JP6713492B2 - Toner binder and toner - Google Patents

Description

The present invention relates to a toner binder and a toner.

In recent years, with the development of electrophotographic systems, the demand for electrophotographic devices such as copying machines and laser printers has been rapidly increasing, and the demand for their performance has also become more sophisticated.
Generally, in the electrophotographic method, after forming an electrostatic charge image (latent image) on a photoconductor, the latent image is developed with toner to form a toner image. The toner image is transferred onto a recording medium such as paper and then fixed by a method such as heating.

In order to pass through these processes without problems, the toner must first hold a stable charge amount, and then it must have good fixability on paper. Further, since the apparatus has a heating element in the fixing unit, the temperature rises in the apparatus, and therefore it is required that the toner does not block in the apparatus.

Further, from the viewpoint of energy saving that the energy consumption in the fixing process is reduced as well as the miniaturization, high speed and high image quality of the electrophotographic apparatus, improvement of low temperature fixing property of the toner is strongly demanded.
As a means for lowering the fixing temperature of the toner, a technique for lowering the glass transition point of the toner binder is generally used. However, if the glass transition point is too low, aggregation (blocking) of the powder is likely to occur, and the heat-resistant storage stability of the toner deteriorates. This glass transition point is a design point of the toner binder, and it is impossible to obtain a toner capable of fixing at a lower temperature by a method of lowering the glass transition point.
As another means, the molecular weight has been reduced. However, when the toner image is fixed by the heat roll fixing method, the heat roll and the molten toner directly contact each other at the time of fixing, but if the molecular weight is made too small, the toner transferred onto the heat roll at There is a drawback in that a so-called offset phenomenon is likely to occur, which stains the transfer paper or the like sent in.

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, etc. are known, but recently, heat resistance Polyester resins have attracted particular attention because they can easily balance storage properties and low-temperature fixability.

As a method of expanding the fixing temperature range, a toner using a reaction product of a mixture of a polymerizing resin and a polyester resin and an isocyanate has been proposed (Patent Document 1).
However, although this method can prevent the offset phenomenon at a high temperature to some extent, it also makes it difficult to fix at a low temperature because the lower limit fixing temperature rises at the same time. Also, due to the high aggregation property of the urea group or urethane group derived from isocyanate, The pulverizability of is significantly deteriorated. Further, the homogeneity of the resin is impaired and the heat-resistant storage stability is deteriorated, and the demands for high speed and energy saving have not yet been fully met.

Therefore, a toner using a product obtained by crosslinking a polyester resin having an unsaturated double bond with a radical reaction initiator has been proposed (Patent Document 2).
However, although the pulverizability of the resin is improved by this method, if the organic solvent derived from the decomposed product of the initiator remains, the odor due to the volatile gas component becomes a problem.

On the other hand, when the radical reaction of the polyester resin having an unsaturated double bond is performed by heating or the like without using an initiator, the reaction does not proceed sufficiently.

As described above, even if the decomposed product of the initiator is generated, the heat resistant storage stability is sufficient, further, there is no odor due to the volatile gas component, the offset resistance is maintained, the low temperature fixability, the crushability and the image strength Until now, no excellent toner binder and toner satisfying all of them have been available.

JP, 4-212172, A JP, 2017-003985, A

The present invention has an excellent toner binder that has a high level of heat-resistant storage stability, has no odor due to volatile gas components, and maintains offset resistance while satisfying all of low-temperature fixability, pulverizability and image strength. The purpose is to provide toner.

The present inventors have arrived at the present invention as a result of extensive studies to solve these problems.
That is, the present invention is a toner binder containing a non-linear polyester resin (A) and an organic solvent, wherein the (A) is a resin having a structure in which a polyester (A0) is crosslinked, and at least forms a crosslinked structure. One bond is a direct bond between at least one of the carbon atoms contained in the polyester (A0) and the carbon atom contained in the polyester (A0), and the content of the organic solvent in the toner binder is 50 ppm. A toner binder of 2,000 ppm or more; and a toner containing this toner binder.

According to the present invention, an excellent toner binder having a high level of heat-resistant storage stability, no odor due to volatile gas components, and maintaining hot offset resistance while satisfying all of low-temperature fixability, pulverizability and image strength. And toner can be provided. Further, the toner of the present invention is excellent in toner fluidity, charge stability, bending resistance, and document offset property in addition to the above performance.

