Toner binder

Abstract

To provide a toner binder and a toner which satisfy all of low-temperature fixability, hot offset resistance, as well as maintainability and hydrolysis resistance at high temperature and high humidity.SOLUTION: A toner binder contains a crystalline vinyl resin (A). The crystalline vinyl resin (A) is a polymer of a monomer composition (A0) containing a monomer (a) and a monomer (b). The monomer (a) is a C21-40 (meth)acrylate with a chain hydrocarbon group. The monomer (b) is a monomer with an amide bond and a cyclic structure. Based on weight of the monomer composition (A0), a weight ratio of the monomer (a) is 40-90 wt.%.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a toner binder.

Background Art

[0002] As a method for fixing an image in a copying machine, a printer, etc., a toner binder for a heat fixing method generally adopted is required to achieve both low-temperature fixability, hot offset resistance, storage stability, etc. For this reason, the toner binder has a high storage elastic modulus at a temperature lower than the fixing temperature, a low storage elastic modulus in a short time at the temperature at which fixing starts, and maintains a constant storage elastic modulus up to a high temperature. It is required that the storage elastic modulus changes to an appropriate value before and after the fixing temperature. As a method for satisfying the above heat characteristics of the toner binder, a technique using a crystalline resin has been proposed. However, the crystalline resin has a problem that the molecular weight decreases due to hydrolysis under long-term storage or high temperature and high humidity, and particularly when used in combination with an amorphous resin having an acid value, the decrease in molecular weight is remarkable. Therefore, in recent years, a technique has been proposed in which a polymer of a monomer having an ethylenically unsaturated bond excellent in hydrolysis resistance is imparted with crystallinity and used as a toner binder (Patent Documents 1 and 2). However, even in this case, there is a problem that hydrolysis occurs under specific high temperature and high humidity conditions, and the physical properties of the resin change.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] An object of the present invention is to provide a toner binder and a toner that satisfy all of low-temperature fixability, hot offset resistance, storage stability under high temperature and high humidity, and hydrolysis resistance.

Means for Solving the Problems

[0005] As a result of intensive studies, the present inventor has reached the present invention. That is, the present invention is a toner binder containing a crystalline vinyl resin (A), and the crystalline vinyl resin (A) is a polymer of a monomer composition (A0) containing a monomer (a) and a monomer (b). The monomer (a) is a (meth)acrylate having a chain hydrocarbon group and 21 to 40 carbon atoms, the monomer (b) is a monomer having an amide bond and a cyclic structure, and based on the weight of the monomer composition (A0). It is a toner binder in which the weight ratio of the monomer (a) is 40 to 90% by weight.

Effects of the Invention

[0006] According to the present invention, it becomes possible to provide a toner binder and a toner that satisfy all of low-temperature fixability, hot offset resistance, storage stability under high temperature and high humidity, and hydrolysis resistance.

Modes for Carrying Out the Invention

[0007] The toner binder of the present invention is a toner binder containing a crystalline vinyl resin (A). The crystalline vinyl resin (A) is a crystalline vinyl resin, and is a monomer (a) which is a (meth)acrylate having a chain hydrocarbon group and 21 to 40 carbon atoms, and a monomer having an amide bond and a cyclic structure. It is a polymer of the monomer composition (A0) containing (b). In the present invention, "crystalline" means that in the temperature rising process of the differential scanning calorimetry curve obtained by the differential scanning calorimetry (also referred to as DSC measurement) described below, there is a maximum in the DSC curve and it has a peak top temperature of an endothermic peak.

[0008] A method for measuring the peak top temperature of the endothermic peak of the crystalline vinyl resin (A) will be described below. Measure using a differential scanning calorimeter (for example, "DSCQ20" manufactured by TA Instruments Co., Ltd.). For the crystalline vinyl resin (A), perform the first heating from 20°C to 150°C at a rate of 10°C / min, then cool from 150°C to 0°C at a rate of 10°C / min, and then perform the second heating from 0°C to 150°C at a rate of 10°C / min. The temperature indicating the top of the endothermic peak during the second heating process is defined as the peak top temperature of the endothermic peak of the crystalline vinyl resin (A).

[0009] Monomer (a) is a (meth)acrylate having a chain hydrocarbon group and 21 to 40 carbon atoms. The number of carbon atoms of monomer (a) is preferably 21 to 36, and more preferably 21 to 34. When the number of carbon atoms of monomer (a) is less than 21, the crystallinity and storage stability under high temperature and high humidity deteriorate, and when it exceeds 40, the low-temperature fixing property deteriorates. Monomer (a) may be used alone or in combination of two or more. In the present invention, "(meth)acrylate" means "acrylate" and / or "methacrylate".

[0010] Examples of monomer (a) include (meth)acrylates having a linear alkyl group (alkyl group having 18 to 36 carbon atoms) [octadecyl (meth)acrylate (stearyl (meth)acrylate), nonadecyl (meth)acrylate, eicosyl (meth)acrylate, heneicosanyl (meth)acrylate, behenyl (meth)acrylate, lignoceryl (meth)acrylate, cerinyl (meth)acrylate, montanyl (meth)acrylate, triacontyl (meth)acrylate, dotriacontyl (meth)acrylate, etc.] and (meth)acrylates having a branched alkyl group (alkyl group having 18 to 36 carbon atoms) [2-decyltetradecyl (meth)acrylate, etc.]. Among these, from the viewpoints of crystallinity, storage stability under high temperature and high humidity, and low-temperature fixability, it is preferably a (meth)acrylate having a linear alkyl group (the alkyl group having 18 to 36 carbon atoms), more preferably a (meth)acrylate having a linear alkyl group (the alkyl group having 18 to 30 carbon atoms), still more preferably octadecyl (meth)acrylate (stearyl (meth)acrylate), eicosyl (meth)acrylate, behenyl (meth)acrylate, lignoceryl (meth)acrylate, cerinyl (meth)acrylate, and triacontyl (meth)acrylate, particularly preferably octadecyl acrylate (stearyl acrylate), eicosyl acrylate, behenyl acrylate, and lignoceryl acrylate, and most preferably behenyl acrylate.

[0011] Monomer (b) is a monomer having an amide bond and a cyclic structure. Monomer (b) may be used alone or in combination of two or more. When monomer (b) has an amide bond, the storage stability, hydrolysis resistance, and hot offset resistance under high temperature and high humidity are good. When it has a cyclic structure, the low-temperature fixability, storage stability under high temperature and high humidity, hydrolysis resistance, and offset resistance are good. Presumably, by using a monomer having an amide bond and a cyclic structure, compared with a monomer having an acyclic structure, due to the bulkiness of the cyclic group, steric repulsion is more likely to occur when water molecules approach the amide group, so the storage stability and hydrolysis resistance under high temperature and high humidity are improved. In addition, due to the effect of the polar group derived from the amide group, the chemical interaction between the toner binder and the fixing paper takes effect, and it is considered that the low-temperature fixability and hot offset resistance are improved.

[0012] Monomer (b) is not particularly limited as long as it is a monomer having an amide bond and a cyclic structure. From the viewpoints of low-temperature fixability and hot offset resistance, the compounds represented by the following general formula (1) and / or (2) are preferred.

[0013]

Chemical formula

[0014] In general formula (1), R 1 is a hydrogen atom or a methyl group, and R 2 is an alkylene group having 2 to 5 carbon atoms.

[0015] Examples of the alkylene group having 2 to 5 carbon atoms for R 2 include an ethylene group, a propylene group (1,2-propylene group), a trimethylene group (1,3-propylene group), a tetramethylene group, a pentamethylene group, and the like. Among R 2 from the viewpoints of low-temperature fixability and hot offset resistance, R 2 is preferably an alkylene group having 3 to 4 carbon atoms, more preferably an alkylene group having 3 carbon atoms.

[0016] Specific examples of the compound represented by general formula (1) include N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, and the like. Among these, from the viewpoints of low-temperature fixability and hot offset resistance, N-vinylpyrrolidone is preferable.

[0017]

Chemical formula

[0018] In general formula (2), R 3 is a hydrogen atom or a methyl group, and R 4 are each independently an alkylene group having 1 to 5 carbon atoms, and X represents an oxygen atom, a nitrogen atom, or a direct bond.

[0019] Examples of the alkylene group having 1 to 5 carbon atoms for R 4 include a methylene group, an ethylene group, a propylene group (1,2-propylene group), a trimethylene group (1,3-propylene group), a tetramethylene group, a pentamethylene group, and the like. Also, among R 4 from the viewpoints of low-temperature fixability and hot offset resistance, R 4 is preferably an alkylene group having 2 to 3 carbon atoms, more preferably an alkylene group having 2 carbon atoms. Furthermore, among X, from the viewpoints of hot offset resistance and charging stability, it is preferably an oxygen atom.

[0020] Specific examples of the compound represented by the general formula (2) include (meth)acryloylmorpholine, 1-(meth)acryloylpyrrolidine, N-(meth)acryloylaziridine, N-(meth)acryloylazetidine, N-(meth)acryloylpiperidine, N-(meth)acryloylazepane, N-(meth)acryloylazocane, and the like. Among these, from the viewpoints of low-temperature fixability and hot offset resistance, (meth)acryloylmorpholine is preferable. In the present invention, “(meth)acryloyl” means “acryloyl” and / or “methacryloyl”.

[0021] Examples of the monomer (b) other than the compound represented by the general formula (1) and / or (2) include cinnamic acid amide and N,N-dibenzylacrylamide.

[0022] The monomer composition (A0) containing the monomer (a) and the monomer (b) may optionally contain other monomers in combination. For example, a monomer (c) other than the monomer (a) and the monomer (b) can be mentioned. The monomer (c) may be used alone or in combination of two or more. Examples of the monomer (c) include vinyl hydrocarbons (c1), vinyl monomers containing a carboxyl group (c2), vinyl monomers containing a hydroxyl group (c3), nitrogen-containing vinyl monomers (c4), vinyl monomers containing an epoxy group (c5), vinyl monomers containing a halogen element (c6), and other ester monomers (c7).

