JP5912820B2 - 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, with an increase in machine speed and energy saving, a toner having excellent low-temperature fixability has been demanded. Therefore, as a binder resin for toners, instead of an aromatic polyester obtained by using an aromatic alcohol having a rigid structure, which has been conventionally used for achieving both low-temperature fixability and maintainability, an aliphatic polyhydric resin is used. An aliphatic polyester using a monohydric alcohol has been proposed (see Patent Documents 1 and 2).

  On the other hand, Patent Document 3 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 4 discloses a method for producing a polyester resin containing a dicarboxylic acid unit having a furan structure. Furthermore, Patent Document 5 is characterized by having 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 2002-287427 A JP 2006-154686 A JP 2008-291243 A JP 2008-291244 A JP 2009-197110 A

  However, in the future, from the viewpoint of further increasing the printing speed and reducing the environmental load, the performance of the binder resin for toner disclosed in Patent Document 1 and Patent Document 2 is insufficient, and fixing at a lower temperature is achieved. However, in order to achieve both good storage stability, it is desired to develop a binder resin having a high glass transition temperature even at a low softening point. Furthermore, as the print-on-demand market has grown in recent years, there has been an increasing demand for higher image quality for electrophotographic technology. In particular, when color printing is performed by an electrophotographic method, there is a demand for high gloss (high gloss) of an image after low-temperature fixing.

  Further, since the resins described in Patent Document 3 and Patent Document 4 are mainly used for film and injection molded products, they have high crystallinity, and have a high softening point and glass transition point. Not suitable for resin. Further, the resin described in Patent Document 5 is also a molded product composition, and thus has high crystallinity and is not suitable as a binder resin for toner.

  An object of the present invention is to provide a binder resin for toner that is excellent in low-temperature fixability and storability and can provide a high gloss image, and an electrophotographic toner containing the binder resin.

The present invention
[1] Carboxylic acid component and alcohol component, and formula (I):

(Wherein R ¹ , R ² and R ³ each independently represent a carboxyl group or a hydroxymethyl group)
A binder resin for a toner containing an amorphous polyester obtained by condensation polymerization of a raw material monomer containing a compound represented by: and [2] a binder resin according to [1] above, The present invention relates to an electrophotographic toner.

  The binder resin for toner of the present invention is excellent in low-temperature fixability and storage stability of the toner, and has an effect that a high gloss image can be obtained.

  The binder resin of the present invention has the formula (I):

(Wherein R ¹ , R ² and R ³ each independently represent a carboxyl group or a hydroxymethyl group)
Is characterized in that it contains an amorphous polyester used as a raw material monomer. Even if the softening point is set to be low by introducing a hard skeleton ring of the skeleton into the polyester, the molecular motion of the polyester is suppressed and the glass transition temperature is high, that is, as a binder resin for toner. A polyester excellent in low-temperature fixability and storage stability can be obtained. Furthermore, the furan dimer has a very rigid structure, as is apparent from the structure, and because the softening point can be set to a lower molecular weight than general polyester, it has excellent fixing properties and has a printing surface. It is presumed that the smoothness of the material improves and the gloss becomes higher.

  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 “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.

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

  In the present invention, an amorphous polyester having a furan ring is obtained by polycondensing a raw material monomer containing a carboxylic acid component, an alcohol component, and a compound represented by the formula (I).

  In the present invention, the compound represented by the formula (I) is a compound having a furan ring other than the compound represented by the formula (I) described later, that is, a furan ring other than the compound represented by the formula (I). Differentiated from carboxylic acid compounds having an alcohol and furan ring. By introducing a furan dimer skeleton and a trifunctional cross-linked structure into the polyester using the compound represented by the formula (I), good low-temperature fixability, storability and gloss of the present invention are the effects of the present invention. Even if the functional group of the compound represented by the formula (I) is a carboxyl group or a hydroxymethyl group, the effect of the present invention is exhibited. From this viewpoint, in the present invention, the alcohol component and the carboxylic acid component forming the polyester are distinguished. Therefore, the amorphous polyester having a furan ring of the present invention is a compound represented by the formula (I), an alcohol component that may contain an alcohol having a furan ring, and a carboxylic acid that may contain a carboxylic acid compound having a furan ring. The component is configured as an essential component.

In the formula (I), R ^{1 to} R ³ are each independently a carboxyl group or a hydroxymethyl group, and may be any combination. From the viewpoint of toner storage stability, R ^{1 to} R ³ At least one of them is preferably a carboxyl group, and more preferably two or more are carboxyl groups.

