WO2020261676A1

WO2020261676A1 - Toner binder

Info

Publication number: WO2020261676A1
Application number: PCT/JP2020/012610
Authority: WO
Inventors: 将本夛; 宙千葉
Original assignee: 三洋化成工業株式会社
Priority date: 2019-06-27
Filing date: 2020-03-23
Publication date: 2020-12-30
Also published as: JP7028995B2; JPWO2020261676A1

Abstract

The purpose of the present invention is to provide an excellent toner binder that satisfies all of heat resistance storage stability, electrification maintenance rate (particularly, electrification maintenance rate at high temperature and high humidity), blocking properties, image strength, pulverizability, odor, and durability while maintaining low-temperature fixability and hot offset resistance. The present invention pertains to a toner binder containing a polyester resin (A) and a crystalline vinyl resin (B), wherein the polyester resin (A) contains a resin obtained by crosslinking a polyester resin (A1) with an epoxy compound (E).

Description

Toner binder

The present invention relates to a toner binder.

In recent years, with the development of electrophotographic systems, the demand for electrophotographic devices such as copiers and laser printers has increased rapidly, and the demand for toner for their performance has also increased.

Conventionally, in the case of full-color electrophotographic, a latent image based on color image information is formed on a latent image carrier such as an electrophotographic photosensitive member, the latent image is developed with a toner of a corresponding color, and then the toner image is developed. There are known methods and devices for obtaining a multicolor image by heating and fixing a toner image on a transfer material after repeating an image forming step such as transferring onto a transfer material. In order to pass through these processes without problems, the toner first needs to maintain a stable charge amount, and then needs to have good fixability on paper. Further, since the apparatus has a heating body in the fixing portion, the temperature rises in the apparatus, so that the toner is required not to be blocked in the apparatus.

Further, from the viewpoint of energy saving of reducing energy consumption in the fixing process as well as promoting miniaturization, high speed, and high image quality of the electrophotographic apparatus, improvement of low temperature fixability of toner is strongly required.
Recently, many types of paper such as recycled paper having a large surface unevenness and coated paper having a smooth surface are used as transfer materials. In order to correspond to the surface texture of these transfer materials, a fuser having a wide nip width such as a soft roller or a belt roller is preferably used. However, if the nip width is widened, the contact area between the toner and the fixing roller increases, and the so-called high-temperature offset phenomenon in which molten toner adheres to the fixing roller tends to occur. Therefore, it is premised that hot offset resistance is required. Is.
In addition to the above, multicolor images (full color) are required to have much higher gloss than black and white images (monochrome) due to reproduction of photographic images, etc., and it is necessary to make the toner layer of the obtained image smooth. There is.
Therefore, it is necessary to develop low-temperature fixability while maintaining hot offset resistance while having high gloss, and a high-gloss toner image is required in a wide working range.

The toner binder has a great influence on the toner characteristics as described above, and polystyrene resin, styrene-acrylic resin, polyester resin, epoxy resin, polyurethane resin, polyamide resin and the like are known, but recently, heat resistance Polyester resin has attracted particular attention because it is easy to balance storage stability and fixability.

As a means for lowering the fixing temperature of toner, a technique for lowering the glass transition point of polyester resin is generally used. However, if the glass transition point is set too low, the hot offset resistance is lowered, and powder agglutination (blocking) is likely to occur, so that the heat-resistant storage stability of the toner is lowered. This glass transition point is a design point of a toner binder (also referred to as a binder resin), and it is difficult to obtain a toner that can be fixed at a lower temperature by a method of lowering the glass transition point.

As a method other than lowering the glass transition point, a toner composition containing a crystalline polyester resin, which is excellent in both low-temperature fixability and hot offset resistance, is known (see Patent Documents 1 and 2). .. However, in recent years, there has been an increasing demand for heat-resistant storage and both low-temperature fixability and hot offset resistance (fixation temperature range), and these demands have not been fully met.

As another method, it is known that by using an amorphous polyester resin and a long-chain alkyl (meth) acrylate-based crystalline resin in combination, the low-temperature fixability of the toner is improved due to the melting characteristics of the crystalline resin. (Patent Document 3). However, if the content of the crystalline resin is increased, the resin strength may decrease, and the crystalline resin is amorphous due to the compatibility between the crystalline resin and the amorphous polyester resin during melt kneading, and as a result, the toner of the toner As the glass transition point is lowered, problems arise in the same hot offset resistance and heat storage stability of the toner as described above.

On the other hand, a method of reproducing the crystallinity of the crystalline polyester resin by heat treatment after the melt-kneading step (Patent Document 4), long-chain monoalcohol, long-chain monocarboxylic acid, etc. as constituents used in the crystalline polyester resin. A method of reproducing crystallinity using (Patent Document 5) has been proposed.
Although the low-temperature fixability and glossiness of the toner can be ensured by such a method, the hot offset resistance, the fluidity of the toner, and the pulverizability at the time of pulverization are lowered, and the durability is particularly insufficient.
Further, a method of coating a core portion containing a crystalline polyester resin with a shell layer of an amorphous polyester resin obtained by a melt suspension method or an emulsion aggregation method has also been proposed (Patent Document 6). Since the crystalline resin is compatible with the binding resin of the core and the reprecipitation of the crystals is insufficient in a short time, the image intensity after fixing is still insufficient.

On the other hand, as a method for expanding the fixing temperature range, a toner binder in which a polyester resin containing an unsaturated carboxylic acid as a constituent is crosslinked with carbon-carbon double bonds has been proposed (Patent Document 7). However, although this method can prevent the offset phenomenon at high temperatures, the lower limit temperature for fixing is insufficient, and the demands for high speed and energy saving have not yet been sufficiently met.

In addition, as a method of improving the fixing lower limit temperature while maintaining hot offset resistance, a toner binder that polymerizes a long-chain alkyl acrylate to lower the melt viscosity and combines a polyester resin containing an unsaturated carboxylic acid as a constituent is proposed. (Patent Documents 8 and 9). However, in this method, the organic solvent generated when the unsaturated carboxylic acid is crosslinked remains, so that the toner binder has an odor, and the charge retention rate under high temperature and high humidity is insufficient.

As described above, while maintaining low temperature fixability and hot offset resistance, heat storage stability, charge retention rate (especially charge retention rate under high temperature and high humidity), blocking property, image strength, odor and durability. There has never been a good toner binder that satisfies everything.

Japanese Unexamined Patent Publication No. 2005-77930 Japanese Unexamined Patent Publication No. 2012-98719 JP-A-2007-193069 Japanese Unexamined Patent Publication No. 2005-308995 International Publication No. 2015/170705 Japanese Unexamined Patent Publication No. 2011-197193 JP-A-2017-003985 International Publication No. 2018/110593 International Publication No. 2019/073731

The present invention maintains heat-resistant storage property, charge retention rate (particularly charge retention rate under high temperature and high humidity), blocking property, image strength, pulverizability, odor and durability while maintaining low temperature fixability and hot offset resistance. The purpose is to provide an excellent toner binder that satisfies all requirements.

The present inventors have arrived at the present invention as a result of diligent studies to solve these problems.
That is, the present invention is a toner binder containing a polyester resin (A) and a crystalline vinyl resin (B), in which the polyester resin (A1) is crosslinked with an epoxy compound (E). It is a toner binder containing a resin.

According to the present invention, while maintaining low temperature fixability and hot offset resistance, heat storage stability, charge retention rate (particularly charge retention rate under high temperature and high humidity), blocking property, image strength, crushability, odor and durability It becomes possible to provide a toner binder used for an excellent toner.

The toner binder of the present invention is a toner binder containing a polyester resin (A) and a crystalline vinyl resin (B), and the polyester resin (A) is crosslinked with the polyester resin (A1) by an epoxy compound (E). Contains the resin.
Hereinafter, the toner binder of the present invention will be described in sequence.

The toner binder of the present invention is a toner binder containing a polyester resin (A) and a crystalline vinyl resin (B), and the polyester resin (A) is a polyester resin (A1) made of an epoxy compound (E). Contains crosslinked resin.
In the present invention, "crystallinity" means that the DSC curve has a maximum and has a clear endothermic peak in the process of raising the temperature of the differential scanning calorimetry obtained by differential scanning calorimetry (also referred to as DSC measurement). To say. On the other hand, "amorphous" means that the DSC curve does not have a clear endothermic peak.

The polyester resin (A) in the present invention contains a resin in which the polyester resin (A1) is crosslinked with the epoxy compound (E) as an essential component. The polyester resin (A1) is a polyester resin obtained by reacting a polyol component (x) with a polycarboxylic acid component (y) as raw materials, and reacts with an epoxy compound (E) to form a crosslinked structure. If so, the composition of the resin is not particularly limited.
The polyester resin (A1) may be used alone or in combination of two or more.

The polyester resin (A1) is a resin obtained by polycondensing a polyol component (x) and a polycarboxylic acid component (y).

Examples of the polyol component (x) of the polyester resin (A1) include a diol (x1) and a trivalent or higher-valent polyol (x2). These may be one kind alone or a combination of two or more kinds.

Examples of the diol (x1) include alkylene glycols having 2 to 36 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,3, 5-Pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol and 1,12 -Dodecanediol, etc.), alkylene ether glycols with 4 to 36 carbon atoms (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.), alicyclic diols with 6 to 36 carbon atoms (1,4-Cyclohexanedimethanol, hydrogenated bisphenol A, etc.), (poly) alkylene oxide adduct of the above alicyclic diol (preferably, average number of moles added 1 to 30), aromatic diol [monocyclic dihydric phenol] (For example, hydroquinone and the like) and bisphenols and the like] and alkylene oxide adducts of the above aromatic diols (preferably, the average number of moles added is 2 to 30).

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

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, -SO _2- , -O-, -S- or a direct bond, and Ar represents a halogen atom or an alkyl group having 1 to 30 carbon atoms. Represents a phenylene group which may be substituted with. ]

Specific examples of bisphenols include bisphenol A, bisphenol F, bisphenol B, bisphenol AD, bisphenol S, trichlorobisphenol A, tetrachlorobisphenol A, dibromobisphenol F, 2-methylbisphenol A, and 2,6-dimethylbisphenol. A and 2,2'-diethylbisphenol F and the like can be mentioned, and two or more of these can be used in combination.

Examples of the alkylene oxide added to the bisphenols include alkylene oxides having 2 to 30 carbon atoms, for example, ethylene oxide (hereinafter, “ethylene oxide” may be abbreviated as EO), 1,2- or 1,3. -Propylene oxide ("1,2-propylene oxide" may be abbreviated as PO below), 1,2-, 2,3-, 1,3- or iso-butylene oxide, tetrahydrofuran, and these. The combination of two or more of the above can be mentioned.

Of these diols (x1), alkylene glycols having 2 to 36 carbon atoms and alkylene oxide adducts of aromatic diols are preferable from the viewpoint of low temperature fixability and heat storage stability, and alkylene glycols and bisphenols having 2 to 10 carbon atoms are preferable. The alkylene oxide adduct of the same kind (preferably 2 to 5 moles) is more preferable, and the alkylene glycol adduct having 2 to 6 carbon atoms and the alkylene oxide adduct of bisphenol A (preferably 2 to 5 moles). Is more preferable, and an EO and / or PO adduct of bisphenol A (the average number of added moles is preferably 2 to 3) is particularly preferable.

Examples of trivalent or higher-valent polyols (x2) include aliphatic polyhydric alcohols having trivalent or higher valences having 3 to 36 carbon atoms, saccharides and derivatives thereof, and AO adducts of aliphatic polyhydric alcohols (average number of moles added is It preferably contains 1 to 30), AO adducts of trisphenols (trisphenol PA, etc.) (average number of moles added is preferably 2 to 30), novolak resin (phenol novolac, cresol novolak, etc.), and has an average degree of polymerization. Is preferably 3 to 60) AO adduct (the average number of moles to be added is preferably 2 to 30) and the like.

Aliphatic polyhydric alcohols having trivalent or higher valences having 3 to 36 carbon atoms include alkane polyols and their intramolecular or intermolecular dehydrations, such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and the like. Examples thereof include sorbitol, sorbitan, polyglycerin and dipentaerythritol.
Examples of saccharides and derivatives thereof include sucrose and methyl glucoside.

Among these trivalent or higher valent polyols (x2), from the viewpoint of achieving both low temperature fixability and hot offset resistance, an aliphatic polyhydric alcohol having a trivalent or higher valence having 3 to 36 carbon atoms and a novolak resin (novolac resin) It contains phenol novolac, cresol novolac, etc., and has an AO adduct having an average degree of polymerization of preferably 3 to 60) (preferably having an average added molar number of 2 to 30), and is a trivalent fat having 3 to 8 carbon atoms. Group polyhydric alcohols are more preferred, and trimethylolpropane is particularly preferred.

The diol (x1) in the polyol component (x) of the polyester resin (A1) is preferably 80 to 100 mol%. When the diol (x1) and the trivalent or higher polyol (x2) are used in combination, the molar ratio [(x1) / (x2)] of the diol (x1) and the trivalent or higher polyol (x2) is hot-resistant. From the viewpoint of offset property, 80/20 to 99/1 is preferable, and 85/15 to 98/2 is more preferable.

Further, as the alcohol component of the polyester resin (A1), a monool component can be contained in addition to the above-mentioned polyol component (x), if necessary. Examples of monools include linear or branched alkyl alcohols having 1 to 30 carbon atoms (methanol, ethanol, isopropanol, 1-decanol, dodecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol, lignoceryl alcohol and the like. ) Etc. can be mentioned.

Of these monools, linear or branched alkyl alcohols having 8 to 24 carbon atoms are preferable, linear alkyl alcohols having 8 to 24 carbon atoms are more preferable, and dodecyl alcohols and stearyl alcohols are preferable from the viewpoint of image strength and heat storage stability. , Arachidyl alcohol, behenyl alcohol and lignoceryl alcohol are more preferred.

Examples of the polycarboxylic acid component (y) of the polyester resin (A1) include a dicarboxylic acid (y1) and a trivalent or higher valent polycarboxylic acid (y2). These may be one kind alone or a combination of two or more kinds.