[0023] Examples of the vinyl hydrocarbon (c1) include aliphatic vinyl hydrocarbons, alicyclic vinyl hydrocarbons, and aromatic vinyl hydrocarbons. Examples of the aliphatic vinyl hydrocarbon include alkenes and alkadienes. Specific examples of alkenes include ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, and other α-olefins other than those mentioned above. Specific examples of alkadienes include butadiene, isoprene, 1,4-pentadiene, 1,5-hexadiene, 1,7-octadiene, and the like. Examples of alicyclic vinyl hydrocarbons include mono- or di-cycloalkenes and alkadienes. Specific examples include cyclohexene, (di)cyclopentadiene, vinylcyclohexene, ethylidene bicycloheptene, and terpenes (pinene, limonene, indene, etc.). Examples of aromatic vinyl hydrocarbons include styrene and its hydrocarbyl (alkyl, cycloalkyl, aralkyl, and / or alkenyl) substituents. Specifically, α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene, cyclohexylstyrene, benzylstyrene, crotylbenzene, divinylbenzene, divinyltoluene, divinylxylene, trivinylbenzene, and vinylnaphthalene, etc.

[0024] Examples of the carboxyl group-containing vinyl monomer (c2) include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and anhydrides thereof having 3 to 20 carbon atoms. Specifically, carboxyl group-containing vinyl monomers such as (meth)acrylic acid, (anhydrous) maleic acid, maleic acid monoalkyl ester, fumaric acid, fumaric acid monoalkyl ester, crotonic acid, itaconic acid, itaconic acid monoalkyl ester, itaconic acid glycol monoether, citraconic acid, citraconic acid monoalkyl ester, and cinnamic acid, etc.

[0025] Examples of the hydroxyl group-containing vinyl monomer (c3) include hydroxystyrene, N-methylol(meth)acrylamide, hydroxyethyl(meth)acrylate (such as 2-hydroxyethyl acrylate, etc.), hydroxypropyl(meth)acrylate, polyethylene glycol mono(meth)acrylate, (meth)allyl alcohol, crotyl alcohol, isocrotyl alcohol, 1-buten-3-ol, 2-buten-1-ol, 2-buten-1,4-diol, propargyl alcohol, 2-hydroxyethyl propenyl ether, and sucrose allyl ether, etc.

[0026] Examples of the nitrogen-containing vinyl monomer (c4) include amino group-containing vinyl monomers, amide group-containing vinyl monomers, nitrile group-containing vinyl monomers, quaternary ammonium cation group-containing vinyl monomers, and nitro group-containing vinyl monomers, etc. Examples of the amino group-containing vinyl monomer include aminoethyl(meth)acrylate, dimethylaminoethyl(meth)acrylate, diethylaminoethyl(meth)acrylate, t-butylaminoethyl methacrylate, N-aminoethyl(meth)acrylamide, (meth)allylamine, morpholinoethyl(meth)acrylate, 4-vinylpyridine, 2-vinylpyridine, crotylamine, N,N-dimethylaminostyrene, methyl α -acetaminoacrylate, vinylimidazole, N-vinylpyrrole, N-vinylthiopyrrolidone, N-aryl-phenylenediamine, aminocarbazole, aminothiazole, aminoindole, aminopyrrole, aminoimidazole, aminomercaptothiazole, and salts thereof, etc. Examples of the amide group-containing vinyl monomer include those other than the monomer (b) above, and include (meth)acrylamide, N-methyl(meth)acrylamide, N-butylacrylamide, diacetoneacrylamide, N-methylol(meth)acrylamide, N,N'-methylene-bis(meth)acrylamide, N,N-dimethylacrylamide, methacryloylformamide, and N-methyl N-vinylacetamide, etc. Examples of the nitrile group-containing vinyl monomer include acrylonitrile, methacrylonitrile, cyanostyrene, cyanoacrylate, and the like. Examples of the quaternary ammonium cation group-containing vinyl monomer include quaternized products of tertiary amine group-containing vinyl monomers such as dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylamide, diethylaminoethyl (meth)acrylamide, and diallylamine (quaternized using a quaternizing agent such as methyl chloride, dimethyl sulfate, benzyl chloride, and dimethyl carbonate). Examples of the nitro group-containing vinyl monomer include nitrostyrene and the like.

[0027] Examples of the epoxy group-containing vinyl monomer (c5) include glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, and p-vinylphenyl phenyl oxide.

[0028] Examples of the halogen element-containing vinyl monomer (c6) include vinyl chloride, vinyl bromide, vinylidene chloride, allyl chloride, chlorostyrene, bromostyrene, dichlorostyrene, chloromethylstyrene, tetrafluorostyrene, and chloroprene.

[0029] Examples of other ester monomers (c7) include alkyl (meth) acrylates having a chain hydrocarbon group and 20 or less carbon atoms, wherein the alkyl group has 1 to 17 carbon atoms, such as alkyl (meth) acrylates [methyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, etc.], alkylene ether (meth) acrylates having 5 to 30 carbon atoms [methoxy-triethylene glycol (meth) acrylate, ethoxy-diethylene glycol (meth) acrylate, methoxy-polyethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, etc.], poly (meth) acrylates [poly (meth) acrylates of polyhydric alcohols such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and polyethylene glycol di (meth) acrylate, etc.], aliphatic vinyl esters having 4 to 15 carbon atoms and aromatic vinyl esters having 9 to 15 carbon atoms [vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate, and methyl-4-vinylbenzoate, etc.].

[0030] Among these monomers (c), from the viewpoint of storage stability under high temperature and high humidity, vinyl hydrocarbons (c1), nitrogen-containing vinyl monomers (c4), and other ester monomers (c7) are preferred, and aromatic vinyl hydrocarbons, nitrile group-containing vinyl monomers, and alkyl (meth) acrylates having 1 to 17 carbon atoms in the alkyl group are more preferred.

[0031] The weight ratio of the monomer (a) in the monomer composition (A0) in the crystalline vinyl resin (A) is 40 to 90% by weight, preferably 50 to 90% by weight, more preferably 50 to 70% by weight, and still more preferably 50 to 60% by weight, based on the weight of the monomer composition (A0). When the weight ratio of the monomer (a) is less than 40% by weight, the low-temperature fixing property deteriorates. On the other hand, when the weight ratio of the monomer (a) exceeds 90% by weight, the hot offset resistance deteriorates.

[0032] From the viewpoints of storage stability and hydrolysis resistance under high temperature and high humidity, the weight ratio of monomer (b) in monomer composition (A0) in crystalline vinyl resin (A) is preferably 1 to 35% by weight, more preferably 5 to 30% by weight, still more preferably 5 to 15% by weight, based on the weight of monomer composition (A0).

[0033] When monomer composition (A0) contains monomer (c), from the viewpoint of hot offset resistance, the weight ratio of monomer (c) in monomer composition (A0) is preferably 4 to 55% by weight, more preferably 10 to 55% by weight, still more preferably 10 to 45% by weight.

[0034] The crystalline vinyl resin (A) in the present invention can be produced by polymerizing a monomer composition by a known method (for example, radical polymerization, anionic polymerization, cationic polymerization, living radical polymerization, living anionic polymerization, living cationic polymerization, etc.). In the case of radical polymerization, for example, it can be synthesized by a solution polymerization method (such as JP-A-5-117330) in which the above monomer is reacted with a radical reaction initiator (d) in a solvent (such as toluene). Also, a known radical reaction initiator (d) may be used as the radical reaction initiator. The radical reaction initiator (d) is not particularly limited, and examples thereof include inorganic peroxides (d1), organic peroxides (d2), and azo compounds (d3). These radical reaction initiators can also be used in combination.

[0035] The inorganic peroxide (d1) is not particularly limited, and examples thereof include hydrogen peroxide, ammonium persulfate, potassium persulfate, and sodium persulfate.

[0036] The organic peroxide (d2) is not particularly limited, and examples thereof include benzoyl peroxide, di-t-butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, α,α-bis(t-butylperoxy) diisopropylbenzene, 2,5-dimethyl-2,5-bis(t-butylperoxy) hexane, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di-t-butylperoxy hexyne-3, acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,3,5-trimethylhexanoyl peroxide, m-toluoyl peroxide, t-butylperoxy isobutyrate, t-butylperoxy neodecanoate, cumylperoxy neodecanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxy laurate, t-butylperoxy benzoate, t-butylperoxy isopropyl monocarbonate, t-butylperoxy acetate and the like.

[0037] The azo compound (d3) is not particularly limited, and examples thereof include 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, 2,2'-azobis(2-methylbutyronitrile) and azobisisobutyronitrile.

[0038] The peak top temperature (Tm A ) of the endothermic peak of the crystalline vinyl resin (A) is preferably 40 to 100 °C, more preferably 45 to 90 °C, and still more preferably 50 to 60 °C from the viewpoints of low-temperature fixability and storage stability under high temperature and high humidity. When the endothermic peak top temperature is 40 °C or higher, the storage stability under high temperature and high humidity is good, and when it is 100 °C or lower, the low-temperature fixability is good. The peak top temperature (Tm A) can be adjusted mainly by the number of parts by weight of monomer (a) and the number of carbon atoms in the chain hydrocarbon group of monomer (a). When the number of parts by weight of monomer (a) is large, the peak top temperature (Tm A ) can be increased, and when the number of carbon atoms in the chain hydrocarbon group of monomer (a) is large, the peak top temperature (Tm A ) can be increased. However, the endothermic peak top temperature (Tm A ) of the crystalline vinyl resin (A) is the peak top temperature of the endothermic peak of the crystalline vinyl resin (A) in the second heating process in which the crystalline vinyl resin (A) is first heated from 20 °C to 150 °C at a rate of 10 °C / min using a differential scanning calorimeter (DSC), then cooled from 150 °C to 0 °C at a rate of 10 °C / min, and subsequently heated from 0 °C to 150 °C at a rate of 10 °C / min.