  From the above viewpoint, as a preferable example of the compound represented by the formula (I), the formula (Ia):

And a compound represented by formula (Ib):

The compound represented by these is mentioned.

  The compound represented by the formula (Ia) can be produced by a known production method. For example, it can be obtained by a conventional oxidation method (AMOCO method) using 5-hydroxymethylfurfural (HMF) as a starting material. Further, the compound represented by the formula (Ib) is also obtained by oxidation using HMF as a starting material, similarly to the compound represented by the formula (Ia).

  The content of the compound represented by the formula (I) is preferably 0.01 mol% or more, more preferably 0.02 mol% or more, further preferably 0.05 mol% or more, and more preferably 0.1 mol% from the viewpoint of toner gloss in the raw material monomer. % Or more, more preferably 1.0 mol% or more, and from the viewpoint of low-temperature fixability of the toner, 10 mol% or less is preferable, 8 mol% or less is more preferable, 7 mol% or less is further preferable, and 6 mol% or less is preferable. % Or less is even more preferable. Therefore, from the viewpoint of low-temperature fixability and gloss of the toner, the content of the compound represented by the formula (I) is preferably 0.01 to 10 mol%, more preferably 0.02 to 8 mol%, more preferably 0.05 to 8 mol% is more preferable, 0.1-7 mol% is still more preferable, and 1.0-6 mol% is still more preferable. Unless otherwise specified, in the raw material monomer means the total amount of the compound represented by the formula (I), the carboxylic acid component and the alcohol component.

  Further, the content of the compound represented by the formula (I) in the total amount of the compound having a furan ring is preferably 0.02 mol% or more, more preferably 0.05 mol% or more, and more preferably 0.1 mol% from the viewpoint of toner gloss. Or more, more preferably 1 mol% or more, even more preferably 2 mol% or more, from the viewpoint of low-temperature fixability and storage stability of the toner, preferably 100 mol% or less, more preferably 50 mol% or less, 20 mol% or less is more preferable, and 15 mol% or less is more preferable. The content of the compound represented by formula (I) in the total amount of the compound having a furan ring is preferably 0.02 to 100 mol%, and 0.05 to 50 mol% from the viewpoint of low-temperature fixability, storage stability and gloss of the toner. Is more preferable, 0.1 to 50 mol% is more preferable, 1 to 20 mol% is still more preferable, and 2 to 15 mol% is still more preferable. In the present invention, the “total amount of the compound having a furan ring” means a compound represented by the formula (I), a carboxylic acid compound having a furan ring other than the compound represented by the formula (I), and the formula (I ) Is the total amount of alcohol having a furan ring other than the compound represented by.

The compound represented by the formula (I) is:
(a): a compound in which R ^{1 to} R ³ are all carboxyl groups in the formula (I), like the compound represented by the formula (Ib),
(b): a compound in which two of R ^{1 to} R ³ are carboxyl groups and one is a hydroxymethyl group in the formula (I) as in the compound represented by the formula (Ia),
(c): a compound in which ^one of R ^{1 to} R ³ is a carboxyl group and two are hydroxymethyl groups in formula (I), and
(d): In the formula (I), R ^{1 to} R ³ are all hydroxymethyl groups, but in the present invention, each may be used alone or in combination with a plurality of compounds. The total content of the compounds (a) to (d) is preferably from 0.02 to 25 mol, preferably from 0.1 to 20 mol, based on 100 mol of the carboxylic acid component, from the viewpoint of low-temperature fixability, storage stability and gloss of the toner. Is more preferable, 1 to 18 mol is more preferable, and 2 to 15 mol is even more preferable. Moreover, 0.02-25 mol is preferable with respect to 100 mol of alcohol components, 0.1-20 mol is more preferable, 1-18 mol is further more preferable, and 2-15 mol is still more preferable.

  The raw material monomer preferably further contains a carboxylic acid compound having a furan ring and / or an alcohol having a furan ring other than the compound represented by the formula (I). The furan ring possessed by such compounds has the formula (IIa) or (IIb):

It is preferable that it is a structure represented by these.

  Examples of the alcohol having a furan ring other than the compound represented by the formula (I) include furan alcohol such as dihydroxyfuran; hydroxymethylfurfuryl alcohol such as 5-hydroxymethylfurfuryl alcohol; furfuryl alcohol; 5-hydroxymethylfurfural. Etc.

