it is preferable that the alcohol component and carboxylic acid component of the amorphous polyester B do not contain a compound having a furan ring from the viewpoint of filming resistance. Even if contained, from the viewpoint of filming resistance, the total amount of the alcohol component and the carboxylic acid component is preferably 30 mol% or less, and more preferably 10 mol% or less.

  In both amorphous polyester A and amorphous polyester B, from the viewpoint of adjusting the molecular weight and improving offset resistance, the alcohol component contains a monovalent alcohol having 5 or less carbon atoms, and the carboxylic acid component contains A monovalent carboxylic acid compound having 5 or less carbon atoms may be contained as appropriate.

  In both amorphous polyester A and amorphous polyester B, the molar ratio of the carboxylic acid component to the alcohol component (carboxylic acid component / alcohol component) is 0.6 to 1.3 from the viewpoint of reactivity, molecular weight adjustment, and physical property adjustment. Is preferable, 0.7 to 1.2 is more preferable, and 0.8 to 1.1 is more preferable.

  In any of the amorphous polyester A and the amorphous polyester B, the condensation polymerization reaction between the alcohol component and the carboxylic acid component is carried out in an inert gas atmosphere as necessary. In the presence of a polymerization inhibitor, it can be produced by condensation polymerization at a temperature of about 180 to 250 ° C. Examples of the esterification catalyst include tin compounds such as dibutyltin oxide and tin (II) 2-ethylhexanoate, titanium compounds such as titanium diisopropylate bistriethanolaminate, among others, reactivity, molecular weight adjustment and From the viewpoint of adjusting the physical properties of the resin, tin (II) 2-ethylhexanoate is preferred. Examples of esterification promoters include pyrogallol, gallic acid, gallic acid esters, benzophenone derivatives such as 2,3,4-trihydroxybenzophenone, 2,2 ', 3,4-tetrahydroxybenzophenone, epigallocatechin, epigallocatechin Examples thereof include catechin derivatives such as gallate, and among these, gallic acid is preferable from the viewpoint of reactivity. The amount of esterification catalyst used is preferably from 0.01 to 1.5 parts by weight, more preferably from 0.1 to 1.0 parts by weight, based on 100 parts by weight of the total amount of alcohol component and carboxylic acid component, from the viewpoints of reactivity, molecular weight adjustment and physical property adjustment. Preferably, 0.2 to 0.7 parts by weight is more preferable. From the same viewpoint, the amount of the esterification promoter used is preferably 0.001 to 0.5 parts by weight, more preferably 0.01 to 0.1 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, the amorphous polyester refers to a resin containing 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 storage 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.

  Even if the amorphous polyester A has a low molecular weight, it can be adjusted to a high glass transition temperature. The glass transition temperature is 40 to 100 ° C. from the viewpoint of low-temperature fixability and storage stability of the toner. Preferably, 45 to 90 ° C is more preferable, 50 to 85 ° C is more preferable, and 55 to 80 ° C is even more preferable.

  The softening point of the amorphous polyester A is preferably 180 ° C. or lower from the viewpoint of low-temperature fixability of the toner, preferably 80 ° C. or higher from the viewpoint of storage stability of the toner, and from the viewpoint of low-temperature fixability and storage stability of the toner. 80 to 180 ° C is preferable, 90 to 160 ° C is more preferable, 95 to 150 ° C is more preferable, and 100 to 120 ° C is even more preferable from the viewpoint of low-temperature fixability of the toner.

  The acid value of the amorphous polyester A is preferably 0.5 to 80 mgKOH / g, more preferably 0.8 to 70 mgKOH / g, and 0.9 to 60 mgKOH / g from the viewpoints of low-temperature fixability, storage stability and filming resistance of the toner. Is more preferably 1 to 25 mgKOH / g, 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, from the same viewpoint as above. More preferred is -60 mg KOH / g.

  The number average molecular weight of the amorphous polyester A is preferably from 800 to 10,000, more preferably from 1000 to 5,000, further preferably from 1300 to 4000, and from 1400 to 3000 from the viewpoint of low-temperature fixability and storage stability of the toner. Even more preferred, 1400-2800 is even more preferred, and 1600-2700 is even more preferred.

  The softening point of the amorphous polyester B is preferably 90 to 160 ° C., more preferably 95 to 150 ° C., and further preferably 100 to 145 ° C. from the viewpoint of low-temperature fixability and storage stability of the toner.

  The glass transition temperature of the amorphous polyester B is preferably 50 to 80 ° C., more preferably 55 to 75 ° C., from the viewpoints of low-temperature fixability and storage stability of the toner.