[0039] The xylene-insoluble content of the crystalline vinyl resin (A) is preferably 6% by weight or less, more preferably 1 to 3% by weight, from the viewpoints of low-temperature fixability, storage stability under high temperature and high humidity, and hydrolysis resistance. The xylene-insoluble content can be adjusted by the number of parts by weight of monomer (b). When the number of parts by weight of monomer (b) is large, the xylene-insoluble content becomes high. The measuring method of the xylene-insoluble content of the crystalline vinyl resin (A) is as follows. For sample preparation, 1.00 g of the crystalline vinyl resin (A) is dissolved or dispersed in 100 g of xylene at a temperature above the peak top temperature of the endothermic peak, cooled to 25 °C, centrifuged using a centrifuge, the supernatant is removed, and then dried under reduced pressure (170 °C, 2 hours) to obtain the xylene-insoluble content. The weight of the xylene-insoluble content is measured to the fourth decimal place, and the xylene-insoluble content of (A) is calculated by the following formula. Xylene-insoluble content of crystalline vinyl resin (A) (wt%) = (weight of xylene-insoluble content (g) / 1.00)×100 In addition, the conditions for centrifugation are as follows. <Centrifugation conditions> Centrifuge: H-19F (manufactured by Kokusan Co., Ltd.) Rotation speed: 4000 rpm Rotation time: 20 minutes

[0040] In the present invention, the weight-average molecular weight of the crystalline vinyl resin (A) in gel permeation chromatography (GPC) is preferably from 2,000 to 200,000, more preferably from 5,000 to 100,000, still more preferably from 10,000 to 70,000, and particularly preferably from 20,000 to 40,000, from the viewpoints of low-temperature fixability and hot offset resistance.

[0041] In the present invention, the number-average molecular weight (hereinafter sometimes abbreviated as Mn) and the weight-average molecular weight (hereinafter sometimes abbreviated as Mw) of the crystalline vinyl resin (A) and the resin for toner binder other than (A) described below can be measured under the following conditions using GPC. Apparatus (example): HLC-8120 [manufactured by Tosoh Corporation] Column (example): Two TSK GEL GMH6 [manufactured by Tosoh Corporation] Measurement temperature: 40 °C Sample solution: 0.25 wt% THF solution Mobile phase: Tetrahydrofuran (excluding polymerization inhibitor) Solution injection volume: 100 μL Detector: Refractive index detector Reference substance: 12 standard polystyrenes (TSKstandard POLYSTYRENE) (molecular weights 500, 1,050, 2,800, 5,970, 9,100, 18,100, 37,900, 96,400, 190,000, 355,000, 1,090,000, 2,890,000) [manufactured by Tosoh Corporation] For the measurement of the molecular weight, the sample is dissolved in tetrahydrofuran (hereinafter abbreviated as THF) so as to be 0.25 wt%, and the undissolved matter is filtered through a glass filter to obtain a sample solution. It should be noted that for the amorphous vinyl resin (B) and the toner binder described below, Mn and Mw can also be determined by the same method as above.

[0042] The toner binder of the present invention may contain other resins known as resins for toner binders other than the crystalline vinyl resin (A). Examples of other resins include vinyl resins, polyurethane resins, epoxy resins, polyester resins, polyamide resins, polyimide resins, ionomer resins, polycarbonate resins, etc., and two or more of the above resins may be used in combination. These resins may be linear resins or non-linear resins, and in the case of non-linear resins, they may be cross-linked. Among these, from the viewpoints of low-temperature fixability and hydrolysis resistance, vinyl resins and polyester resins are preferred, and particularly preferred are amorphous vinyl resin (B) and non-linear polyester resin (C).

[0043] The composition of the amorphous vinyl resin (B) is not particularly limited as long as it is an amorphous vinyl resin, but from the viewpoints of storage stability and hydrolysis resistance under high temperature and high humidity, it is preferably a polymer of a monomer composition (B0) containing styrene. In the present invention, "amorphous" means that when the transition temperature of a sample is measured using a differential scanning calorimeter (DSC) under the same measurement conditions as the method for measuring the peak top temperature of the endothermic peak of the crystalline vinyl resin (A), there is no peak top temperature of the endothermic peak.

[0044] The monomer composition (B0) containing styrene may be used in combination with other monomers as necessary, and examples thereof are the same as the monomer (c) exemplified for the crystalline vinyl resin (A). These monomers may be used alone or in combination of two or more. For example, styrene-alkyl (meth)acrylate copolymer, styrene-(meth)acrylic acid copolymer, styrene-alkyl (meth)acrylate-(meth)acrylic acid copolymer, styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, and styrene-alkyl (meth)acrylate-acrylonitrile copolymer, etc. may be mentioned. Among the above, preferably, they are styrene-alkyl (meth)acrylate copolymers, styrene-(meth)acrylic acid copolymers, styrene-alkyl (meth)acrylate-(meth)acrylic acid copolymers, styrene-acrylonitrile copolymers, and styrene-alkyl (meth)acrylate-acrylonitrile copolymers, etc., and more preferably, they are styrene-alkyl (meth)acrylate-(meth)acrylic acid copolymers, and styrene-alkyl (meth)acrylate-acrylonitrile copolymers, etc.

[0045] From the viewpoints of low-temperature fixing property, storage stability under high temperature and high humidity, and hydrolysis resistance, the acid value of the amorphous vinyl resin (B) is preferably 0 to 50 mgKOH / g, and more preferably 0.1 to 30 mgKOH / g. The acid value can be measured by the method specified in JIS K0070.

[0046] From the viewpoints of storage stability under high temperature and high humidity and low-temperature fixing property, the glass transition temperature of the amorphous vinyl resin (B) is preferably 50 to 75 °C, and more preferably 55 to 70 °C. The glass transition temperature (Tg) of the amorphous vinyl resin (B) can be determined by the method specified in ASTM D3418-82 (DSC method). For the measurement of the glass transition temperature (Tg), for example, DSC Q20 manufactured by TA Instruments Co., Ltd. etc. can be used. The glass transition temperature (Tg) can be measured under the following conditions. <Measurement Conditions> (1) Heat up from 30 °C to 150 °C at 20 °C / min (2) Hold at 150 °C for 10 minutes (3) Cool to -35 °C at 20 °C / min (4) Hold at -35 °C for 10 minutes (5) Heat up from -35 °C to 150 °C at 20 °C / min (6) Analyze the differential scanning calorimetry curve measured in the process of (5), and take the position of the inflection point as the glass transition temperature.

[0047] The amorphous vinyl resin (B) in the present invention can be produced in the same manner as the crystalline vinyl resin (A). Examples of the radical reaction initiator (d) in the case of radical polymerization are the same.

[0048] The non-linear polyester resin (C) is not particularly limited in its resin composition as long as it is a non-linear polyester resin. The non-linear polyester resin (C) is a polyester resin obtained by polycondensing an alcohol component containing a polyol component (x) and a carboxylic acid component containing a polycarboxylic acid component (y), and it may be crosslinked.

[0049] Examples of the polyol component (x) include diol (x1) and polyol (x2) having a valence of 3 or more. These may be used alone or in combination of two or more.

[0050] Examples of the diol (x1) include alkylene glycols having 2 to 36 carbon atoms (ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, etc.), alkylene ether glycols having 4 to 36 carbon atoms (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.), alicyclic diols having 6 to 36 carbon atoms (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.), (poly)alkylene oxide adducts of the above alicyclic diols (preferably with an average addition mole number of 1 to 30), aromatic diols [monocyclic dihydric phenols (such as hydroquinone, etc.) and bisphenols, etc.] and alkylene oxide adducts of the above aromatic diols (preferably with an average addition mole number of 2 to 30), etc.

[0051] The alkylene oxide adduct of the above-mentioned bisphenols is obtained by adding an alkylene oxide (hereinafter, "alkylene oxide" may be abbreviated as AO) to bisphenols.

[0052] Examples of bisphenols include those represented by the following general formula (1). HO-Ar-P-Ar-OH (1) [In the formula, P represents an alkylene group having 1 to 3 carbon atoms, -SO2-, -O-, -S- or a direct bond, and Ar represents a phenylene group which may be substituted by a halogen atom or an alkyl group having 1 to 30 carbon atoms.]

[0053] Specific examples of bisphenols include, for example, bisphenol A, bisphenol F, bisphenol B, bisphenol AD, bisphenol S, trichlorobisphenol A, tetrachlorobisphenol A, dibromobisphenol F, 2-methylbisphenol A, 2,6-dimethylbisphenol A, and 2,2'-diethylbisphenol F, etc. These can also be used in combination of two or more.

[0054] Examples of the alkylene oxide added to bisphenols include alkylene oxides having 2 to 30 carbon atoms, such as ethylene oxide (hereinafter, "ethylene oxide" may be abbreviated as EO), propylene oxide (may be abbreviated as PO), butylene oxide, tetrahydrofuran, and a combination of two or more of these.

[0055] Among these diols (x1), from the viewpoints of low-temperature fixing property and storage stability under high temperature and high humidity, alkylene glycols having 2 to 36 carbon atoms and alkylene oxide adducts of aromatic diols are preferable, alkylene glycols having 2 to 10 carbon atoms and alkylene oxide adducts of bisphenols (the average addition mole number is preferably 2 to 5) are more preferable, and alkylene glycols having 2 to 6 carbon atoms and alkylene oxide adducts of bisphenol A (the average addition mole number is preferably 2 to 5) are even more preferable.

[0056] Examples of the polyol (x2) having a valency of 3 or more include aliphatic polyhydric alcohols having a valency of 3 or more and 3 to 36 carbon atoms, saccharides and their derivatives, alkylene oxide adducts of aliphatic polyhydric alcohols (the average number of added moles is preferably 1 to 30), alkylene oxide adducts of trisphenols (such as trisphenol PA, etc.) (the average number of added moles is preferably 2 to 30), and alkylene oxide adducts of novolak resins (including phenol novolak and cresol novolak, etc., and the average degree of polymerization is preferably 3 to 60) (the average number of added moles is preferably 2 to 30), etc.

[0057] Examples of the aliphatic polyhydric alcohol having a valency of 3 or more and 3 to 36 carbon atoms include alkane polyols and their intramolecular or intermolecular dehydrates, such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, polyglycerin, and dipentaerythritol, etc. Examples of the saccharides and their derivatives include sucrose and methyl glucoside, etc.