  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.

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

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

  Examples of carboxylic acid compounds having a furan ring other than the compound represented by formula (I) include 2,5-furandicarboxylic acid, 2,4-furandicarboxylic acid, 2,3-furandicarboxylic acid, and 3,4-furandi Flanged carboxylic acid compounds such as carboxylic acids (in the present specification, carboxylic acid compounds include carboxylic acids, esters of carboxylic acids and alcohols having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, and acid anhydrides); Furancarboxylic acid compounds such as 2-furancarboxylic acid and 3-furancarboxylic acid; hydroxyfurancarboxylic acid compounds such as 5-hydroxymethyl-furan-2-carboxylic acid; furfurylacetic acid compound, 3-carboxy-4-methyl-5 And carboxylic acid compounds such as -propyl-2-furanpropionate.

  Among these, at least one carboxylic acid compound 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. Carboxylic acid compounds are more preferred.

  Examples of the carboxylic acid compound having a furan ring represented by the formula (IIa) include 2,5-furan-dicarboxylic acid, 2,4-furandicarboxylic acid, 2,3-furandicarboxylic acid, and 3,4-furandicarboxylic acid. Flanged carboxylic acid compounds; carboxylic acid compounds such as hydroxyfuran carboxylic acid compounds such as 5-hydroxymethyl-furan-2-carboxylic acid.

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

  Among the above carboxylic acid compounds and alcohols, 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 (IIa) are preferable. Methylfurfuryl alcohol is more preferred, and furandicarboxylic acid compounds are more preferred. Specifically, from the viewpoint of low-temperature fixability and storage stability of the toner, 5-hydroxymethylfurfuryl alcohol and 2,5-furan-dicarboxylic acid are preferred. Preferably, 2,5-furan-dicarboxylic acid is more preferable.

  When a compound having a furan ring other than the compound represented by formula (I) is used in combination, the content of a carboxylic acid compound having a furan ring other than the compound represented by formula (I) and / or an alcohol having a furan ring Is preferably from 9 to 99.99 mol%, more preferably from 20 to 80 mol%, and even more preferably from 40 to 60 mol% in the raw material monomer from the viewpoint of low-temperature fixability and storage stability of the toner. The content of a carboxylic acid compound having a furan ring other than the compound represented by formula (I) and / or an alcohol having a furan ring refers to a carboxyl having a furan ring other than the compound represented by formula (I). It means the content of an alcohol having an acid compound or a furan ring, or the total content of a carboxylic acid compound having a furan ring other than the compound represented by formula (I) and an alcohol having a furan ring.

  A carboxylic acid compound having two or more furan rings may be used for the carboxylic acid component, and an alcohol having two or more furan rings may be used for the alcohol component. Note that one type is a structural type, and those having the same structural formula but different structural formulas are regarded as different types.

  As the alcohol component other than the alcohol having a furan ring, an aliphatic diol is preferable from the viewpoint of low-temperature fixability of the toner. The carbon number of the aliphatic diol is preferably 2 to 10, more preferably 3 to 8, and further preferably 3 to 6 from the viewpoint of low-temperature fixability of the toner.

  Aliphatic diols 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, 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 1,5-hexanediol, 1,6-hexanediol, 1,4-butenediol, neopentyl glycol, 2,3-butanediol, 2,3-pentanediol, 2,4-pentanediol, 2,3-hexanediol, 3,4- Examples include hexanediol, 2,4-hexanediol, and 2,5-hexanediol.

  Among these, an aliphatic group having a hydroxyl group bonded to a secondary carbon atom from the viewpoint of further improving the storage stability of the toner and improving the low-temperature fixability by further reducing the mobility of the resin together with the furan ring. Diols are preferred. The number of carbon atoms of the aliphatic diol is preferably 3-8, more preferably 3-6, from the viewpoint of low-temperature fixability and storage stability of the toner. Specific preferred examples include 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 2,3-pentanediol, 2,4-pentanediol, and the like, from the viewpoint of low-temperature fixability and storage stability of the toner, 1,2-propanediol and 2,3-butanediol are preferred, and 1,2- Propanediol is more preferred.