The toner binder of the present invention is a toner binder containing a non-linear polyester resin (A) and an organic solvent, wherein (A) is a resin having a structure in which a polyester (A0) is crosslinked, and forms a crosslinked structure. At least one bond is a direct bond between at least one carbon atom of the carbon atoms contained in the polyester (A0) and the carbon atom contained in the polyester (A0), and the content of the organic solvent in the toner binder. Is 50 ppm or more and 2000 ppm or less.
Hereinafter, the toner binder of the present invention will be sequentially described.

The toner binder of the present invention contains the non-linear polyester resin (A) as an essential component. In the above (A), at least one bond forming a structure in which the polyester (A0) is crosslinked is contained in the polyester (A0) and at least one carbon atom contained in the polyester (A0). Any polyester may be used as long as it is directly bonded to the carbon atom. Examples of the polyester (A0) include a polyester (A1) having a carbon-carbon double bond, and the like (A1) is preferable from the viewpoint of easily forming a crosslinked structure, and the carbon-of the non-linear polyester resin (A) is At least a part of the carbon bonds is preferably a carbon-carbon bond obtained by bridging the carbon-carbon double bonds derived from the polyester (A1) having the carbon-carbon double bond.
The non-linear polyester resin (A) reacts with the carbon-carbon double bond of the above (A1) and also withdraws hydrogen atoms bonded to carbon atoms contained in the polyester resin by a hydrogen abstraction reaction such as heating to crosslink (hydrogen. It is also known as an atom abstraction reaction).
The non-linear polyester resin (A) contained in the toner binder of the present invention may be one kind or a mixture of two or more kinds of polyester resins containing (A). Further, the toner binder of the present invention includes, for example, the non-linear polyester resin (A) specified in the present invention, and an amorphous polyester resin (B) and/or a crystalline resin (C) which is a resin other than (A) described later. ) May be contained.
The non-linear polyester resin is a polyester resin having a branch (crosslinking point) in the main chain. On the other hand, the linear polyester resin is a polyester resin having no branch (crosslinking point) in the main chain.
The content of the non-linear polyester resin (A) in the toner binder is preferably 1 to 95% by weight based on the weight of the toner binder, and more preferably from the viewpoint of low-temperature fixability, heat resistant storage stability, and hot offset resistance. It is 3 to 80% by weight, and most preferably 5 to 50% by weight.

Further, as the polyester (A1) having a carbon-carbon double bond in the present invention, one or more kinds of unsaturated carboxylic acid component (y) and/or one or more kinds of unsaturated alcohol component (z) are essential constituent units. Examples thereof include polyester resins used as monomers.
Further, (A1) is polycondensed by using, in addition to (y) and (z), one or more kinds of saturated alcohol component (x) and one or more kinds of saturated carboxylic acid component (w) as constituent monomers. You may.

Examples of the saturated alcohol component (x) include monools (x1), diols (x2), and polyols (x3) having a valence of 3 to 8 or higher. The saturated alcohol component (x) may be used alone or in combination of two or more kinds.

Examples of the monool (x1) include linear or branched alkyl alcohols having 1 to 30 carbon atoms (methanol, ethanol, isopropanol, dodecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, etc.).
Among these monools, linear alkyl alcohols having 8 to 24 carbon atoms are preferable, and dodecyl alcohol, myristyl alcohol, stearyl alcohol, behenyl alcohol, and combinations thereof are more preferable.

The diol (x2) is an alkylene glycol having 2 to 36 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol). , 3-methyl-1,5-pentanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, etc.) (x21); C4-C36 alkylene ether glycol (diethylene glycol, (Triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.) (x22); C6-C36 alicyclic diol (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.) (X23); (Poly)oxyalkylene adduct of the alicyclic diol (preferably the number of moles added is 1 to 30) (x24); aromatic diol [monocyclic divalent phenol (for example, hydroquinone) and bisphenols Alkylene oxide adduct (preferably 2 to 30 moles added)] (x25); and the like.
Of these diols (x2), aromatic diols (x25) are preferable, and alkylene oxide adducts of bisphenols are more preferable, from the viewpoints of low-temperature fixability and heat-resistant storage stability. In the alkylene oxide, the carbon number of the alkylene group is preferably 2 to 4 (ethylene oxide, 1,2- or 1,3-propylene oxide, 1,2-, 2,3-, 1,3- or iso-butylene oxide. And tetrahydrofuran).