[0058] Among these polyols (x2) having a valency of 3 or more, from the viewpoint of achieving both low-temperature fixability and hot offset resistance, aliphatic polyhydric alcohols having a valency of 3 or more and 3 to 36 carbon atoms, and alkylene oxide adducts of novolak resins (including phenol novolak and cresol novolak, etc., and the average degree of polymerization is preferably 3 to 60) (the average number of added moles is preferably 2 to 30) are preferred, aliphatic polyhydric alcohols having a valency of 3 and 3 to 8 carbon atoms are more preferred, and trimethylolpropane is particularly preferred.

[0059] The diol (x1) in the polyol component (x) of the non-linear polyester resin (C) is preferably 80 to 100 mol%. When the diol (x1) and a polyol (x2) having a valency of 3 or more are used in combination, the molar ratio [(x1) / (x2)] of the diol (x1) to the polyol (x2) having a valency of 3 or more is preferably 80 / 20 to 99 / 1, more preferably 85 / 15 to 98 / 2, from the viewpoint of hot offset resistance.

[0060] Further, as the alcohol component of the non-linear polyester resin (C), a monoalcohol component can be contained as necessary in addition to the above polyol component (x). Examples of the monoalcohol include linear or branched alkyl alcohols having 1 to 30 carbon atoms (such as methanol, ethanol, isopropanol, 1-decanol, dodecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol, and lignoceryl alcohol).

[0061] Among these monoalcohols, linear or branched alkyl alcohols having 8 to 24 carbon atoms are preferred, linear alkyl alcohols having 8 to 24 carbon atoms are more preferred, and dodecyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol, and lignoceryl alcohol are even more preferred, from the viewpoint of storage stability under high temperature and high humidity.

[0062] Examples of the polycarboxylic acid component (y) include dicarboxylic acids (y1) and polycarboxylic acids (y2) having a valency of 3 or more. These may be used alone or in combination of two or more.

[0063] Examples of the dicarboxylic acid (y1) include aromatic dicarboxylic acids having 8 to 36 carbon atoms (such as terephthalic acid, phthalic acid, isophthalic acid, and naphthalenedicarboxylic acid), aliphatic dicarboxylic acids having 2 to 50 carbon atoms (such as oxalic acid, malonic acid, succinic acid, adipic acid, azelaic acid, and sebacic acid), alicyclic dicarboxylic acids having 6 to 40 carbon atoms [such as dimer acid (dimerized linoleic acid)], alkenedicarboxylic acids having 4 to 36 carbon atoms (such as alkenyl succinic acids like dodecenyl succinic acid, maleic acid, fumaric acid, citraconic acid, and mesaconic acid), and ester-forming derivatives thereof. Here, the ester-forming derivative means a carboxylic anhydride, an alkyl (methyl, ethyl, butyl, stearyl, etc. having 1 to 24 carbon atoms, preferably an alkyl having 1 to 4 carbon atoms) ester, and a partial alkyl ester.

[0064] Among these dicarboxylic acids (y1), from the viewpoint of achieving both low-temperature fixability, hot offset resistance, and storage stability under high temperature and high humidity, aromatic dicarboxylic acids having 8 to 36 carbon atoms, aliphatic dicarboxylic acids having 2 to 50 carbon atoms, and alkenedicarboxylic acids having 4 to 36 carbon atoms are preferred, terephthalic acid, phthalic acid, isophthalic acid, adipic acid, succinic acid, maleic acid, and fumaric acid are more preferred, terephthalic acid, phthalic acid, isophthalic acid, adipic acid, and fumaric acid are still more preferred, and terephthalic acid, isophthalic acid, adipic acid, and fumaric acid are particularly preferred. Also, anhydrides or lower alkyl esters of these acids may be used.

[0065] Examples of the polycarboxylic acid (y2) having a valence of 3 or more include aromatic polycarboxylic acids having 9 to 20 carbon atoms and a valence of 3 or more (such as trimellitic acid and pyromellitic acid), aliphatic (including alicyclic) tricarboxylic acids having 6 to 36 carbon atoms (such as hexanetricarboxylic acid and decanetricarboxylic acid), and ester-forming derivatives thereof.

[0066] Among these polycarboxylic acids (y2) having a valence of 3 or more, from the viewpoint of achieving both low-temperature fixability and hot offset resistance, aromatic polycarboxylic acids having 9 to 20 carbon atoms are preferred, and trimellitic acid and pyromellitic acid are more preferred. Also, anhydrides or lower alkyl esters of these acids may be used.

[0067] The total proportion of terephthalic acid and isophthalic acid in the polycarboxylic acid component of the non-linear polyester resin (C) may be 80 to 100 mol%, or may be 100 mol%. That is, the non-linear polyester resin (C) may not contain a carboxylic acid component other than terephthalic acid and isophthalic acid as the polycarboxylic acid component.

[0068] Also, as the carboxylic acid component of the non-linear polyester resin (C), a monocarboxylic acid component can be contained as necessary. Examples of the monocarboxylic acid include aromatic monocarboxylic acids having 7 to 37 carbon atoms (benzoic acid, toluic acid, 4-ethylbenzoic acid, 4-propylbenzoic acid, etc.), and aliphatic (including alicyclic) monocarboxylic acids having 2 to 50 carbon atoms (acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, behenic acid, etc.).

[0069] Among these monocarboxylic acids, from the viewpoint of storage stability under high temperature and high humidity, aliphatic (including alicyclic) monocarboxylic acids having 2 to 50 carbon atoms are preferable, and behenic acid is more preferable.

[0070] The weight average molecular weight of the non-linear polyester resin (C) is preferably 3,000 to 10,000, and more preferably 5,000 to 9,000, from the viewpoints of low-temperature fixability and storage stability under high temperature and high humidity.

[0071] The acid value of the non-linear polyester resin (C) is preferably 0 to 50 mgKOH / g, and more preferably 0.1 to 30 mgKOH / g, from the viewpoints of low-temperature fixability, storage stability under high temperature and high humidity, and hydrolysis resistance. The acid value can be measured by the method specified in JIS K0070.

[0072] The glass transition temperature of the non-linear polyester resin (C) is preferably 43 to 60 °C, and more preferably 48 to 55 °C, from the viewpoints of storage stability under high temperature and high humidity and low-temperature fixability. The glass transition temperature of the non-linear polyester resin (C) can be measured by the same method as the method for measuring the glass transition temperature of the amorphous vinyl resin (B) described above.

[0073] Specifically, the non-linear polyester resin (C) can be produced, for example, as follows. For example, an alcohol component and a carboxylic acid component are subjected to a polycondensation reaction in an atmosphere of an inert gas (such as nitrogen gas) at a reaction temperature preferably of 150 to 280°C, more preferably 160 to 250°C, and still more preferably 170 to 235°C. Also, from the viewpoint of ensuring the polycondensation reaction, the reaction time is preferably 30 minutes or more, more preferably 2 to 40 hours. It is also effective to reduce the pressure in order to improve the reaction rate at the end of the reaction.

[0074] At this time, an esterification catalyst can be used as necessary. Examples of the esterification catalyst include tin-containing catalysts (such as dibutyltin oxide, etc.), antimony trioxide, titanium-containing catalysts [such as titanium alkoxides (tetrabutoxy titanate, etc.), potassium titanate oxalate, titanium terephthalate, titanium alkoxide terephthalate, catalysts described in JP-A-2006-243715 {titanium diisopropoxybis(triethanolamineate), titanium dihydroxybis(triethanolamineate), titanium monohydroxytri(triethanolamineate), titanyl bis(triethanolamineate) and their intramolecular polycondensates, etc.} and catalysts described in JP-A-2007-11307 (titanium tributoxy terephthalate, titanium triisopropoxy terephthalate and titanium diisopropoxy diterephthalate, etc.), etc.], zirconium-containing catalysts (such as zirconyl acetate, etc.) and zinc acetate, etc. Among these, a titanium-containing catalyst is preferred.

[0075] Also, for the purpose of promoting the polymerization of the polyester stably, a stabilizer may be added. Examples of the stabilizer include hydroquinone, methyl hydroquinone and hindered phenol compounds, etc.

[0076] In addition, when the non-linear polyester resin (C) is crosslinked, the following methods are preferably used as the method for producing the non-linear polyester resin (C). First, at least one of an unsaturated carboxylic acid component and an unsaturated alcohol component, and if necessary, a saturated carboxylic acid component and / or a saturated alcohol component are subjected to a condensation reaction as constituent components to obtain a polyester resin (C0) having a carbon-carbon double bond in the molecule. Next, a radical reaction initiator is allowed to act in (C0), and using the radicals generated from the radical reaction initiator, the carbon-carbon double bonds derived from the unsaturated carboxylic acid component and / or the unsaturated alcohol component are bonded to each other by a crosslinking reaction. Thereby, the non-linear polyester resin (C) can be produced. This method is a preferable method in that the crosslinking reaction can be made uniform in a short time. Among the unsaturated carboxylic acid components, from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability, unsaturated monocarboxylic acids having 2 to 10 carbon atoms and alkenedicarboxylic acids having 4 to 18 carbon atoms are preferable, and alkenyl succinic acids such as acrylic acid, methacrylic acid, and dodecenyl succinic acid, maleic acid, and fumaric acid are more preferable. Even more preferably, acrylic acid, methacrylic acid, maleic acid, fumaric acid, and combinations thereof are used. Also, anhydrides and lower alkyl esters of these acids are similarly preferable. Examples of the unsaturated alcohol component include unsaturated monools and unsaturated diols. Examples of the unsaturated monool include 2-propen-1-ol and 2-hydroxyethyl methacrylate. Examples of the unsaturated diol include ricinoleyl alcohol. These may be used alone or in combination of two or more.

[0077] The radical reaction initiator (c) used for the crosslinking reaction of the polyester resin (C0) having a carbon-carbon double bond is not particularly limited, and examples include the inorganic peroxides, organic peroxides, and azo compounds described above. Also, these radical reaction initiators (c) may be used alone or in combination of two or more.