  The content of the aliphatic diol is preferably 10 mol% or more, more preferably 30 mol% or more, further preferably 50 mol% or more, and even more preferably 80 mol% in the alcohol component from the viewpoint of low-temperature fixability of the toner. % Or more, more preferably substantially 100 mol%, and the content of the aliphatic diol having a hydroxyl group bonded to a secondary carbon atom in the alcohol component from the viewpoint of low-temperature fixability and storage stability of the toner. Preferably, it is at least 10 mol%, more preferably at least 30 mol%, even more preferably at least 50 mol%, even more preferably at least 80 mol%, even more preferably substantially at 100 mol%.

  Other alcohol components include formula (III):

(Wherein R ⁴ O and OR ⁴ are oxyalkylene groups, R ⁴ is an ethylene and / or propylene group, x and y indicate the number of moles of alkylene oxide added, each being 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 aromatic diol such as an alkylene oxide adduct of bisphenol A represented by the formula: a trihydric or higher polyhydric alcohol such as glycerin.

  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, and glutacone. Acid, succinic acid, adipic acid, sebacic acid, azelaic acid and other aliphatic dicarboxylic acid compounds, trimellitic acid, pyromellitic acid and other polyvalent carboxylic acid compounds, their acid anhydrides, alkyl (carbon number) 1-6) Ester etc. are mentioned.

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

  The alcohol component may contain a monovalent alcohol, and the carboxylic acid component may contain a monovalent carboxylic acid compound as appropriate from the viewpoint of adjusting the molecular weight and improving offset resistance.

  The molar ratio of the carboxylic acid component and the alcohol component (carboxylic acid component / alcohol component) is preferably 0.7 to 1.5, more preferably 0.7 to 1.4, and more preferably 0.7 to 1.0 from the viewpoint of low-temperature fixability, storage stability and gloss of the toner. Further preferred.

  The polycondensation reaction between the alcohol component and the carboxylic acid component can be performed in an inert gas atmosphere in the presence of an esterification catalyst such as a tin compound or a titanium compound, or a polymerization inhibitor. From a viewpoint of property, 180-250 degreeC is preferable.

  As the tin compound, for example, dibutyltin oxide is known, but a tin (II) compound having no Sn—C bond is preferable from the viewpoint of reactivity.

  Examples of the tin (II) compound having no Sn—C bond include a tin (II) compound having an Sn—O bond and a tin having an Sn—X (X represents a halogen atom) bond from the viewpoint of reactivity. (II) compounds are preferred, tin (II) compounds having Sn-O bonds are more preferred, and tin (II) 2-ethylhexanoate is more preferred.

  As the titanium compound, a titanium compound having a Ti-O bond is preferable from the viewpoint of reactivity, an alkoxy group having 1 to 28 carbon atoms, an alkenyloxy group having 2 to 28 carbon atoms, or 1 to 28 carbon atoms. A compound having an acyloxy group is more preferable.

  The said tin (II) compound and titanium compound can be used 1 type or in combination of 2 or more types.

  From the viewpoint of reactivity, the amount of the esterification catalyst is preferably 0.01 to 2.0 parts by weight, preferably 0.1 to 1.5 parts by weight with respect to 100 parts by weight of the total amount of the compound represented by formula (I) and the alcohol component and carboxylic acid component. Part by weight is more preferable, and 0.2 to 1.0 part by weight is further preferable.

  In the present invention, the amorphous polyester 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 viewpoints of stability and charge 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 urethane-modified polyester in which polyester is modified with a urethane bond, epoxy-modified polyester in which polyester is modified with an epoxy bond, and two or more resin components including a polyester component and an addition polymerization resin component. And a composite resin.

  The softening point of the amorphous polyester is preferably from 80 to 180 ° C, more preferably from 85 to 150 ° C, further preferably from 90 to 120 ° C, from the viewpoint of low-temperature fixability, storage stability and gloss of the toner, and from 100 to 110 Even more preferred is ° C.

  In general, the softening point of the resin and the glass transition temperature are correlated. Since the amorphous polyester can have a higher glass transition temperature than a resin having a similar softening point, even one type of resin satisfies the low-temperature fixability and storage stability of the toner. However, a resin having a high softening point and a resin having a low softening point may be used in combination. When a resin having a high softening point and a low resin are used in combination, specifically, the binder resin is preferably a softening point resin having a softening point of 10 ° C. or higher, more preferably 20 to 60 ° C. It is preferably made of a low softening point resin. The softening point of the high softening point resin is preferably 125 to 160 ° C, more preferably 130 to 150 ° C, and the softening point of the low softening point resin is preferably 90 to 120 ° C, more preferably 90 to 110 ° C. is there. 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 1/3 to 3/1 from the viewpoint of low temperature fixability, storage stability and gloss of the toner. / 2 to 2/1 is more preferable.

