JP6814779B2 - Toner binder and toner - Google Patents

Description

The present invention relates to toner binders and toners.

In recent years, with the development of electrophotographic systems, the demand for electrophotographic devices such as copiers and laser printers has been rapidly increasing, and the demand for their performance is also increasing.
Conventionally, for 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 transferred. 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 the image onto the material.

In order to pass through these processes without any problem, the toner first needs to maintain a stable charge amount, and then needs to have good fixability to 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 improving the productivity of the toner and reducing the particle size of the toner, the pulverizability of the toner binder is required. Toner productivity is directly linked to production cost, and reducing the particle size of toner is related to higher image quality.

Hot offset resistance can be considered as a contradictory item of crushability. Having a wide fixing temperature range is necessary for the stability of the fixing process, but in order to improve the hot offset resistance, it is known that the toner binder has a higher molecular weight, a crosslinked structure is introduced, and a gel component is introduced. However, all of them significantly impair the pulverizability and reduce the productivity.

In order to improve the pulverizability without lowering the hot offset resistance, it has been proposed to use low molecular weight polyethylene or a graft polymer obtained by grafting a vinyl monomer on low molecular weight polypropylene as an additive (Patent Document 1). And 2), the effect of pulverizability is insufficient.

As another technique, a manufacturing method is known in which an external additive such as a fluidizing agent is added after the rough pulverization step of the toner and then finely pulverized (Patent Documents 3 to 5), but the external addition is more than necessary. It is considered that the amount of the agent is required and that the external additive may enter the toner and hinder the fixing performance.

In addition, various other pulverizing aids have been proposed in Patent Documents 6 to 9 below, but all of them impair some performance such as fixing performance, storage stability, and charging characteristics due to their composition and physical properties, and pulverization property is deteriorated. It may be insufficient.

As described above, there has been no excellent toner binder and toner having improved pulverizability while maintaining low temperature fixability, hot offset resistance, storage stability, and charging characteristics.

Japanese Unexamined Patent Publication No. 2000-075459 JP-A-2007-293323 Japanese Unexamined Patent Publication No. 2002-131979 Japanese Unexamined Patent Publication No. 2005-326842 Japanese Unexamined Patent Publication No. 2017-0585887 Japanese Patent Application Laid-Open No. 5-224436 Japanese Unexamined Patent Publication No. 2008-089829 Japanese Unexamined Patent Publication No. 2008-191491 JP 2015-132645

An object of the present invention is to provide a toner excellent in low temperature fixability, hot offset resistance, storage stability and charging characteristics, and also excellent in pulverizability, and a toner binder used therefor.

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 vinyl resin (B), wherein the vinyl resin (B) has a weight average molecular weight of 4,000 to 40,000, and the vinyl resin (B). ) Has a solubility parameter of 10.6 to 12.6 (cal / cm ³ ) ^1/2 , and the total weight ratio of the polyethylene unit (C11) and the polypropylene unit (C12) in the vinyl resin (B) is vinyl. It is 0 to 9% by weight based on the weight of the resin (B), the polyethylene unit (C11) is a polyethylene unit having a degree of polymerization of 70 to 210, and the polypropylene unit (C12) has a degree of polymerization of 70 to 210. It is a polypropylene unit having, and the number average dispersed particle diameter of the vinyl resin (B) in the toner binder is 0.02 to 2 μm; and the toner containing the toner binder and the colorant.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a toner and a toner binder which are excellent in low temperature fixability, hot offset resistance, storage stability and charging characteristics, have improved pulverizability of the toner binder, and are excellent in productivity.

The toner binder of the present invention is a toner binder containing a polyester resin (A) and a vinyl resin (B), and the weight average molecular weight of the vinyl resin (B) is 4,000 to 40,000, and the vinyl resin. The solubility parameter of (B) is 10.6 to 12.6 (cal / cm ³ ) ^1/2 , and the total weight ratio of the polyethylene unit (C11) and the polypropylene unit (C12) in the vinyl resin (B) is , 0-9% by weight based on the weight of the vinyl resin (B), the polyethylene unit (C11) is a polyethylene unit having a degree of polymerization of 70 to 210, and the polypropylene unit (C12) is 70 to 210. It is a polypropylene unit having a degree of polymerization, and is characterized in that it is a toner binder in which the number average dispersed particle size of the vinyl resin (B) in the toner binder is 0.02 to 2 μm.
Hereinafter, the toner binder of the present invention will be described in sequence.

The polyester resin (A) in the present invention contains a polyester resin obtained by polycondensing one or more alcohol components (x) and one or more carboxylic acid components (y), and has a grindability of a toner binder. From this point of view, it is preferably an amorphous polyester resin.
Examples of the alcohol component (x) include a diol (x1) and / or a trivalent or higher-valent polyol (x2).
Examples of the carboxylic acid component (y) include a dicarboxylic acid (y1) and / or a trivalent or higher valent polycarboxylic acid (y2). Moreover, you may use monocarboxylic acid (y3) if necessary.

Examples of the diol (x1) include alkylene glycols having 2-36 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); carbon. Alkylene ether glycols of number 4 to 36 (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols of 6 to 36 carbon atoms (1,4-cyclohexanedi). Methanol and hydrogenated bisphenol A, etc.); The alkylene oxide adduct of the alicyclic diol (preferably, the average number of moles added is 1 to 30); (Bisphenol A, Bisphenol F, Bisphenol S, etc.)] alkylene oxide adducts (preferably, the average number of moles added is 2 to 30) and the like. In alkylene oxide (hereinafter, "alkylene oxide" may be abbreviated as AO), the carbon number of the alkylene group is preferably 2 to 4, and the alkylene oxide is ethylene oxide, 1,2- or 1, 3-Propylene oxide, 1,2-, 2,3-, 1,3- or iso-butylene oxide and tetrahydrofuran are preferable, and ethylene oxide, 1,2- or 1,3-propylene oxide is more preferable.

Of these, alkylene oxide adducts of bisphenols (preferably with an average number of moles of 2 to 30) and alkylene glycols having 2 to 12 carbon atoms are preferable from the viewpoint of low temperature fixability and storage stability. More preferred are alkylene oxide adducts of bisphenols (more preferably bisphenol A) (more preferably an average addition molar number of 2-8) and alkylene glycols having 2-12 carbon atoms (more preferably ethylene glycol and 1). , 2-Propylene glycol, particularly preferably 1,2-propylene glycol).

Examples of the trivalent or higher-valent polyol (x2) include an aliphatic polyhydric alcohol (x21) having a trivalent or higher valence having 3 to 36 carbon atoms, a saccharide and its derivative (x22), and an AO adduct of the aliphatic polyhydric alcohol. (The average number of added moles is preferably 1 to 30) (x23), AO additions of trisphenols (trisphenol PA, etc.) (average number of added moles is preferably 2 to 30) (x24), novolak resin (phenol novolac). And cresol novolac and the like, and the average degree of polymerization is preferably 3 to 60), and examples thereof include AO adducts (average number of moles added is preferably 2 to 30) (x25).

Examples of the trihydric or higher valence aliphatic polyhydric alcohol (x21) having 3 to 36 carbon atoms include alkane polyols and their intramolecular or intermolecular dehydrations, and examples thereof include glycerin, trimethylolethane, and trimethylolpropane. Examples thereof include pentaerythritol, sorbitol, sorbitan, polyglycerin and dipentaerythritol.

Of these, from the viewpoint of low-temperature fixability and hot offset resistance of the toner binder and the toner containing the same, those preferable are the AO adduct of novolak resin (the average number of moles added is preferably 2 to 30) and trivalent or higher. Of the aliphatic polyhydric alcohols of the above, particularly preferable are AO adducts (average number of moles added is preferably 2) of novolak resin (containing phenol novolac, cresol novolac, etc., preferably 3 to 60 in average degree of polymerization). ~ 30), Glycerin and Trimethylol Propane.

Examples of the dicarboxylic acid (y1) include alcandicarboxylic acids having 4 to 36 carbon atoms (for example, succinic acid, adipine and sebacic acid), alkenyl succinic acid (for example, dodecenyl saconic acid), and alicyclic dicarboxylic acids having 6 to 40 carbon atoms [ For example, dimer acid (dimerized linoleic acid, etc.)], arcendicarboxylic acid having 4 to 36 carbon atoms (eg, maleic acid, phthalic acid, citraconic acid, mesaconic acid, etc.), and aromatic dicarboxylic acid having 8 to 36 carbon atoms (eg, maleic acid, fumaric acid, citraconic acid, mesaconic acid, etc.) For example, phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc.) and the like can be mentioned.
Further, as the dicarboxylic acid (y1), an anhydride of these carboxylic acids, a lower alkyl (carbon number 1 to 4) ester (methyl ester, ethyl ester, isopropyl ester, etc.) may be used, or these carboxylic acids. May be used in combination with.

Of these, from the viewpoint of low-temperature fixability and storage stability, preferred ones are alkanedicarboxylic acids having 4 to 36 carbon atoms, alkendicarboxylic acids having 4 to 20 carbon atoms, and aromatic dicarboxylic acids having 8 to 20 carbon atoms. More preferably, it is adipic acid, fumaric acid and terephthalic acid. Further, it may be an anhydride or a lower alkyl ester of these acids.

Examples of the trivalent or higher valent polycarboxylic acid (y2) include an aliphatic tricarboxylic acid having 6 to 36 carbon atoms (hexanetricarboxylic acid, etc.) and an aromatic polycarboxylic acid having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, etc.). ) Etc. can be mentioned.
Further, as the trivalent or higher valent polycarboxylic acid (y2), an anhydride of these carboxylic acids and a lower alkyl (carbon number 1 to 4) ester (methyl ester, ethyl ester, isopropyl ester, etc.) may be used. , These may be used in combination with a carboxylic acid.