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

Among these dicarboxylic acids (y1), aromatic dicarboxylic acids having 8 to 36 carbon atoms and aliphatic dicarboxylic acids having 2 to 50 carbon atoms, from the viewpoint of achieving both low-temperature fixability, hot offset resistance and heat-resistant storage stability, Alkendicarboxylic acids having 4 to 36 carbon atoms are preferable, phthalic acid, terephthalic acid, isophthalic acid, adipic acid, succinic acid, maleic acid and fumaric acid are more preferable, and phthalic acid, terephthalic acid, isophthalic acid, adipic acid and fumaric acid. Is more preferable, and phthalic acid, adipic acid, and terephthalic acid are particularly preferable. Further, it may be an anhydride or a lower alkyl ester of these acids.

Examples of the trivalent or higher polycarboxylic acid (y2) include trivalent or higher aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, etc.) and aliphatic groups having 6 to 36 carbon atoms (alicyclic). Examples thereof include tricarboxylic acids (including formulas) (hexanetricarboxylic acids, decantricarboxylic acids, etc.) and ester-forming derivatives thereof.

Among these trivalent or higher valent polycarboxylic acids (y2), aromatic polycarboxylic acids having 9 to 20 carbon atoms are preferable from the viewpoint of achieving both low-temperature fixability and hot offset resistance, and trimellitic acid and pyromerit. Acids are more preferred. Further, it may be an anhydride or a lower alkyl ester of these acids.

The dicarboxylic acid (y1) in the polycarboxylic acid component (y) of the polyester resin (A1) is preferably 80 to 100 mol%. When a dicarboxylic acid (y1) and a trivalent or higher polycarboxylic acid (y2) are used in combination, the molar ratio of the dicarboxylic acid (y1) and the trivalent or higher polycarboxylic acid (y2) [(y1) / (y2). )] Is preferably 80/20 to 99/1, more preferably 85/15 to 98/2, from the viewpoint of hot offset resistance.

Further, as the carboxylic acid component of the polyester resin (A1), a monocarboxylic acid component can be contained in addition to the polycarboxylic acid component (y), if necessary. Examples of the monocarboxylic acid include aromatic monocarboxylic acids having 7 to 37 carbon atoms (benzoic acid, toluic acid, 4-ethylbenzoic acid, 4-propyl benzoic acid, etc.) and aliphatics having 2 to 50 carbon atoms (aliphatic type). Monocarboxylic acids (including acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, capric acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid and behenic acid, etc.) ) Etc. can be mentioned.

Of these monocarboxylic acids, aromatic monocarboxylic acids having 7 to 37 carbon atoms are preferable, and benzoic acid is more preferable, from the viewpoint of image strength and heat storage stability.

The polyester resin (A1) in the present invention can be produced in the same manner as a known polyester resin production method. For example, the reaction temperature of the polyol component (x) and the polycarboxylic acid component (y) in an inert gas (nitrogen gas or the like) atmosphere is preferably 150 to 280 ° C, more preferably 160 to 250 ° C, still more preferable. Can be carried out by subjecting to a polycondensation reaction at 170 to 235 ° C. The reaction time is preferably 30 minutes or more, more preferably 2 to 40 hours, from the viewpoint of reliably performing the polycondensation reaction. It is also effective to reduce the pressure in order to improve the reaction rate at the end of the reaction.

At this time, an esterification catalyst can be used if necessary.
Examples of esterification catalysts include tin-containing catalysts (eg dibutyltin oxide, etc.), antimony trioxides, titanium-containing catalysts [eg titanium alkoxide, potassium titanate oxalate, titanium terephthalate, titanium terephthalate alkoxide, JP-A-2006-243715. The catalysts described in Japanese Patent Publication No. {Titanium diisopropoxybis (triethanolaminete), titaniumdihydroxybis (triethanolamineate), titanium monohydroxytris (triethanolamineate), titanylbis (triethanolamineate) and theirs. Intramolecular polycondensate, etc.} and catalysts described in JP-A-2007-11307 (titanium tributoxyterephthalate, titanium triisopropoxyterephthalate, titanium diisopropoxyterephthalate, etc.), etc.], zirconium-containing catalysts (eg, zirconyl acetate, etc.) ) And zinc acetate and the like. Of these, a titanium-containing catalyst is preferable.

Further, a stabilizer may be added for the purpose of stably promoting the polymerization of polyester. Examples of the stabilizer include hydroquinone, methylhydroquinone, hindered phenol compounds and the like.

The weight ratio of the polyol component (x) and the polycarboxylic acid component (y) used in the polycondensation reaction is preferably 1/2 to 2/1 as the equivalent ratio ([OH] / [COOH]) of the hydroxyl group and the carboxy group. , More preferably 1 / 1.5 to 1.5 / 1, still more preferably 1 / 1.3 to 1.3 / 1.

The presence or absence of crystallinity of the polyester resin (A1) is not particularly limited, but it is preferably an amorphous polyester resin from the viewpoint of charge retention, image strength and durability. The amorphous polyester resin is obtained by increasing the content of the branched monomer, for example, the monomer content such as the alkylene oxide adduct of bisphenols, as the polyol component (x) and the polycarboxylic acid component (y) to be used. be able to.

The polyester resin (A1) may be any of a linear polyester resin, a crosslinked polyester resin, or a mixture of the linear polyester resin and the crosslinked polyester resin, but from the viewpoint of hot offset resistance, image strength and durability. , A crosslinked polyester resin, or a mixture of a linear polyester resin and a crosslinked polyester resin, and more preferably a crosslinked polyester resin. The crosslinked polyester resin uses a trivalent or higher polyol (x2) and / or a trivalent or higher polycarboxylic acid (y2) as the polyol component (x) and polycarboxylic acid component (y) of the polyester resin (A1). By doing so, it can be manufactured.

The peak top molecular weight of the polyester resin (A1) (hereinafter, may be abbreviated as Mp) has low temperature fixability, glossiness, toner fluidity, heat storage stability, pulverizability, image strength after fixing, and bending resistance. From the viewpoint of property and document offset property, 2,000 to 200,000 is preferable, more preferably 2,500 to 100,000, still more preferably 3,000 to 60,000, and particularly preferably 5,000 to 30, It is 000.
The Mp of the polyester resin (A1) is measured by gel permeation chromatography (GPC) under the following conditions.

First, a calibration curve is prepared using a standard polystyrene sample by gel permeation chromatography (GPC).
Next, the samples are separated by GPC, and the count number of the separated samples is measured at each holding time.
Next, a chart of the molecular weight distribution of the sample is created from the logarithmic value of the calibration curve and the obtained count number. The maximum peak value in the molecular weight distribution chart is the peak top molecular weight Mp.
If there are a plurality of peaks in the molecular weight distribution chart, the maximum value among those peaks is defined as the peak top molecular weight (Mp). The measurement conditions for GPC measurement are as follows.

In the present invention, the peak top molecular weight Mp, the number average molecular weight (hereinafter, may be abbreviated as Mn), and the weight average molecular weight (hereinafter, may be abbreviated as Mw) of the polyester resin (A1) are GPCs. It can be measured under the following conditions.
Equipment (example): HLC-8120 manufactured by Tosoh Corporation
Column (example): 2 TSK GEL GMH6 [manufactured by Tosoh Corporation]
Measurement temperature: 40 ° C
Sample solution: 0.25 wt% THF solution Solution injection amount: 100 μL
Detection device: Refractive index detector Reference material: Standard polystyrene (TSK standard POLYSTYRENE) manufactured by Tosoh Corporation 12 points (molecular weight 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)
For the measurement of the molecular weight, the sample is dissolved in tetrahydrofuran (THF) so as to have a molecular weight of 0.25% by weight, and the insoluble matter is filtered by a glass filter to prepare a sample solution.
For the crystalline vinyl resin (B) and the toner binder, which will be described later, Mp, Mn, and Mw can be obtained by the same method as described above.

The glass transition temperature (Tg) of the polyester resin (A1) is preferably −35 to 60 ° C., more preferably −15 to 58 ° C., and even more preferably 15 to 15 ° C. from the viewpoint of low temperature fixability, heat storage stability, and image intensity. It is 58 ° C., particularly preferably 15 to 55 ° C., and most preferably 25 to 45 ° C.
Tg is measured by a method (DSC method) specified in ASTM D3418-82 using a differential scanning calorimeter (DSC).

The acid value of the polyester resin (A1) is preferably 5 to 50 mgKOH / g from the viewpoints of low temperature fixability, charge retention rate (particularly charge retention rate under high temperature and high humidity), blocking property, pulverizability and image strength. It is preferably 8 to 48 mgKOH / g, more preferably 10 to 48 mgKOH / g, particularly preferably 10 to 45 mgKOH / g, and most preferably 15 to 40 mgKOH / g.
The acid value can be measured by the method specified in JIS K0070.

The softening point (T1 / 2) measured by the flow tester of the polyester resin (A1) is preferably 50 to 130 ° C., more preferably 60 to 125 ° C., and further preferably 65 to 120 ° C.
The softening point (T1 / 2) is measured by the following method.
Using a descent type flow tester {for example, CFT-500D manufactured by Shimadzu Corporation}, a load of 1.96 MPa was applied by a plunger while heating 1 g of the measurement sample at a temperature rising rate of 6 ° C./min. Extrude from a nozzle with a diameter of 1 mm and a length of 1 mm, draw a graph of "plunger drop (flow value)" and "temperature", and graph the temperature corresponding to 1/2 of the maximum value of the plunger drop. This value (the temperature at which half of the measurement sample flows out) is defined as the softening point [T1 / 2].

It is preferable that the polyester resin (A1) does not contain a THF insoluble matter from the viewpoint of low temperature fixability. When the polyester resin (A1) contains a THF-insoluble matter, the content of the THF-insoluble matter is preferably 1% by weight or less, more preferably 0.1 to 1.0% by weight.

The content (% by weight) of the THF-insoluble content of the polyester resin (A1) in the present invention was determined by the following method.
50 mL of THF is added to 0.5 g of the sample, and the mixture is stirred and refluxed for 3 hours. After cooling, the insoluble matter is filtered off with a glass filter, and the resin component on the glass filter is dried under reduced pressure at 80 ° C. for 3 hours. The weight of the dried resin on the glass filter is defined as the weight of THF insoluble, and the weight obtained by subtracting the weight of THF insoluble from the weight of the sample is defined as the weight of THF insoluble and THF soluble. Calculate the weight percent of the minute.
For the crystalline vinyl resin (B) and the toner binder, which will be described later, the content of the THF insoluble matter can be determined by the same method as described above.

The epoxy compound (E) is not particularly limited as long as it has an epoxy group in the molecule, but from the viewpoint of hot offset resistance and heat storage stability, it is a polyfunctional compound having two or more epoxy groups in the molecule. Epoxy compounds are preferred. Examples of the polyfunctional epoxy compound include aromatic polyepoxy compounds, heterocyclic polyepoxy compounds, alicyclic polyepoxy compounds, and aliphatic polyepoxy compounds. The epoxy compound (E) may be used alone or in combination of two or more.

Examples of the aromatic polyepoxy compound include a glycidyl ether compound of a polyhydric phenol, a glycidyl ester compound of an aromatic polyvalent carboxylic acid, a glycidyl aromatic polyamine, and other aromatic polyepoxy compounds.

Examples of the polyhydric phenol glycidyl ether form include bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol B diglycidyl ether, bisphenol AD diglycidyl ether, bisphenol S diglycidyl ether, halogenated bisphenol A diglycidyl ether, and tetrachloro. Bisphenol A diglycidyl ether, catechin diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, pyrogallol triglycidyl ether, 1,5-dihydroxynaphthalin diglycidyl ether, dihydroxybiphenyl diglycidyl ether, octachloro-4,4'-dihydroxy Biphenyl diglycidyl ether, tetramethyl biphenyl diglycidyl ether, dihydroxynaphthyl cresol triglycidyl ether, tris (hydroxyphenyl) methanetriglycidyl ether, dinaphthyl triol triglycidyl ether, tetrakis (4-hydroxyphenyl) ethanetetraglycidyl ether, p- Glycidylphenyldimethyltril bisphenol A glycidyl ether, trismethyl-t-butyl-butylhydroxymethane triglycidyl ether, 9,9'-bis (4-hydroxyphenyl) floorange glycidyl ether, 4,4'-oxybis (1,4) -Phenylethyl) tetracresol glycidyl ether, 4,4'-oxybis (1,4-phenylethyl) phenylglycidyl ether, bis (dihydroxynaphthalene) tetraglycidyl ether, novolac type epoxy resin (phenol novolac type epoxy resin, cresol novolac type) (Epoxy resin, bisphenol A novolac type epoxy resin, limonenephenol novolac type epoxy resin, etc.), bisphenol A type epoxy resin, polyphenol polyglycidyl ether form of polyphenol obtained by condensation reaction of polyhydric phenol with glioxal, glutaaldehyde or formaldehyde, and Examples thereof include a polyglycidyl ether form of polyphenol obtained by a condensation reaction of resorcin and acetone.

Examples of the glycidyl ester of an aromatic polyvalent carboxylic acid include phthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, and terephthalic acid diglycidyl ester.

Examples of the glycidyl aromatic polyamine include N, N-diglycidylaniline, N, N, N', N'-tetraglycidylxylylenediamine and N, N, N', N'-tetraglycidyldiphenylmethanediamine.

Other aromatic polyepoxy compounds include triglycidyl ether of p-aminophenol, tolylene diisocyanate, diglycidyl urethane compound obtained by the addition reaction of diphenylmethane diisocyanate and glycidol, and the above two reactants obtained by reacting polyol. Also includes a glycidyl group-containing polyurethane (pre) polymer and a diglycidyl ether compound of the AO adduct of bisphenol A.

Examples of the heterocyclic polyepoxy compound include trisglycidyl melamine.

Examples of the alicyclic polyepoxy compound include vinylcyclohexendioxide, limonendioxide, dicyclopentadiendioxide, bis (2,3-epoxycyclopentyl) ether, ethylene glycol bisepoxydicyclopentyl ether, and 3,4-epoxycyclohexyl. Methyl-3', 4'-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3', 4'-epoxy-6'-methylcyclohexanecarboxylate, bis (3,4-epoxy-6) -Methylcyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) butylamine, 2,2-bis (hydroxymethyl) -1-butanol 1,2-epoxy-4- (2-oxylanyl) Cyclohexane adducts and dimeric acid diglycidyl esters and the like can be mentioned. The alicyclic polyepoxy compound also includes a nuclear hydrogenated product of the aromatic polyepoxy compound.