  The acid value of the amorphous polyester B is preferably 1 to 40 mgKOH / g, more preferably 1.5 to 30 mgKOH / g, and further preferably 2 to 25 mgKOH / g, from the viewpoint of low-temperature fixability and storage stability of the toner. The hydroxyl value is preferably 10 to 70 mgKOH / g, more preferably 15 to 60 mgKOH / g, and still more preferably 20 to 58 mgKOH / g from the same viewpoint as described above.

  The number average molecular weight of the amorphous polyester B is preferably 1000 to 5000, more preferably 1500 to 4000, and further preferably 1700 to 3500, from the viewpoints of low-temperature fixability and storage stability of the toner.

  The amorphous polyester A and the amorphous polyester B used in the present invention include a resin having a high softening point (hereinafter referred to as a high softening point resin) and a resin having a low softening point (hereinafter referred to as a low softening point resin). ) In combination, the toner becomes more excellent in terms of low-temperature fixability and storage stability. When the high softening point resin and the low softening point resin are used in combination, one or both of them may be used.

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

  The softening point, glass transition temperature, acid value, hydroxyl value, and number average molecular weight of the amorphous polyester are easily adjusted by adjusting the raw material monomer composition, polymerization initiator, molecular weight, catalyst amount, etc., or by selecting reaction conditions. be able to. For example, by increasing the reaction temperature of polycondensation, increasing the reaction time, increasing the amount of catalyst, or using a cocatalyst together, the polycondensation reaction can be advanced to increase the softening point and glass transition temperature. Can do. In the case of amorphous polyester A, 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 is increased. Thus, the glass transition temperature can also be increased.

  In the binder resin of the present invention, the weight ratio of amorphous polyester A to amorphous polyester B (amorphous polyester A / amorphous polyester B) is low temperature fixability, storage stability and filming resistance of the toner. From the viewpoint of safety, 99/1 to 35/65 is preferable, 95/5 to 40/60 is more preferable, 90/10 to 50/50 is more preferable, 85/15 to 60/40 is further preferable, and 85 / Even more preferred is 15 to 70/30.

  By using the binder resin of the present invention, it is possible to obtain an electrophotographic toner having good filming resistance 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 binder resin of the present invention, for example, a vinyl resin such as styrene-acrylic resin, an epoxy resin, a polycarbonate, a polyurethane, etc., within a range not impairing the effects of the present invention. Although other resins may be used in combination, the content of the binder resin of the present invention is 70% by weight in the binder resin from the viewpoint of low-temperature fixability, storage stability, and filming resistance of the toner. The above is preferable, 80% by weight or more is more preferable, 90% by weight or more is further preferable, and substantially 100% by weight is further more preferable.

  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 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 from the viewpoint of improving the image quality and improving the low-temperature fixability of the toner. preferable.

  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 viewpoint 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 with respect to 100 parts by weight of the binder resin from the viewpoint of dispersibility in the binder resin, low-temperature fixability and offset resistance of the toner, 1 to 8 parts by weight is more preferable, and 1.5 to 7 parts by weight is more preferable.

  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.

  In the present invention, a charge control resin is preferably contained in order to improve the charging stability. 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.

  Examples of the quaternary ammonium base-containing styrene acrylic copolymer include “FCA-201PS” and “FCA-701PT” (manufactured by Fujikura Kasei Co., Ltd.).

  Examples of other styrene acrylic resins include “FCA-1001NS” (manufactured by Fujikura Kasei Co., Ltd.), which is a styrene acrylic copolymer containing no quaternary ammonium base. Other charge control resins include polyamine resins such as “AFP-B” (manufactured by Orient Chemical), and phenolic resins such as “FCA-2521NJ” and “FCA-2508N” (above, Fujikura Kasei). Etc.).

  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 charging stability of the toner. Preferably, 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 volume median particle size (D ₅₀ ) of the toner of the present invention is preferably from 3 to 15 μm, more preferably from 3 to 10 μm, from the viewpoint of improving image quality. 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 100 parts by weight with respect to 100 parts by weight of the toner before processing with the external additive, from the viewpoint of chargeability, fluidity and transferability of the toner. Is 0.1 to 3 parts by weight, more preferably 0.3 to 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 (manufactured by Shimadzu Corporation, CFT-500D), a 1 g sample is heated at a heating rate of 6 ° C / min, and a load of 1.96 MPa is applied by a plunger and extruded from a nozzle with a diameter of 1 mm and a length of 1 mm. . The amount of plunger drop of the flow tester is plotted against the temperature, and the temperature at which half of the sample flows out is taken as the softening point.