Of these, those preferable from the viewpoint of hot offset resistance and charging characteristics of the toner binder and the toner are trimellitic acid and pyromellitic acid, anhydrides of these carboxylic acids, and lower alkyl (1 to 4 carbon atoms) esters.

The monocarboxylic acid (y3) includes an aliphatic monocarboxylic acid and an aromatic monocarboxylic acid, and specifically, an aliphatic monocarboxylic acid having 2 to 50 carbon atoms (acetic acid, propionic acid, butyric acid, benzoic acid). , Caproic acid, enanthic acid, capric acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, behenic acid, etc.), aromatic monocarboxylic acid with 7 to 37 carbon atoms (benzoic acid) , Torylic acid, 4-ethylbenzoic acid, 4-propylbenzoic acid, etc.) and the like.
Of these, benzoic acid is preferable from the viewpoint of storage stability.

In the present invention, the polyester resin (A) can be produced in the same manner as a general polyester production method. For example, in an atmosphere containing an alcohol component (x) and a carboxylic acid component (y) and an inert gas (nitrogen gas or the like), the reaction temperature is preferably 150 to 280 ° C, more preferably 160 to 250 ° C, and further. It can be preferably carried out by reacting 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.

At this time, an esterification catalyst can also 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 (triethanolaminate), titanium monohydroxytris (triethanolaminete), titanylbis (triethanolamineate) and theirs. Intramolecular polycondensate, etc.}, catalysts described in JP-A-2007-11307 (titanium tributoxyterephthalate, titanium triisopropoxyterephthalate, titanium diisopropoxyditerephthalate, etc.), etc.], zirconium-containing catalysts (eg, zirconyl acetate). Etc.) and zinc acetate and the like. Of these, a titanium-containing catalyst is preferable. It is also effective to reduce the pressure in order to improve the reaction rate at the end of the reaction.

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

The reaction ratio of the alcohol component and the carboxylic acid component is preferably 2/1 to 1/2, more preferably 1.5 / 1-1, as the equivalent ratio of the hydroxyl group to the carboxyl group {[OH] / [COOH]}. /1.3, more preferably 1.3 / 1-1 / 1.2.

The polyester resin (A) used in the present invention includes a linear polyester resin (A1) and a non-linear polyester (branched or crosslinked polyester) resin (A2), which may be used alone or in combination of two or more. You may. Further, the linear polyester resin (A1) and the non-linear polyester resin (A2) may be mixed and used.
Further, the polyester resin (A) is preferably composed of a linear polyester resin (A1) and a non-linear polyester resin (A2) from the viewpoint of achieving both low temperature fixability and hot offset resistance. The weight ratio ((A1) / (A2)) of the linear polyester resin (A1) and the non-linear polyester resin (A2) is preferably 10/90 to 90 from the viewpoint of achieving both low temperature fixability and hot offset resistance. It is / 10, more preferably 15/85 to 85/15, still more preferably 20/80 to 80/20, and particularly preferably 30/70 to 70/30.

The linear polyester resin (A1) is obtained by polycondensing the diol (x1) and a dicarboxylic acid (y1). Further, the molecular end may be modified with an anhydride of the carboxylic acid component (y) (which may be trivalent or higher).
The non-linear polyester resin (A2) is obtained by reacting the above dicarboxylic acid (y1) and diol (x1) with the above trivalent or higher polycarboxylic acid (y2) and / or trivalent or higher polyol (x2). Be done. Total molar ratio of trivalent or higher polycarboxylic acid (y2) and trivalent or higher polyol (x2) when obtaining a non-linear polyester resin (A2) [{(y2) + (x2)} / {(x) + (Y)}] is preferably 0.1 to 40 mol% with respect to the total number of moles of the total alcohol component (x) and the carboxylic acid component (y) from the viewpoint of low temperature fixability and hot offset resistance. , More preferably 1 to 30 mol%, still more preferably 2 to 25 mol%, and particularly preferably 3 to 20 mol%.

The glass transition point of the linear polyester resin (A1) is preferably 40 to 75 ° C, more preferably 45 to 70 ° C, still more preferably 47 to 67 ° C, and particularly preferably 50, from the viewpoint of low temperature fixability and storage stability. ~ 65 ° C.
In the present invention, the glass transition point can be measured by the method (DSC method) specified in ASTM D3418-82, for example, using a differential scanning calorimeter.

The weight average molecular weight of the linear polyester resin (A1) is preferably 4,000 to 10,000, more preferably 4,500 to 8,000, still more preferably 5,000, from the viewpoint of low temperature fixability and storage stability. ~ 7,000.
The weight average molecular weights of the polyester resin (A), the vinyl resin (B), and the crystalline resin (E) described below (hereinafter, may be abbreviated as Mw) are gel permeation chromatography (hereinafter, abbreviated as GPC). 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, the sample is dissolved in tetrahydrofuran (hereinafter abbreviated as THF) so as to be 0.25% by weight, and the insoluble matter is filtered by a glass filter to prepare a sample solution.

The THF insoluble content of the linear polyester resin (A1) is preferably 3% by weight or less, more preferably 1% by weight or less, still more preferably 0% by weight, from the viewpoint of low temperature fixability.

The acid value (mgKOH / g) of the linear polyester resin (A1) is preferably 3 to 35, more preferably 4 to 30, still more preferably 5 to 28, from the viewpoint of low temperature fixability, storage stability and charge stability. , Particularly preferably 7 to 25.
In the present invention, the acid value is a value measured by a method specified in JIS K0070 (1992 edition).

The hydroxyl value (mgKOH / g) of the linear polyester resin (A1) is preferably 20 to 80, more preferably 25 to 75, still more preferably 30 to 70, and particularly preferably 30 to 70, from the viewpoint of low temperature fixability and storage stability. It is 35 to 65.
In the present invention, the hydroxyl value is a value measured by a method specified in JIS K0070 (1992 edition).

The glass transition point of the non-linear polyester resin (A2) is preferably 40 to 75 ° C, more preferably 45 to 70 ° C, still more preferably 47 to 67 ° C, and particularly preferably 50, from the viewpoint of low temperature fixability and storage stability. ~ 65 ° C.

The weight average molecular weight of the THF-soluble component of the nonlinear polyester resin (A2) is preferably 8,000 or more, more preferably 10,000 or more, still more preferably 13,000, from the viewpoint of low temperature fixability and hot offset resistance. ~ 1,000,000.

The THF insoluble content of the non-linear polyester resin (A2) is preferably 1% by weight or more, more preferably 3% by weight or more, still more preferably 5% by weight or more, particularly preferably from the viewpoint of low temperature fixability and hot offset resistance. Is 10 to 50% by weight.

The acid value (mgKOH / g) of the non-linear polyester resin (A2) is preferably 2 to 35, more preferably 2 to 30, still more preferably 2 to 28, most preferably from the viewpoint of toner charge stability and productivity. Is 2 to 25.

The hydroxyl value (mgKOH / g) of the non-linear polyester resin (A2) is preferably 1 to 50, more preferably 1 to 45, still more preferably 1 to 40, and particularly preferably 1 to 40, from the viewpoint of hot offset resistance and productivity. 1 to 35.

The acid value of the polyester resin (A) is preferably 2 mgKOH / g or more from the viewpoint of low temperature fixability and charge stability. When the acid value of the polyester resin (A) is 2 mgKOH / g or more, low temperature fixability and charge stability are good. The acid value of the polyester resin (A) is preferably 2 to 35 mgKOH / g, more preferably 3 to 30 mgKOH / g, still more preferably 4 to 28 mgKOH / g, and particularly preferably 5 to 25 mgKOH / g. Is.
The types of the linear polyester resin (A1) and the non-linear polyester resin (A2) and their weight ratios may be set so that the acid value of the polyester resin (A) is within the above range.

The glass transition point of the polyester resin (A) is preferably 40 to 75 ° C., more preferably 45 to 70 ° C., still more preferably 47 to 67 ° C., and particularly preferably 50 to 50 ° C. from the viewpoint of heat storage stability and low temperature fixability. It is 65 ° C.

The THF insoluble content of the polyester resin (A) is preferably 1% by weight or more, more preferably 2% by weight or more, still more preferably 2 to 50% by weight, from the viewpoint of low temperature fixability and hot offset resistance.
It is preferable to set the types of the linear polyester resin (A1) and the non-linear polyester resin (A2) and their weight ratios so that the glass transition point of the polyester resin (A) and the insoluble content of THF are within the above ranges.

The solubility parameter of the polyester resin (A) (may be abbreviated as SP value below) [(cal / cm ³ ) ^1/2 , the same applies to the following SP value units] is the storage stability and vinyl resin (B). ), It is preferably 10.5-12.5, more preferably 10.7 to 12.3, still more preferably 10.8 to 12.0, and particularly preferably 10.9 to 11. It is 9.9. When the SP value is 12.5 or less and 10.5 or more, the difference in SP value from the vinyl resin (B) becomes appropriate, and the vinyl resin (B) is well dispersed in the polyester resin (A).

The solubility parameter of the vinyl resin (B) is 10.6 to 12.6, preferably 10.6 to 11.8, and more preferably 10 from the viewpoint of storage stability and dispersibility of the vinyl resin (B). It is .6 to 11.7, more preferably 10.7 to 11.6, and particularly preferably 10.8 to 11.5.
Even if the SP value exceeds 12.6 or less than 10.6, the difference in SP value from the polyester resin (A) becomes too large and the dispersion in the polyester resin (A) becomes poor.
The method for calculating the SP value in the present invention is the method described in the literature by Robert F Fedors et al. (Polymer Engineering and Science, Polymery, 1974, Vol. 14, No. 2 P. 147 to 154).

The weight average molecular weight of the vinyl resin (B) is 4,000 to 40,000, preferably 4,000 to 20,000, more preferably 4, from the viewpoint of storage stability, low temperature fixability and pulverizability. It is 500 to 15,000, more preferably 4,500 to 10,000, and particularly preferably 5,000 to 8,000.