Examples of the aliphatic polyepoxy compound include a polyglycidyl ether form of an aliphatic polyhydric alcohol, a polyglycidyl ester form of an aliphatic polyvalent carboxylic acid, and a glycidyl aliphatic amine.

Polyglycidyl ethers of aliphatic polyhydric alcohols include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol. Diglycidyl ether, polytetramethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether and the like. Be done.

Examples of the polyglycidyl ester of the aliphatic polyvalent carboxylic acid include diglycidyl oxalate, diglycidyl malate, diglycidyl succinate, diglycidyl glutarate, diglycidyl adipate and diglycidyl pimerate.

Examples of the glycidyl aliphatic amine include N, N, N', N'-tetraglycidyl hexamethylenediamine and the like.
The aliphatic polyepoxy compound also includes a (co) polymer of diglycidyl ether and glycidyl (meth) acrylate.

Among these polyfunctional epoxy compounds, from the viewpoint of hot offset resistance and heat storage stability, aromatic polyepoxy compounds, alicyclic polyepoxy compounds, and aliphatic polyepoxy compounds are preferable, and more preferable. Is an aromatic polyepoxy compound, more preferably a novolak type epoxy resin or a bisphenol A type epoxy resin. The above-mentioned epoxy compound (E) may be used alone or in combination of two or more.

The epoxy compound (E) in the present invention preferably has an epoxy equivalent of 150 to 1000 (g / eq, the same applies hereinafter), more preferably 160 to 500, and even more preferably 170 to 300. If the epoxy equivalent of the epoxy compound (E) is less than 150, the charge retention rate may be insufficient, while if it is larger than 1000, the image intensity and durability may be insufficient.

The polyester resin (A) in the present invention is obtained by adding an epoxy compound (E) to the polyester resin (A1) obtained by the above-mentioned production method or the like and reacting the polyester resin (A1) with the epoxy compound (E). A polyester resin (A) containing a crosslinked resin can be obtained. The reaction is preferably carried out in an atmosphere of an inert gas (nitrogen gas or the like). The reaction temperature is preferably 160 to 260 ° C, more preferably 170 to 250 ° C, and even more preferably 180 to 240 ° C. The reaction time is preferably 3 minutes or longer, more preferably 30 minutes or longer, still more preferably 2 to 40 hours, from the viewpoint of ensuring the reaction.

A known epoxy reaction catalyst (tertiary amines, imidazoles, quaternary ammonium salts, etc.) can be added to the reaction between the polyester resin (A1) and the epoxy compound (E). Further, as the reactor, a normal batch reactor or a horizontal reactor (plus mill, kneader, extruder, etc.) can also be used.

Further, as a preferable method for producing the polyester resin (A) in the present invention, it is also possible to react the polyester resin (A1) with the epoxy compound (E) in the presence of the crystalline vinyl resin (B) described later. By cross-linking the polyester resin (A1) with the epoxy compound (E) in the presence of the crystalline vinyl resin (B), low temperature fixability, hot offset resistance, and charge retention rate (particularly charge retention rate under high temperature and high humidity). ), A toner binder having excellent blocking properties and durability can be obtained. Therefore, the present invention includes a toner binder obtained by reacting a polyester resin (A1) with an epoxy compound (E) in the presence of a crystalline vinyl resin (B), and a method for producing the same. The details of this manufacturing method will be described later.

The weight ratio of the epoxy compound (E) to the weight of the polyester resin (A1) is determined from the viewpoints of hot offset resistance, charge retention rate (particularly charge retention rate under high temperature and high humidity), blocking property, image strength and durability. It is preferably 1 to 42% by weight, preferably 1 to 40% by weight, more preferably 3 to 33% by weight, further preferably 5 to 31% by weight, and particularly preferably 7 to 30% by weight.

In the present invention, the polyester resin (A) contains a resin in which the polyester resin (A1) is crosslinked with the epoxy compound (E), but the polyester resin (A1) is an epoxy compound in a part of the polyester resin (A). The resin crosslinked in (E) may be present, and a part of the unreacted uncrosslinked polyester resin (A1) may be contained. The polyester resin (A) may contain any resin as long as the polyester resin (A1) is crosslinked with the epoxy compound (E), and may further contain the polyester resin (A1).

The toner binder of the present invention contains a crystalline vinyl resin (B).

The crystalline vinyl resin (B) is not particularly limited as long as it is a crystalline vinyl resin, but is preferably a polymer of a monomer composition containing the monomer (a), and the monomer (a). ) Is a (meth) acrylate having 21 to 40 carbon atoms having a chain hydrocarbon group. If the carbon number of the monomer (a) is less than 21, the heat-resistant storage stability may deteriorate, and if the carbon number is larger than 40, the low-temperature fixability may deteriorate.

As the monomer (a), a (meth) acrylate having a linear alkyl group (18 to 36 carbon atoms) [octadecyl (meth) acrylate, nonadecil (meth) acrylate, eicosyl (meth) acrylate, heneicosanyl (meth)) Acrylate, behenyl (meth) acrylate, lignoceryl (meth) acrylate, ceryl (meth) acrylate, montanyl (meth) acrylate, triacontyl (meth) acrylate, dotriaconta (meth) acrylate, etc.] and branched alkyl groups (18 to 36 carbon atoms). ) (Meta) acrylate [2-decyltetradecyl (meth) acrylate, etc.] can be mentioned.
Of these, a (meth) acrylate having a linear alkyl group (18 to 36 carbon atoms) is preferable from the viewpoint of achieving both heat storage resistance, low temperature fixability, hot offset resistance, image strength and crushability of the toner. A (meth) acrylate having a linear alkyl group (18 to 30 carbon atoms) is more preferable, and octadecyl (meth) acrylate (stearyl (meth) acrylate), eikosyl (meth) acrylate, and more preferably. Behenyl (meth) acrylates, lignoceryl (meth) acrylates, ceryl (meth) acrylates and triacontyl (meth) acrylates, with particular preference being octadecyl acrylates, eicosyl acrylates, behenyl acrylates and lignoceryl acrylates.
The monomer (a) may be used alone or in combination of two or more.

The crystalline vinyl resin (B) has a vinyl group in addition to the above-mentioned monomer (a) from the viewpoints of hot offset resistance, heat storage resistance, charge retention rate, image strength, crushability and durability of the toner. It may be a polymer of a monomer composition containing a monomer (b) having 6 or less carbon atoms.

As the monomer (b), a (meth) acrylic monomer having 6 or less carbon atoms [(meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl (meth) ) Acrylate and ethyl-2- (hydroxymethyl) acrylate, etc.], vinyl ester monomer with 6 or less carbon atoms [vinyl acetate, vinyl propionate, isopropenyl acetate, etc.], aliphatic hydrocarbon-based vinyl monomer with 6 or less carbon atoms [ Ethylene, propylene, butene, butadiene, isoprene and 1,5-hexadien, etc.], monomers having a nitrile group and having 6 or less carbon atoms [(meth) acrylonitrile, etc.] and the like can be mentioned.
Of these, (meth) acrylate, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, vinyl acetate, and (meth) acrylonitrile are preferred.
The monomer (b) may be used alone or in combination of two or more.

The crystalline vinyl resin (B) is a monomer composition containing a monomer (d) other than the above-mentioned monomer (a) and the monomer (b) from the viewpoint of heat storage resistance and hot offset resistance. It may be a polymer, and the monomer (d) includes a styrene-based monomer (d1) and a (meth) acrylic excluding the monomer (a) among the (meth) acrylic monomers having more than 6 carbon atoms. At least one selected from the group consisting of a system monomer (d2), a vinyl ester monomer (d3) having more than 6 carbon atoms, and a nitrile group, a urethane group, a urea group, an amide group, an imide group, an allophanate group and a burette group. A monomer (d4) having more than 6 carbon atoms and having a functional group of the seed and an ethylenically unsaturated bond is preferable.
The monomer (d) may be used alone or in combination of two or more.

Examples of the styrene-based monomer (d1) include styrene and alkylstyrene having an alkyl group having 1 to 3 carbon atoms (for example, α-methylstyrene and p-methylstyrene).

Examples of the (meth) acrylic monomer (d2) include alkyl (meth) acrylates having an alkyl group having 4 to 17 carbon atoms [butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, etc.], Hydroxyalkyl (meth) acrylates with 4 to 17 carbon atoms in the alkyl group, aminoalkyl group-containing (meth) acrylates with 4 to 17 carbon atoms in the alkyl group [dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate Etc.], ester of unsaturated carboxylic acid having 8 to 20 carbon atoms and polyhydric alcohol [ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethyl propantri (Meta) acrylate, 1,6-hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, etc.] and the like.

Examples of the vinyl ester monomer (d3) include aliphatic vinyl esters having 7 to 15 carbon atoms and aromatic vinyl esters having 9 to 15 carbon atoms (for example, methyl-4-vinylbenzoate).

A single amount having more than 6 carbon atoms having at least one functional group selected from the group consisting of a nitrile group, a urethane group, a urea group, an amide group, an imide group, an allophanate group and a burette group and an ethylenically unsaturated bond. As the body (d4), a monomer having a urethane group (d41), a monomer having a urea group (d42), a monomer having an amide group (d43), and a monomer having an imide group (d44) , A monomer having an allophanate group (d45), a monomer having a burette group (d46), and the like.

As the monomer having a urethane group (d41), an alcohol having an ethylenically unsaturated bond having 2 to 22 carbon atoms (-2-hydroxyethyl methacrylate, vinyl alcohol, etc.) and an isocyanate having 1 to 30 carbon atoms are used. Examples thereof include a monomer reacted by a known method and a monomer obtained by reacting an alcohol having 1 to 26 carbon atoms with an isocyanate having an ethylenically unsaturated bond and having 2 to 30 carbon atoms by a known method. Be done. In the present specification, the carbon number in the compound having an isocyanate group and the structure does not include the carbon number contained in isocyanate (NCO).
Examples of isocyanates having 1 to 30 carbon atoms include monoisocyanate compounds (benzenesulfonyl isocyanate, tosyl isocyanate, phenylisocyanate, p-chlorophenylisocyanate, butylisocyanate, hexylisocyanate, t-butylisocyanate, cyclohexylisocyanate, octylisocyanate, 2- Ethylhexyl isocyanate, dodecyl isocyanate, adamantyl isocyanate, 2,6-dimethylphenyl isocyanate, 3,5-dimethylphenyl isocyanate and 2,6-dipropylphenyl isocyanate, etc.), aliphatic diisocyanate compounds (trimethylene diisocyanate, tetramethylene diisocyanate, hexa) Methylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate), alicyclic diisocyanate compounds (1,3-cyclopentene diisocyanate) , 1,3-Cyclohexan diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated tetramethylxylylene diisocyanate, etc.) and aromatic diisocyanate Compounds (phenylenediisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-toluidine diisocyanate, 4,4 ′ -Diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalenedi isocyanate, xylylene diisocyanate, etc.) and the like.
Alcohols having 1 to 26 carbon atoms include methanol, ethanol, propanol, isopropyl alcohol, butanol, t-butyl alcohol, pentanol, heptanol, octanol, 2-ethylhexanol, nonanol, decanol, undecyl alcohol, lauryl alcohol and dodecyl. Alcohol, myristyl alcohol, pentadecyl alcohol, cetanol, heptadecanol, stearyl alcohol, isostearyl alcohol, ellaidyl alcohol, oleyl alcohol, linoleil alcohol, linolenyl alcohol, nonadecil alcohol, henei cosanol, behenyl alcohol, el Syl alcohol and the like can be mentioned.
Examples of the isocyanate having 2 to 30 carbon atoms having an ethylenically unsaturated bond include 2-isocyanatoethyl (meth) acrylate and 2- [0- (1'-methylpropyrine amino) carboxyamino] ethyl (meth) acrylate. , 2-[(3,5-Dimethylpyrazolyl) carbonylamino] ethyl (meth) acrylate and 1,1- (bis (meth) acryloyloxymethyl) ethyl isocyanate and the like.

Examples of the monomer having a urea group (d42) include amines having 3 to 22 carbon atoms [for example, primary amines (normal butylamine, t-butylamine, propylamine, isopropylamine, etc.) and secondary amines as monovalent amines. (Diethylamine, dinormal propylamine, dinormal butylamine, etc.), aniline, cyclohexylamine, etc.] and an isocyanate having an ethylenically unsaturated bond and having 2 to 30 carbon atoms are reacted by a known method. Can be mentioned.

As the monomer (d43) having an amide group, an amine having 1 to 30 carbon atoms and a carboxylic acid having an ethylenically unsaturated bond having 3 to 30 carbon atoms (acrylic acid, methacrylic acid, etc.) are reacted by a known method. Examples thereof include the made monomer.

As the monomer having an imide group (d44), an carboxylic acid anhydride (maleic anhydride, dialic anhydride, etc.) having 4 to 10 carbon atoms having an ethylenically unsaturated bond with ammonia was reacted by a known method. Examples thereof include a monomer and a monomer obtained by reacting a primary amine having 1 to 30 carbon atoms with an anhydrous carboxylic acid having 4 to 10 carbon atoms having an ethylenically unsaturated bond by a known method.

Examples of the monomer having an allophanate group (d45) include a monomer obtained by reacting a monomer having a urethane group (d41) with an isocyanate having 1 to 30 carbon atoms by a known method.

Examples of the monomer having a burette group (d46) include a monomer obtained by reacting a monomer having a urea group (d42) with an isocyanate having 1 to 30 carbon atoms by a known method.

By using the monomer (d4), at least one functional group selected from the group consisting of a nitrile group, a urethane group, a urea group, an amide group, an imide group, an allophanate group and a burette group, preferably a urethane group. , At least one functional group selected from the group consisting of a urea group, an amide group, an imide group, an allophanate group and a burette group can be introduced into the crystalline vinyl resin (B).
The method for introducing at least one functional group selected from the group consisting of a urethane group, a urea group, an amide group, an imide group, an allophanate group and a burette group into the crystalline vinyl resin (B) is described above. In addition to the method using the monomers (d41) to (d46), the following methods can also be used.
First, of the two compounds (a compound having an ethylenically unsaturated bond and the other compound) for obtaining the monomers (d41) to (d46), the compound having an ethylenically unsaturated bond is selected as the monomer (a). ). Subsequently, the other compound is reacted with the polymer of the compound having an ethylenically unsaturated bond and the monomer (a). By the above procedure, the "polymer of a compound having an ethylenically unsaturated bond and the monomer (a)" and the "other compound" are bonded to obtain a crystalline vinyl resin (B). At the time of this reaction, the "polymer of the compound having an ethylenically unsaturated bond and the monomer (a)" and the "other compound" are a urethane group, a urea group, an amide group, an imide group, and an allophanate group. Alternatively, since it is bonded by a burette group, at least one functional group selected from the group consisting of a urethane group, a urea group, an amide group, an imide group, an allophanate group and a burette group is contained in the crystalline vinyl resin (B). Can be introduced in.