The alkylene oxide adduct of bisphenols is generally obtained by adding alkylene oxide (hereinafter, "alkylene oxide" may be abbreviated as AO) to bisphenols. Examples of the 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; Ar represents a hydrogen atom other than a hydroxyl group and a part to which P is bonded; It represents a phenylene group which may be substituted with an atom or an alkyl group having 1 to 30 carbon atoms. ]

Specific examples of the bisphenols include bisphenol A, bisphenol F, bisphenol B, bisphenol AD, bisphenol S, trichlorobisphenol A, tetrachlorobisphenol A, dibromobisphenol F, 2-methylbisphenol A, 2,6- Dimethyl bisphenol A and 2,2'-diethyl bisphenol F are mentioned, and these can also use 2 or more types together.

As the alkylene oxide added to these bisphenols, an alkylene oxide having 2 to 4 carbon atoms is preferable, and specifically, ethylene oxide (hereinafter, "ethylene oxide" may be abbreviated as EO), 1,. 2- or 1,3-propylene oxide (hereinafter, "1,2-propylene oxide" may be abbreviated as PO), 1,2-, 2,3-, 1,3- or iso-butylene oxide. , Tetrahydrofuran and a combination of two or more of these.

Of these, EO and/or PO are preferable from the viewpoints of heat resistant storage stability and low temperature fixability. The number of moles of AO added is preferably 2 to 30 moles, more preferably 2 to 10 moles from the viewpoint of heat resistant storage stability and low temperature fixability.
Among the alkylene oxide adducts of bisphenols, preferred are EO and/or PO adducts of bisphenol A (average added mole number 2 to 4, more preferably 2 to 3) from the viewpoint of low-temperature fixability of the toner. Is.

Examples of the polyol (x3) having a valence of 3 to 8 or more include a polyhydric aliphatic alcohol (x31) having 3 to 8 carbon atoms and having 3 to 36 carbon atoms, a saccharide and a derivative thereof (x32), and a fat. (Poly)oxyalkylene ether of group polyhydric alcohol (preferably 1 to 30 as the number of oxyalkylene units) (x33), polyoxyalkylene ether of trisphenols (trisphenol PA etc.) (preferably as the number of oxyalkylene units) 2 to 30) (x34), novolac resins (phenol novolac and cresol novolac, etc. are included, and the average degree of polymerization is preferably 3 to 60) of polyoxyalkylene ether (preferably 2 to 30 as the number of oxyalkylene units). ) (X35) and the like.

The aliphatic polyhydric alcohol (X31) having 3 to 8 or more valences having 3 to 36 carbon atoms includes alkane polyol and its intramolecular or intermolecular dehydration product, such as glycerin, trimethylolethane, Examples thereof include trimethylolpropane, pentaerythritol, sorbitol, sorbitan, polyglycerin and dipentaerythritol.

Among the above saturated alcohol components (x), preferable ones from the viewpoint of achieving both low-temperature fixability and hot offset resistance are preferable alkylene glycols having 2 to 12 carbon atoms (x21) and alkylene oxide adducts of bisphenols (AO). The number of units is preferably 2 to 30) (x25), a C3 to C3 to C8 or higher aliphatic polyhydric alcohol (x31), and a novolac resin polyoxyalkylene ether (of oxyalkylene units). The number is preferably 2 to 30) (x35).

More preferable from the viewpoint of heat resistant storage stability are alkylene glycols (x21) having 2 to 10 carbon atoms, alkylene oxide adducts of bisphenols (preferably 2 to 5 as the number of AO units), and 3 to 4 valent aliphatics. A polyoxyalkylene ether of a polyhydric alcohol and a novolak resin (preferably 2 to 30 as the number of oxyalkylene units) (x35).
Particularly preferred are alkylene glycols having 2 to 6 carbon atoms, trivalent aliphatic polyhydric alcohols and alkylene oxide adducts of bisphenol A (preferably 2 to 5 as the number of AO units), and most preferably It is an alkylene oxide adduct of ethylene glycol, propylene glycol, 3-methyl-1,5-pentanediol, trimethylolpropane and bisphenol A (preferably 2-3 as the number of AO units).