The vinyl resin (B) is preferably a polymer having a monomer (m) having a solubility parameter of 11.5 to 16.5 as a constituent monomer, and the SP of the homopolymer. The SP value of the homopolymer, which is a monomer other than the monomer (m) having a value of 11.5 to 16.5 and the olefin (c) having 2 to 12 carbon atoms, is 8.0 to 11. More preferably, it is a copolymer having a monomer (n) of less than 5 as a constituent monomer. One type of each of the monomer (m) and the monomer (n) may be used, or two or more types may be used in combination.

Examples of the monomer (m) include unsaturated nitrile monomer (m1) and α, β-unsaturated carboxylic acid (m2).

The unsaturated nitrile monomer (m1) includes a monomer having a vinyl group and a nitrile group, and includes those having 3 to 20 carbon atoms. Specifically, (meth) acrylonitrile (SP value of acrylonitrile: SP value: 14.4, SP value of methacrylonitrile: 12.7), cyanostyrene (SP value: 13.1), trimerol propantriacrylate (SP value: 11.9) and the like can be mentioned. Of these, (meth) acrylonitrile is preferred.
In the present invention, "(meth) acrylo" means "acrylic" and / or "methacrylo".
The α, β-unsaturated carboxylic acid (m2) includes those having 3 to 20 carbon atoms, and the unsaturated carboxylic acid and its anhydride [(meth) acrylic acid (SP value of acrylic acid: 14.0, SP value of methacrylic acid: 12.5), maleic acid (SP value: 16.4), fumaric acid (SP value: 16.4) and itaconic acid (SP value: 15.1) and their anhydrides, etc.] , And unsaturated dicarboxylic acid monoesters [monomethyl maleate (SP value: 13.2), monomethyl itaconic acid (SP value: 12.6), etc.] and the like. Of these, preferred are (meth) acrylic acid and unsaturated dicarboxylic acid monoesters, and more preferred are (meth) acrylic acid and monomethyl maleate.
In the present invention, "(meth) acrylic" means "acrylic" and / or "methacryl".

Examples of the monomer (n) include styrene-based monomers [for example, styrene (SP value: 10.6), α-methylstyrene (SP value: 10.1), p-methylstyrene (SP value: 10.1). , M-Methylstyrene (SP value: 10.1), p-methoxystyrene (SP value: 10.5), p-acetoxystyrene (SP value: 11.3), vinyl toluene (SP value: 10.3) , Ethylstyrene (SP value: 10.1), phenylstyrene (SP value: 11.1) and benzylstyrene (SP value: 10.9), etc.], Alkyl of unsaturated carboxylic acid (preferably having 1 to 18 carbon atoms) ) Esters [For example, (meth) acrylic acid alkyl ester {methyl (meth) acrylate (SP value of methyl acrylate: 10.6, SP value of methyl methacrylate: 9.9), ethyl (meth) acrylate (SP of ethyl acrylate) Value: 10.2, SP value of ethyl methacrylate: 10.0), butyl (meth) acrylate (SP value of butyl acrylate: 9.8, SP value of butyl methacrylate: 9.4) and 2-ethylhexyl (meth). Acrylate (SP value of 2-ethylhexyl acrylate: 9.2, SP value of 2-ethylhexyl methacrylate: 9.0) and stearyl (meth) acrylate (SP value of stearyl acrylate: 9.0, SP value of stearyl methacrylate: 8) .9) etc.} etc.], vinyl ester-based monomers [eg, vinyl acetate (SP value: 10.6), etc.] and halogen element-containing vinyl monomers [eg, vinyl chloride (SP value: 11.0), etc.], and Examples thereof include a combination of these.
Of these, styrene-based monomers, unsaturated carboxylic acid alkyl esters and halogen element-containing vinyl monomers are preferable, styrene-based monomers and unsaturated carboxylic acid alkyl esters are more preferable, and styrene and styrene are even more preferable. It is used in combination with (meth) acrylic acid alkyl ester.

The weight ratio of the monomer (m) in the monomer constituting the vinyl resin (B) is based on the total weight of the monomers constituting the vinyl resin (B) from the viewpoint of storage stability and grindability. It is preferably 1% by weight or more, more preferably 1.5 to 50% by weight, still more preferably 2 to 20% by weight, and particularly preferably 3 to 15% by weight.

The vinyl resin (B) may contain an olefin (c) having 2 to 12 carbon atoms in its constituent monomer. The olefin (c) is an olefin having 2 to 12 carbon atoms, and specific examples thereof include ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-dodecene and 1-octadecene.
When the vinyl resin (B) contains the monomer (c) in the constituent monomer, the monomer (c) may constitute the polyolefin resin unit (C) contained in the vinyl resin (B). The polyolefin resin unit (C) is a polymer unit composed of a polyolefin resin. For example, the vinyl resin (B) may have a structure in which a copolymer containing a monomer (m) and a monomer (n) is grafted on a polyolefin resin unit (C).
As the polyolefin resin of the polyolefin resin unit (C), the polymer (C-1) of the olefin (c), the oxide (C-2) of the polymer of the olefin (c), and the modification of the polymer of the olefin (c) The thing (C-3) and the like can be mentioned.
Examples of the olefin (c) polymer (C-1) include polyethylene, polypropylene, ethylene / propylene copolymer, ethylene / 1-butene copolymer, and propylene / 1-hexene copolymer having 2 to 12 carbon atoms. Examples thereof include a polymer composed of the above olefin. The unit of the polymer (C-1) of the olefin (c) can also be referred to as a polyolefin unit or a polyolefin block. For example, the polyethylene unit can also be referred to as a polyethylene block or an ethylene homopolymerization section. The polypropylene unit can also be referred to as a polypropylene block or a propylene homopolymerized portion.
Examples of the oxide (C-2) of the polymer of the olefin (c) include the oxide of the polymer (C-1) of the olefin (c), and examples thereof include oxidized polyethylene and oxidized polypropylene. Be done.
Examples of the modified product (C-3) of the polymer of the olefin (c) include maleic acid derivatives (maleic anhydride, monomethyl maleate, monobutyl maleate, maleic acid) of the polymer (C-1) of the olefin (c). (Dimethyl, etc.) Additives and the like, for example, maleic anhydride and the like.
The vinyl resin (B) containing the polyolefin resin unit (C) may be, for example, a vinyl resin obtained by reacting a monomer (m), a monomer (n), and the above-mentioned polyolefin resin.
For example, when the polymer (C-1) of the olefin (c) is used as the polyolefin resin in the production of the vinyl resin (B), the polymer (C-1) of the olefin (c) is used as the vinyl resin (B). The unit is included.

From the viewpoint of pulverizability of the toner binder, when the vinyl resin (B) has a polyethylene unit and / or a polypropylene unit, the degree of polymerization of the polyethylene unit and the polypropylene unit is preferably less than 70.
In the toner binder of the present invention, the polyethylene unit (C11) having a degree of polymerization of 70 to 210 and the polypropylene unit (C12) having a degree of polymerization of 70 to 210 are optional components, and vinyl is used from the viewpoint of grindability of the toner binder. When the resin (B) contains a polyethylene unit (C11) having a degree of polymerization of 70 to 210 and / or a polypropylene unit (C12) having a degree of polymerization of 70 to 210, the polyethylene unit in the vinyl resin (B). The total weight ratio of (C11) and the polypropylene unit (C12) is 0 to 9% by weight based on the weight of the vinyl resin (B).
The total weight ratio of the polyethylene unit (C11) having a degree of polymerization of 70 to 210 and the polypropylene unit (C12) having a degree of polymerization of 70 to 210 in the vinyl resin (B) is based on the weight of the vinyl resin (B). It is preferably less than 9% by weight, preferably 1% by weight or less, more preferably 0.5% by weight or less, still more preferably 0.3% by weight or less, and particularly preferably 0.1% by weight or less. In one aspect, the vinyl resin (B) preferably does not contain a polyethylene unit (C11) having a degree of polymerization of 70 to 210 and a polypropylene unit (C12) having a degree of polymerization of 70 to 210.
The total weight ratio of the polyethylene unit (C11) and the polypropylene unit (C12) in the vinyl resin (B) is the monomer (m) and the monomer (n) used in the production of the vinyl resin (B). , The total weight ratio of the polyethylene unit (C11) and the polypropylene unit (C12) based on the total weight of the olefin (c) and the polyolefin resin, and is a value obtained by rounding off the first fraction.
When the olefin (c) is used, the total weight ratio of the polyethylene unit (C11) and the polypropylene unit (C12) in the vinyl resin (B) is the total weight of the monomers constituting the vinyl resin (B). It can also be regarded as the total weight ratio of ethylene constituting the polyethylene unit (C11) and propylene constituting the polypropylene unit (C12) as a reference.

In one embodiment, the vinyl resin (B) preferably does not contain polyethylene units and polyethylene units, and is a polyethylene unit, a polypropylene unit, an ethylene / propylene polymer unit, an oxidized polyethylene unit, an oxidized polypropylene unit and a maleinated polypropylene unit. It is more preferable that the polypropylene resin unit (C) of the above is not provided, and the unit of the polymer (C-1) of the olefin (c), the unit of the oxide (C-2) of the polymer of the olefin (c) and the olefin. It is more preferable that the unit of the modified product (C-3) of the polymer of (c) is not contained.