Of these monomers (d), styrene, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate are preferable from the viewpoints of low-temperature fixability, heat-preservability, charge retention, grindability, and raw material price. It is a reaction product of 2-isocyanatoethyl (meth) acrylate and methanol and a reaction product of 2-isocyanatoethyl (meth) acrylate and dinormal butylamine, more preferably styrene or butyl (meth) acrylate, and further preferably. It is styrene.

The crystalline vinyl resin (B) may be a polymer of a monomer composition containing the above-mentioned monomer (a), monomer (b) and other monomers other than the monomer (d). Good. Examples of the monomer other than the above-mentioned monomer (a), monomer (b) and monomer (d) include divinylbenzene and sodium alkylallyl sulfosuccinate.

The weight ratio of the monomer (a) in the monomer composition is preferably 30% by weight or more, more preferably 40% by weight or more, based on the total weight of the monomer composition. , More preferably 60% by weight. If the weight ratio of the monomer (a) is lower than 30% by weight, the low temperature fixability may deteriorate. On the other hand, the upper limit of the weight ratio of the monomer (a) is preferably 99 weights based on the total weight of the monomer composition from the viewpoint of achieving both low temperature fixability, hot offset resistance and heat storage stability. % Or less, more preferably 95% by weight or less. In one embodiment, the weight ratio of the monomer (a) in the monomer composition is preferably 30 to 99% by weight, more preferably 40 to 99, based on the total weight of the monomer composition. By weight%, more preferably 40-95% by weight, particularly preferably 60-95% by weight.

From the viewpoint of heat-resistant storage, the monomer composition preferably contains the monomer (b), and more preferably contains the monomer (b) and the monomer (d). The total weight ratio of the monomer (b) and the monomer (d) in the monomer composition may be 1 to 70% by weight based on the total weight of the monomer composition. It is preferably 1 to 60% by weight, more preferably 5 to 60% by weight, and particularly preferably 5 to 40% by weight.

The crystalline vinyl resin (B) is a method known for a monomer composition containing a monomer (a), a monomer (b) used as needed, and a monomer (d) (Japanese Patent Laid-Open No. 5). It can be produced by polymerizing according to the method described in -117330A. For example, it can be synthesized by a solution polymerization method in which the above-mentioned monomer is reacted with a radical reaction initiator (azobisisobutyronitrile or the like) in a solvent (toluene or the like).
Moreover, you may use the known radical reaction initiator (c) as a radical reaction initiator. The radical reaction initiator (c) is not particularly limited, and examples thereof include an inorganic peroxide (c1), an organic peroxide (c2), and an azo compound (c3). In addition, these radical reaction initiators can also be used in combination.

The inorganic peroxide (c1) is not particularly limited, and examples thereof include hydrogen peroxide, ammonium persulfate, potassium persulfate, and sodium persulfate.

The organic peroxide (c2) is not particularly limited, and is, for example, benzoyl peroxide, di-t-butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, α, α-bis (t-butyl). Peroxy) diisopropylbenzene, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di-t- Butyl peroxyhexin-3, acetyl peroxide, isobutyryl peroxide, octaninol peroxide, decanolyl peroxide, lauroyl peroxide, 3,3,5-trimethylhexanoyl peroxide, m-toluyl peroxide, t -Butylperoxyisobutyrate, t-butylperoxyneodecanoate, cumylperoxyneodecanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxy-3,5,5 -Trimethylhexanoate, t-butylperoxylaurate, t-butylperoxybenzoate, t-butylperoxyisopropyl monocarbonate, t-butylperoxyacetate and the like can be mentioned.

The azo compound (c3) is not particularly limited, and for example, 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), azobisisobutyronitrile, etc. Can be mentioned.

Among these, organic peroxide (c2) is preferable because it has high initiator efficiency and does not produce toxic by-products such as cyanide.

It is preferable that the crystalline vinyl resin (B) satisfies the following relational expression (1) from the viewpoint of heat storage stability and charge retention rate.
Relational expression (1): 1.1 ≤ | SP (x) -SP (a) | ≤ 8.0
In the relational expression (1), SP (a) is a solubility parameter (hereinafter abbreviated as SP value) of the homopolymer of the monomer (a), and SP (x) is the monomer (a). It is the SP value of the polymer of all the monomers other than).
The SP value (cal / cm ³ ) ^0.5 in the present invention is a value at 25 ° C. calculated by the method described in Polymer engineering and science Vol. 14, pages 151 to 154 by Robert F Fedors et al. Is.
Further, from the viewpoint of heat-resistant storage stability when the toner is used, it is more preferable to satisfy 1.5 ≦ | SP (x) −SP (a) | ≦ 6.0.

The content of the THF insoluble component of the crystalline vinyl resin (B) is preferably 0 to 1.0% by weight, more preferably 0 to 0.5% by weight, from the viewpoint of low temperature fixability of the toner. Yes, more preferably 0 wt%.
The THF insoluble content can be measured by the method described above.

The acid value of the crystalline vinyl resin (B) is preferably 60 mgKOH / g or less, more preferably 40 mgKOH, from the viewpoint of the heat-resistant storage stability of the toner and the charge retention rate (particularly, the charge retention rate under high temperature and high humidity). It is less than / g, and more preferably 0 to 5 mgKOH / g.
The acid value of the crystalline vinyl resin (B) can be measured by the method specified in JIS K0070.

The number average molecular weight (Mn) of the THF-soluble component of the crystalline vinyl resin (B) is preferably 1,000 to 300,000 from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability of the toner.

The weight average molecular weight (Mw) of the THF-soluble component of the crystalline vinyl resin (B) is 1,000 to 300,000 from the viewpoint of achieving both low-temperature fixability of the toner, hot offset resistance and heat-resistant storage stability. Is preferable, 10,000 to 100,000 is more preferable, and 15,000 to 70,000 is even more preferable.
The Mn and Mw of the crystalline vinyl resin (B) can be measured by the method described above.

The toner binder of the present invention contains the polyester resin (A) and the crystalline vinyl resin (B) described above.

In the toner binder of the present invention, the weight ratio [(A1): (B)] of the polyester resin (A1) and the crystalline vinyl resin (B) is from the viewpoint of achieving both low temperature fixability, hot offset resistance and heat storage stability. Therefore, it is preferably 8:92 to 80:20, more preferably 10:90 to 70:30, further preferably 15:85 to 65:35, and particularly preferably 20:80 to 60:40. Is.

The method for producing the toner binder is not particularly limited as long as the polyester resin (A) and the crystalline vinyl resin (B) are uniformly mixed. In one aspect, for example, the polyester resin (A) and the crystalline vinyl resin (B) can be mixed by a known mixing method to produce a toner binder. Known mixing methods include, for example, powder mixing, melt mixing, solvent mixing and the like. Further, the polyester resin (A) and the crystalline vinyl resin (B) may be mixed at the same time together with other necessary toner raw materials when producing the toner.

Examples of the mixing device for powder mixing include a Henschel mixer, a Nauter mixer, a Banbury mixer and the like. A Henschel mixer is preferred.
Examples of the mixing device in the case of melt mixing include a batch type mixing device such as a reaction tank and a continuous mixing device. A continuous mixing device is preferable for uniform mixing at an appropriate temperature in a short time. Examples of the continuous mixing device include a static mixer, an extruder, a continuous sneaker, and a three-roll device.
As a solvent mixing method, a method of dissolving the polyester resin (A) and the crystalline vinyl resin (B) in a solvent (ethyl acetate, THF, acetone, etc.), homogenizing the solvent, and then removing the solvent and pulverizing the solvent, or polyester. Examples thereof include a method in which the resin (A) and the crystalline vinyl resin (B) are dissolved in a solvent (ethyl acetate, THF, acetone, etc.), dispersed in water, and then granulated and desolved.

Further, as a more preferable method for producing the toner binder of the present invention, the polyester resin (A1) and the epoxy compound (E) are crosslinked after or while being mixed in the presence of the crystalline vinyl resin (B) to obtain the polyester resin. A toner binder containing (A) and crystalline vinyl (B) can also be obtained. The polyester resin (A) in which the polyester resin (A1) is crosslinked with the epoxy compound (E), which comprises a step of reacting the polyester resin (A1) with the epoxy compound (E) in the presence of the crystalline vinyl resin (B). A method for producing a toner binder containing the resin and the crystalline vinyl (B) is also included in the present invention.
Specifically, a mixture of polyester resin (A1) and vinyl resin (B) is injected into a twin-screw extruder at a constant rate, and at the same time, epoxy compound (E) is also injected at a constant rate to a temperature of 100 to 200 ° C. There is a method such as allowing the reaction to be carried out while kneading and transporting. At this time, the reaction raw materials such as polyester resin (A1) and vinyl resin (B) charged or injected into the twin-screw extruder are directly injected into the extruder as they are without cooling the reacted resins from the molten state. Alternatively, the resin once produced may be cooled and crushed, and the resin may be supplied to a twin-screw extruder.
Further, the method of melt-mixing is not limited to these specifically exemplified methods, and for example, an appropriate method such as a method of charging a raw material in a reaction vessel, heating it to a temperature at which it becomes a melted state, and mixing the raw materials is used. Of course you can do it.

Further, in the toner binder obtained by reacting the polyester resin (A1) with the epoxy compound (E) in the presence of the crystalline vinyl resin (B), the polyester resin (A1) and the crystalline vinyl resin (B) The weight ratio [(A1): (B)] is preferably 8:92 to 80:20, more preferably 10:90 to, from the viewpoint of achieving both low-temperature fixability, hot offset resistance, and heat-resistant storage stability. It is 70:30, more preferably 15:85 to 65:35, and particularly preferably 20:80 to 60:40. Such a toner binder can be obtained by setting the weight ratio [(A1): (B)] of the polyester resin (A1) and the crystalline vinyl resin (B) used in the production to the above range.

The toner binder of the present invention may contain a resin other than the polyester resin (A) and the vinyl resin (B), and a known additive (release agent, etc.).

The toner binder of the present invention preferably has at least one endothermic peak top temperature (Tm) in the range of 40 to 100 ° C. in the differential scanning calorimetry curve obtained by differential scanning calorimetry (also referred to as DSC measurement). It is more preferable to have at least one endothermic peak top temperature (Tm) in the range of 45 to 80 ° C. In one aspect, the toner binder of the present invention preferably has an endothermic peak top temperature (Tm) of 40 to 100 ° C, more preferably 45 to 80 ° C. When the endothermic peak top temperature (Tm) is in the above range, the low temperature fixability and heat storage stability of the toner binder are well balanced. However, the endothermic peak top temperature (Tm) is defined as 150 ° C after the first temperature rise of the toner binder from 20 ° C to 150 ° C under the condition of 10 ° C / min using a differential scanning calorimeter (DSC). This is the peak top temperature of the endothermic peak in the second heating process in which the temperature is cooled from 0 ° C. to 0 ° C. at 10 ° C./min and then raised from 0 ° C. to 150 ° C. at 10 ° C./min.
In the present invention, the endothermic peak top temperature (Tm) is preferably the endothermic peak top temperature derived from the crystalline vinyl resin (B). In one aspect, the toner binder of the present invention preferably has an endothermic peak top temperature derived from the crystalline vinyl resin (B) of 40 to 100 ° C, more preferably 45 to 80 ° C. When the endothermic peak top temperature (Tm) derived from the crystalline vinyl resin (B) is in the above range, the balance between the low temperature fixability and the heat storage property of the toner binder becomes better. This is because the crystalline vinyl resin (B) is rapidly melted at the endothermic peak top temperature (Tm) derived from the crystalline vinyl resin (B) to reduce the viscosity of the toner binder, and when the toner binder is converted into toner. This is to satisfy the required storage stability.
However, the endothermic peak top temperature (Tm) derived from the crystalline vinyl resin (B) is the first temperature of the toner binder from 20 ° C. to 150 ° C. at 10 ° C./min using a differential scanning calorimeter (DSC). In the second temperature raising process, after the second temperature rise, the temperature is cooled from 150 ° C. to 0 ° C. under the condition of 10 ° C./min, and then the temperature is raised from 0 ° C. to 150 ° C. under the condition of 10 ° C./min. This is the peak top temperature of the endothermic peak derived from the crystalline vinyl resin (B).
The heat absorption peak top temperature (Tm) derived from the crystalline vinyl resin (B) of the toner binder is adjusted by adjusting the carbon number of the monomer (a) constituting the crystalline vinyl resin (B), and the crystalline vinyl resin. It can be adjusted to the above-mentioned preferable range by adjusting the weight ratio of the monomer (a) constituting (B), satisfying the relational expression (1), and the like. Generally, the endothermic peak top temperature (Tm) is increased by increasing the carbon number of the monomer (a), increasing the weight ratio of the monomer (a), and increasing the weight average molecular weight of the crystalline vinyl resin (B). Tends to rise. When the content of the crystalline vinyl resin (B) is small, the heat absorption peak top temperature (Tm) is lowered by increasing the difference in SP value between the polyester resin (A) and the crystalline vinyl resin (B). It becomes difficult.

The endothermic peak top temperature (Tm) is a value measured under the following conditions using a differential scanning calorimeter. As the differential scanning calorimetry, for example, DSC Q20 manufactured by TA Instruments Co., Ltd. can be used.
<Measurement conditions>
(1) Raise from 20 ° C to 150 ° C at 10 ° C / min (2) Cool from 150 ° C to 0 ° C at 10 ° C / min (3) Raise from 0 ° C to 150 ° C at 10 ° C / min (4) Each endothermic peak of the differential scanning calorimetry measured in the process of (3) is analyzed.