Examples of the unsaturated carboxylic acid component (y) include unsaturated monocarboxylic acid (y1), unsaturated dicarboxylic acid (y2), and anhydrides and lower alkyl esters of these acids. As the unsaturated carboxylic acid component (y), one type may be used, or two or more types may be used in combination.

Examples of the unsaturated monocarboxylic acid (y1) include unsaturated monocarboxylic acids having 2 to 30 carbon atoms, and specifically, acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, 3-butenoic acid, angelica. Acid, tiglic acid, 4-pentenoic acid, 2-ethyl-2-butenoic acid, 10-undecenoic acid, 2,4-hexadienoic acid, myristoleic acid, palmitoleic acid, sapienoic acid, oleic acid, elaidic acid, vaccenic acid, Examples thereof include gadoleic acid, eicosenoic acid, erucic acid and nervonic acid.

Examples of the unsaturated dicarboxylic acid (y2) include alkene dicarboxylic acids having 4 to 50 carbon atoms, and specific examples thereof include alkenyl succinic acid such as dodecenyl succinic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid and itacone. Examples thereof include acids and glutaconic acid.

Among these unsaturated carboxylic acids (y), an unsaturated monocarboxylic acid having 2 to 10 carbon atoms and an alkenedicarboxylic acid having 4 to 18 carbon atoms are preferable from the viewpoint of achieving both low temperature fixability and hot offset resistance. Of these, alkenyl succinic acid such as acrylic acid, methacrylic acid and dodecenyl succinic acid, maleic acid and fumaric acid are more preferable.
Most preferred are acrylic acid, methacrylic acid, maleic acid, fumaric acid and combinations thereof. Further, anhydrides and lower alkyl esters of these acids are also preferable.

Examples of the unsaturated alcohol component (z) include unsaturated monoalcohol (z1) and unsaturated diol (z2). The unsaturated alcohol component (z) may be used alone or in combination of two or more.

Examples of the unsaturated monoalcohol (z1) include unsaturated monoalcohols having 2 to 30 carbon atoms, and specific examples thereof include 2-propen-1-ol, oleyl alcohol, and 2-hydroxyethyl methacrylate. To be

Examples of the unsaturated diol (z2) include unsaturated monoalcohols having 2 to 30 carbon atoms, and specific examples thereof include ricinoleyl alcohol.

Examples of the saturated carboxylic acid component (w) include aromatic carboxylic acid (w1) and aliphatic carboxylic acid (w2). As the saturated carboxylic acid component (w), one type may be used, or two or more types may be used in combination.

As the aromatic carboxylic acid (w1), for example, an aromatic monocarboxylic acid having 7 to 37 carbon atoms (benzoic acid, toluic acid, 4-ethylbenzoic acid, 4-propylbenzoic acid, etc.), 8 to 36 carbon atoms. Examples thereof include aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc.), trivalent or higher aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, etc.), and the like.
Examples of the aliphatic carboxylic acid (w2) include an aliphatic monocarboxylic acid having 2 to 50 carbon atoms (acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid). Acid, myristic acid, palmitic acid, margaric acid, stearic acid, behenic acid, etc.), aliphatic dicarboxylic acid having 2 to 50 carbon atoms (oxalic acid, malonic acid, succinic acid, adipic acid, leparginic acid, sebacic acid, etc.), Examples thereof include aliphatic tricarboxylic acids having 6 to 36 carbon atoms (hexane tricarboxylic acid, etc.) and the like.

As the saturated carboxylic acid component (w), an anhydride or a lower alkyl (C1-4) ester (methyl ester, ethyl ester, isopropyl ester, etc.) of these carboxylic acids may be used, or these carboxylic acids may be used. You may use together with.