In one aspect, from the viewpoint of low temperature fixability and greasability, the total weight ratio of ethylene and propylene in the monomers constituting the vinyl resin (B) is the total of the monomers constituting the vinyl resin (B). Based on the weight, 20% by weight or less is preferable, 15% by weight or less is more preferable, and 10% by weight or less is further preferable. The weight ratio of the olefin (c) in the monomers constituting the vinyl resin (B) is preferably 20% by weight or less based on the total weight of the monomers constituting the vinyl resin (B). More preferably, it is 10% by weight or less, and further preferably 10% by weight or less. The weight ratio of the olefin (c) is a value obtained by rounding off the first decimal place. In one aspect, the vinyl resin (B) preferably does not contain ethylene and propylene in the constituent monomers, and may not contain the olefin (c). The vinyl resin (B) preferably does not contain the polyolefin resin unit (C).

To exemplify an example of the method for producing the vinyl resin (B), a polyolefin resin is dissolved in toluene or xylene heated to 100 ° C. to 200 ° C., if necessary, and a mixture of vinyl monomers [(m) and (n)]. , If necessary, olefin (c), etc.] and radical reaction initiator (d) are carried out by dropping polymerization, and then the solvent is distilled off to obtain a vinyl resin (B).

The radical reaction initiator (d) is not particularly limited, and examples thereof include an inorganic peroxide (d1), an organic peroxide (d2), and an azo compound (d3). In addition, these radical reaction initiators may be used in combination.

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

The organic peroxide (d2) is not particularly limited, and is, for example, benzoyl peroxide, di-t-butyl peroxide, t-butylcumylperoxide, dicumylperoxide, 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-butylperoxy2-ethylhexanoate, t-butylperoxy3,5,5-trimethyl Hexanoate, t-butylperoxylaurate, t-butylperoxybenzoate, t-butylperoxyisopropyl monocarbonate, t-butylperoxyacetate and the like can be mentioned.

The azo compound or the diazo compound (d3) is not particularly limited, and is, for example, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1. Examples thereof include'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile and azobisisobutyronitrile.

Among these, the organic peroxide (d2) is preferable because it has high initiator efficiency and does not produce toxic by-products such as cyanide.
Further, since the cross-linking reaction proceeds efficiently and the amount used is small, a reaction initiator having a high hydrogen abstraction ability among organic peroxides (d2) is more preferable, and benzoyl peroxide and di-t-butylper are more preferable. Oxide, t-butylcumylperoxide, dicumylperoxide, α, α-bis (t-butylperoxy) diisopropylbenzene, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane and A radical reaction initiator having a high hydrogen abstraction ability such as di-t-hexyl peroxide is particularly preferable.

The amount of the radical reaction initiator (d) used for synthesizing the vinyl resin (B) is preferably 0.1 to 20% by weight based on the total weight of the monomers constituting the vinyl resin (B). It is more preferably 0.15 to 15% by weight, still more preferably 0.2 to 10% by weight, and particularly preferably 0.3 to 8% by weight.

From the viewpoint of storage stability, the polymerization rate of the vinyl resin (B) is preferably 98% or more, more preferably 98.5% or more, still more preferably 99% or more, and particularly preferably 99.5% or more.
The polymerization rate of the vinyl resin (B) can be determined by the following method. As an example, the case where a styrene monomer is used is shown.
Equipment: GC-14A manufactured by Shimadzu Corporation
Column: PEG20M 20% Chromosolve W-supported 2m glass column (manufactured by phenomenex)
Internal standard: Amil alcohol detector: FID detector Column temperature: 100 ° C
Sample concentration: 5% DMF solution A calibration curve of styrene and amyl alcohol is prepared in advance, and the content of styrene monomer in the sample is determined based on this calibration curve. The polymerization rate is calculated from the residual amount of styrene monomer with respect to the charged amount. The sample is dissolved in dimethylformamide (DMF) so as to be 5% by weight, and the supernatant solution allowed to stand for 10 minutes is used as the sample solution.

From the viewpoint of storage stability, the residual amount of the organic solvent used in synthesizing the vinyl resin (B) is preferably 1% by weight or less, more preferably 0.5% by weight, based on the weight of the vinyl resin (B). % Or less, more preferably 0.3% by weight or less, and particularly preferably 0.2% by weight or less.

The toner binder in the present invention can be obtained, for example, by adding the vinyl resin (B) to the polyester resin (A) by melt-kneading.
The number average dispersed particle size of the vinyl resin (B) in the toner binder is 0.02 to 2 μm, preferably 0.03 to 1 from the viewpoint of storage stability, charging characteristics and pulverizability of the toner and the toner binder. It is 0.7 μm, more preferably 0.05 to 1.5 μm, still more preferably 0.07 to 1.3 μm, and particularly preferably 0.1 to 1 μm. The number average dispersed particle size of the vinyl resin (B) can be measured by the method described in Examples.
Setting the number average dispersed particle size of the vinyl resin (B) in the toner binder within the above range means that the weight ratio [(A) / (B)] of the polyester resin (A) and the vinyl resin (B) is 80/20. Set to the range of ~ 99.5 / 0.5, and set the SP value of the polyester resin (A), the SP value of the vinyl resin (B), the acid value of the polyester resin (A), and the acid value of the vinyl resin (B). It can be easily done by adjusting.

The weight ratio [(A) / (B)] of the polyester resin (A) and the vinyl resin (B) in the toner binder is preferably 80/20 to 80/20 from the viewpoint of low temperature fixability, hot offset resistance and pulverization property. It is 99.5 / 0.5, more preferably 85/15 to 99/1, still more preferably 90 / 10-98.5 / 1.5, and particularly preferably 93/7 to 98/2.

The toner binder of the present invention preferably satisfies the following relational expression (1).
Relational expression (1): 0.1 ≤ | SP (a) -SP (b) | ≤ 1.4
[In the relational expression (1), SP (a) is a solubility parameter of the polyester resin (A), and SP (b) is a solubility parameter of the vinyl resin (B). ]
The absolute value of the difference between the solubility parameter {SP (a)} of the polyester resin (A) and the solubility parameter {SP (b)} of the vinyl resin (B) (| SP (a) -SP (b) |) is From the viewpoint of fixability, storage stability and pulverizability, it is preferably 0.1 to 1.4, more preferably 0.1 to 1.3, and further preferably 0.2 to 1.1. , Particularly preferably 0.2 to 1.0. By satisfying the relational expression (1), the compatibility between the polyester resin (A) and the vinyl resin (B) is improved, and a sufficient fixing region is secured. In order to satisfy the relational expression (1), the SP values of the polyester resin (A) and the vinyl resin (B) may be brought close to each other, and in particular, the monomers (m) and (n) used for the vinyl resin (B). It is necessary to consider the weight ratio of. Specifically, a monomer (m) having a higher SP value than the polyester resin (A) (for example, acrylonitrile (SP value: 14.4) and acrylic acid (SP value: 14.0)) and a polyester resin (for example, Weight of monomer (n) having a lower SP value than A) (for example, styrene (SP value: 10.6), butyl acrylate (SP value: 9.8) and ethyl acrylate (SP value: 10.2)) Consider the ratio.

The glass transition point (Tg) of the vinyl resin (B) is preferably 35 ° C. to 75 ° C., more preferably 40 ° C. to 72 ° C., and further preferably 45 ° C. from the viewpoint of fixability and storage stability. It is about 70 ° C., particularly preferably 50 ° C. to 68 ° C.

The acid value of the vinyl resin (B) is preferably less than 8 mgKOH / g, more preferably less than 3 mgKOH / g, and even more preferably less than 1 mgKOH / g from the viewpoint of storage stability and pulverizability.

The softening point of the vinyl resin (B) is preferably 70 to 130 ° C., more preferably 75 to 125 ° C., and even more preferably 80 to 120 ° C. from the viewpoint of fixability, storage stability and pulverizability. Yes, especially preferably 85-115 ° C.
<Measurement method of softening point [Tm]>
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 [Tm].

The glass transition point of the toner binder is preferably 40 to 90 ° C., more preferably 45 to 85 ° C., still more preferably 50 to 70 ° C. from the viewpoint of heat resistance storage property and low temperature fixability.

The THF insoluble content of the toner binder may be 50% by weight or less, preferably 1 to 50% by weight, and more preferably 2 to 40% by weight, from the viewpoint of hot offset resistance and pulverization property. It is more preferably 3 to 30% by weight, and particularly preferably 4 to 20% by weight.

Further, the toner binder may contain a binder resin other than the polyester resin (A) and the vinyl resin (B). Examples of other binder resins include known binder resins such as styrene / (meth) acrylic acid ester copolymers, styrene / butadiene copolymers, styrene / (meth) acrylonitrile copolymers, epoxy resins and polyurethanes.

The content of the other binder resin in the toner binder is preferably 20% by weight or less, more preferably 10% by weight or less, based on the weight of the toner binder.

Further, a crystalline resin (E) which is a fixing aid may be contained in order to improve the low temperature fixability. The chemical structure of the crystalline resin (E) is not particularly limited as long as it is a crystalline resin compatible with the polyester resin (A).
For example, known resins such as crystalline polyester resin, crystalline polyurethane resin, crystalline polyurea resin, crystalline polyamide resin and crystalline polyvinyl resin (for example, crystalline resin described in International Publication No. 2015-170705) can be mentioned. Be done. Of these, crystalline polyester resins and crystalline polyvinyl resins are preferable from the viewpoint of compatibility. From the viewpoint of crystallinity, the crystalline polyester resin preferably has a linear aliphatic diol content of 80 mol% or more as a diol component, and the crystalline polyvinyl resin has a long-chain aliphatic vinyl content. It is preferably 50% by weight or more.
The content of the fixing aid in the toner binder is preferably 20% by weight or less, more preferably 10% by weight or less, based on the weight of the toner binder, from the viewpoint of low temperature fixability, storage stability and charge stability. is there.