The toner binder of the present invention has an inflection that indicates a glass transition temperature (Tg _T ) in the temperature range of −30 ° C. to 80 ° C. in the differential scanning calorimetry curve obtained by performing differential scanning calorimetry (DSC). It is preferable to have at least one point. Further, the inflection point indicating the glass transition temperature (Tg _T ) is more preferably in the temperature range of 35 to 65 ° C. When the inflection point indicating the glass transition temperature (Tg _T ) is in the temperature range of −30 ° C. or higher, the heat-resistant storage stability is good, and when it is in the temperature range of 80 ° C. or lower, the fixability is good.
The glass transition temperature (Tg _T ) can be determined by the method (DSC method) specified in ASTM D3418-82. For the measurement of the glass transition temperature (Tg _T ), for example, DSC Q20 manufactured by TA Instruments Co., Ltd. can be used. The glass transition temperature (Tg _T ) can be measured under the following conditions.
<Measurement conditions>
(1) Raise from 30 ° C to 20 ° C / min to 150 ° C (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) ) The differential scanning calorimetry measured in the steps of (6) and (5) is analyzed.

The toner binder of the present invention preferably contains a THF-insoluble component.
The content (% by weight) of the THF insoluble matter of the toner binder of the present invention is preferably 3 to 70% by weight, more preferably 3 to 70% by weight, from the viewpoint of achieving both glossiness, hot offset resistance and low temperature fixability. It is 5 to 60% by weight, more preferably 10 to 55% by weight, and particularly preferably 15 to 50% by weight.

The THF-soluble Mn of the toner binder of the present invention is preferably 500 to 24,000, more preferably 700 to 17,000, and even more preferably 700 to 17,000, from the viewpoint of achieving both heat storage stability and low temperature fixability of the toner. It is 900 to 12,000.

The THF-soluble Mw of the toner binder of the present invention is preferably 5,000 to 120,000, more preferably 7,000 to 100, from the viewpoint of achieving both hot offset resistance and low temperature fixability of the toner. It is 000, more preferably 9,000 to 90,000, and particularly preferably 10,000 to 80,000.

The molecular weight distribution Mw / Mn of the THF-soluble component of the toner binder of the present invention is preferably 2 to 30 from the viewpoint of achieving both hot offset resistance, heat storage resistance and low temperature fixability of the toner, and more preferably 2. It is 5 to 28, more preferably 3 to 26.

The acid value of the toner binder of the present invention is preferably 50 mgKOH / g or less, more preferably 0 to 30 mgKOH, from the viewpoint of the heat-resistant storage stability of the toner and the charge retention rate (particularly, the charge retention rate under high temperature and high humidity). / G, more preferably 1 to 20 mgKOH / g.
The acid value of the toner binder can be measured by the method specified in JIS K0070.

The content of the organic solvent in the toner binder of the present invention is preferably 50 to 2000 ppm based on the weight of the toner binder. When the organic solvent content is 2000 ppm or less, the heat-resistant storage property, charge retention rate, blocking property and odor are good, and when it is 50 ppm or more, the low temperature fixability and glossiness are good. The content of the organic solvent in the toner binder is more preferably 100 to 1500 ppm, further preferably 150 to 1000 ppm, and particularly preferably 200 to 500 ppm.

Examples of the method for controlling the organic solvent content include (1) control of the amount of organic solvent used in producing the polyester resin (A), the crystalline vinyl resin (B) and the toner binder, and (2) the amount of the initiator. (Control of the decomposed product of the initiator), control by removing the solvent of the organic solvent used in (3), (1) and (2), and the decomposition residue of the initiator.

In (3), the method for removing the solvent from the organic solvent and the method for removing the decomposition residue of the initiator are not particularly limited, but a crushed toner binder is supplied to the twin-screw extruder and vented while being melted and conveyed. A method of depressurizing from the mouth can be mentioned. At this time, the amount of the organic solvent in the toner binder can be controlled by adjusting the melting temperature, the shaft rotation speed, the degree of decompression, and the like. Further, the solvent can be removed by operating the toner binder under an arbitrary temperature under reduced pressure. The pressure may be reduced while stirring using a stirrer. At this time, the amount of the organic solvent in the toner binder can be controlled by adjusting the temperature, the degree of reduced pressure, the stirring speed, and the like. The temperature of the solvent removal is preferably 20 to 200 ° C, more preferably 30 to 170 ° C, and even more preferably 40 to 160 ° C. The degree of pressure reduction when removing the solvent is preferably 0.01 to 100 kPa, more preferably 0.1 to 95 kPa, and even more preferably 1 to 90 kPa.
On the other hand, it is also possible to reduce the pressure from the vent port while reacting the raw materials with a twin-screw extruder. Further, when the raw material is charged in the reaction vessel and reacted, the solvent can be removed by the method of removing the solvent by the reduced pressure operation as it is after the reaction. At this time, the amount of the organic solvent in the toner binder can be controlled by adjusting the same items as described above.
Alternatively, the amount of organic solvent in the toner binder can be reduced by placing the crushed toner binder in a dryer whose temperature and pressure (normal pressure or reduced pressure) are adjusted according to the type of organic solvent to be desolvated. Can be controlled.
Further, the method of removing the solvent in a short time is preferable because the transesterification reaction between the polyester resin (A) and the crystalline vinyl resin (B) is unlikely to occur, and the hot offset resistance and low temperature fixability are good.
The content (ppm) of the organic solvent can be measured under the following conditions, for example, by gas chromatograph analysis or the like.
The content of the organic solvent in the toner binder according to Examples and Comparative Examples was measured under the following conditions.

[Gas chromatograph analysis measurement conditions]
Gas chromatograph: Agilent 6890N
Mass spectrometer: Agilent 5973 inert
Column: ZB-WAX (Liquid phase: (14% -cyanopropyl-phenyl) methylpolysiloxane) 0.25 mm x 30 m df = 1.0 μm
Column temperature: 70 ° C → 300 ° C (10 ° C / min)
Injection temperature: 200 ° C
Split ratio: 50: 1
Injection volume: 1 μL
Helium flow rate: 1 mL / min Detector: MSD

The organic solvent contained in the toner binder is not particularly limited, and for example, ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol, s-butanol, t-butanol, diacetone alcohol, 2-ethylhexanol, acetone, and methyl ethyl ketone. , Methylisobutylketone, methyl n-butylketone, acetonitrile, dimethylacetamide, dimethylformamide, N-methylpyrrolidone, ethylene glycol, diethyl ether, diisopropyl ether, tetrahydrofuran, 1,4-dioxane, 1,3-dioxane, 1,3- Oxolane, methyl cellosolve, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 1,2-dichloroethane, 1,2-dichloroethylene, 1,1,2,2-tetra Chloroethane, trichloroethylene, tetrachloroethylene, hexane, pentane, benzene, heptane, toluene, xylene, cresol, chlorobenzene, styrene, isobutyl acetate, isopropyl acetate, isopentyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, n-acetate Pentyl, methyl acetate, cyclohexanol, cyclohexanone, methylcyclohexanol, methylcyclohexanone, dichloromethane, orthodichlorobenzene, dimethylsulfoxide, anhydrous acetic acid, acetic acid, hexamethylphosphoric triamide, triethylamine, pyridine, acetphenone, t-hexyl alcohol, Examples thereof include t-amyl alcohol and t-butoxybenzene.
Of these, from the viewpoint of heat storage stability and odor, a compound having 2 to 10 carbon atoms is preferable, a compound having 3 to 8 carbon atoms is more preferable, and acetone, isopropyl alcohol, and the like are more preferable. It is t-butanol.

Conventionally, as a method for controlling the organic solvent content, the method of removing the solvent according to (3) described above is generally used, but the melt of the crosslinked polyester resin has low fluidity and it takes a long time to remove the solvent. Therefore, the physical properties of the resin were deteriorated due to cutting of the crosslinked structure and the like. In the present invention, since the polyester resin (A1) is crosslinked with the epoxy compound (E), the thermal stability is lowered and odor is generated as compared with the case where the crosslink reaction is carried out using the conventional radical reaction initiator (c). Since it is possible to suppress the organic solvent generated by the decomposition of the radical reaction initiator (c), which causes the above, and it is not necessary to remove the solvent after the cross-linking reaction, which causes deterioration of the resin properties, the heat-resistant storage stability and the charge retention rate ( In particular, it is possible to obtain a toner having good charge retention rate), blocking property and odor under high temperature and high humidity.

It is useful to apply the toner binder of the present invention to toner. The toner contains the toner binder of the present invention. Toners containing the toner binder of the present invention are also included in the present invention.

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

As the colorant, all of the dyes and pigments used as the colorant for toner can be used. For example, Carbon Black, Iron Black, Sudan Black SM, First Yellow G, Benzidine Yellow, Pigment Yellow, India First Orange, Irgasin Red, Paranitroaniline Red, Toluidine Red, Carmine FB, Pigment Orange R, Lake Red 2G, Rhodamin Examples thereof include FB, Rhodamine B lake, Methyl Violet B lake, Phthalocyanine blue, Pigment blue, Brilliant green, Phthalocyanine green, Oil yellow GG, Kayaset YG, Orazole brown B and Oil pink OP. The colorant may be any one of these alone or a mixture of two or more of them. Further, if necessary, a magnetic powder (powder of a ferromagnetic metal such as iron, cobalt, nickel or a compound such as magnetite, hematite, ferrite) can be contained also 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 of the present invention. 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.

The release agent preferably has a flow softening point (T1 / 2) of 50 to 170 ° C. by a flow tester, and is preferably low molecular weight polypropylene, low molecular weight polyethylene, low molecular weight polypropylene polyethylene copolymer, polyolefin wax, microcrystallin wax, etc. Fatty hydrocarbon waxes such as paraffin wax and Fishertroph wax and their oxides, carnauba wax, montan wax, sazole wax and their deoxidizing wax, ester wax such as fatty acid ester wax, fatty acid amides, fatty acids , Higher alcohols, fatty acid metal salts and mixtures thereof.

The flow softening point (T1 / 2) of the release agent can be measured under the following conditions.
<Measurement method of flow softening point (T1 / 2)>
Using a descent-type flow tester [for example, CFT-500D manufactured by Shimadzu Corporation], a load of 1.96 MPa was applied by a plunger while heating 1 g of the measurement sample at a heating rate of 6 ° C./min. Extrude from a nozzle with a diameter of 1 mm and a length of 1 mm, draw a graph of "plunger drop (flow value)" and "temperature", and graph the temperature corresponding to 1/2 of the maximum value of the plunger drop. This value (the temperature at which half of the measurement sample flows out) is defined as the flow softening point (T1 / 2).

The polyolefin wax is a (co) copolymer obtained by [(co) polymerization of olefins (for example, ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-dodecene, 1-octadecene and mixtures thereof). And heat-reduced copolymers], oxides of olefin (co) copolymers with oxygen and / or ozone, maleic anhydride modified olefin (co) polymers [eg maleic anhydride and derivatives thereof (maleic anhydride, Modified products (monomethyl maleate, monobutyl maleate, dimethyl maleate, etc.)], olefins and unsaturated carboxylic acids [(meth) acrylic acid, itaconic acid, maleic anhydride, etc.] and / or unsaturated carboxylic acid alkyl esters [(meth) ) Copolymers with alkyl acrylate (alkyl carbon number 1-18) ester and maleic anhydride (alkyl carbon number 1-18) ester, etc.] and sazole wax.

Examples of higher alcohols include aliphatic alcohols having 30 to 50 carbon atoms, and examples thereof include triacontanol. Examples of the fatty acid include fatty acids having 30 to 50 carbon atoms, and examples thereof include triacontane carboxylic acid.

Charge control agents include niglosin dyes, triphenylmethane dyes containing tertiary amines as side chains, quaternary ammonium salts, polyamine resins, imidazole derivatives, quaternary ammonium base-containing polymers, metal azo dyes, copper phthalocyanine dyes, etc. Examples thereof include salicylic acid metal salts, boron complexes of benzylic acid, sulfonic acid group-containing polymers, fluorine-containing polymers, halogen-substituted aromatic ring-containing polymers and the like.

Examples of the fluidizing agent include colloidal silica, alumina powder, titanium oxide powder, calcium carbonate powder and the like.

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 weight of the toner.
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 weight of the toner.
The total content of the additives is preferably 3 to 70% by weight, more preferably 4 to 58% by weight, still more preferably 5 to 50% by weight, based on the toner weight.
By setting the composition ratio of the toner in the above range, it is possible to easily obtain a toner having good hot offset resistance, image strength, heat storage stability, fluidity, charge stability, bending resistance and document offset resistance. ..

The toner may be obtained by any of known kneading and pulverizing methods, emulsification phase inversion methods, polymerization methods and the like.
For example, when a toner is obtained by a kneading and pulverizing method, the components constituting the toner excluding the fluidizing agent are dry-blended, melt-kneaded, then coarsely pulverized, and finally atomized using a jet mill pulverizer or the like. By further classifying, fine particles having a volume average particle diameter (D50) of preferably 5 to 20 μm can be produced by mixing with a fluidizing agent.
The volume average particle size (D50) is measured using a Coulter counter {for example, trade name: Multisizer III [manufactured by Beckman Coulter Co., Ltd.]}.

When toner is obtained by the emulsification phase inversion method, the components constituting the toner excluding the fluidizing agent can be dissolved or dispersed in an organic solvent, then emulsified by adding water or the like, and then separated and classified for production. it can. The volume average particle size of the toner is preferably 3 to 15 μm.

If necessary, 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.) to develop an electrically latent image. Used as. 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 can be rubbed with a member such as a charging blade to form an electrical latent image.
The toner does not have to contain carrier particles.

Toner is fixed to a support (paper, polyester film, etc.) by a copying machine, printer, etc. and used as a recording material. As a method of fixing to the support, a known heat roll fixing method, flash fixing method, or the like can be applied.

The toner and the toner binder of the present invention are used for developing electrostatically charged images or magnetic latent images in electrophotographic methods, electrostatic recording methods, electrostatic printing methods, and the like. More specifically, it is used for developing an electrostatic charge image or a magnetic latent image particularly suitable for full color.

Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Hereinafter, unless otherwise specified, "parts" indicates parts by weight.

<Endothermic peak top temperature (Tm)>
The endothermic peak top temperature (Tm) of the resin and the toner binder was measured under the above conditions using a differential scanning calorimeter. As the differential scanning calorimetry, DSC Q20 manufactured by TA Instruments Co., Ltd. was used.

<Glass transition temperature>
The glass transition temperature of the polyester resin and the toner binder was determined by the method (DSC method) specified in ASTM D3418-82. As the apparatus, DSC Q20 manufactured by TA Instruments Co., Ltd. was used.