Among these saturated carboxylic acid components (w), preferred are ones having both low-temperature fixability and hot offset resistance, and aromatic monocarboxylic acids having 7 to 37 carbon atoms and aliphatic monocarboxylic acids having 2 to 50 carbon atoms. It is a dicarboxylic acid, an aromatic dicarboxylic acid having 8 to 20 carbon atoms, and a trivalent or higher aromatic polycarboxylic acid having 9 to 20 carbon atoms.
From the viewpoints of heat-resistant storage stability and chargeability, adipic acid, alkylsuccinic acid, terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid and combinations thereof are more preferable.
Particularly preferred are adipic acid, terephthalic acid, trimellitic acid and combinations thereof. It may be an anhydride or a lower alkyl ester of these acids.

The polyester (A1) in the present invention is not particularly limited, but is preferably non-linear from the viewpoint of improving elasticity at high temperature.

The method for producing the polyester (A1) in the present invention is not particularly limited, but as described above, one or more kinds of unsaturated carboxylic acid component (y) and/or unsaturated alcohol component (z) are used as constituent raw materials. .. Further, when the polyester (A1) is non-linear, for example, in addition to the unsaturated carboxylic acid component (y) and/or the unsaturated alcohol component (z), a saturated alcohol component (x) as a constituent raw material having a valence of 3 or more is used. Examples thereof include the case of using a polyol and the case of using a carboxylic acid having a valence of 3 or more, or an acid anhydride or a lower alkyl ester thereof as the saturated carboxylic acid component (w). The non-linearity improves heat resistant storage stability and hot offset resistance.

In the present invention, each polyester resin can be manufactured in the same manner as a known polyester.
For example, the reaction can be carried out in an inert gas (nitrogen gas or the like) atmosphere at a reaction temperature of preferably 150 to 280°C, more preferably 160 to 250°C, particularly preferably 170 to 235°C. The reaction time is preferably 30 minutes or more, particularly preferably 2 to 40 hours, from the viewpoint of surely carrying out the polycondensation reaction.

At this time, an esterification catalyst can be used if necessary.
Examples of esterification catalysts include tin-containing catalysts (for example, dibutyltin oxide), antimony trioxide, titanium-containing catalysts (for example, titanium alkoxide, potassium oxalate titanate, titanium terephthalate, titanium terephthalate alkoxide, JP 2006-243715A). The catalysts described in the official gazette [titanium dihydroxybis(triethanolaminate), titanium monohydroxytris(triethanolaminate), titanylbis(triethanolaminate) and their intramolecular polycondensates], and JP2007- No. 11307, the catalysts (titanium tributoxy terephthalate, titanium triisopropoxy terephthalate, titanium diisopropoxy diterephthalate, etc.)], zirconium-containing catalysts (for example, zirconyl acetate), and zinc acetate. 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 and hindered phenol compounds.

The ratio of the total charged amount of the saturated alcohol component (x) and the unsaturated alcohol component (z) to the total charged amount of the unsaturated carboxylic acid component (y) and the saturated carboxylic acid component (w) is a hydroxyl group and a carboxyl group. The equivalent ratio [OH]/[COOH] is preferably 2/1 to 1/2, more preferably 1.5/1 to 1/1.3, particularly preferably 1.4/1 to 1/1. It is 2.

In the present invention, the glass transition temperature (Tg _A1 ) of the polyester (A1) is preferably −35 to 45° C., and when Tg is 45° C. or lower, low temperature fixability becomes good and is −35° C. or higher. And the heat-resistant storage stability becomes good. The temperature is more preferably -30 to 43°C, particularly preferably -25 to 40°C, and most preferably -20 to 38°C.
The glass transition temperature (Tg) can be measured by a method (DSC method) prescribed in ASTM D3418-82 using, for example, DSC20 and SSC/580 manufactured by Seiko Instruments Inc.

Specific confirmation method of a glass transition temperature (Tg _A1) and the glass transition temperature of below-described toner binder of the polyester _(A1) (Tg T) is as follows.
Put 5 mg of sample into the container of DSC device, heat at 20° C./min to a temperature about 30° C. higher than that at the end of glass transition, and cool at 60° C./min to a temperature about 50° C. lower than glass transition temperature. Heat at 20°C/min to a temperature about 30°C higher than at the end.
Draw a graph of the amount of heat absorbed and emitted from the above measurement, and a straight line that extends the low temperature side of the graph to the high temperature side, and at the point where the gradient of the curve of the step change of glass transition becomes maximum. The temperature at the intersection with the drawn tangent line is taken as the glass transition temperature (Tg).