"Crystallinity" in the present invention means that the DSC curve has a peak top temperature of an endothermic peak in the differential scanning calorimetry (also referred to as DSC measurement) described below. That is, it has a property of being rapidly softened by heat, and a resin having this property is referred to as a crystalline resin.
A method for measuring the peak top temperature of the endothermic peak of the crystalline resin is described.
Measurement is performed using a differential scanning calorimeter {for example, DSC Q20 manufactured by TA Instruments Co., Ltd.}. The crystalline resin was first heated from 20 ° C. to 10 ° C./min to 150 ° C., then cooled to 0 ° C. from 150 ° C. to 10 ° C./min, and then from 0 ° C. to 10 ° C. The temperature indicating the top of the heat absorption peak in the second temperature rise process when the temperature is raised to 150 ° C. under the condition of ° C./min is defined as the peak top temperature of the heat absorption peak of the crystalline resin.
Further, "amorphous" in the present invention means that the peak top temperature of the heat absorption peak does not exist when the transition temperature of the sample is measured using a differential scanning calorimeter.

The weight average molecular weight of the crystalline resin (E) is preferably 8,000 to 50,000, more preferably 10,000 to 40,000, and even more preferably, from the viewpoint of low temperature fixability and storage stability. Is 12,000 to 38,000.

The acid value of the crystalline resin (E) is preferably 5 mgKOH / g or less, more preferably 3 mgKOH / g or less, and further preferably 1 mgKOH / g or less from the viewpoint of storage stability.

The peak top temperature of the endothermic peak of the crystalline resin (E) is preferably 60 to 80 ° C., more preferably 63 to 77 ° C., and further preferably 65 ° C. from the viewpoint of low temperature fixability and storage stability. It is ~ 75 ° C.

The toner binder of the present invention is used as a toner by mixing a colorant and, if necessary, various additives such as a mold release agent, a charge control agent, and a fluidizing agent.

The toner of the present invention contains the toner binder and colorant of the present invention.
The content of the toner binder of the present invention in the toner is preferably 60 to 98% by weight when a dye or pigment is used as a colorant, and preferably 25 to 80% by weight when a magnetic powder is used. Is.
As the colorant, all dyes, pigments and the like used as colorants for toner can be used. Specifically, 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, Rhodamine FB, Rhodamine B Lake, Methyl Violet B Lake, Phthalocyanine Blue, Pigment Blue, Brilliant Green, Phthalocyanine Green, Oil Yellow GG, Kayaset YG, Orazole Brown B, Oil Pink OP, etc. Alternatively, two or more types can be mixed and used. Further, if necessary, a magnetic powder (a powder of a ferromagnetic metal such as iron, cobalt or nickel or a compound such as magnetite, hematite or ferrite) can be contained also as a colorant.
The content of the colorant is preferably 1 to 40 parts by weight, more preferably 2 to 15 parts by weight, based on 100 parts by weight of the toner binder of the present invention. When magnetic powder is used, the content of the magnetic powder is preferably 20 to 150 parts by weight, more preferably 30 to 120 parts by weight, based on 100 parts by weight of the toner binder.

The release agent preferably has a softening point of 50 to 170 ° C. by a flow tester, and is preferably a polyolefin wax, a natural wax, an aliphatic alcohol having 30 to 50 carbon atoms, a fatty acid having 30 to 50 carbon atoms, and two or more of these. Examples include mixtures. 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.

As the polyolefin wax, a (co) copolymer of an olefin (for example, ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-dodecene, 1-octadecene and a mixture of two or more thereof) [(co) polymerization Obtained and including heat-reduced polyolefins], oxides of olefin (co) copolymers with oxygen and / or ozone, maleic anhydrides of olefin (co) polymers [eg maleic anhydride and derivatives thereof (anhydrous). Maleic acid, monomethyl maleate, monobutyl maleate, dimethyl maleate, etc.) modified products], olefins and unsaturated carboxylic acids [(meth) acrylic acid, itaconic acid, maleic anhydride, etc.] and / or unsaturated carboxylic acid alkyl esters. Examples thereof include copolymers with [(meth) alkyl acrylate (alkyl carbon number 1-18) ester and maleic anhydride alkyl (alkyl carbon number 1-18) ester, etc.], and sazole wax.

Examples of natural waxes include carnauba wax, montan wax, paraffin wax and rice wax. Examples of the fatty alcohol having 30 to 50 carbon atoms include triacontanol. Examples of fatty acids having 30 to 50 carbon atoms 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, and copper phthalocyanine dyes. , Salicylate metal salt, boron complex of benzylic acid, sulfonic acid group-containing polymer, fluorine-containing polymer, halogen-substituted aromatic ring-containing polymer and the like. The content of the charge control agent may be 0 to 20% by weight, preferably 0.1 to 10% by weight, and more preferably 0.5 to 7.5% by weight, based on the toner weight.

Examples of the fluidizing agent include colloidal silica, alumina powder, titanium oxide powder, calcium carbonate powder and the like. The content of the fluidizing agent may be 0 to 10% by weight, preferably 0 to 5% by weight, and more preferably 0.1 to 4% by weight, based on the weight of the toner.

The total amount of the additives may be 3 to 70% by weight, preferably 4 to 58% by weight, and more preferably 5 to 50% by weight, based on the toner weight. When the composition ratio of the toner is in the above range, it is possible to easily obtain a toner having good charging characteristics.

The toner of the present invention may be obtained by any of known methods such as a kneading and pulverizing method, an emulsion phase inversion method, and a polymerization method.
For example, when the toner is obtained by the kneading and pulverizing method, the components constituting the toner excluding the fluidizing agent are dry-blended with a Henschel mixer, a Nauter mixer, a Banbury mixer or the like, and then an extruder, a continuous sneader, a three-roll or the like, etc. By melt-kneading with a continuous mixer, coarsely pulverizing with a mill, etc., and finally atomizing with a jet mill crusher, etc., and further adjusting the particle size distribution with a classifier such as an elbow jet. It can be produced by making fine particles having a volume average particle size (D50) of 4 to 12 μm and then mixing the fluidizing agent with a mill or the like.
The volume average particle size (D50) is measured using a Coulter counter [for example, trade name: Multisizer III (manufactured by Beckman Coulter, Inc.)].

The toner of the present invention is electrically latent by being mixed with carrier particles such as iron powder, glass beads, nickel powder, ferrite, magnetite, and ferrite whose surface is coated with a resin (acrylic resin, silicone resin, etc.), if necessary. Used as an image developer. The weight ratio of toner to carrier particles is usually 1/99 to 100/0. 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 of the present invention using the toner binder of the present invention can be used for electrophotographic, electrostatic recording, electrostatic printing and the like. More specifically, it is fixed to a support (paper, polyester film, etc.) by a copying machine, a printer, or the like to be 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.

Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
In the following, Examples 9, 10, 13 to 16 mean Reference Examples 1 to 6.

The weight average molecular weight was measured by gel permeation chromatography (GPC) under the following conditions. The sample solution was prepared by dissolving the sample (resin) in THF so as to be 0.25% by weight, and filtering the insoluble portion with a glass filter.
Equipment: HLC-8120 manufactured by Tosoh Corporation
Column: 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: Tosoh standard polystyrene (TSK standard POLYSTYRENE) 12 points (molecular weight 500 1050 280 5970 9100 18100 37900 96400 1900000 355000 1090000 2890000)

The glass transition point was measured by a method (DSC method) specified in ASTM D3418-82 using a differential scanning calorimeter (DSC Q20 manufactured by TA Instruments Co., Ltd.).
<Measurement conditions for glass transition temperature>
(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 (5) Hold at -35 ° C for 10 minutes (6) ) The temperature was raised to 150 ° C. at 20 ° C./min. (7) The differential scanning calorimetry measured in the process of (6) was analyzed to determine the glass transition temperature.

The acid value and hydroxyl value were measured by the method specified in JIS K0070.
The SP value was calculated by the method described in the literature by Robert F Fedors et al. (Polymer Engineering and Science, February, 1974, Vol. 14, No. 2 P. 147 to 154).

The softening point was measured by the following method.
Using a high-grade flow tester {CFT-500D manufactured by Shimadzu Corporation}, while heating 1 g of the measurement sample at a temperature rise rate of 6 ° C./min, a load of 1.96 MPa was applied by a plunger to obtain a diameter. Extrude from a nozzle of 1 mm and 1 mm in length, draw a graph of "plunger drop (flow value)" and "temperature", and draw a temperature corresponding to 1/2 of the maximum value of the plunger drop from the graph. It was read and this value (the temperature when half of the measurement sample flowed out) was taken as the softening point.

The THF insoluble content was determined by the following method.
50 mL of THF was added to 0.5 g of the sample, and the mixture was stirred and refluxed for 3 hours. After cooling, the insoluble matter was filtered off with a glass filter, and the resin component on the glass filter was dried under reduced pressure at 80 ° C. for 3 hours. The insoluble content was calculated from the weight ratio of the dry resin content on the glass filter to the weight of the sample.

Production Example 1 [Production of Linear Polyester Resin (A1-1)]
In the reaction vessel, 320 parts by weight of an ethylene oxide 2 mol adduct of bisphenol A, 421 parts by weight of a propylene oxide 2 mol adduct of bisphenol A, 272 parts by weight of terephthalic acid, and titanium diisopropoxybistriethanol aminated as a condensation catalyst. Add 5 parts by weight, react at 220 ° C. under reduced pressure of 0.5 to 2.5 kPa, react for 10 hours while distilling off the produced water, and cool to 180 ° C. after the acid value becomes 1 mgKOH / g or less. did. 44 parts by weight of trimellitic anhydride was added and the mixture was reacted for 1 hour. The mixture was cooled to 150 ° C. and a linear polyester resin (A1-1) was obtained using a steel belt cooler.