<Acid value>
It was measured by the method specified in JIS K0070.

<Molecular weight>
The peak top molecular weight Mp, number average molecular weight (Mn), and weight average molecular weight (Mw) were measured using GPC under the above conditions. The apparatus used was HLC-8120 manufactured by Tosoh Corporation, and the column used was two TSK GEL GMH6 [manufactured by Tosoh Corporation].

<Manufacturing Example 1> [Manufacturing of polyester resin (A1-1)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 721 parts of bisphenol A / PO 2 mol adduct, 101 parts of terephthalic acid, 53 parts of trimellitic anhydride, and titanium diisopropoxybis (triethanol) as a condensation catalyst. (Aminate) 2.5 parts was added, and the reaction was carried out at 230 ° C. under a nitrogen stream for 2 hours while distilling off the generated water. Next, the reaction was carried out under a reduced pressure of 0.5 to 2.5 kPa for 5 hours, and after confirming that the acid value was less than 1 mgKOH / g, the temperature was lowered to 180 ° C. After adding 205 parts of adipic acid and reacting for 2 hours, the mixture was reacted under reduced pressure of 0.5 to 2.5 kPa for 3 hours to confirm an acid value of 48 mgKOH / g and then taken out to obtain a polyester resin (A1-1). ..

<Manufacturing Example 2> [Manufacturing of polyester resin (A1-2)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 695 parts of bisphenol A / EO 2 mol adduct, 182 parts of terephthalic acid, 12 parts of trimethylolpropane, and titanium diisopropoxybis (triethanolami) as a condensation catalyst. (Nate) 2.5 parts was added, and the reaction was carried out at 230 ° C. under a nitrogen stream for 2 hours while distilling off the generated water. Next, the reaction was carried out under a reduced pressure of 0.5 to 2.5 kPa for 5 hours, and after confirming that the acid value was less than 1 mgKOH / g, the temperature was lowered to 180 ° C. After adding 195 parts of adipic acid and reacting for 2 hours, the mixture was reacted under reduced pressure of 0.5 to 2.5 kPa for 3 hours to confirm an acid value of 28 mgKOH / g and then taken out to obtain a polyester resin (A1-2). ..

<Manufacturing Example 3> [Manufacturing of polyester resin (A1-3)]
371 parts of bisphenol A / PO 2 mol adduct, 171 parts of bisphenol A / PO 3 mol adduct, 195 part of bisphenol A / EO 2 mol adduct, 146 terephthalic acid in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube. Part, 33 parts of trimellitic anhydride, and 2.5 parts of titanium diisopropoxybis (triethanolaminate) as a condensation catalyst were added and reacted at 230 ° C. under a nitrogen stream for 2 hours while distilling off the generated water. It was. Next, the reaction was carried out under a reduced pressure of 0.5 to 2.5 kPa for 5 hours, and after confirming that the acid value was less than 1 mgKOH / g, the temperature was lowered to 180 ° C. After adding 157 parts of adipic acid and reacting for 2 hours, the reaction was carried out under reduced pressure of 0.5 to 2.5 kPa for 3 hours, and after confirming an acid value of 19 mgKOH / g, the mixture was taken out to obtain a polyester resin (A1-3). ..

<Manufacturing Example 4> [Manufacturing of polyester resin (A1-4)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 766 parts of bisphenol A / PO 3 mol adduct, 214 parts of terephthalic acid, 14 parts of trimellitic anhydride, and titanium diisopropoxybis (triethanol) as a condensation catalyst. (Aminate) 2.5 parts was added, and the reaction was carried out at 230 ° C. under a nitrogen stream for 2 hours while distilling off the generated water. Next, the reaction was carried out under a reduced pressure of 0.5 to 2.5 kPa for 5 hours, and after confirming that the acid value was less than 1 mgKOH / g, the temperature was lowered to 180 ° C. After adding 66 parts of isophthalic acid and reacting for 2 hours, the reaction was carried out under reduced pressure of 0.5 to 2.5 kPa for 3 hours, and after confirming an acid value of 10 mgKOH / g, the mixture was taken out to obtain a polyester resin (A1-4). ..

<Manufacturing Example 5> [Manufacturing of polyester resin (A1-5)]
741 parts of bisphenol A / EO 2 mol adduct, 118 parts of terephthalic acid, 120 parts of adipic acid, 13 parts of trimethylolpropane, and titanium diisopropoxy as a condensation catalyst in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube. 2.5 parts of bis (triethanolamineate) was added, and the reaction was carried out at 230 ° C. under a nitrogen stream for 2 hours while distilling off the generated water. Next, the reaction was carried out under a reduced pressure of 0.5 to 2.5 kPa for 5 hours, and then the temperature was lowered to 180 ° C. One part of tert-butylcatechol was added as a polymerization inhibitor, 86 parts of fumaric acid was further added, and the mixture was reacted under reduced pressure of 0.5 to 2.5 kPa for 8 hours and then taken out to obtain a polyester resin (A1-5). ..

Table 1 shows the glass transition temperature, peak top molecular weight, and acid value of the polyester resins (A1-1) to (A1-5).

In Production Examples 6 to 10 and 12 to 14, behenyl acrylate, stearyl acrylate or triacontyl acrylate was used as the monomer (a).

<Manufacturing Example 6> [Manufacturing of Crystalline Vinyl Resin (B-1)]
After charging 138 parts of xylene into an autoclave and replacing it with nitrogen, the temperature was raised to 165 ° C. in a sealed state with stirring. Behenyl acrylate [manufactured by Nichiyu Co., Ltd., same below] 450 parts, styrene [manufactured by Idemitsu Kosan Co., Ltd., same below] 150 parts, acrylonitrile [manufactured by Nacalai Tesque Co., Ltd., same below] 150 parts, dit- A mixed solution of 1.0 part of butyl peroxide [Perbutyl D, manufactured by Nichiyu Co., Ltd., the same applies hereinafter] and 100 parts of xylene was adjusted to 60 ° C., and the temperature inside the autoclave was controlled to 165 ° C. for 3 hours. It was dropped over and polymerized. After the dropping, the dropping line was washed with 12 parts of xylene. Further, the temperature was maintained at the same temperature for 0.5 hours, and the reaction rate of the monomer (a) was confirmed. Since the reaction rate of the monomer (a) was less than 95%, 0.5 part of dit-butyl peroxide was further added to cause the reaction to a reaction rate of 95% or more. The solvent was removed at 165 ° C. for 5 hours under a reduced pressure of 0.5 to 2.5 kPa to obtain a crystalline vinyl resin (B-1).

<Manufacturing Example 7> [Manufacturing of crystalline vinyl resin (B-2)]
335 parts of behenyl acrylate and 363 parts of ethyl acetate [manufactured by Sankyo Chemical Co., Ltd., the same applies hereinafter] were charged in an autoclave, replaced with nitrogen, and then heated to 78 ° C. in a sealed state with stirring. 50 parts of acrylonitrile, 79 parts of styrene, methyl acrylate [manufactured by Mitsubishi Chemical Industries, Ltd., same below] 15 parts, methacrylic acid [manufactured by Mitsubishi Chemical Industries, Ltd., same below] 21 parts, 2,2'-azobis (2- Methylbutyronitrile) [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., the same applies hereinafter] A mixed solution of 12 parts and 112 parts of ethyl acetate was added dropwise over 2 hours while controlling the temperature inside the autoclave to 78 ° C. for polymerization. went. After the dropping, the dropping line was washed with 25 parts of ethyl acetate. After maintaining the same temperature for 5 hours, the temperature inside the autoclave was raised to 92 ° C. over 1 hour. After keeping the temperature at the same temperature for 2 hours, the temperature was lowered to 60 ° C., and the reaction rate of the monomer (a) was confirmed. Since the reaction rate of the monomer (a) was less than 95%, the temperature was raised to 80 ° C., and 2,2'-azobis (2,4-dimethylvaleronitrile) [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., The same applies hereinafter] A mixed solution of 2 parts and 38 parts of ethyl acetate was added dropwise over 1 hour. After the dropping, the mixture was kept at 80 ° C. for 2 hours, and the reaction was carried out until the reaction rate was 95% or more. The solvent was removed at 120 ° C. for 6 hours under a reduced pressure of 0.5 to 2.5 kPa to obtain a crystalline vinyl resin (B-2).

<Manufacturing Example 8> [Manufacturing of crystalline vinyl resin (B-3)]
After charging 138 parts of xylene into an autoclave and replacing it with nitrogen, the temperature was raised to 165 ° C. in a sealed state with stirring. A mixed solution of 525 parts of stearyl acrylate [manufactured by NOF CORPORATION, the same applies hereinafter], 150 parts of styrene, 75 parts of acrylonitrile, 0.2 parts of dit-butyl peroxide, and 100 parts of xylene was adjusted to 60 ° C. , While controlling the temperature inside the autoclave to 165 ° C., the mixture was dropped over 3 hours to carry out polymerization. After the dropping, the dropping line was washed with 12 parts of xylene. Further, the temperature was maintained at the same temperature for 0.5 hours, and the reaction rate of the monomer (a) was confirmed. Since the reaction rate of the monomer (a) was less than 95%, 0.1 part of dit-butyl peroxide was further added to cause the reaction to a reaction rate of 95% or more. The solvent was removed at 165 ° C. for 5 hours under a reduced pressure of 0.5 to 2.5 kPa to obtain a crystalline vinyl resin (B-3).

<Manufacturing Example 9> [Manufacturing of crystalline vinyl resin (B-4)]
200 parts of behenyl acrylate and 363 parts of ethyl acetate were charged in an autoclave, replaced with nitrogen, and then heated to 78 ° C. in a sealed state with stirring. 67 parts of styrene, 35 parts of methyl acrylate, 150 parts of methacrylnitrile [manufactured by Asahi Kasei Corporation, the same applies hereinafter], 48 parts of methacrylic acid, 8 parts of 2,2'-azobis (2-methylbutyronitrile), ethyl acetate. 112 parts of the mixed solution was added dropwise over 2 hours while controlling the temperature inside the autoclave to 78 ° C. for polymerization. After the dropping, the dropping line was washed with 25 parts of ethyl acetate. After maintaining the same temperature for 5 hours, the temperature inside the autoclave was raised to 92 ° C. over 1 hour. After keeping the temperature at the same temperature for 2 hours, the temperature was lowered to 60 ° C., and the reaction rate of the monomer (a) was confirmed. Since the reaction rate of the monomer (a) was less than 95%, the temperature was raised to 80 ° C., and a mixed solution of 2 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) and 38 parts of ethyl acetate was prepared. It was added dropwise over 1 hour. After the dropping, the mixture was kept at 80 ° C. for 2 hours, and the reaction was carried out until the reaction rate was 95% or more. The solvent was removed at 120 ° C. for 6 hours under a reduced pressure of 0.5 to 2.5 kPa to obtain a crystalline vinyl resin (B-4).

<Manufacturing Example 10> [Manufacturing of crystalline vinyl resin (B-5)]
250 parts of behenyl acrylate and 363 parts of ethyl acetate were charged in an autoclave, replaced with nitrogen, and then heated to 78 ° C. in a sealed state with stirring. Styrene 100 parts, methyl acrylate 50 parts, methacrylonitrile 70 parts, acrylic acid [manufactured by Mitsubishi Chemical Co., Ltd., the same applies hereinafter] 30 parts, 2,2'-azobis (2-methylbutyronitrile) 2 parts, acetate A mixed solution of 112 parts of ethyl was added dropwise over 2 hours while controlling the temperature inside the autoclave to 78 ° C. for polymerization. After the dropping, the dropping line was washed with 25 parts of ethyl acetate. After maintaining the same temperature for 5 hours, the temperature inside the autoclave was raised to 92 ° C. over 1 hour. After keeping the temperature at the same temperature for 2 hours, the temperature was lowered to 60 ° C., and the reaction rate of the monomer (a) was confirmed. Since the reaction rate of the monomer (a) was less than 95%, the temperature was raised to 80 ° C., and 0.5 part of 2,2′-azobis (2,4-dimethylvaleronitrile) and 38 parts of ethyl acetate were mixed. The solution was added dropwise over 1 hour. After the dropping, the mixture was kept at 80 ° C. for 2 hours, and the reaction was carried out until the reaction rate was 95% or more. The solvent was removed at 120 ° C. for 6 hours under a reduced pressure of 0.5 to 2.5 kPa to obtain a crystalline vinyl resin (B-5).

<Production Example 11> [Synthesis of triacity acrylate]
50 parts of 1-triacontanol, 50 parts of toluene, 12 parts of acrylic acid, and 0.05 part of hydroquinone are put into a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, an air introduction pipe, a decompression device, and a water reducing device. And stirred to homogenize. Then, 2 parts of p-toluenesulfonic acid was added, and after stirring for 30 minutes, the reaction was carried out for 5 hours while removing the water generated at 100 ° C. while blowing air at a flow rate of 30 mL / min. Then, the pressure in the reaction vessel was adjusted to 300 mmHg, and the reaction was carried out for another 3 hours while removing the generated water. The reaction solution was cooled to room temperature, 30 parts of a 10 wt% sodium hydroxide aqueous solution was added, the mixture was stirred for 1 hour, and then allowed to stand to separate the organic phase and the aqueous phase. The organic phase was sampled by liquid separation and centrifugation, 0.01 part of hydroquinone was added, and the solvent was removed under reduced pressure while blowing air to obtain a triacontyl acrylate.

<Manufacturing Example 12> [Manufacturing of crystalline vinyl resin (B-6)]
After charging 138 parts of xylene into an autoclave and replacing it with nitrogen, the temperature was raised to 165 ° C. in a sealed state with stirring. The mixed solution of 600 parts of triacontyl acrylate, 75 parts of styrene, 75 parts of butyl acrylate, 1.5 parts of di-t-butyl peroxide, and 100 parts of xylene obtained in Production Example 11 was temperature-controlled to 60 ° C. and autoclaved. Polymerization was carried out by dropping over 3 hours while controlling the internal temperature to 165 ° C. After the dropping, the dropping line was washed with 12 parts of xylene. Further, the temperature was maintained at the same temperature for 0.5 hours, and the reaction rate of the monomer (a) was confirmed. Since the reaction rate of the monomer (a) was less than 95%, 0.5 part of dit-butyl peroxide was further added to cause the reaction to a reaction rate of 95% or more. The solvent was removed at 165 ° C. for 5 hours under a reduced pressure of 0.5 to 2.5 kPa to obtain a crystalline vinyl resin (B-6).