[Maximum peak temperature of resin endotherm]
Using a differential scanning calorimeter (Q-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. And let it stand for 1 minute. Thereafter, the temperature is raised at a heating rate of 50 ° C./min and measured. Among the observed endothermic peaks, the temperature of the peak on the highest temperature side is defined as the highest endothermic peak temperature.

[Glass transition temperature of resin]
Using a differential scanning calorimeter (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. After that, the temperature is raised at a heating rate of 10 ° C./min and measured. The glass transition temperature is defined as the temperature at the intersection of the base line extension below the maximum peak temperature of endotherm and the tangent line indicating the maximum slope from the peak rising portion to the peak apex.

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

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

[Number average molecular weight of resin]
The molecular weight distribution is measured by the gel permeation chromatography (GPC) method according to the following method to determine the number average molecular weight.
(1) Preparation of sample solution Dissolve the sample in chloroform at 25 ° C so that the concentration is 0.5 g / 100 ml. Next, this solution is filtered using a fluororesin filter (manufactured by ADVANTEC, DISMIC-25JP) having a pore size of 0.2 μm to remove insoluble components, thereby obtaining a sample solution.
(2) Molecular weight measurement Using the following measuring device and analytical column, flow chloroform at 1 ml / min as the eluent and stabilize the column in a constant temperature bath at 40 ° C. Measurement is performed by injecting 100 μl of the sample solution. The molecular weight of the sample is calculated based on a calibration curve prepared in advance. At this time, several types of monodisperse polystyrene (A-500 (5.0 × 10 ² ), A-1000 (1.01 × 10 ³ ), A-2500 (2.63 × 10 ³ ), A- 5000 (5.97 × 10 ³ ), F-1 (1.02 × 10 ⁴ ), F-2 (1.81 × 10 ⁴ ), F-4 (3.97 × 10 ⁴ ), F-10 (9.64 × 10 ⁴ ), F- 20 (1.90 × 10 ⁵ ), F-40 (4.27 × 10 ⁵ ), F-80 (7.06 × 10 ⁵ ), F-128 (1.09 × 10 ⁶ )) prepared as standard samples are used.
Measuring device: LC-9130NEXT (manufactured by Nippon Analytical Industrial Co., Ltd.)
Analytical column: TSKGel HXL-H + GMHXL + G3000HXL (manufactured by Tosoh Corporation)

[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.

Production Example of Alkylene Compound A By using propylene tetramer (trade name: “Light Tetramer” manufactured by Nippon Oil Corporation), fractionation was carried out under heating conditions of 183 to 208 ° C. to obtain alkylene compound A. The resulting alkylene compound A had 40 peaks in gas chromatography mass spectrometry. The distribution of the alkylene compound was as follows: C ₉ H ₁₈ : 0.5 wt%, C ₁₀ H ₂₀ : 4 wt%, C ₁₁ H ₂₂ : 20 wt%, C ₁₂ H ₂₄ : 66 wt%, C ₁₃ H ₂₆ : 9 wt% , C ₁₄ H ₂₈ : 0.5% by weight. Gas chromatography mass spectrometry was performed according to the method described in JP-A-2008-256845.

Example of production of alkenyl succinic anhydride A 1 L autoclave made by Nitto High Pressure Co., Ltd., alkylene compound A 542.4 g, maleic anhydride 157.2 g, Chelex-O 0.4 g as an antioxidant (SC Organic Chemicals, Triisooctyl phosphite), polymerization prohibited As an agent, 0.1 g of butylhydroquinone was charged, and pressurized nitrogen substitution (0.2 MPaG) was repeated three times. After starting stirring at 60 ° C., the temperature was raised to 230 ° C. over 1 hour and the reaction was carried out for 6 hours. The pressure when the reaction temperature was reached was 0.3 MPaG. After completion of the reaction, the mixture was cooled to 80 ° C., returned to normal pressure (101.3 kPa), and transferred to a 1 L four-necked flask. The temperature was raised to 180 ° C. with stirring, and the remaining alkylene compound was distilled off at 1.3 kPa over 1 hour. Subsequently, after cooling to room temperature (25 ° C.), the pressure was returned to normal pressure (101.3 kPa) to obtain 406.1 g of the target alkenyl succinic anhydride A. The average molecular weight (Mw) of alkenyl succinic anhydride determined from the acid value was 268.