Production Example 2 [Production of Linear Polyester Resin (A1-2)]
In the reaction vessel, 616 parts by weight of the propylene oxide adduct of bisphenol A, 161 parts by weight of the propylene oxide 3 mol adduct of bisphenol A, 268 parts by weight of terephthalic acid, 1 part by weight of fumaric acid, and titanium diiso as a condensation catalyst. Add 2.5 parts by weight of propoxybistriethanol aminate and react at 220 ° C. under reduced pressure of 0.5 to 2.5 kPa, and react for 10 hours while distilling off the generated water to bring the acid value to 1 mgKOH / g or less. After that, it was cooled to 180 ° C. 10 parts by weight of trimellitic anhydride was added, and the mixture was reacted for 1 hour. The mixture was cooled to 150 ° C. and a linear polyester resin (A1-2) was obtained using a steel belt cooler.

Production Example 3 [Production of non-linear polyester resin (A2-1)]
In the reaction vessel, 167 parts by weight of ethylene oxide 2 mol adduct of bisphenol A, 128 parts by weight of propylene oxide 2 mol adduct of bisphenol A, 473 parts by weight of propylene oxide 3 mol adduct of bisphenol A, 184 parts by weight of terephthalic acid, fumal. Add 1 part by weight of acid and 2.5 parts by weight of titanium diisopropoxybistriethanol amine as a condensation catalyst and react at 220 ° C. under reduced pressure of 0.5 to 2.5 kPa, and distill off the generated water. After reacting for a time and the acid value became 2 mgKOH / g or less, 53 parts by weight of trimellitic anhydride was added and the reaction was carried out for 1 hour. The reaction was further carried out at 220 ° C. under a reduced pressure of 0.5 to 2.5 kPa, and after the acid value became 3 mgKOH / g or less, 52 parts by weight of trimellitic anhydride was added and the reaction was carried out for 1 hour. Further, the reaction was carried out under a reduced pressure of 0.5 to 2.5 kPa, and when the softening point (Tm) reached 135 ° C., a non-linear polyester resin (A2-1) was obtained using a steel belt cooler.

Production Example 4 [Production of non-linear polyester resin (A2-2)]
In the reaction vessel, 193 parts by weight of bisphenol A propylene oxide 2 mol adduct, 539 parts by weight of bisphenol A propylene oxide 3 mol adduct, 173 parts by weight of terephthalic acid, 67 parts by weight of adipic acid, 6 parts by weight of trimellitic anhydride. , And 2.5 parts by weight of titanium diisopropoxybistriethanolaminate as a condensation catalyst, reacted at 220 ° C. under reduced pressure of 0.5 to 2.5 kPa, and reacted for 10 hours while distilling off the produced water. After the acid value became 1 mgKOH / g or less, the mixture was cooled to 180 ° C. 81 parts by weight of trimellitic anhydride was added and reacted for 1 hour. The temperature was raised to 200 ° C., the reaction was further advanced under a reduced pressure of 0.5 to 2.5 kPa, and when the softening point (Tm) reached 130 ° C., a non-linear polyester resin (A2-2) was applied using a steel belt cooler. Obtained.

Production Example 5 [Production of non-linear polyester resin (A2-3)]
In the reaction vessel, 581 parts by weight of 1,2-propylene glycol, 50 parts by weight of propylene oxide 2 mol addition of bisphenol A, 625 parts by weight of terephthalic acid, 8 parts by weight of adipic acid, 49 parts by weight of benzoic acid, trimellitic anhydride. 58 parts by weight and 2.5 parts by weight of titanium diisopropoxybistriethanol amineate were added as a condensation catalyst and reacted at 220 ° C. under pressure, and the reaction was carried out for 20 hours while distilling off the produced water. Then, the pressure was gradually released and returned to normal pressure, and the reaction was further proceeded under a reduced pressure of 0.5 to 2.5 kPa. After the acid value became 1 mgKOH / g or less, the mixture was cooled to 180 ° C. 17 parts by weight of trimellitic anhydride was added, and the mixture was reacted for 1 hour. It was cooled to 150 ° C. and a non-linear polyester resin (A2-3) was obtained using a steel belt cooler. The amount of 1,2-propylene glycol removed was 234 parts by weight.

Production Example 6 [Production of non-linear polyester resin (A2-4)]
In the reaction vessel, 649 parts by weight of 1,2-propylene glycol, 1 part by weight of ethylene oxide 2 mol addition of bisphenol A, 1 part by weight of propylene oxide 2 mol addition of bisphenol A, 673 parts by weight of terephthalic acid, 32 parts by weight of adipic acid. 40 parts by weight of benzoic acid, 52 parts by weight of trimellitic anhydride, and 2.5 parts by weight of titanium diisopropoxybistriethanol amine as a condensation catalyst were added and reacted at 220 ° C. under pressure to retain the water produced. It was allowed to react for 10 hours while leaving. Next, the pressure is gradually released and returned to normal pressure, and the reaction is further proceeded under a reduced pressure of 0.5 to 2.5 kPa. When the acid value becomes 2 mgKOH / g or less, a non-linear polyester resin is used using a steel belt cooler. (A2-4) was obtained. The amount of propylene glycol removed was 275 parts by weight.

Table 1 shows the compositions and physical properties of the linear polyester resin (A1) and the non-linear polyester resin (A2) obtained in Production Examples 1 to 6.

Production Example 7 [Production of vinyl resin (B-1)]
480 parts by weight of xylene was placed in the reaction vessel, and the temperature was raised to 170 ° C. In another container, 850 parts by weight of styrene (SP value: 10.6), 50 parts by weight of butyl acrylate (SP value: 9.8), 100 parts by weight of acrylonitrile (SP value: 14.4), 106 parts by weight of xylene, di 40 parts by weight of −t-butylperoxide was added and added dropwise to the reaction vessel over 3 hours. The dropping line was washed with 14 parts by weight of xylene and aged at 170 ° C. for 30 minutes. After confirming that the polymerization rate was 99% or more, the pressure was reduced and xylene was topped and taken out from the reaction vessel to obtain a vinyl resin (B-1).

Production Example 8 [Production of vinyl resin (B-2)]
480 parts by weight of xylene was placed in the reaction vessel, and the temperature was raised to 170 ° C. In another container, 841 parts by weight of styrene (SP value: 10.6), 120 parts by weight of butyl acrylate (SP value: 9.8), 39 parts by weight of acrylonitrile (SP value: 14.4), 106 parts by weight of xylene, di 40 parts by weight of −t-butylperoxide was added and added dropwise to the reaction vessel over 3 hours. The dropping line was washed with 14 parts by weight of xylene and aged at 170 ° C. for 30 minutes. After confirming that the polymerization rate was 99% or more, the pressure was reduced and xylene was topped and taken out from the reaction vessel to obtain a vinyl resin (B-2).

Production Example 9 [Production of vinyl resin (B-3)]
500 parts by weight of xylene was placed in the reaction vessel, and the temperature was raised to 190 ° C. In another container, 961 parts by weight of styrene (SP value: 10.6), 20 parts by weight of butyl acrylate (SP value: 9.8), 19 parts by weight of acrylonitrile (SP value: 14.4), 190 parts by weight of xylene, di 30 parts by weight of −t-butylperoxide was added and added dropwise to the reaction vessel over 3 hours. The dropping line was washed with 14 parts by weight of xylene and aged at 170 ° C. for 30 minutes. After confirming that the polymerization rate was 99% or more, the pressure was reduced and xylene was topped and taken out from the reaction vessel to obtain a vinyl resin (B-3).

Production Example 10 [Production of vinyl resin (B-4)]
500 parts by weight of xylene was placed in the reaction vessel, and the temperature was raised to 190 ° C. 1000 parts by weight of styrene (SP value: 10.6), 180 parts by weight of xylene, and 20 parts by weight of di-t-butyl peroxide were placed in another container and added dropwise to the reaction vessel over 3 hours. The dropping line was washed with 14 parts by weight of xylene and aged at 190 ° C. for 30 minutes. After confirming that the polymerization rate was 99% or more, the pressure was reduced and xylene was topped and taken out from the reaction vessel to obtain a vinyl resin (B-4).

Production Example 11 [Production of vinyl resin (B-5)]
480 parts by weight of xylene was placed in the reaction vessel, and the temperature was raised to 170 ° C. In another container, 875 parts by weight of styrene (SP value: 10.6), 25 parts by weight of butyl acrylate (SP value: 9.8), 95 parts by weight of acrylonitrile (SP value: 14.4), trimethylolpropane triacrylate ( SP value: 11.9) 5 parts by weight and 14 parts by weight of di-t-butyl peroxide were added and added dropwise to the reaction vessel over 3 hours. The dropping line was washed with 14 parts by weight of xylene and aged at 170 ° C. for 30 minutes. After confirming that the polymerization rate was 99% or more, the pressure was reduced and xylene was topped and taken out from the reaction vessel to obtain a vinyl resin (B-5).

Production Example 12 [Production of vinyl resin (B-6)]
480 parts by weight of xylene was placed in the reaction vessel, and the temperature was raised to 170 ° C. In another container, 600 parts by weight of styrene (SP value: 10.6), 100 parts by weight of vinyl chloride (SP value: 11.0), 298 parts by weight of acrylonitrile (SP value: 14.4), fumaric acid (SP value:: 16.4) 2 parts and 10 parts by weight of di-t-butyl peroxide were added and added dropwise to the reaction vessel over 3 hours. The dropping line was washed with 14 parts by weight of xylene and aged at 170 ° C. for 30 minutes. After confirming that the polymerization rate was 99% or more, the pressure was reduced and xylene was topped and taken out from the reaction vessel to obtain a vinyl resin (B-6).