<Manufacturing Example 13> [Manufacturing of crystalline vinyl resin (B-7)]
260 parts of behenyl acrylate and 140 parts of xylene were charged in an autoclave and replaced with nitrogen. After raising the temperature to 140 ° C. in the open state under stirring, the temperature was raised to 170 ° C. in the closed state under stirring, and the temperature was adjusted at 170 ° C. for 2 hours. 1.5 parts of a mixed solution of 234 parts of styrene, 130 parts of methyl acrylate, 26 parts of acrylic acid, 2.6 parts of di-t-butyl peroxide, and 203 parts of xylene while controlling the temperature in the autoclave to 170 ° C. It was dropped over time to carry out polymerization. After the dropping, the dropping line was washed with 7 parts of xylene. Further, the temperature was maintained at the same temperature for 0.5 hours, and the reaction rate of the monomer (a) was confirmed to be 95% or more. The solvent was removed at 170 ° C. for 5 hours under a reduced pressure of 0.5 to 2.5 kPa to obtain a crystalline vinyl resin (B-7).

<Manufacturing Example 14> [Manufacturing of crystalline vinyl resin (B-8)]
325 parts of behenyl acrylate and 140 parts of xylene were charged in an autoclave and replaced with nitrogen. After raising the temperature to 140 ° C. in the open state under stirring, the temperature was raised to 170 ° C. in the closed state under stirring, and the temperature was adjusted at 170 ° C. for 2 hours. A mixed solution of 130 parts of styrene, 65 parts of acrylonitrile, methyl methacrylate [manufactured by Mitsubishi Gas Chemical Company, Inc., the same applies hereinafter] 130 parts, di-t-butyl peroxide 1.3 parts, and xylene 203 parts at the temperature in the autoclave. Was dropped over 1.5 hours while controlling the temperature at 170 ° C. to carry out polymerization. After the dropping, the dropping line was washed with 7 parts of xylene. Further, the temperature was maintained at the same temperature for 0.5 hours, and the reaction rate of the monomer (a) was confirmed to be 95% or more. The solvent was removed at 170 ° C. for 5 hours under a reduced pressure of 0.5 to 2.5 kPa to obtain a crystalline vinyl resin (B-8).

Table 2 shows the endothermic peak top temperature (Tm _B ), weight average molecular weight, and acid value of the obtained crystalline vinyl resins (B-1) to (B-8). Table 2 shows the weight ratio (% by weight) of the monomer (a) in the monomer composition used for producing the crystalline vinyl resins (B-1) to (B-8).

<Example 1> [Manufacturing of toner binder (C-1)]
50 parts of polyester resin (A1-1), 50 parts of crystalline vinyl resin (B-1), jER157S70 [bisphenol A novolac type epoxy resin, manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent 209] (epoxy compound (E) -1)) 8.9 parts and 0.1 part of imidazole [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., the same applies hereinafter], which is an epoxidation catalyst, are mixed, and a twin-screw kneader [Kurimoto Iron Works Co., Ltd., S5KRC kneader] was supplied at 80 kg / hour, and kneaded and extruded at 180 ° C. for 5 minutes at 90 rpm to carry out a cross-linking reaction. By cooling what was obtained by mixing, a toner binder (C-1) containing a polyester resin in which the polyester resin (A1-1) was modified (crosslinked) with an epoxy compound was obtained.

<Example 2> [Manufacturing of toner binder (C-2)]
40 parts of polyester resin (A1-2), 60 parts of crystalline vinyl resin (B-2), 10.2 parts of jER157S70 (epoxy compound (E-1)) and 0.1 part of imidazole which is an epoxy catalyst are mixed. , 80 kg / hour was supplied to a twin-screw kneader, and kneaded and extruded at 180 ° C. for 5 minutes at 90 rpm to carry out a cross-linking reaction. By cooling what was obtained by mixing, a toner binder (C-2) containing a polyester resin in which the polyester resin (A1-2) was modified with an epoxy compound was obtained.

<Example 3> [Manufacturing of toner binder (C-3)]
70 parts of polyester resin (A1-2), 30 parts of crystalline vinyl resin (B-3), EHPE3150 [2,2-bis (hydroxymethyl) -1-butanol 1,2-epoxy-4- (2-oxylanyl) ) Cyclohexane adduct, manufactured by Daicel Co., Ltd., epoxy equivalent 175] (epoxy compound (E-2)) 6.1 parts and 0.1 part of imidazole, which is an epoxidation catalyst, are mixed and a biaxial kneader. Was supplied at 80 kg / hour and kneaded and extruded at 180 ° C. for 5 minutes at 90 rpm to carry out a cross-linking reaction. By cooling what was obtained by mixing, a toner binder (C-3) containing a polyester resin in which the polyester resin (A1-2) was modified with an epoxy compound was obtained.

<Example 4> [Manufacturing of toner binder (C-4)]
50 parts of polyester resin (A1-3), 50 parts of crystalline vinyl resin (B-4), jER1001 [bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent 470] (epoxy compound (E-) 3)) 16.5 parts and 0.1 part of imidazole as an epoxidation catalyst were mixed, supplied to a twin-screw kneader at 80 kg / hour, kneaded and extruded at 180 ° C. for 5 minutes at 90 rpm, and a cross-linking reaction was carried out. By cooling what was obtained by mixing, a toner binder (C-4) containing a polyester resin in which the polyester resin (A1-3) was modified with an epoxy compound was obtained.

<Example 5> [Manufacturing of toner binder (C-5)]
60 parts of polyester resin (A1-4), 40 parts of crystalline vinyl resin (B-5), pentaerythritol polyglycidyl ether [manufactured by Nagase ChemteX Corporation, epoxy equivalent 229] (epoxy compound (E-4) )) 9.0 parts and 0.1 part of imidazole as an epoxidation catalyst were mixed, supplied to a twin-screw kneader at 80 kg / hour, kneaded and extruded at 180 ° C. for 5 minutes at 90 rpm to carry out a cross-linking reaction. By cooling what was obtained by mixing, a toner binder (C-5) containing a polyester resin in which the polyester resin (A1-4) was modified with an epoxy compound was obtained.

<Example 6> [Manufacturing of toner binder (C-6)]
20 parts of polyester resin (A1-1), 80 parts of crystalline vinyl resin (B-2), 5.8 parts of jER157S70 (epoxy compound (E-1)) and 0.1 part of imidazole which is an epoxy catalyst are mixed. , 80 kg / hour was supplied to a twin-screw kneader, and the mixture was kneaded and extruded at 160 ° C. for 5 minutes at 90 rpm to carry out a cross-linking reaction. By cooling what was obtained by mixing, a toner binder (C-6) containing a polyester resin in which the polyester resin (A1-1) was modified with an epoxy compound was obtained.

<Example 7> [Manufacturing of toner binder (C-7)]
70 parts of polyester resin (A1-4), 30 parts of crystalline vinyl resin (B-6), 2.2 parts of EHPE3150 (epoxy compound (E-2)) and 0.1 part of imidazole which is an epoxidation catalyst are mixed. , 80 kg / hour was supplied to a twin-screw kneader, and the mixture was kneaded and extruded at 160 ° C. for 5 minutes at 90 rpm to carry out a cross-linking reaction. By cooling what was obtained by mixing, a toner binder (C-7) containing a polyester resin in which the polyester resin (A1-4) was modified with an epoxy compound was obtained.

<Example 8> [Manufacturing of toner binder (C-8)]
30 parts of polyester resin (A1-1), 70 parts of crystalline vinyl resin (B-1), jER828 [bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent 190] (epoxy compound (E-) 5)) 4.9 parts and 0.1 part of imidazole as an epoxidation catalyst were mixed and supplied to a twin-screw kneader at 80 kg / hour, and kneaded and extruded at 150 ° C. for 5 minutes at 90 rpm to carry out a cross-linking reaction. By cooling what was obtained by mixing, a toner binder (C-8) containing a polyester resin in which the polyester resin (A1-1) was modified with an epoxy compound was obtained.

<Example 9> [Manufacturing of toner binder (C-9)]
80 parts of polyester resin (A1-1), 20 parts of crystalline vinyl resin (B-1), 14.3 parts of jER157S70 (epoxy compound (E-1)) and 0.1 part of imidazole which is an epoxy catalyst are mixed. , 80 kg / hour was supplied to a twin-screw kneader, and kneaded and extruded at 180 ° C. for 5 minutes at 90 rpm to carry out a cross-linking reaction. By cooling what was obtained by mixing, a toner binder (C-9) containing a polyester resin in which the polyester resin (A1-1) was modified with an epoxy compound was obtained.

<Example 10> [Manufacturing of toner binder (C-10)]
8 parts of polyester resin (A1-1), 92 parts of crystalline vinyl resin (B-1), 1.4 parts of jER157S70 (epoxy compound (E-1)) and 0.1 part of imidazole which is an epoxy catalyst are mixed. , 80 kg / hour was supplied to a twin-screw kneader, and kneaded and extruded at 180 ° C. for 5 minutes at 90 rpm to carry out a cross-linking reaction. By cooling what was obtained by mixing, a toner binder (C-10) containing a polyester resin in which the polyester resin (A1-1) was modified with an epoxy compound was obtained.

<Example 11> [Manufacturing of toner binder (C-11)]
40 parts of polyester resin (A1-3), 60 parts of crystalline vinyl resin (B-7), EPPN-201 [phenol novolac type epoxy resin, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 193, the same applies hereinafter] (epoxy compound (E-6)) 9.0 parts and 0.1 part of 2-phenylimidazole [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., the same applies hereinafter] which is an epoxidation catalyst are mixed, and 80 kg / hour in a twin-screw kneader. The epoxy was kneaded and extruded at 180 ° C. for 5 minutes at 90 rpm to carry out a cross-linking reaction. By cooling what was obtained by mixing, a toner binder (C-11) containing a polyester resin in which the polyester resin (A1-3) was modified with an epoxy compound was obtained.

<Example 12> [Manufacturing of toner binder (C-12)]
60 parts of polyester resin (A1-1), 40 parts of crystalline vinyl resin (B-8), jER1004 [bisphenol A type epoxy resin, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 900, the same applies hereinafter] (epoxy compound (E) -7)) 23.1 parts and 0.1 part of 2-ethyl-4-methylimidazole [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., the same applies hereinafter], which is an epoxidation catalyst, are mixed, and 80 kg in a biaxial kneader. The mixture was supplied at / hour and kneaded and extruded at 180 ° C. for 5 minutes at 90 rpm to carry out a cross-linking reaction. By cooling what was obtained by mixing, a toner binder (C-12) containing a polyester resin in which the polyester resin (A1-1) was modified with an epoxy compound was obtained.

<Example 13> [Manufacturing of toner binder (C-13)]
30 parts of polyester resin (A1-1), 70 parts of crystalline vinyl resin (B-1), jER1007FS [manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent 1300] (epoxy compound (E-8)) 10.0 A part and 0.1 part of 2-phenylimidazole, which is an epoxidation catalyst, were mixed and supplied to a twin-screw kneader at 80 kg / hour, and kneaded and extruded at 180 ° C. for 5 minutes at 90 rpm to carry out a crosslinking reaction. By cooling what was obtained by mixing, a toner binder (C-13) containing a polyester resin in which the polyester resin (A1-1) was modified with an epoxy compound was obtained.

<Example 14> [Manufacturing of toner binder (C-14)]
30 parts of polyester resin (A1-1), 70 parts of crystalline vinyl resin (B-2), 12.6 parts of jER1001 (epoxy compound (E-3)) and 2-ethyl-4-methylimidazole, which is an epoxidation catalyst. 0.1 parts were mixed, supplied to a twin-screw kneader at 80 kg / hour, kneaded and extruded at 180 ° C. for 5 minutes at 90 rpm, and a cross-linking reaction was carried out. By cooling what was obtained by mixing, a toner binder (C-14) containing a polyester resin in which the polyester resin (A1-1) was modified with an epoxy compound was obtained.

<Comparative Example 1> [Manufacturing of Toner Binder (C'-1)]
40 parts of polyester resin (A1-5) and 60 parts of crystalline vinyl resin (B-1) are mixed and supplied to a twin-screw kneader at 52 kg / hour, and at the same time, t-butylper as a radical reaction initiator (c). 1.0 part of oxyisopropyl monocarbonate is supplied at 0.52 kg / hour, kneaded and extruded at 160 ° C. for 7 minutes at 90 rpm to carry out a cross-linking reaction, and further reduced pressure at 50 kPa from the vent port to mix while removing the organic solvent. did. By cooling what was obtained by mixing, a toner binder (C'-1) containing a polyester resin in which the polyester resin (A1-5) was crosslinked by a carbon-carbon bond was obtained.

<Comparative Example 2> [Manufacturing of Toner Binder (C'-2)]
60 parts of polyester resin (A1-5) and 40 parts of crystalline vinyl resin (B-2) are mixed and supplied to a biaxial kneader at 80 kg / hour, and at the same time, t-butylper as a radical reaction initiator (c). 1.0 part of oxyisopropyl monocarbonate is supplied at 0.80 kg / hour, kneaded and extruded at 160 ° C. for 5 minutes at 90 rpm to carry out a cross-linking reaction, and further reduced pressure at 50 kPa from the vent port to mix while removing the organic solvent. did. By cooling what was obtained by mixing, a toner binder (C'-2) containing a polyester resin in which the polyester resin (A1-5) was crosslinked by a carbon-carbon bond was obtained.

<Comparative Example 3> [Manufacturing of Toner Binder (C'-3)]
40 parts of polyester resin (A1-5) and 60 parts of crystalline vinyl resin (B-1) are mixed and supplied to a biaxial kneader at 10 kg / hour, and at the same time, Duranate TPA-100 [isocyanurate structure] is used as a cross-linking agent. HDI-based polyisocyanate, manufactured by Asahi Kasei Chemicals Co., Ltd.] was supplied at 0.2 kg / hr and kneaded and extruded at 150 ° C. for 20 minutes at 90 rpm to carry out a crosslinking reaction. By cooling what was obtained by mixing, a toner binder (C'-3) containing a polyester resin in which the polyester resin (A1-5) was crosslinked by a urethane group was obtained.