  Further, the glass transition temperature of the amorphous polyester is preferably 45 to 85 ° C, more preferably 50 to 80 ° C, and further preferably 60 to 78 ° C, from the viewpoint of low temperature fixability, storage stability and gloss of the toner. Even more preferred is 64-76 ° C.

  The acid value of the amorphous polyester is preferably 0.5 to 60 mgKOH / g, more preferably 2 to 40 mgKOH / g, and further preferably 5 to 20 mgKOH / g, from the viewpoint of charge stability. From the same viewpoint, the hydroxyl value is preferably 10 to 100 mgKOH / g, more preferably 15 to 80 mgKOH / g, and further preferably 30 to 50 mgKOH / g.

  The binder resin of the present invention includes known binder resins other than the amorphous polyester, for example, vinyl resins such as polyester and styrene-acrylic resins, epoxy resins, polycarbonates, as long as the effects of the present invention are not impaired. In addition, a resin such as polyurethane may be used together, but the content of the binder resin of the amorphous polyester is 30% by weight in the total binder resin from the viewpoint of low-temperature fixability, storage stability and gloss of the toner. % Or more, preferably 50% by weight or more, more preferably 70% by weight or more, further preferably 80% by weight or more, further preferably 90% by weight or more, and further preferably substantially 100% by weight.

  By using the binder resin of the present invention, it is possible to obtain the electrophotographic toner of the present invention which is excellent in both low-temperature fixability and storage stability, which are mutually contradictory performances, and has a high gloss.

  However, when the binder resin of the present invention is composed only of a high softening point resin, for example, when the softening point is preferably composed of only a resin having a softening point of 125 to 160 ° C, more preferably 130 to 150 ° C, a low softening point resin is used. It is preferable to use together. Specifically, the difference in softening point from the binder resin of the present invention is preferably 10 ° C. or higher, more preferably 20 to 60 ° C. from the above viewpoint. The softening point of the low softening point resin is preferably 90 to 120 ° 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 1/3 to 3/1 from the viewpoint of low temperature fixability, storage stability and gloss of the toner. / 2 to 2/1 is more preferable.

  The toner of the present invention further includes a colorant, a release agent, a charge control agent, a magnetic powder, a fluidity improver, a conductivity modifier, a reinforcing filler such as a fibrous substance, an antioxidant, and a cleaning property improver. Such additives may be appropriately contained.

  As the colorant, all of dyes and pigments used as toner colorants can be used. Carbon black, black pigment, 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, Isoindoline, Disazo yellow and the like can be used alone or in combination of two or more. The toner may be either black toner or 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 image quality.

  Examples of the charge control agent include chromium-based azo dyes, iron-based azo dyes, aluminum azo dyes, salicylic acid metal complexes, and the like, and these can be used alone or in admixture of two or more.

  The content of the charge control agent is preferably 0.1 to 8 parts by weight and more preferably 0.5 to 7 parts by weight with respect to 100 parts by weight of the binder resin from the viewpoint of improving the image quality.

  The toner of the present invention preferably contains a charge control resin in order to improve 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 more preferable, and from the viewpoint of developing negative chargeability of the toner, sulfonic acid group-containing Styrenic resins are more preferred.

  The amount of the charge control resin used is preferably 3 to 40 parts by weight, more preferably 4 to 30 parts by weight, and 4 to 20 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. Is more 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 viewpoints of low-temperature fixability and offset resistance of the toner.

  The content of the release agent is preferably from 0.5 to 10 parts by weight, more preferably from 1 to 8 parts by weight, more preferably from 1.5 to 10 parts by weight, based on 100 parts by weight of the binder resin, from the viewpoint of low-temperature fixability and offset resistance of the toner. More preferred is 7 parts by weight.

  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. Specifically, in the case of pulverized toner by a melt kneading method, for example, a raw material such as a binder resin, a colorant, a charge control agent, and a release agent is uniformly mixed with a mixer such as a Henschel mixer, and then a sealed kneader. Examples thereof include a method of melt-kneading with a monoaxial or biaxial extruder, an open roll kneader, etc., 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.