Resin Production Example 1 [Resin A1, A3, A5, A6, A8]
The raw material monomers and esterification catalyst excluding trimellitic anhydride shown in Table 1 are put into a 5-liter four-necked flask equipped with a thermometer, a stainless steel stirring rod, a rectifying column, a dehydrating tube, a condenser and a nitrogen introducing tube. After heating up to 180 ° C. in a mantle heater in a nitrogen atmosphere, the temperature was raised to 210 ° C. over 10 hours. Thereafter, it was confirmed that the reaction rate reached 95% or higher at 210 ° C., and trimellitic anhydride shown in Table 1 was added. After carrying out the reaction at normal pressure for 1 hour, the reaction was carried out at 20 kPa until the softening point shown in Table 1 was reached to obtain an amorphous polyester. The reaction rate means a value of the amount of produced reaction water / theoretical product water amount × 100.

Resin Production Example 2 [Resin A2, A4, A7]
The raw material monomer and esterification catalyst shown in Table 1 are put into a 5-liter four-necked flask equipped with a thermometer, a stainless steel stirring rod, a rectifying column, a dehydrating tube, a condenser, and a nitrogen introducing tube. After heating up to 180 ° C. in the heater, the temperature was raised to 210 ° C. over 10 hours. Thereafter, it was confirmed that the reaction rate reached 95% or higher at 210 ° C., and the reaction was carried out at 20 kPa until the softening point shown in Table 1 was reached, thereby obtaining an amorphous polyester.

Resin Production Example 3 [Resin B1, B2]
The raw material monomer and esterification catalyst shown in Table 2 were put into a 5-liter four-necked flask equipped with a thermometer, a stainless steel stirring rod, a dehydrating tube, a condenser and a nitrogen introducing tube, and in a mantle heater in a nitrogen atmosphere. The temperature was raised to 235 ° C., it was confirmed that the reaction rate reached 95% or more at 235 ° C., and the reaction was carried out at 8 kPa until the softening point shown in Table 2 was reached, to obtain an amorphous polyester.

Resin Production Example 4 [Resin B3, B5]
Raw material monomer and esterification catalyst other than trimellitic anhydride and alkenyl succinic anhydride A shown in Table 2 and a 5-liter four-necked flask equipped with a thermometer, stainless steel stirring rod, dehydrating tube, condenser and nitrogen introducing tube The temperature was raised to 235 ° C. in a mantle heater in a nitrogen atmosphere, and it was confirmed that the reaction rate reached 95% or higher at 235 ° C., and the reaction was performed at 8 kPa for 1 hour. Then, it is cooled to 210 ° C., trimellitic anhydride or alkenyl succinic anhydride A is added, reacted at normal pressure for 1 hour, and then reacted at 20 kPa until the softening point shown in Table 2 is reached. An amorphous polyester was obtained.

Resin Production Example 5 [Resin B4]
The raw material monomer and esterification catalyst shown in Table 2 were put into a 5-liter four-necked flask equipped with a thermometer, a stainless steel stirring rod, a dehydrating tube, a condenser and a nitrogen introducing tube, and in a mantle heater in a nitrogen atmosphere. The temperature was raised to 180 ° C. and then raised to 210 ° C. at 10 ° C./h. After confirming that the reaction rate reached 80% or higher at 210 ° C., the reaction was carried out at 8 kPa until the softening point reached 107.8 ° C. to obtain an amorphous polyester.

[Example of toner production]
Examples 1-14 and Comparative Examples 1-3
100 parts by weight of binder resin shown in the table, 1 part by weight of negatively chargeable charge control agent “Bontron E-81” (manufactured by Orient Chemical Co., Ltd.), 5 parts by weight of colorant “Regal 330R” (manufactured by Cabot, carbon black) , And 2 parts by weight of the release agent “Mitsui High Wax NP-055” (Mitsui Chemicals, Polypropylene wax, melting point: 125 ° C.) are thoroughly mixed with a Henschel mixer, and then rolled using a co-rotating twin screw extruder. Melting and kneading were performed at a rotation speed of 200 r / min and a heating temperature of 80 ° C. 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 15
Charge control resin `` FCA-701PT '' (manufactured by Fujikura Kasei Co., Ltd., quaternary ammonium base-containing styrene acrylic resin, softening point: 123 ° C) is used together with binder resin, colorant, etc., and negatively charged 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 16-18
As a negatively chargeable charge control agent, instead of “Bontron E-81” (manufactured by Orient Chemical Co., Ltd.), in Examples 16 and 18, “LR-147” (manufactured by Nippon Carlit Co., Ltd.) 1 part by weight, in Example 17, `` LR-297 '' (Nippon Carlit Co., Ltd.) 1 part by weight, as a release agent, instead of `` Mitsui High Wax NP-055 '', `` HNP-9 '' (Nippon Seiki Co., Ltd., paraffin wax, In Example 16, instead of carbon black “Regal 330R”, 5 parts by weight of cyan pigment “Toner Cyan BG” (manufactured by Clariant, PB15: 3) was used. In Example 17, 5 parts by weight of magenta pigment “Super Magenta R” (manufactured by Dainippon Ink and Chemicals, PR122), and in Example 18, 6 parts by weight of yellow pigment “Paliotol Yellow D1155” (manufactured by BASF, PY185) In addition to `` NAX-50 '' as an external additive, hydrophobic silica `` R-972 '' (Nippon Aerosil A toner was obtained in the same manner as in Example 1 except that 1.0 part by weight of an average particle size of 16 nm, a hydrophobic treatment agent: dimethyldichlorosilane) was used.