Production Example 13 [Production of vinyl resin (B-7)]
90 parts by weight of low molecular weight polyethylene [Sunwax 151-P, manufactured by Sanyo Chemical Industries, Ltd.] and 480 parts by weight of xylene were placed in the reaction vessel, and the temperature was raised to 170 ° C. In another container, 730 parts by weight of styrene (SP value: 10.6), 100 parts by weight of butyl acrylate (SP value: 9.8), 80 parts by weight of acrylonitrile (SP value: 14.4), di-t-butylper. 4 parts by weight of oxide was added and added dropwise to the reaction vessel over 3 hours. The dropping line was washed with 14 parts by weight of xylene and aged at 170 ° C. for 30 minutes. After confirming that the polymerization rate was 99% or more, the pressure was reduced and xylene was topped and taken out from the reaction vessel to obtain a vinyl resin (B-7). Sunwax 151-P is a polyethylene having a degree of polymerization of 71.

Production Example 14 [Production of vinyl resin (B-8)]
480 parts by weight of xylene was placed in the reaction vessel, and the temperature was raised to 170 ° C. In another container, 740 parts by weight of styrene (SP value: 10.6), 210 parts by weight of methyl methacrylate (SP value: 9.9), 40 parts by weight of acrylonitrile (SP value: 14.4), acrylic acid (SP value:: 14.0) 10 parts by weight and 7 parts by weight of di-t-butylperoxide were added and added dropwise to the reaction vessel over 3 hours. The dropping line was washed with 14 parts by weight of xylene and aged at 170 ° C. for 30 minutes. After confirming that the polymerization rate was 99% or more, the pressure was reduced and xylene was topped and taken out from the reaction vessel to obtain a vinyl resin (B-8).

Production Example 15 [Production of vinyl resin (B-9)]
480 parts by weight of xylene was placed in the reaction vessel, and the temperature was raised to 170 ° C. In another container, 450 parts by weight of styrene (SP value: 10.6), 100 parts by weight of methyl methacrylate (SP value: 9.9), 300 parts by weight of 2-ethylhexyl acrylate (SP value: 9.2), acrylonitrile (SP). Value: 14.4) 145 parts by weight, 5 parts by weight of fumaric acid (SP value: 16.4) and 6 parts by weight of di-t-butyl peroxide were added and added dropwise to the reaction vessel over 3 hours. The dropping line was washed with 14 parts by weight of xylene and aged at 170 ° C. for 30 minutes. After confirming that the polymerization rate was 99% or more, the pressure was reduced and xylene was topped and taken out from the reaction vessel to obtain a vinyl resin (B-9).

Comparative Production Example 1 [Production of Vinyl Resin (B'-1)]
100 parts by weight of low molecular weight polyethylene [Sunwax 151-P, manufactured by Sanyo Chemical Industries, Ltd.] and 480 parts by weight of xylene are placed in a reaction vessel, and the temperature is raised to 170 ° C. In another container, 765 parts by weight of styrene (SP value: 10.6), 45 parts by weight of butyl acrylate (SP value: 9.8), 90 parts by weight of acrylonitrile (SP value: 14.4), 106 parts by weight of xylene, di 37 parts by weight of -t-butylperoxide was added and added dropwise to the reaction vessel over 3 hours. The dropping line was washed with 14 parts by weight of xylene and aged at 170 ° C. for 1 hour. After confirming that the polymerization rate was 99% or more, the pressure was reduced and xylene was topped and taken out from the reaction vessel to obtain a vinyl resin (B'-1).

Comparative Production Example 2 [Production of Vinyl Resin (B'-2)]
500 parts by weight of xylene was placed in the reaction vessel, and the temperature was raised to 190 ° C. In another container, 850 parts by weight of styrene (SP value: 10.6), 50 parts by weight of butyl acrylate (SP value: 9.8), 100 parts by weight of acrylonitrile (SP value: 14.4), 106 parts by weight of xylene, di 38 parts by weight of −t-butylperoxide was added and added dropwise to the reaction vessel over 3 hours. The dropping line was washed with 14 parts by weight of xylene and aged at 190 ° C. for 30 minutes. After confirming that the polymerization rate was 99% or more, the pressure was reduced and xylene was topped and taken out from the reaction vessel to obtain a vinyl resin (B'-2).

Comparative Production Example 3 [Production of Vinyl Resin (B'-3)]
200 parts by weight of xylene was placed in the reaction vessel, and the temperature was raised to 150 ° C. In another container, 850 parts by weight of styrene (SP value: 10.6), 50 parts by weight of butyl acrylate (SP value: 9.8), 100 parts by weight of acrylonitrile (SP value: 14.4), 106 parts by weight of xylene, di 5 parts by weight of −t-butylperoxide was added and added dropwise to the reaction vessel over 3 hours. The dropping line was washed with 14 parts by weight of xylene and aged at 150 ° C. for 60 minutes. After raising the temperature to 170 ° C., the mixture was aged for 60 minutes, and it was confirmed that the polymerization rate was 99% or more. The pressure was reduced, xylene was topped, and the mixture was taken out from the reaction vessel to obtain a vinyl resin (B'-3). ..

Comparative Production Example 4 [Production of Vinyl Resin (B'-4)]
480 parts by weight of xylene was placed in the reaction vessel, and the temperature was raised to 170 ° C. Put 940 parts by weight of styrene (SP value: 10.6), 60 parts by weight of stearyl methacrylate (SP value: 8.9), and 35 parts by weight of di-t-butyl peroxide in another container, and take 3 hours to put the reaction tank. Dropped into. The dropping line was washed with 14 parts by weight of xylene and aged at 170 ° C. for 30 minutes. After confirming that the polymerization rate was 99% or more, the pressure was reduced and xylene was topped and taken out from the reaction vessel to obtain a vinyl resin (B'-4).

The compositions and physical properties of the vinyl resin (B) and the vinyl resin (B') obtained in Production Examples 7 to 15 and Comparative Production Examples 1 to 4 are shown in Tables 2 and 3.

Henshell mixer [Nippon Coke Industries] so that the weight ratio {(A1-1) / (A2-1)} of the obtained linear polyester resin (A1-1) and non-linear polyester resin (A2-1) is 50/50. FM10B manufactured by Co., Ltd.] was homogenized to obtain a polyester resin (A-1). The acid value of the polyester resin (A-1) was 23 mgKOH / g.
Similarly, the polyester resin (A-2) is replaced with the non-linear polyester resin (A2-3) so that the linear polyester resin (A1-2) / non-linear polyester resin (A2-2) (weight ratio) is 70/30. ) / (A2-4) (weight ratio) was 50/50 to obtain a polyester resin (A-3). The acid value of the polyester resin (A-2) was 10 mgKOH / g, and the acid value of the polyester resin (A-3) was 6 mgKOH / g.

Production Example 16 [Production of crystalline resin (E-1)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 714 parts by weight of dodecane diic acid and 373 parts by weight of 1,6-hexanediol, 22 parts by weight of behenyl alcohol and 0.5 parts by weight of tetrabutoxytitanate as a condensation catalyst. Was put in and reacted at 170 ° C. under a nitrogen stream for 8 hours while distilling off the generated water. Then, while gradually raising the temperature to 220 ° C., the reaction was carried out under a nitrogen stream for 4 hours while distilling off the generated water, and further reacted under a reduced pressure of 0.5 to 2.5 kPa, and the acid value was 1 mgKOH / g. It was taken out when it became the following. The removed resin was cooled to room temperature and then pulverized into particles to obtain a crystalline resin (E-1). The weight average molecular weight of the crystalline resin (E-1) was 37,000, the acid value was 1, and the peak top temperature of the endothermic peak was 74 ° C.
The peak top temperature of the endothermic peaks of the crystalline polyester resins (E-1) and (E-2) was measured using DSC Q20 manufactured by TA Instruments Co., Ltd. As the temperature raising / cooling conditions, the temperature is raised to 180 ° C. under the condition of 10 ° C./min (first temperature raising process), then left at 180 ° C. for 10 minutes, and then 0 ° C. under the condition of 10 ° C./min. (1st cooling process). Then, after leaving it at 0 ° C. for 10 minutes, the temperature was raised to 180 ° C. under the condition of 10 ° C./min (second temperature raising process). The temperature indicating the top of the endothermic peak in the second temperature raising process was defined as the peak top temperature of the endothermic peak.

Production Example 17 [Production of crystalline resin (E-2)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 677 parts by weight of sebacic acid, 422 parts by weight of 1,6-hexanediol, 22 parts by weight of behenic acid and 0.5 parts by weight of tetrabutoxytitanate as a condensation catalyst. Was put in and reacted at 170 ° C. under a nitrogen stream for 8 hours while distilling off the generated water. Then, while gradually raising the temperature to 220 ° C., the reaction was carried out under a nitrogen stream for 4 hours while distilling off the generated water, and further reacted under a reduced pressure of 0.5 to 2.5 kPa, and the acid value was 1 mgKOH / g. It was taken out when it became the following. The removed resin was cooled to room temperature and then pulverized into particles to obtain a crystalline resin (E-2). The weight average molecular weight of the crystalline resin (E-2) was 19,000, the acid value was 1, and the peak top temperature of the endothermic peak was 68 ° C.

<Examples 1 to 16 and Comparative Examples 1 to 5>
Using the polyester resin (A), vinyl resin (B), crystalline resin (E) and vinyl resin (B') obtained in Production Examples and Comparative Production Examples, the compounding ratios (parts by weight) in Tables 4 and 5 are used. ), The toner raw material containing the toner binder and the additive is converted into toner by the following method to obtain toners (T-1) to (T-16) and (T'-1) to (T'-5). It was.
Carbon black [MA-100 manufactured by Mitsubishi Chemical Co., Ltd.] as a colorant, carnauba wax [purified carnauba wax manufactured by Nippon Wax Co., Ltd.] as a release agent, and Eisenspiron black [Hodoya] as a charge control agent. T-77 manufactured by Kagaku Kogyo Co., Ltd.] and colloidal silica [Aerosil R972 manufactured by Nippon Aerosil Co., Ltd.] were used as the fluidizing agent.
First, a colorant, a mold release agent, and a charge control agent are added to the polyester resin (A), vinyl resin (B), and vinyl resin (B') shown in Tables 4 and 5, and a Henshell mixer [Nippon Coke Industries Co., Ltd. After pre-mixing using FM10B manufactured by FM10B], the mixture was kneaded with a twin-screw kneader [PCM-30 manufactured by Ikegai Co., Ltd.]. Then, after pulverizing with an airflow type pulverizer [KJ-25 manufactured by Kurimoto, Ltd.], it is classified with an elbow jet classifier [EJ-L-3 (LABO) type manufactured by Matsubo Co., Ltd.]. Toner particles having a volume average particle diameter D50 of 6.5 μm were obtained. Next, the fluidizing agent was mixed with the toner particles by a sample mill to obtain a toner containing a toner binder, a colorant, a mold release agent, a charge control agent, and a fluidizing agent. The number average dispersed particle size of the vinyl resin (B) in the toner binder was measured by the following measuring method using the obtained toner.