  An external additive may be added to the surface of the toner. Examples of the external additive include inorganic fine particles such as silica, alumina, titanium oxide, zirconia, tin oxide, and zinc oxide, and organic fine particles such as resin fine particles. These surfaces have been subjected to hydrophobic treatment. Also good. The addition amount of the external additive is preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the toner particles before being processed with the external additive, from the viewpoint of improving the image quality.

The volume median particle size (D ₅₀ ) of the toner of the present invention is preferably 3 to 15 μm, more preferably 3 to 12 μm, and even more preferably 5 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.

  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 was heated at a heating rate of 6 ° C / min, and a load of 1.96 MPa was applied by a plunger, from a nozzle 1 mm in diameter and 1 mm in length. Extrude. 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. 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.

[Acid value of the resin]
Measured according to the method of JIS K0070. However, only the measurement solvent was 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.

[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 1 of Compound Represented by Formula (I) [Compound Represented by Formula (Ia)]
To the autoclave, 5.0 g of 5-hydroxymethylfurfural (HMF) (manufactured by Sigma Aldrich Japan Co., Ltd.), 45.7 g of acetic acid, 0.29 g of cobalt acetate, 0.57 g of manganese acetate, and 0.12 g of sodium bromide were added, and oxygen substitution was performed. And reacted at 0.3 MPa for 3 hours. The reaction product was concentrated with a rotary evaporator (50 ° C. warm bath) to obtain a solid. This solid and 50 g of methanol were added to a glass reactor and reacted at 60 ° C. with stirring to obtain a methyl ester of the compound represented by the formula (Ia). The ethyl ester / hexane was used as a solvent, and the methyl ester form of the compound represented by the formula (Ia) was isolated by a column. Add 0.32 g of sodium hydroxide to the methyl ester, react at 60 ° C. for 2 hours, hydrolyze, transfer to a separatory funnel, add 100 ml of diisopropyl ether, 100 ml of 1 wt% ammonium chloride aqueous solution, 1N hydrochloric acid The extract was washed twice with 100 ml of an aqueous solution, and the organic phase was dried using anhydrous sodium sulfate. By distilling off the solvent, furan dimer (Ia) was obtained.

Production Example 2 of Compound Represented by Formula (I) [Compound Represented by Formula (Ib)]
Furan dimer (Ib) was obtained by oxidation of HMF in the same manner as in Production Example 1, except that the reaction conditions after oxygen substitution were changed to 180 ° C. and 0.5 MPa, and the reaction time was changed to 5 hours.

Resin production example 1 [resins A to H]
The raw material monomer and the esterification catalyst shown in Table 1 were put into a 5-liter four-necked flask equipped with a thermometer, a stainless steel stirring rod, a flow-down condenser, and a nitrogen introduction tube, and in a mantle heater in a nitrogen atmosphere, 180 The temperature was raised to 210 ° C. and then 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 desired softening point was reached to obtain a polyester. The reaction rate means a value of the amount of produced reaction water / theoretical product water amount × 100.

[Example of toner production]
Examples 1 to 6 and Comparative Examples 1 and 2
100 parts by weight of binder resin shown in Table 2, 1 part by weight of negatively chargeable charge control agent “LR-147” (manufactured by Nippon Carlit), 5 weight by cyan pigment “Toner Cyan BG” (manufactured by Clariant, PB15: 3) 2 parts by weight and release agent “HNP-9” (manufactured by Nippon Seiki Co., Ltd., paraffin wax, melting point: 80 ° C.) are 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 toner particles obtained, 1.0 part by weight of hydrophobic silica “R-972” (manufactured by Nippon Aerosil Co., Ltd., average particle diameter of 16 nm, hydrophobizing agent: dimethyldichlorosilane) is added and mixed with a Henschel mixer. As a result, a toner was obtained.

Example 7
A toner was obtained in the same manner as in Example 1 except that 6 parts by weight of a yellow pigment “Paliotol Yellow D1155” (manufactured by BASF, PY185) was used instead of the cyan pigment “Toner Cyan BG”. .

Example 8
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 E-84” (Orient Chemical Co., Ltd.) is used, and hydrophobic silica “TG” is used instead of “R-972” 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.