The polyester resin (A1) preferably has a peak top molecular weight in gel permeation chromatography (GPC) of 2,000 to 30,000, more preferably a peak top molecular weight of 3,000 to 20,000, and most preferably It is preferably 4,000 to 12,000.
When the peak top molecular weight is 2,000 to 30,000, glossiness, low temperature fixing property and hot offset property are preferable.

The peak top molecular weight (hereinafter sometimes abbreviated as Mp) is obtained by calculating the molecular weight distribution of a sample from the relationship between the logarithmic value of a calibration curve prepared using a standard polystyrene sample and the count number. It is the molecular weight obtained from the peak maximum value in the obtained molecular weight distribution chart. Since the number of peaks in the chart is not limited to one, when there are multiple peaks, the peak showing the maximum value among the peak values is obtained. The measurement conditions for GPC measurement are as follows.

In the present invention, GPC is used for the peak top molecular weight, the number average molecular weight (hereinafter sometimes abbreviated as Mn), and the weight average molecular weight (hereinafter sometimes abbreviated as Mw) of a resin such as a polyester resin. Can be measured under the following conditions.
Device (example): HLC-8120 manufactured by Tosoh Corporation
Column (one example): TSK GEL GMH6 2 [manufactured by Tosoh Corporation]
Measurement temperature: 40℃
Sample solution: 0.25 wt% THF solution Injection volume of solution: 100 μl
Detector: Refractive index detector Reference substance: Standard polystyrene (TSK standard POLYSTYRENE) 12 points (molecular weight 500 1,050 2,800 5,970 9,100 100,18,100 37,900 96,400 190,000) 355,000 1,090,000 2,890,000)
For the measurement of the molecular weight, a polyester resin or the like is dissolved in THF so as to be 0.25% by weight, and the insoluble matter is filtered off with a glass filter to obtain a sample solution.

The nonlinear polyester resin (A) of the present invention is one in which at least one carbon atom of the carbon atoms contained in the polyester (A0) and the carbon atom contained in the polyester (A0) are directly bonded and crosslinked. .. When the polyester (A0) is a polyester containing a polyester (A1) having a carbon-carbon double bond, the above reaction occurs between carbon-carbon double bonds derived from the polyester (A1) having a carbon-carbon double bond. And at least a part thereof may be crosslinked. The form of the cross-linking reaction for forming the cross-linked structure is not particularly limited, but, for example, introducing a carbon-carbon double bond into the main chain or side chain of the polyester resin, radical addition reaction, cation addition reaction, or anion addition It is a form of reaction in which an intermolecular carbon-carbon bond is generated by reacting by a reaction or the like.

The crosslinking reaction is preferably a radical addition reaction, a cation addition reaction and an anion addition reaction, more preferably a radical addition reaction, and particularly preferably a radical reaction initiator (c) from the viewpoints of pulverizability and low temperature fixing property. This is the radical addition reaction used.
Although it is difficult to specify the crosslinked structure by using the radical reaction initiator (c), it is presumed that the pulverizability and the low temperature fixability are improved because the crosslinking reaction can be made uniform in a short time.

The method for producing the non-linear polyester resin (A) is, for example, as described above, after obtaining the polyester (A1) having a carbon-carbon double bond in the molecule by condensation polymerization, a radical reaction initiator (c) or the like is optionally added. By using a radical generated from the radical reaction initiator (c) or the like to carry out a radical addition reaction, carbon-carbon double bonds caused by the unsaturated carboxylic acid component (y) in (A1) A method of producing a non-linear polyester resin (A) by causing a cross-linking reaction to chemically bond with the above.

Examples of the radical reaction initiator (c) used for the crosslinking reaction of the polyester (A1) in the present invention include an inorganic peroxide (c1), an organic peroxide (c2) and an azo compound (c3), Among them, the inorganic peroxide (c1) and the organic peroxide (c2) are preferable because they have high initiator efficiency and do not form a cyanide by-product. Further, these radical reaction initiators may be used in combination.