The number average dispersed particle size of the vinyl resin (B) in the toner binder was determined by the following method.
The toners obtained in Examples and Comparative Examples were ultra-thin sectioned to about 100 μm, and the vinyl resin (B) dispersed in the polyester resin (A) was subjected to a vacuum electron dyeing apparatus with ruthenium tetroxide (VSC1R1H manufactured by Filgen Co., Ltd.). After dyeing at a concentration of 1 for 3 minutes, the dispersed state of the vinyl resin (B) displayed in gray or black by ruthenium tetroxide dyeing was measured by a transmission electron microscope (TEM) at a magnification of 10,000 times. The cross section was observed, and the particle size of the vinyl resin (B) in the toner (toner binder) was calculated by image analysis using an image processing device (digital microscope VHX-700F manufactured by Keyence). The measurement is performed at a distance between two points, and when the vinyl resin (B) is perfectly circular, the diameter is measured, and when the vinyl resin (B) is elliptical, the major axis is measured, and the results of randomly measuring 30 points are calculated by averaging the numbers. The number average dispersed particle diameter of the vinyl resin (B) in the toner binder was calculated.

The volume average particle size (D50) (μm), number average particle size (μm), and particle size distribution (volume average particle size / number average particle size) of the toner particles (T) are determined by the Coulter counter [trade name: Multisizer III (trade name: Multisizer III). Beckman Coulter Co., Ltd.]] was used for measurement.
First, 0.1 to 5 mL of a surfactant (alkylbenzene sulfonate) was added as a dispersant to 100 to 150 mL of ISOTON-II (manufactured by Beckman Coulter) which is an electrolytic aqueous solution. Further, 2 to 20 mg of the measurement sample is added, and the electrolytic solution in which the sample is suspended is dispersed for about 1 to 3 minutes with an ultrasonic disperser, and the volume of the toner particles is dispersed by the measuring device using a 50 μm aperture as an aperture. , The number was measured, and the volume distribution and the number distribution were calculated. From the obtained distribution, the volume average particle size (D50) (μm), the number average particle size (μm), and the particle size distribution (volume average particle size / number average particle size) of the toner particles were determined.

[Evaluation method]
The measurement method, evaluation method and judgment criteria of the low temperature fixability, hot offset resistance, storage stability, charge stability and pulverization property of the obtained toner will be described below.

<Low temperature fixability>
The toner was uniformly placed on the paper surface so as to be 0.6 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. Other methods may be used as long as the powder can be uniformly placed at the above weight density.
Measure the low temperature fixing temperature, which is the temperature at which cold offset occurs when this paper is passed through a pressure roller under the conditions of fixing speed (heating roller peripheral speed) 213 mm / sec and fixing pressure (pressurized roller pressure) 10 kg / cm ^2. did.
The lower the low temperature fixing temperature, the better the low temperature fixing property. The low temperature fixing temperature of the toner was defined as low temperature fixing property (° C.).

<Hot offset resistance (hot offset generation temperature)>
The fixing was evaluated in the same manner as the low temperature fixability, and the presence or absence of hot offset in the fixed image was visually evaluated.
The temperature at which the hot offset occurred after passing through the pressure roller was defined as the hot offset resistance (° C.).

<Storage stability>
The toner was allowed to stand in an atmosphere of 50 ° C. for 24 hours, the degree of blocking was visually judged, and the heat-resistant storage stability was evaluated according to the following criteria.
[Criteria]
◯: No blocking has occurred.
X: Blocking has occurred.

<Charging stability>
(1) 0.5 g of toner and 20 g of ferrite carrier (F-150 manufactured by Powdertech 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 or more.
(2) Friction stir welding was performed at 50 rpm for 10 minutes and 60 minutes with a tubler shaker mixer, and the amount of charge at each time was measured.
A blow-off charge measuring device [manufactured by Toshiba Chemical Co., Ltd.] was used for the measurement.
"Charge amount of friction time 60 minutes / charge amount of friction time 10 minutes" was calculated and used as an index of charge stability.
[Criteria]
⊚: 0.8 or more ○: 0.7 or more and less than 0.8 Δ: 0.6 or more and less than 0.7 ×: less than 0.6

<Crushability>
The coarsely crushed product (8.6 mesh pass to 30 mesh-on particle size) obtained by kneading and cooling the toner raw material with a twin-screw kneader is applied to the supersonic jet crusher Lab Jet [Kurimoto, Ltd., KJ-25]. ], It was finely pulverized under the following conditions.
Crushing pressure: 0.64 MPa
Grinding time: 15 minutes Separater frequency: 150Hz
Adjuster ring: 15mm
Louver size: Medium The volume average particle size (μm) was measured with a Coulter counter- [trade name: Multisizer III (manufactured by Beckman Coulter Co., Ltd.)] without classifying the obtained finely pulverized product. The pulverizability was evaluated according to the following criteria.
[Criteria]
◯: Volume average particle size less than 8 μm Δ: Volume average particle size 8 μm or more and less than 10 μm ×: Volume average particle size 10 μm or more

The above evaluation results are shown in Tables 4 and 5. The glass transition temperature and THF insoluble content of (A) in the table are the glass transition temperature and THF insoluble content of the polyester resin (A). The average dispersed particle size of (B) indicates the number average dispersed particle size of the vinyl resin (B) in the toner binder.

As is clear from the evaluation results in Tables 4 and 5, all the performance evaluations of the toners of Examples 1 to 16 of the present invention were excellent. On the other hand, the total weight ratio of the polyethylene unit (C11) having a degree of polymerization of 70 to 210 and the polypropylene unit (C12) having a degree of polymerization of 70 to 210 in the vinyl resin (B) is the weight of the vinyl resin (B). In Comparative Example 1, which exceeds 9% by weight based on the above, the pulverizability was poor. Further, in Comparative Examples 2 and 3 in which the weight average molecular weight of the vinyl resin (B) was less than 4,000 or more than 40,000, performance items such as storage stability and pulverizability were poor. Further, Comparative Example 4 containing no vinyl resin (B) had poor pulverizability. Further, in Comparative Example 5 in which the solubility parameter of the vinyl resin (B) was less than 10.6 (cal / cm ³ ) ^1/2 , the charge stability was poor.

The toner binder and toner of the present invention have excellent low-temperature fixability, storage stability, and charging characteristics while maintaining crushability while having a high level of offset resistance, and are excellent in electrophotographic, electrostatic recording, electrostatic printing, etc. It can be suitably used as a toner for developing a static charge image for full color and a toner binder used in the above.
Further, it is suitable for applications such as paint additives, adhesive additives, and particles for electronic paper.

Claims (8)

A toner binder composed of a polyester resin (A) and a vinyl resin (B).
The polyester resin (A) is composed of an amorphous linear polyester resin (A1) having a THF insoluble content of 1% by weight or less and an amorphous non-crystalline polyester resin (A2) having a THF insoluble content of 5% by weight or more. Ri non-crystalline polyester resin der that Do,
The acid value of the polyester resin (A) is 5 to 25 mgKOH / g.
The weight average molecular weight of the vinyl resin (B) is 4,000 to 40,000.
The solubility parameter of the vinyl resin (B) is 10.6 to 12.6 (cal / cm ³ ) ^1/2 .
The total weight ratio of the polyethylene unit (C11) and the polypropylene unit (C12) in the vinyl resin (B) is 0 to 9% by weight based on the weight of the vinyl resin (B), and the polyethylene unit (C11) is It is a polyethylene unit having a degree of polymerization of 70 to 210, and the polypropylene unit (C12) is a polypropylene unit having a degree of polymerization of 70 to 210, and the number average dispersed particle size of the vinyl resin (B) in the toner binder is 0. .02 to 2 μm toner binder. The vinyl resin (B) is a polymer having a monomer (m) having a solubility parameter of 11.5 to 16.5 (cal / cm ³ ) ^1/2 of a homopolymer as a constituent monomer. , The toner binder according to claim 1, wherein the weight ratio of (m) in the monomer constituting (B) is 1% by weight or more based on the total weight of the monomers constituting (B). .. The toner binder according to claim 1 or 2, wherein the weight ratio [(A) / (B)] of the polyester resin (A) to the vinyl resin (B) is 80/20 to 99.5 / 0.5. The toner binder according to any one of claims 1 to 3, which satisfies the following relational expression (1).
Relational expression (1): 0.1 ≤ | SP (a) -SP (b) | ≤ 1.4
[In the relational expression (1), SP (a) is a solubility parameter of the polyester resin (A), and SP (b) is a solubility parameter of the vinyl resin (B). ] The toner binder according to any one of claims 1 to 4, wherein the glass transition point of the vinyl resin (B) is 35 ° C to 75 ° C. The toner binder according to any one of claims 1 to 5, wherein the acid value of the vinyl resin (B) is 8 mgKOH / g or less. The toner binder according to any one of claims 1 to 6, wherein the vinyl resin (B) has a softening point of 70 to 130 ° C. A toner containing the toner binder and the colorant according to any one of claims 1 to 7.