[0078] The amount of the radical reaction initiator (c) used is not particularly limited, but is preferably 0.1 to 50 parts by weight based on 100 parts by weight of the total weight of the unsaturated carboxylic acid component and the unsaturated alcohol component used in the polymerization reaction for obtaining the polyester resin (C0) having a carbon-carbon double bond. When the amount of the radical reaction initiator used is 0.1 part by weight or more, the crosslinking reaction tends to proceed easily, and when it is 50 parts by weight or less, the odor tends to be good. This amount used is more preferably 30 parts by weight or less, still more preferably 20 parts by weight or less, and particularly preferably 10 parts by weight or less. When the polyester (A1) is a polyester (A11) having a carbon-carbon double bond, the content of the carbon-carbon double bond in the polyester (A11) is not particularly limited, but is preferably 0.1 to 1.2 mmol / g based on the weight of the polyester (A11), more preferably 0.1 to 0.9 mmol / g. When the content of the carbon-carbon double bond is 0.1 to 1.2 mmol / g based on the weight of the polyester (A11), the crosslinking reaction occurs preferably, and the storage stability of the toner under high temperature and high humidity is improved.

[0079] When the non-linear polyester resin (C) is prepared by radical polymerization using the above-mentioned type of radical reaction initiator (c) and the above-mentioned amount used, the crosslinking reaction between the carbon-carbon double bonds in the polyester resin (C0) occurs preferably, and the low-temperature fixability, hot offset resistance and storage stability under high temperature and high humidity of the toner are improved, which is preferable.

[0080] In the present invention, from the viewpoints of low-temperature fixability, hot offset resistance and storage stability under high temperature and high humidity, the weight ratio of the crystalline vinyl resin (A) is preferably 10 to 60% by weight based on the weight of the toner binder.

[0081] In the present invention, when other resins such as amorphous vinyl resin (B) and non-linear polyester resin (C) are included, the content ratio of the other resins is preferably 40 to 90% by weight based on the weight of the toner binder from the viewpoints of low-temperature fixability, hot offset resistance, and storage stability under high temperature and high humidity.

[0082] A method for manufacturing a toner binder will be described. The toner binder is not particularly limited as long as it contains crystalline vinyl resin (A). For example, when mixing crystalline vinyl resin (A), other resins used as necessary, and additives, a known method may be used. Examples of the mixing method include powder mixing, melt mixing, and solvent mixing. Further, crystalline vinyl resin (A), other resins used as necessary, and additives may be mixed simultaneously when manufacturing the toner.

[0083] Examples of the mixing apparatus for powder mixing include Henschel mixers, Nauta mixers, and Banbury mixers. A Henschel mixer is preferred. Examples of the mixing apparatus for melt mixing include batch-type mixing apparatuses such as reaction tanks and continuous mixing apparatuses. A continuous mixing apparatus is preferred for uniformly mixing at an appropriate temperature in a short time. Examples of the continuous mixing apparatus include static mixers, extruders, continuous kneaders, and three-roll mills. Examples of the solvent mixing method include a method in which crystalline vinyl resin (A) and other resins are dissolved in a solvent (such as ethyl acetate, THF, and acetone), homogenized, and then desolvated and pulverized, and a method in which crystalline vinyl resin (A) and other resins are dissolved in a solvent (such as ethyl acetate, THF, and acetone), dispersed in water, and then granulated and desolvated.

[0084] The toner binder of the present invention is useful for application to toners. The toner contains the toner binder of the present invention.

[0085] In addition to the toner binder of the present invention, the toner may contain one or more known additives selected from colorants, release agents, charge control agents, fluidizing agents, etc., if necessary.

[0086] As the colorant, all dyes and pigments used as colorants for toners can be used. For example, carbon black, iron black, Sudan black SM, Fast Yellow G, benzidine yellow, pigment yellow, indanthrone orange, Irgasin red, paranitroaniline red, toluidine red, carmine FB, pigment orange R, lake red 2G, rhodamine FB, rhodamine B lake, methyl violet B lake, phthalocyanine blue, pigment blue, brilliant green, phthalocyanine green, oil yellow GG, Kayaset YG, olazol brown B, oil pink OP, etc. can be mentioned. The colorant may be any one of these alone or a mixture of two or more. Further, if necessary, magnetic powder (powder of ferromagnetic metals such as iron, cobalt, nickel, etc. or compounds such as magnetite, hematite, ferrite, etc.) can be contained having the function as a colorant. The content of the colorant is preferably 1 to 40 parts by weight, more preferably 3 to 10 parts by weight, based on 100 parts by weight of the toner binder. When magnetic powder is used, it is preferably 20 to 150 parts by weight, more preferably 40 to 120 parts by weight, based on 100 parts by weight of the toner binder.

[0087] As the release agent, those having a flow softening point (T 1 / 2 ) of 50 to 170 °C are preferred, and aliphatic hydrocarbon waxes such as polyolefin wax, microcrystalline wax, paraffin wax, Fischer-Tropsch wax and their oxides, carnauba wax, montan wax and their deacidified waxes, ester waxes, fatty acid amides, fatty acids, higher alcohols, fatty acid metal salts, etc. can be mentioned.

[0088] The flow softening point (T 1 / 2) is the value measured under the following conditions. <Flow softening point (T 1 / 2 ) measurement method> Using a test force extrusion type capillary rheometer flow tester [for example, manufactured by Shimadzu Corporation, CFT-500D], while heating a 1 g measurement sample at a heating rate of 6 °C / min, applying a load of 1.96 MPa to the plunger, extruding from a nozzle with a diameter of 1 mm and a length of 1 mm, drawing a graph of "plunger descent amount (flow value)" and "temperature", reading the temperature corresponding to 1 / 2 of the maximum value of the plunger descent amount from the graph, and taking this value (the temperature when half of the measurement sample has flowed out) as the flow softening point (T 1 / 2 ).

[0089] Examples of polyolefin waxes include (co)polymers of olefins (such as ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-dodecene, 1-octadecene, and mixtures thereof, etc.) [(including those obtained by (co)polymerization and those further obtained by thermal degradation), such as low molecular weight polypropylene, low molecular weight polyethylene, low molecular weight polypropylene polyethylene copolymer], oxides of (co)polymers of olefins by oxygen and / or ozone, maleic acid modified products of (co)polymers of olefins [such as modified products of maleic acid and its derivatives (maleic anhydride, monomethyl maleate, monobutyl maleate, dimethyl maleate, etc.)], copolymers of olefins and unsaturated carboxylic acids [(meth)acrylic acid, itaconic acid, maleic anhydride, etc.] and / or unsaturated carboxylic acid alkyl esters [(alkyl (meth)acrylate with 1 to 18 carbon atoms in the alkyl group) esters and maleic acid alkyl (alkyl with 1 to 18 carbon atoms) esters, etc.], etc.

[0090] Examples of microcrystalline waxes include, for example, Hi-Mic-2095, Hi-Mic-1090, Hi-Mic-1080, Hi-Mic-1070, Hi-Mic-2065, Hi-Mic-1045, Hi-Mic-2045, etc. manufactured by Nippon Seiro Co., Ltd.

[0091] Examples of paraffin waxes include Paraffin WAX-155, Paraffin WAX-150, Paraffin WAX-145, Paraffin WAX-140, Paraffin WAX-135, HNP-3, HNP-5, HNP-9, HNP-10, HNP-11, HNP-12, HNP-51, etc. manufactured by Nippon Seiro Co., Ltd.

[0092] Examples of Fischer-Tropsch waxes include Sasolwax C80 manufactured by Sasol.

[0093] Examples of carnauba waxes include refined carnauba wax special grade 1 manufactured by Kato Yoko Co., Ltd.

[0094] Examples of ester waxes include fatty acid ester waxes (e.g., Nissan Electol WEP-2, WEP-3, WEP-4, WEP-5, and WEP-8 manufactured by NOF Corporation).

[0095] Examples of higher alcohols include aliphatic alcohols having 30 to 50 carbon atoms, such as triacontanol. Examples of fatty acids include fatty acids having 30 to 50 carbon atoms, such as triacontane carboxylic acid.

[0096] Examples of fatty acid amides include Diamond Y and Diamond 200 manufactured by Mitsubishi Chemical Corporation.

[0097] The charge control agent may contain either a positive charge control agent or a negative charge control agent, and examples thereof include nigrosine dyes, triphenylmethane dyes containing a tertiary amine as a side chain, quaternary ammonium salts, polyamine resins, imidazole derivatives, quaternary ammonium base-containing polymers, metal-containing azo dyes, copper phthalocyanine dyes, metal salts of salicylic acid, boron complexes of benzoic acid, sulfonic acid group-containing polymers, fluorine-containing polymers, and halogen-substituted aromatic ring-containing polymers.

[0098] Examples of the fluidizing agent include silica, titania, alumina, calcium carbonate, fatty acid metal salts, silicone resin particles, and fluororesin particles, and two or more of them may be used in combination. From the viewpoint of the chargeability of the toner, silica is preferred. Further, the silica is preferably hydrophobic silica from the viewpoint of the transferability of the toner.

[0099] The content of the toner binder in the toner is preferably 30 to 97% by weight, more preferably 40 to 95% by weight, still more preferably 45 to 92% by weight based on the toner weight. The content of the colorant is preferably 0.05 to 60% by weight, more preferably 0.1 to 55% by weight, still more preferably 0.5 to 50% by weight based on the toner weight. The content of the release agent is preferably 0 to 30% by weight, more preferably 0.5 to 20% by weight, still more preferably 1 to 10% by weight based on the toner weight. The content of the charge control agent is preferably 0 to 20% by weight, more preferably 0.1 to 10% by weight, still more preferably 0.5 to 7.5% by weight based on the toner weight. The content of the fluidizing agent is preferably 0 to 10% by weight, more preferably 0 to 5% by weight, still more preferably 0.1 to 4% by weight based on the toner weight. Further, the total amount of the content of the additives is preferably 3 to 70% by weight, more preferably 5 to 60% by weight, still more preferably 8 to 55% by weight based on the toner weight. By setting the composition ratio of the toner within the above range, it is possible to easily obtain a toner having good charge stability while achieving both low-temperature fixability and high separability from the fixing roller.