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

The organic peroxide (c2) is not particularly limited, and examples thereof include 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- Butylperoxyhexyne-3, acetyl peroxide, isobutyryl peroxide, octaninor peroxide, decanolyl peroxide, lauroyl peroxide, 3,3,5-trimethylhexanoyl peroxide, m-toluyl peroxide, t -Butyl peroxyisobutyrate, t-butyl peroxy neodecanoate, cumene hydroperoxide, succinic acid peroxide, di(2-ethoxyethyl) peroxydicarbonate, cumyl peroxy neodecanoate, t- Butyl peroxy 2-ethylhexanoate, t-butyl peroxy 3,5,5-trimethylhexanoate, t-butyl peroxy laurate, t-butyl peroxy benzoate, t-butyl peroxy isopropyl mono Examples thereof include carbonate and t-butyl peroxyacetate.

Examples of the azo compound (c3) include 2,2'-azobis(2-methylpropionitrile) and 2,2'-azobis(2,4-dimethylvaleronitrile).

Furthermore, since the crosslinking reaction proceeds efficiently, a reaction initiator having a hydrogen abstraction ability and having a peroxide structure (—O—O—) as a functional group is preferable. Specifically, benzoyl peroxide, di-t-butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, α,α-bis(t-butylperoxy)diisopropylbenzene, cumene hydroperoxide, 2, 5-Dimethyl-2,5-bis(t-butylperoxy)hexane, di-t-hexyl peroxide, t-butylperoxyisopropyl monocarbonate and the like are preferable.

Further, in the present invention, it is preferable to use the reducing agent (d) for the crosslinking reaction of the polyester (A1), and it is more preferable to combine the radical reaction initiator (c) and the reducing agent (d). By using the reducing agent (d) together, the activation energy for radical generation can be lowered, and the crosslinking reaction proceeds efficiently, resulting in a smaller amount of radical reaction initiator (c) used.

The reducing agent (d) is not particularly limited, but examples thereof include an inorganic reducing agent and an organic reducing agent. Examples of the inorganic reducing agent include sulfites or bisulfites of alkali metals, ammonium sulfite, ammonium bisulfite, ferric chloride, ferric sulfate, and diphosphates (pyrophosphate, etc.). Examples of the organic reducing agent include ascorbic acid.

The temperature of the radical reaction is preferably 50 to 250°C.

The radical reaction initiator (c) is used in an amount of 0. 0, based on the total weight of the polyester (A1) having a carbon-carbon double bond, the amorphous polyester resin (B) and the crystalline resin (C). 4 to 5.0% by weight is preferable.
When the amount of the radical reaction initiator (c) used is 0.4% by weight or more, the crosslinking reaction tends to proceed easily, and when it is 5.0% by weight or less, the odor tends to be good. .. The upper limit of the amount used is more preferably 4% by weight or less, further preferably 3% by weight or less, and particularly preferably 2% by weight or less.

From the viewpoint of reactivity, the amount of the reducing agent (d) used is based on the total weight of the polyester (A1) having a carbon-carbon double bond, the amorphous polyester resin (B) and the crystalline resin (C). , 0.01 to 2.5% by weight is preferable.

When the polyester (A1) is radically polymerized with the initiator species and amount in the above range, a crosslinking reaction effectively occurs, and the hot offset resistance, heat resistant storage stability and image strength of the toner are improved, which is preferable.

In the case of a cross-linking reaction in which a carbon-carbon bond is generated between the molecules by a radical addition reaction when producing the non-linear polyester resin (A), for example, a carbon-carbon dicarbonate is contained in the main chain or the side chain of the polyester (A1). In order to introduce a heavy bond, the unsaturated carboxylic acid component (y) having an unsaturated double bond and/or the unsaturated alcohol component (z) having an unsaturated double bond is used as an essential constituent monomer, or hydrogen is used. It may be possible to incorporate a component that easily extracts radicals.