Test Example 1 [low temperature fixability]
Toner was installed in a machine that improved the fixing machine of the copier `` AR-505 '' (manufactured by Sharp Corporation) so that fixing outside the apparatus was possible, and paper manufactured by Sharp Corporation [CopyBond SF-70NA ( 4 cm × 4 cm solid print unfixed image was obtained on 75 g / m ² )]. 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 at each temperature. “UNICEF Cellophane” (Mitsubishi Pencil Co., Ltd., width: 18mm, JISZ-1522) is pasted on the fixed image, passed through a fixing roller adjusted to a temperature of 30 ° C and a total fixing pressure of 40kgf, and then the tape is I peeled it off. The optical reflection density before and after the tape was peeled off was measured using a reflection densitometer “RD-915” (manufactured by Macbeth), and the ratio between the two (after peeling / before sticking × 100) was initially 90%. The fixing roller temperature exceeding the minimum fixing temperature was used, and the low-temperature fixing property of the toner was evaluated. The results are shown in Table 2.

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

〔Evaluation criteria〕
A: Aggregation is not observed at all after 48 hours and 72 hours.
B: Aggregation is not observed after 48 hours, but slight aggregation is observed after 72 hours.
C: Aggregation is not observed after 48 hours, but aggregation is clearly observed after 72 hours.
D: Aggregation is observed after 48 hours.

Test Example 3 [Gloss]
Toner was installed in a machine that improved the fixing machine of the copier `` AR-505 '' (manufactured by Sharp Corporation) so that fixing outside the apparatus was possible, and paper manufactured by Sharp Corporation [CopyBond SF-70NA ( 4 cm × 4 cm solid print unfixed image was obtained on 75 g / m ² )]. Using an external fixing device modified from the oilless fixing method DL-2300 (manufactured by Konica Minolta), the fixing roll rotation speed is set to 265 mm / sec and the fixing roll temperature in the fixing device is set to 170 ° C. Setting and fixing processing were performed to obtain a fixed image. The glossiness was measured using the fixed image. Glossiness was measured by using a gloss meter “PG-1” (Nippon Denshoku Industries Co., Ltd.) with a light source set at 60 ° to measure gloss. The results are shown in Table 2. The higher the glossiness, the better the gloss. In the present invention, if the glossiness is 8 or more, it is determined that the effect is achieved.

  From the above results, it can be seen that the toners of Examples 1 to 8 are excellent in low-temperature fixability and storage stability and high in gloss. In contrast, although the compound having a furan ring is used, the toner of Comparative Example 1 containing an amorphous polyester in which the compound represented by the formula (I) is not used has low gloss. . In addition, the toner of Comparative Example 2 containing an amorphous polyester in which a compound having a furan ring is not used at all, including the compound represented by the formula (I), has poor low-temperature fixability and storage stability. It can also be seen that the gloss is also low.

  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)

Carboxylic acid component and alcohol component, and formula (I):

(Wherein R ¹ , R ² and R ³ each independently represent a carboxyl group or a hydroxymethyl group)
In raw material monomers polycondensation Monodea Ru amorphous polyester toner binder resin comprising a containing a compound represented.   The toner according to claim 1, wherein the raw material monomer further contains 10 to 99.99 mol% of a carboxylic acid compound having a furan ring and / or an alcohol having a furan ring other than the compound represented by the formula (I). Landing resin.   The binder resin for toner according to claim 1, wherein the content of the compound represented by formula (I) is 0.01 to 10 mol% in the raw material monomer.   The content of the compound represented by the formula (I) is represented by the compound represented by the formula (I), the carboxylic acid compound having a furan ring other than the compound represented by the formula (I), and the formula (I). The binder resin for toner according to claim 1, which is contained in an amount of 0.02 to 100 mol% in the total amount of alcohol having a furan ring other than the compound.   The binder resin for toner according to any one of claims 1 to 4, wherein the amorphous polyester has a softening point of 80 to 180 ° C.   The binder resin for toner according to claim 1, wherein the raw material monomer further contains 10 mol% or more of an aliphatic diol having a hydroxyl group bonded to a secondary carbon atom in the alcohol component.   A carboxylic acid compound having a furan ring other than the compound represented by formula (I) is at least one carboxylic acid compound selected from the group consisting of furandicarboxylic acid compounds, furancarboxylic acid compounds and hydroxyfurancarboxylic acid compounds. The binder resin for toner according to claim 2, further comprising:   The alcohol compound having a furan ring other than the compound represented by the formula (I) contains at least one alcohol selected from the group consisting of furan alcohol, hydroxymethylfurfuryl alcohol and furfuryl alcohol. 7. The binder resin for toner according to any one of 7 above.   An electrophotographic toner comprising the binder resin according to claim 1.