[0100] The toner may be obtained by any method such as a known kneading and grinding method, an emulsion phase inversion method, and a polymerization method. For example, when obtaining a toner by a kneading and grinding method, the components constituting the toner excluding the fluidizing agent are dry-blended, then melt-kneaded, then coarsely ground, and finally atomized using a jet mill or the like and further classified to obtain fine particles having a volume average particle diameter (D50) of preferably 5 to 20 μm, and then the fluidizing agent is mixed to produce the toner. The volume average particle diameter (D50) is measured using a Coulter counter (for example, trade name: Multisizer III [manufactured by Beckman Coulter, Inc.]).

[0101] When toner is obtained by the emulsion phase inversion method, the components constituting the toner excluding the fluidizing agent are dissolved or dispersed in an organic solvent, and then emulsified by adding water or the like, and then separated and classified for production. The volume average particle diameter of the toner is preferably 3 to 15 μm.

[0102] The toner is mixed with carrier particles such as ferrite whose surface is coated with iron powder, glass beads, nickel powder, ferrite, magnetite, and resin (acrylic resin, silicone resin, etc.) as needed, and used as a developer for an electrostatic latent image. When carrier particles are used, the weight ratio of the toner to the carrier particles is preferably 1 / 99 to 99 / 1. Further, instead of the carrier particles, it is also possible to form an electrostatic latent image by friction with a member such as a charging blade. Note that the toner may not contain carrier particles.

[0103] The toner is fixed on a support (paper, polyester film, etc.) by a copying machine, a printer, etc. to be a recording material. As a method of fixing on the support, known thermal roll fixing methods, flash fixing methods, etc. can be applied.

[0104] The toner produced using the toner binder of the present invention is used for developing an electrostatic charge image or a magnetic latent image in an electrophotographic method, an electrostatic recording method, an electrostatic printing method, etc. More specifically, it is used for developing an electrostatic charge image or a magnetic latent image particularly suitable for full color.

Example

[0105] Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto. Hereinafter, unless otherwise specified, "parts" indicates parts by weight.

[0106] <Production Example 1> [Production of Crystalline Vinyl Resin (A1)] 110 parts of xylene was charged into an autoclave, replaced with nitrogen, and then heated to 167°C with stirring under a sealed state. A mixed solution of 435 parts of behenyl acrylate [hereinafter abbreviated as C22 acrylate, manufactured by NOF Corporation, the same applies hereinafter], 109 parts of N-vinylpyrrolidone [manufactured by Nippon Shokubai Co., Ltd., the same applies hereinafter], 36 parts of styrene [manufactured by Idemitsu Kosan Co., Ltd., the same applies hereinafter], 73 parts of methyl acrylate [manufactured by Toagosei Co., Ltd., the same applies hereinafter], 113 parts of methacrylonitrile [manufactured by Nacalai Tesque, Inc., the same applies hereinafter], 0.7 part of di-t-butyl peroxide [Perbutyl D, manufactured by NOF Corporation, the same applies hereinafter], and 157 parts of xylene was dropped over 3 hours while controlling the temperature inside the autoclave at 167°C to carry out polymerization. After the dropping, the dropping line was washed with 8 parts of xylene. After further holding at the same temperature for 0.7 hours, it was cooled to 70°C and then the reaction rate of monomer (a) was confirmed. Since the reaction rate of monomer (a) was less than 95%, it was heated to 170°C again, and 1.1 parts of di-t-butyl peroxide was further added and reacted until the reaction rate reached 95% or more. Thereafter, the solvent was removed under reduced pressure at 170°C and 0.5 to 2.5 kPa for 5 hours to obtain a crystalline vinyl resin (A1). The weight average molecular weight of the crystalline vinyl resin (A1) measured by the above method was 30,000, the endothermic peak top temperature was 58°C, and the xylene-insoluble content was 1% by weight.

[0107] <Production Example 2> [Production of crystalline vinyl resin (A2)] 120 parts of xylene was charged into an autoclave, replaced with nitrogen, and then heated to 170 °C with stirring under a sealed state. A mixed solution of 420 parts of C22 acrylate, 105 parts of acryloylmorpholine [manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., the same applies hereinafter], 35 parts of styrene, 56 parts of methyl acrylate, 84 parts of methacrylonitrile, 0.7 part of di-t-butyl peroxide, and 156 parts of xylene was added dropwise over 3 hours while controlling the temperature inside the autoclave at 170 °C to carry out polymerization. After the dropping, the dropping line was washed with 9 parts of xylene. After further holding at the same temperature for 0.5 hour, it was cooled to 70 °C and the reaction rate of monomer (a) was confirmed. Since the reaction rate of monomer (a) was less than 95%, it was heated to 170 °C again, and 1.1 parts of di-t-butyl peroxide was further added and reacted until the reaction rate reached 95% or more. Thereafter, the solvent was removed under reduced pressure at 170 °C and 0.5 - 2.5 kPa for 5 hours to obtain a crystalline vinyl resin (A2). The weight average molecular weight of the crystalline vinyl resin (A2) measured by the above method was 20,000, the endothermic peak top temperature was 58 °C, and the xylene insoluble content was 1% by weight.

[0108] <Production Example 3> [Production of Crystalline Vinyl Resin (A3)] 110 parts of xylene was charged into an autoclave, replaced with nitrogen, and then heated to 170 °C with stirring under a sealed state. A mixed solution of 290 parts of C22 acrylate, 36 parts of N-vinylpyrrolidone, 145 parts of styrene, 181 parts of methyl acrylate, 73 parts of methacrylonitrile, 0.7 part of di-t-butyl peroxide, and 157 parts of xylene was added dropwise over 3 hours while controlling the temperature inside the autoclave at 170 °C to carry out polymerization. After the dropping, the dropping line was washed with 8 parts of xylene. After further holding at the same temperature for 0.5 hour, it was cooled to 70 °C and the reaction rate of monomer (a) was confirmed. Since the reaction rate of monomer (a) was less than 95%, it was heated to 170 °C again, and 1.1 parts of di-t-butyl peroxide was further added and reacted until the reaction rate reached 95% or more. Thereafter, the solvent was removed under reduced pressure at 170 °C and 0.5 - 2.5 kPa for 5 hours to obtain a crystalline vinyl resin (A3). The weight average molecular weight of the crystalline vinyl resin (A3) measured by the above method was 39,000, the endothermic peak top temperature was 55 °C, and the xylene-insoluble content was 1% by weight.

[0109] <Production Example 4> [Production of Crystalline Vinyl Resin (A4)] 110 parts of xylene was charged into an autoclave, replaced with nitrogen, and then heated to 170 °C with stirring under a sealed state. A mixed solution of 363 parts of C22 acrylate, 7 parts of N-vinylpyrrolidone, 109 parts of styrene, 73 parts of methyl acrylate, 174 parts of methacrylonitrile, 0.7 part of di-t-butyl peroxide, and 157 parts of xylene was dropped over 3 hours while controlling the temperature inside the autoclave at 170 °C to carry out polymerization. After dropping, the dropping line was washed with 8 parts of xylene. After holding at the same temperature for 0.5 hour, it was cooled to 70 °C and the reaction rate of monomer (a) was confirmed. Since the reaction rate of monomer (a) was less than 95%, it was heated to 170 °C again, and 1.1 parts of di-t-butyl peroxide was further added to react until the reaction rate reached 95% or more. Then, the solvent was removed under reduced pressure at 170 °C and 0.5 - 2.5 kPa for 5 hours to obtain a crystalline vinyl resin (A4). The weight average molecular weight of the crystalline vinyl resin (A4) measured by the above method was 35,000, the endothermic peak top temperature was 56 °C, and the xylene-insoluble content was 1% by weight.

[0110] <Production Example 5> [Production of Crystalline Vinyl Resin (A5)] 435 parts of stearyl acrylate [manufactured by Kyoeisha Chemical Co., Ltd., the same applies hereinafter], 110 parts of xylene were charged into an autoclave, and after purging with nitrogen, the temperature was raised to 170 ° C with stirring under a sealed state, and the temperature was controlled at 170 ° C for 2 hours. A mixed solution of 261 parts of N-vinylpyrrolidone, 29 parts of styrene, 2.2 parts of di-t-butyl peroxide, and 157 parts of xylene was added dropwise over 1.5 hours while controlling the temperature inside the autoclave at 170 ° C to carry out polymerization. After the dropping, the dropping line was washed with 8 parts of xylene. After holding at the same temperature for 0.5 hours, the temperature was cooled to 70 ° C, and the reaction rate of monomer (a) was confirmed. Since the reaction rate of monomer (a) was 95% or more, the temperature was raised to 170 ° C again, and the solvent was removed under reduced pressure of 0.5 to 2.5 kPa for 5 hours to obtain a crystalline vinyl resin (A5). The weight average molecular weight of the crystalline vinyl resin (A5) measured by the above method was 28,000, the endothermic peak top temperature was 52 ° C, and the xylene-insoluble content was 3% by weight.

[0111] <Production Example 6> [Production of Crystalline Vinyl Resin (A6)] 110 parts of xylene was charged into an autoclave, and after purging with nitrogen, the temperature was raised to 160 ° C with stirring under a sealed state. A mixed solution of 508 parts of C22 acrylate, 218 parts of N-vinylpyrrolidone, 0.7 part of di-t-butyl peroxide, and 157 parts of xylene was added dropwise over 3 hours while controlling the temperature inside the autoclave at 160 ° C to carry out polymerization. After the dropping, the dropping line was washed with 8 parts of xylene. After holding at the same temperature for 1.3 hours, the temperature was cooled to 70 ° C, and the reaction rate of monomer (a) was confirmed. Since the reaction rate of monomer (a) was less than 95%, the temperature was raised to 170 ° C again, and 1.1 parts of di-t-butyl peroxide was further added, and the reaction was carried out until the reaction rate reached 95% or more. Then, the solvent was removed under reduced pressure of 170 ° C and 0.5 to 2.5 kPa for 5 hours to obtain a crystalline vinyl resin (A6). The weight average molecular weight of the crystalline vinyl resin (A6) measured by the above method was 33,000, the endothermic peak top temperature was 60 ° C, and the xylene-insoluble content was 2% by weight.