<Comparative Example 4> [Manufacturing of Toner Binder (C'-4)]
40 parts of polyester resin (A1-5) and 60 parts of crystalline vinyl resin (B-1) are mixed and supplied to a twin-screw kneader at 10 kg / hour, and at the same time, 0.1 kg / hour of trimellitic anhydride as a cross-linking agent. It was supplied at hr, kneaded and extruded at 180 ° C. for 20 minutes at 90 rpm, and further reduced pressure at 50 kPa from the vent port for esterification to carry out a crosslinking reaction. By cooling what was obtained by mixing, a toner binder (C'-4) containing a polyester resin in which the polyester resin (A1-5) was crosslinked with an acid was obtained.

<Comparative Example 5> [Manufacturing of Toner Binder (C'-5)]
40 parts of polyester resin (A1-2) and 60 parts of crystalline vinyl resin (B-1) are mixed and supplied to a twin-screw kneader at 10 kg / hour, and at the same time, trimethylolpropane as a cross-linking agent is 0.1 kg / hr. The mixture was kneaded and extruded at 180 ° C. for 20 minutes at 90 rpm, and further reduced pressure at 50 kPa from the vent port for esterification to carry out a crosslinking reaction. By cooling what was obtained by mixing, a toner binder (C'-5) containing a polyester resin in which the polyester resin (A1-2) was crosslinked with alcohol was obtained.

Tables 3 to 4 show the endothermic peak top temperature (Tm _c ), glass transition temperature (Tg _c ), acid value and organic solvent content of the toner binders obtained in Examples and Comparative Examples. The content of the organic solvent was measured by the above method. The “weight ratio of (E) based on (A1)” shown in Tables 3 to 4 is the weight ratio (100) of the epoxy compound (E) to the weight of the polyester resin (A1) used in the production of the toner binder. × Weight of epoxy compound (E) / weight of polyester resin (A1)) (%).

<Manufacturing of toner>
For 88 parts of the toner binder [toner binder obtained in each example and comparative example], 7 parts of carbon black pigment [manufactured by Mitsubishi Chemical Co., Ltd., MA-100], 3 parts of carnauba wax as a release agent, A part of a charge control agent [T-77 manufactured by Hodoya Chemical Industry Co., Ltd.] was added to make a toner by the following method.
First, it was premixed using a Henschel mixer [manufactured by Nippon Coke Industries Co., Ltd., FM10B] and then kneaded with a twin-screw kneader [manufactured by Ikekai Co., Ltd., PCM-30]. Then, after fine crushing using a supersonic jet crusher Lab Jet [Kurimoto, Ltd., KJ-25], an elbow jet classifier [Matsubo Co., Ltd., EJ-L-3 (LABO) type) ] To obtain toner particles having a volume average particle diameter D50 of 7 μm. The volume average particle size (D50) was measured using a Coulter counter (product name: Multisizer III, manufactured by Beckman Coulter, Inc.).
Then, 1 part of colloidal silica [Aerosil R972 manufactured by Nippon Aerosil Co., Ltd.] was mixed with 100 parts of the toner particles by a sample mill to obtain a toner.

Toners were produced using the toner binders obtained in each Example and Comparative Example with the number of parts of the raw materials blended shown in Tables 5 to 6. In Tables 5 to 6, the toners obtained by using the toner binders (C-1) to (C-14) of Examples 1 to 14 are shown in (T-1) to (T-14), and The toners obtained by using the toner binders (C'-1) to (C'-5) of Comparative Examples 1 to 5 are shown as (T'-1) to (T'-5), respectively.

[Toner performance evaluation]
Below, the obtained toners (T-1) to (T-14) and (T'-1) to (T'-5) have low temperature fixability, hot offset resistance, heat storage resistance, and charge retention rate ( The evaluation methods of low temperature and low humidity conditions and high temperature and high humidity conditions), blocking property, image intensity, pulverizability, odor and durability will be described including judgment criteria.

<Low temperature fixability>
The toner was uniformly placed on the paper surface so as to be 1.0 mg / cm ² . At this time, as a method of placing the powder on the paper surface, a printer with the heat fixing machine removed was used. This paper was passed through a soft roller in a fixing speed (peripheral speed of a heating roller) of 213 mm / sec and a temperature range of 90 to 200 ° C. in 5 ° C. increments. Next, the presence or absence of cold offset on the fixed image was visually observed, and the temperature at which the cold offset occurred (MFT) was measured. MFTs are shown in Tables 5 to 6 as the evaluation results of low temperature fixability.
The lower the temperature at which the cold offset is generated, the better the low temperature fixability, and under this evaluation condition, the MFT is generally preferably 125 ° C. or lower.

<Hot offset resistance>
Toner is placed on the paper surface by the same method as described in the above low temperature fixability, and the paper is placed on a soft roller with a fixing speed (peripheral speed of the heating roller) of 213 mm / sec and a heating roller temperature in the range of 90 to 200 ° C. It was passed in 5 ° C increments. Next, the presence or absence of hot offset on the fixed image was visually observed, and the temperature at which the hot offset occurred was measured. Tables 5 to 6 show the hot offset generation temperatures as the evaluation results of the hot offset resistance.
The higher the temperature at which hot offset occurs, the better the hot offset resistance. Under these evaluation conditions, it is preferably 180 ° C. or higher.

<Heat-resistant storage>
1 g of toner and 0.01 g of Aerosil R8200 (manufactured by Evonik Japan Co., Ltd.) were mixed with a shaker for 1 hour. The mixture was placed in a closed container and allowed to stand in an atmosphere of a temperature of 40 ° C. and a humidity of 80% for 48 hours, and the cohesiveness was measured with a powder tester to evaluate the heat-resistant storage stability.
The lower the value (cohesion) of the cohesion test obtained by the following method, the better the heat-resistant storage property. The degree of cohesion (%) is shown in Tables 5 to 6 as the evaluation result of the heat-resistant storage property. Under these evaluation conditions, the degree of cohesion is preferably 5% or less.
Equipment: POWDER TESTER model PT-X (manufactured by Hosokawa Micron Co., Ltd.)
Sieve opening: 355 μm, 250 μm, 150 μm
Vibration width: 1 mm
Vibration time: 30 seconds Operation method: Set the sieve in the order of 355 μm in the upper stage, 250 μm in the middle stage, and 150 μm in the lower stage on the shaking table of the powder tester, put 1 g of toner on the upper sieve, and vibrate for 30 seconds with a vibration width of 1 mm. , Weigh the toner remaining on each sieve.
Cohesion: Calculated from the weight of toner used for measurement and the weight of residual toner after sieving.
Cohesion (%) = (U / N + M / N x 3/5 + L / N x 1/5) x 100
U: upper weight, M: middle weight, L: lower weight, N: sample weight (1 g)

<Charging retention rate (low temperature and low humidity conditions and high temperature and high humidity conditions)>
(1) 1 g of toner and 0.01 g of Aerosil R8200 (manufactured by Evonik Japan Co., Ltd.) were mixed with a shaker for 1 hour. 0.5 g of this mixture and 20 g of ferrite carrier (F-150 manufactured by Powder Tech Co., Ltd.) were placed in a 50 mL glass bottle, and the humidity was adjusted at 23 ° C. and 50% relative humidity for 8 hours (referred to as low temperature and low humidity conditions). ). Similarly, the humidity was adjusted at 50 ° C. and 95% relative humidity for 24 hours (referred to as high temperature and high humidity conditions).
(2) Friction stir welding was performed at 50 rpm for 10 minutes and 60 minutes with a tubler shaker mixer, and the charge amount at each time was measured using a blow-off charge amount measuring device [manufactured by Kyocera Chemical Co., Ltd.].
Using the obtained value, "charge amount after 60 minutes of friction time / charge amount after 10 minutes of friction time" was calculated, and this was used as a charge stability index. Tables 5 to 6 show the charge stability index as the evaluation result of the charge retention rate.
The larger the main charge stability index, the better the charge retention rate. Under this evaluation condition, it is preferably 0.8 or more.

<Blocking property>
(1) 1 g of toner and 0.01 g of Aerosil R8200 (manufactured by Evonik Japan Co., Ltd.) were mixed with a shaker for 1 hour. 0.5 g of this mixture and 20 g of a ferrite carrier (F-150 manufactured by Powder Tech Co., Ltd.) were placed in a 50 mL glass bottle, and the humidity was adjusted at 50 ° C. and 95% relative humidity for 24 hours.
(2) The degree of blocking was visually judged, and the blocking property was evaluated according to the following criteria. The results are shown in Tables 5-6.

[Criteria]
◯: No blocking has occurred and the blocking property is excellent.
Δ: Blocking has occurred in a part, but the blocking property is excellent.
X: Blocking occurs as a whole, and the blocking property is significantly inferior.

<Image strength>
Among the images fixed by the above evaluation of low temperature fixability, the image with the lowest fixing temperature is fixed at an angle of 45 degrees according to JIS K5600-5-4 (1999), and a load of 10 g is applied from directly above the pencil. Then, a scratch hardness test was performed by the hand-scraping method, and the image strength was evaluated from the scratch-free pencil hardness. As the evaluation result of the image strength, the pencil hardness without scratches is shown in Tables 5 to 6.
The higher the pencil hardness, the better the image strength. Generally, it is preferably HB or higher.

<Crushability>
In the production of toner, the mixture obtained by kneading with a twin-screw kneader is cooled and then pulverized to a size of 8.6 mesh passes to 30 mesh-on, and the particles are used as particles for pulverization evaluation. The particles were pulverized by a supersonic jet crusher Lab Jet under the following conditions.
Crushing pressure: 0.64 MPa
Grinding time: 15 minutes Separater frequency: 150Hz
Adjuster ring: 15mm
Luber size: Medium Grindability The volume average particle size (μm) is measured with a Coulter counter [trade name: Multisizer III (manufactured by Coulter)] without classifying finely pulverized particles for evaluation, and the pulverizability. Was evaluated. As the evaluation result of pulverizability, the volume average particle diameter (μm) is shown in Tables 5 to 6.
The smaller the particle size, the better the pulverizability. Under these evaluation conditions, the volume average particle size is preferably 8.0 μm or less.

<Odor>
1.0 g of toner was placed in a glass test tube with a lid (φ15 mm × 150 mm), sealed, and heated at 210 ° C. for 5 minutes. After that, the lid was removed, and 10 monitors confirmed the odor and evaluated according to the following criteria. The results are shown in Tables 5-6.
[Criteria]
○: 1 person answered that it does not smell or only 1 person smells △: 2 to 6 people answered that it smells ×: 7 or more people answered that it smells

<Durability>
Continuous copying was performed using a commercially available monochrome copier [AR5030, manufactured by Sharp Corporation] using toner as a two-component developer, and the durability was evaluated according to the following criteria. The results are shown in Tables 5-6.

[Criteria]
⊚: There is no change in image quality and no fog even after copying 10,000 sheets.
◯: Fog has occurred after copying 10,000 sheets.
Δ: Fog has occurred after copying 6,000 sheets.
X: Fog has occurred after copying 2,000 sheets.

As is clear from the evaluation results in Tables 5 to 6, the toners (T-1) to (T-14) using the toner binders produced in each example all gave excellent results in all the performance evaluations. It was. On the other hand, the toners (T'-1) to (T'-5) using the toner binder produced in each comparative example had some performance items defective. Specifically, Comparative Examples 1 and 2 contain a polyester resin cross-linked by a carbon-carbon bond, but since the cross-linking reaction is carried out using the radical polymerization initiator (c), the content of the organic solvent is large and the blocking property is high. The odor was further exacerbated due to a decrease in the charge retention rate under high temperature and high humidity. Since Comparative Example 3 contains a polyester resin crosslinked by a urethane bond, the pulverizability deteriorated due to the deterioration of the charging characteristics due to the urethane group and the high cohesive force of the urethane group. Comparative Examples 4 and 5 contained a polyester resin crosslinked by an esterification reaction accompanying a condensation reaction of an acid and a hydroxyl group, but the ester crosslink was weaker than the epoxy crosslink, and the heat storage property and blocking property were inferior.

The toner binder of the present invention maintains low-temperature fixability and hot offset resistance, while maintaining heat-resistant storage stability, charge retention rate (particularly charge retention rate under high temperature and high humidity), blocking property, image strength, grindability, odor, and It has excellent durability and can be suitably used as a toner for static charge image development used for electrophotographic, electrostatic recording, electrostatic printing, and the like.
The toner binder of the present invention is also suitable for applications such as paint additives, adhesive additives, and electronic paper particles.

Claims

A toner binder containing a polyester resin (A) and a crystalline vinyl resin (B), wherein the polyester resin (A) contains a resin in which the polyester resin (A1) is crosslinked with an epoxy compound (E). binder.
The crystalline vinyl resin (B) is a polymer of a monomer composition containing the monomer (a), and the monomer (a) has a chain hydrocarbon group and has 21 to 40 carbon atoms (meth). ) The toner binder according to claim 1, wherein the weight ratio of the monomer (a) in the monomer composition is 30% by weight or more based on the total weight of the monomer composition. ..
Endothermic peak top temperature (Tm) [However, the endothermic peak top temperature (Tm) is the first time using a differential scanning calorimeter (DSC) under the condition of 10 ° C / min from 20 ° C to 150 ° C. After raising the temperature, the temperature is cooled from 150 ° C. to 0 ° C. under the condition of 10 ° C./min, and then the temperature is raised from 0 ° C. to 150 ° C. under the condition of 10 ° C./min. It is the peak top temperature of. ] Is 40 to 100 ° C., according to claim 1 or 2.
The toner binder according to any one of claims 1 to 3, wherein the epoxy compound (E) is a polyfunctional epoxy compound having an epoxy equivalent of 150 to 1000.
The toner binder according to any one of claims 1 to 4, wherein the weight ratio of the epoxy compound (E) to the weight of the polyester resin (A1) is 1 to 40% by weight.
A toner binder obtained by reacting a polyester resin (A1) with an epoxy compound (E) in the presence of a crystalline vinyl resin (B), and the weight of the polyester resin (A1) and the crystalline vinyl resin (B). The toner binder according to any one of claims 1 to 5, wherein the ratio [(A1): (B)] is 10:90 to 70:30.
The toner binder according to any one of claims 1 to 6, wherein the polyester resin (A1) has an acid value of 5 to 50 mgKOH / g, and the crystalline vinyl resin (B) has an acid value of 60 mgKOH / g or less.
The toner binder according to any one of claims 1 to 7, wherein the polyester resin (A1) has a glass transition temperature of −35 to 60 ° C.