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 15, a non-magnetic single-component developing printer “ Toner is mounted on HL-2040 (a machine modified from Brother Industries), and 4cm x 4cm solid printing is undecided on Sharp's paper [CopyBond SF-70NA (75g / m ² )] I got a wearing image. Using a fixing machine (fixing speed 390 mm / sec) adjusted so that the total fixing pressure is 40 kgf, while gradually increasing the temperature of the fixing roller from 100 ° C to 240 ° C in steps of 5 ° 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 of the toner was evaluated. The results are shown in Table 3.

Test Example 2 [storage stability]
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 the storage stability of the toner was evaluated according to the following evaluation criteria. The results are shown in Table 3.

〔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 [Film resistance]
A non-magnetic one-component developing device “MICROLINE 3010cW” (Oki Data, A4 14 sheets / min) was used (in Example 15, the non-magnetic one-component developing system printer “HL-2040” (Brother Kogyo) was remodeled. Device), printing of 3000 character images (A4 paper) with a printing area ratio of 4%, and at the time of printing 1000 sheets and 3000 sheets, the presence or absence of filming on the photoreceptor was visually confirmed. The filming resistance of the toner was evaluated according to the following evaluation criteria. The results are shown in Table 3.

〔Evaluation criteria〕
A: Filming has not occurred even after printing 3000 sheets.
B: Filming does not occur when printing 1000 sheets, but filming occurs when printing 3000 sheets.
C: Filming occurs when printing 1000 sheets.

  From the above results, compared with Comparative Examples 1 to 3, in Examples 1 to 18, the toner has good low-temperature fixability and storage stability, and filming on the photoreceptor is effectively suppressed. I understand that.

  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 (10)

Ru polycondensation Monodea of an alcohol component and a carboxylic acid component containing an aliphatic diol, an amorphous polyester A having a furan ring, of formula (I):

(In the formula, RO and OR are oxyalkylene groups, R is an ethylene and / or propylene group, x and y represent the number of added moles of alkylene oxide, and each is a positive number)
Condensation polymerization product of a carboxylic acid component containing in one or more carboxylic acid compound selected from an alcohol component containing an alkylene oxide adduct and an aromatic dicarboxylic acid compound and fumaric acid of bisphenol A represented by toner binder resin comprising a amorphous polyester B Ru der.   The binder resin for toner according to claim 1, wherein a weight ratio of the amorphous polyester A to the amorphous polyester B (amorphous polyester A / amorphous polyester B) is 99/1 to 35/65.   The binder resin for toner according to claim 1, wherein the amorphous polyester A has a number average molecular weight of 800 to 10,000.   The binder resin for toner according to any one of claims 1 to 3, wherein the amorphous polyester B has a softening point of 90 to 160 ° C and a glass transition temperature of 50 to 80 ° C.   The binder resin for toner according to claim 1, wherein the aliphatic diol includes an aliphatic diol having 3 to 5 carbon atoms and having a hydroxyl group bonded to a secondary carbon atom.   The toner according to claim 1, wherein at least one of the carboxylic acid component and the alcohol component is a carboxylic acid component containing at least a carboxylic acid compound having a furan ring and / or an alcohol component containing an alcohol having a furan ring. Binder resin.   The binder resin for toner according to claim 6, 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.   The binder resin for toner according to claim 6 or 7, 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.   The binder resin for toner according to any one of claims 6 to 8, wherein the alcohol having a furan ring is at least one selected from the group consisting of furan alcohol, hydroxymethylfurfuryl alcohol and furfuryl alcohol.   An electrophotographic toner comprising the toner binder resin according to claim 1.