[0112] <Production Example 7> [Synthesis of Triacontyl Acrylate] Into a reaction vessel equipped with a stirring device, a heating and cooling device, a thermometer, an air introduction pipe, a decompression device, and a water reduction device, 50 parts of 1-triacontanol [manufactured by Tokyo Chemical Industry Co., Ltd.], 50 parts of toluene, 12 parts of acrylic acid [manufactured by Mitsubishi Chemical Corporation, the same hereinafter], and 0.05 part of hydroquinone were charged and stirred to homogenize. Then, 2 parts of p-toluenesulfonic acid were added, and after stirring for 30 minutes, while blowing air at a flow rate of 30 mL / min, the reaction was carried out for 5 hours while removing the water generated at 100 °C. Then, the pressure inside the reaction vessel was adjusted to 300 mmHg, and the reaction was further carried out for 3 hours while removing the water generated. After the reaction solution was cooled to room temperature, 30 parts of a 10 wt% aqueous sodium hydroxide solution was added, stirred for 1 hour, and then allowed to stand to separate the organic phase and the aqueous phase. The organic phase was collected by liquid separation and centrifugation operations, 0.01 part of hydroquinone was added, and the solvent was removed under reduced pressure while blowing air to obtain triacontyl acrylate.

[0113] <Production Example 8> [Production of Crystalline Vinyl Resin (A7)] 110 parts of xylene was charged into an autoclave, replaced with nitrogen, and then heated to 160 °C with stirring under a sealed state. A mixed solution of 653 parts of triacontyl acrylate, 73 parts of N-vinylpyrrolidone, 0.7 part of di-t-butyl peroxide, and 157 parts of xylene was dropped over 3 hours while controlling the temperature inside the autoclave at 170 °C to carry out polymerization. After dropping, the dropping line was washed with 8 parts of xylene. After further holding at the same temperature for 0.5 hour, it was cooled to 70 °C, and then the reaction rate of monomer (a) was confirmed. Since the reaction rate of monomer (a) was less than 95%, it was heated to 170 °C again, and 1.1 parts of di-t-butyl peroxide was further added and reacted until the reaction rate was 95% or more. Then, solvent removal was carried out under reduced pressure at 170 °C and 0.5 - 2.5 kPa for 5 hours to obtain crystalline vinyl resin (A7). The weight average molecular weight of the crystalline vinyl resin (A7) measured by the above method was 30,000, the endothermic peak top temperature was 89 °C, and the xylene-insoluble content was 1 wt%.

[0114] <Comparative Production Example 1> [Production of Crystalline Vinyl Resin (A'1)] 110 parts of xylene was charged into an autoclave, replaced with nitrogen, and then heated to 167 °C with stirring under a sealed condition. A mixed solution of 435 parts of C22 acrylate, 36 parts of styrene, 73 parts of methyl acrylate, 181 parts of methacrylonitrile, 0.7 part of di-t-butyl peroxide, and 157 parts of xylene was added dropwise over 3 hours while controlling the temperature inside the autoclave at 167 °C to carry out polymerization. After the addition, the dropping line was washed with 8 parts of xylene. After holding at the same temperature for 0.7 hour, it was cooled to 70 °C and the reaction rate of monomer (a) was confirmed. Since the reaction rate of monomer (a) was less than 95%, it was heated to 170 °C again, and 1.1 parts of di-t-butyl peroxide was further added to react until the reaction rate reached 95% or more. Thereafter, the solvent was removed under reduced pressure at 170 °C and 0.5 - 2.5 kPa for 5 hours to obtain a crystalline vinyl resin (A’1). The weight average molecular weight of the crystalline vinyl resin (A’1) measured by the above method was 30,000, the endothermic peak top temperature was 58 °C, and the xylene-insoluble content was 1 wt%.

[0115] <Comparative Production Example 2> [Production of Crystalline Vinyl Resin (A’2)] 110 parts of xylene was charged into an autoclave, replaced with nitrogen, and then heated to 170 °C with stirring under a sealed condition. A mixed solution of 283 parts of C22 acrylate, 36 parts of N-vinylpyrrolidone, 152 parts of styrene, 181 parts of methyl acrylate, 73 parts of methacrylonitrile, 0.7 part of di-t-butyl peroxide, and 157 parts of xylene was added dropwise over 3 hours while controlling the temperature inside the autoclave at 170 °C to carry out polymerization. After the addition, the dropping line was washed with 8 parts of xylene. After holding at the same temperature for 0.5 hour, it was cooled to 70 °C and the reaction rate of monomer (a) was confirmed. Since the reaction rate of monomer (a) was less than 95%, it was heated to 170 °C again, and 1.1 parts of di-t-butyl peroxide was further added to react until the reaction rate reached 95% or more. Thereafter, the solvent was removed under reduced pressure at 170 °C and 0.5 - 2.5 kPa for 5 hours to obtain a crystalline vinyl resin (A’2). The weight average molecular weight of the crystalline vinyl resin (A’2) measured by the above method was 40,500, the endothermic peak top temperature was 55 °C, and the xylene-insoluble content was 1 wt%.

[0116] <Comparative Production Example 3> [Production of Crystalline Vinyl Resin (A'3)] 110 parts of xylene was charged into an autoclave, replaced with nitrogen, and then heated to 160°C with stirring under a sealed state. A mixed solution of 660 parts of triacontyl acrylate, 65 parts of N-vinylpyrrolidone, 0.7 part of di-t-butyl peroxide, and 157 parts of xylene was dropped over 3 hours while controlling the temperature inside the autoclave at 170°C to carry out polymerization. After the dropping, the dropping line was washed with 8 parts of xylene. After further holding at the same temperature for 0.5 hour, it was cooled to 70°C and the reaction rate of monomer (a) was confirmed. Since the reaction rate of monomer (a) was less than 95%, it was heated to 170°C again, and 1.1 parts of di-t-butyl peroxide was further added to react until the reaction rate reached 95% or more. Thereafter, the solvent was removed under reduced pressure at 170°C and 0.5 - 2.5 kPa for 5 hours to obtain a crystalline vinyl resin (A'3). The weight average molecular weight of the crystalline vinyl resin (A'3) measured by the above method was 29,000, the endothermic peak top temperature was 89°C, and the xylene-insoluble content was 1% by weight.

[0117] <Comparative Production Example 4> [Production of Crystalline Vinyl Resin (A'4)] 110 parts of xylene was charged into an autoclave, replaced with nitrogen, and then heated to 160°C with stirring under a sealed state. A mixed solution of 508 parts of C22 acrylate, 218 parts of dimethylacrylamide [manufactured by Fujifilm Wako Pure Chemical Corporation, the same hereinafter], 0.7 part of di-t-butyl peroxide, and 157 parts of xylene was dropped over 3 hours while controlling the temperature inside the autoclave at 160°C to carry out polymerization. After the dropping, the dropping line was washed with 8 parts of xylene. After further holding at the same temperature for 1.3 hours, it was cooled to 70°C and the reaction rate of monomer (a) was confirmed. Since the reaction rate of monomer (a) was less than 95%, it was heated to 170°C again, and 1.1 parts of di-t-butyl peroxide was further added to react until the reaction rate reached 95% or more. Thereafter, the solvent was removed under reduced pressure at 170°C and 0.5 - 2.5 kPa for 5 hours to obtain a crystalline vinyl resin (A'4). The weight average molecular weight of the crystalline vinyl resin (A'4) measured by the above method was 34,000, the endothermic peak top temperature was 60 °C, and the xylene-insoluble content was 2% by weight.

[0118] The compositions and physical property values of the crystalline vinyl resins (A1) to (A7) and (A'1) to (A'4) are shown in Table 1.

[0119]

Table 1

[0120] <Production Example 9> [Production of amorphous vinyl resin (B1)] 100 parts of xylene was charged into an autoclave, replaced with nitrogen, and then heated to 150 °C with stirring under a sealed state. A mixed solution of 443 parts of styrene, 167 parts of butyl acrylate [manufactured by Idemitsu Kosan Co., Ltd., the same applies hereinafter], 9.3 parts of acrylic acid, 0.5 part of di-t-butyl peroxide, and 143 parts of xylene was dropped over 3 hours while controlling the temperature inside the autoclave at 150 °C to carry out polymerization. After dropping, the dropping line was washed with 11 parts of xylene. After further holding at the same temperature for 1 hour, the temperature was raised to 170 °C over 1 hour and held at the same temperature for 0.5 hour. Then it was cooled to 100 °C, and the reaction rate of butyl acrylate was confirmed. Since the reaction rate of butyl acrylate was less than 95%, the temperature was raised to 170 °C again, and 1.5 parts of di-t-butyl peroxide was further added to react until the reaction rate reached 95% or more. Then, the solvent was removed under reduced pressure at 170 °C and 0.5 to 2.5 kPa for 5 hours to obtain an amorphous vinyl resin (B1). The weight average molecular weight of the amorphous vinyl resin (B1) measured by the above method was 56,500, the glass transition temperature was 58 °C, and the acid value was 11 mgKOH / g.

[0121] <Example 1> [Production of toner binder (D1) and toner (Ts1)] 30 parts of crystalline vinyl resin (A1) and 70 parts of amorphous vinyl resin (B1) were preliminarily mixed to obtain a toner binder (D1). Next, 6 parts of carbon black [manufactured by Mitsubishi Chemical Corporation, MA-100] as a pigment, 4 parts of carnauba wax [manufactured by Nippon Wax Co., Ltd., carnauba wax] as a release agent, and 4 parts of isenspirone black [manufactured by Hodogaya Chemical Co., Ltd., T-77] as a charge control agent were toned by the following method. First, each raw material was preliminarily mixed using a Henschel mixer [manufactured by Nippon Coke & Engineering Co., Ltd., FM10B], and then kneaded using a twin-screw kneader [manufactured by Ikegai Corporation, PCM-30]. Then, it was finely pulverized using a supersonic jet mill Labojet [manufactured by Nippon Pneumatic Mfg. Co., Ltd., LJ type], and then classified using an air classifier [manufactured by Nippon Pneumatic Mfg. Co., Ltd., MDS-1] to obtain colored resin particles. Finally, 1 part of hydrophobic silica [manufactured by Nippon Aerosil Co., Ltd., Aerosil R972] as a fluidizing agent was mixed with 100 parts of the colored resin particles using a sample mill to obtain toner (Ts1).

[0122] <Examples 2 to 9> [Production of Toner Binders (D2) to (D9) and Toners (Ts2) to (Ts7)] Except for changing to the compositions shown in Table 2, toner binders (D2) to (D9) and toners (Ts1) to (Ts9) were obtained in the same manner as in Example 1.

[0123] <Production Example 10> [Production of Polyester Resin (C0)] In a pressurized reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, an air inlet tube, a pressure reducing device, and a water reducing device, 251 parts of neopentyl glycol, 334 parts of 1,2-propanediol, 633 parts of terephthalic acid, and 31 parts of behenic acid were added and stirred to homogenize. Then, 2 parts of titanium diisopropoxy bistriethanol aminate were added and homogenized for 30 minutes, and pressure esterification was performed at 227°C and 0.45MPa for 5 hours, and it was confirmed that the acid value was 10mgKOH / g. Then, pressure esterification was performed at 4kPa or less, 161 parts of 1,2-propanediol was recovered, and it was confirmed that the acid value was 1mgKOH / g and Mw was 2500, and it was cooled to 180°C, and 2 parts of 2,6-di-tert-butyl-4-methylphenol were added and homogenized for 30 minutes. Then, 68 parts of fumaric acid was added, and esterification at normal pressure at 180°C for 2 hours was carried out, followed by esterification at reduced pressure at 4 kPa or less for 15 hours, and the mixture was taken out of the reaction vessel to obtain polyester resin (C0). The weight average molecular weight of polyester resin (C0) measured by the above method was 7600, the glass transition temperature was 50°C, and the acid value was 3 mgKOH / g.

[0124] Example 10: [Production of toner binder (D10) and toner (Ts10)] In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a nitrogen inlet tube, a pressure reducing device, and a water reducing device, 60 parts of polyester resin (C0) and 40 parts of crystalline vinyl resin (A1) were charged, and the temperature was raised to 115°C while nitrogen was flowing. After holding at 115°C for 1 hour, the nitrogen flow was stopped, and 0.6 parts of t-butylperoxy-2-ethylhexanoate as a radical reaction initiator (c-1) was dropped under normal pressure over 15 minutes while controlling the temperature in the reaction vessel to 115°C, and the same temperature was held for another 40 minutes. After that, the solvent was removed at 110°C for 1 hour under a reduced pressure of 0.5 to 2.5 kPa, and a toner binder (D10) containing a nonlinear polyester resin (C1) in which polyester resin (C0) was crosslinked by carbon-carbon bonds and a crystalline vinyl resin (A1) was obtained. When only the polyester resin (C0) was crosslinked using t-butyl peroxy-2-ethylhexanoate to obtain the non-linear polyester resin (C1), the glass transition temperature of the non-linear polyester resin (C1) measured by the above method was 50°C, and the acid value was 3 mgKOH / g. Next, the obtained toner binder (D10), 6 parts of carbon black as a pigment [MA-100, manufactured by Mitsubishi Chemical Corporation], 4 parts of carnauba wax as a release agent [carnauba wax, manufactured by Nippon Wax Co., Ltd.], and 4 parts of isenspirone black as a charge control agent [T-77, manufactured by Hodogaya Chemical Co., Ltd.] were toned by the following method. First, each raw material was preliminarily mixed using a Henschel mixer [FM10B, manufactured by Nippon Coke & Engineering Co., Ltd.], and then kneaded using a twin-screw kneader [PCM-30, manufactured by Ikegai Corporation]. Then, after finely pulverizing using a supersonic jet mill Labojet [LJ type, manufactured by Nippon Pneumatic Mfg. Co., Ltd.], classification was performed using an air classifier [MDS-1, manufactured by Nippon Pneumatic Mfg. Co., Ltd.] to obtain colored resin particles. Finally, 1 part of hydrophobic silica [Aerosil R972, manufactured by Nippon Aerosil Co., Ltd.] as a fluidizing agent was mixed with 100 parts of the colored resin particles using a sample mill to obtain toner (Ts10).

[0125] <Comparative Examples 1 to 4> [Production of Toner Binders (D’1) to (D’4) and Toners (Ts’1) to (Ts’4)] Toner binders (D’1) to (D’4) and toners (Ts’1) to (Ts’4) were obtained in the same manner as in Example 1, except that the compositions shown in Table 2 were used.

[0126] Regarding the toners (Ts1) to (Ts10) obtained in Examples 1 to 10 and the comparative toners (Ts’1) to (Ts’4) obtained in Comparative Examples 1 to 4, low-temperature fixability (MFT), hot offset resistance (hot offset temperature), storage stability under high temperature and high humidity, and hydrolysis resistance were evaluated by the following methods. The results are shown in Table 2.

[0127]

Table 2

[0128] <Low-temperature Fixing Property> The toner was uniformly placed on the paper surface at 1.00 mg / cm 2 At this time, the method of placing the powder on the paper surface was to use a printer with the heat fixing unit removed. This paper was passed through a soft roller at a fixing speed (circumferential speed of the heating roller) of 213 mm / second and in the range of 90 to 230 °C for the heating roller in 5 °C increments. Next, the presence or absence of cold offset in the fixed image was visually inspected, and the occurrence temperature (MFT) of the cold offset was measured. The lower the occurrence temperature of the cold offset, the better the low-temperature fixing property. Under this evaluation condition, it is generally preferable that the MFT is 125 °C or lower.

[0129] <Hot Offset Resistance (Hot Offset Temperature)> Using the same method as described for the low-temperature fixing property above, the toner was placed on the paper surface, and this paper was passed through a soft roller at a fixing speed (circumferential speed of the heating roller) of 213 mm / second and in the range of 90 to 230 °C for the heating roller in 5 °C increments. Next, the presence or absence of hot offset in the fixed image was visually inspected, and the occurrence temperature of the hot offset was measured. The higher the occurrence temperature of the hot offset, the better the hot offset resistance. Under this evaluation condition, it is preferably 150 °C or higher.

[0130] <Storage Stability under High Temperature and High Humidity> 1 g of toner and 0.01 g of hydrophobic silica (Aerosil R8200, manufactured by Evonik Japan Co., Ltd.) were mixed with a shaker for 1 hour. The mixture was placed in a glass container without a lid and left in an atmosphere of 40 °C and 80% humidity for 48 hours. The degree of blocking was visually judged, and the storage stability was evaluated according to the following criteria. ◎: Blocking did not occur, and there was no change in fluidity visually. 〇: Blocking occurred partially, but when the container was shaken, the aggregation dispersed and it flowed. △: Blocking occurred throughout, but when the container was shaken, the aggregation dispersed and it flowed. ×: Blocking occurred, and even when the container was shaken, the aggregation did not disperse (did not flow). Under these evaluation conditions, it is preferably 〇 or more.

[0131] <Hydrolysis resistance> Put 1 g of toner into a glass container without a lid, leave it in an atmosphere of 95 °C and 95% humidity for 10 days, measure the weight-average molecular weight by GPC and the storage elastic modulus (Pa) at 100 °C before and after the test, confirm the change in the weight-average molecular weight and the change in the storage elastic modulus, and evaluate the hydrolysis resistance according to the following criteria. ◎: The changes in both the weight-average molecular weight and the storage elastic modulus are less than ±3%. 〇: The changes in both the weight-average molecular weight and the storage elastic modulus are both ±3% or more and less than 5%. △: The change in the weight-average molecular weight is ±5% or more, but the change in the storage elastic modulus is less than ±5%. ×: The changes in both the weight-average molecular weight and the storage elastic modulus are both ±5% or more. Note that the storage elastic modulus (Pa) at 100 °C is the storage elastic modulus (Pa) at 100 °C when a sample pressure-molded on a disk with a diameter of 8 mm and a thickness of 2.0 ± 0.3 mm is mounted on parallel plates using a viscoelasticity measuring device (ARES-24A, manufactured by Rheometric), heated from room temperature (25 °C) to 100 °C, the shape of the sample is adjusted, then cooled to 40 °C, and measured from 40 to 180 °C. The measurement was performed under the following conditions. Jig: 8 mm parallel plate Frequency: 1 Hz Strain rate: 1% Heating rate: 5 °C / min Under these evaluation conditions, it is preferably 〇 or more.

[0132] As is clear from the evaluation results in Table 2, the toners (Ts1) to (Ts10) containing the toner binder of the present invention have good low-temperature fixing property, hot offset resistance, storage stability under high temperature and high humidity, and hydrolysis resistance. On the other hand, for the toners (Ts’1) to (Ts’4) containing the comparative toner binder, at least one of the low-temperature fixing property, hot offset resistance, storage stability under high temperature and high humidity, and hydrolysis resistance had inferior evaluation results.

Claims

1. A toner binder containing a crystalline vinyl resin (A), wherein the crystalline vinyl resin (A) is a polymer of a monomer composition (A0) containing a monomer (a) and a monomer (b), the monomer (a) is a (meth)acrylate having a chain hydrocarbon group and 21 to 40 carbon atoms, the monomer (b) is a monomer having an amide bond and a cyclic structure, which is N-vinylpyrrolidone and / or acryloylmorpholine, the weight ratio of the monomer (a) is 40 to 90% by weight based on the weight of the monomer composition (A0), and the weight ratio of the monomer (b) is 1 to 35% by weight based on the weight of the monomer composition (A0).

2. The toner binder according to claim 1, wherein the xylene-insoluble content of the crystalline vinyl resin (A) is 6% by weight or less.

3. The toner binder according to claim 1 or 2, wherein the weight ratio of the crystalline vinyl resin (A) is 10 to 60% by weight based on the weight of the toner binder.

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