The content of the organic solvent in the toner binder of the present invention is 50 to 2000 ppm based on the weight of the toner binder, and if the content of the organic solvent is more than 2000 ppm, the odor may be deteriorated, and if it is less than 50 ppm, the resistance is high. The hot offset property, pulverizability, image strength and toner fluidity may deteriorate. It is preferably 100 to 1500 ppm, particularly preferably 150 to 1000 ppm, and most preferably 200 to 500 ppm.
In particular, in the present invention, even when a reaction in which a polyester (A1) is cross-linked using a radical reaction initiator (c) and a decomposition product of (c) is generated, an organic solvent containing the generated decomposition product is contained. By controlling the amount within the above range, it is possible to obtain a toner excellent in odor, hot offset resistance, pulverizability, image strength and toner fluidity.

Examples of the method for controlling the content of the organic solvent include (1) control of the amount of the organic solvent used, (2) control of the amount of the initiator (control of the decomposed product of the initiator), (3) (1) and/or (2) Controlling the organic solvent contained in () by removing the solvent.

In (3), the method for removing the organic solvent is not particularly limited, but a method in which a pulverized toner binder is supplied to a twin-screw extruder and melted and conveyed to reduce the pressure from the vent port can be mentioned. .. At this time, the amount of organic solvent in the toner binder can be controlled by adjusting the melting temperature, the number of rotations of the shaft, the degree of pressure reduction, and the like. Further, the solvent can be removed by depressurizing the toner binder at an arbitrary temperature. The pressure may be reduced while stirring with a stirrer. At this time, the amount of 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 for solvent removal is preferably 20 to 200°C, more preferably 30 to 170°C, and most preferably 40 to 160°C. The depressurization degree of solvent removal is preferably 0.01 to 100 kPa, more preferably 0.1 to 95 kPa, and most preferably 1 to 90 kPa.
On the other hand, it is also possible to simultaneously reduce the pressure from the vent while reacting the raw materials with the twin-screw extruder. Further, when raw materials are charged in a reaction vessel and reacted, the solvent can be removed by a method of removing the solvent by depressurizing 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 above.
Alternatively, the amount of the organic solvent in the toner binder can be controlled by putting the pulverized toner binder in a dryer whose temperature and pressure (normal pressure or reduced pressure) are adjusted.
When the toner binder contains the amorphous polyester resin (B) and/or the crystalline resin (C), the method of removing the solvent in a short time is the polyester resin (A) and the amorphous polyester resin ( B) and/or the crystalline resin (C) are less likely to undergo a transesterification reaction, and the hot offset resistance and the low-temperature fixability are good, which is preferable.
The content (ppm) of the organic solvent can be measured, for example, by gas chromatograph analysis or gas chromatograph mass spectrometry under the following conditions.
The content of the organic solvent in the toner binders of Examples and Comparative Examples of the present invention 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×30 m df=1.0 μm
Column temperature: 70°C → 300°C (10°C/min)
Injection temperature: 200℃
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 examples thereof include ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol, s-butanol, t-butanol, diacetone alcohol, 2-ethylhexanol, acetone, methyl ethyl ketone. , Methyl isobutyl ketone, methyl n-butyl ketone, 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, acetic anhydride, acetic acid, hexamethylphosphoric triamide, triethylamine, pyridine, acetophenone, t-hexyl alcohol, Examples thereof include t-amyl alcohol and t-butoxybenzene.
Of these, from the viewpoints of heat-resistant storage stability and odor, compounds having 2 to 10 carbon atoms are preferable, more preferably 3 to 8 carbon atoms, and particularly preferably acetone, isopropyl alcohol and t-butanol. Is.

The organic solvent contained in the toner binder has a melting point of less than 30° C., more preferably a melting point of less than 10° C., and particularly preferably a melting point of less than −10° C., from the viewpoint of heat resistant storage stability and odor.
The organic solvent contained in the toner binder has a boiling point of higher than 30° C. and 300° C. or lower, more preferably a boiling point of higher than 40° C. and 200° C. or lower, and particularly preferably a boiling point, from the viewpoint of heat resistant storage stability and odor. It is higher than 50°C and 150°C or lower.

The content of the surfactant in the toner binder is preferably 1000 ppm or less from the viewpoint of chargeability. When the content of the surfactant in the toner binder is 1000 ppm or less, the saturated charge amount and charge stability are good, the charge control agent and the fluidizing agent can be added in small amounts, and the low-temperature fixability is good. It is more preferably 500 ppm or less, still more preferably 100 ppm or less, and particularly preferably 10 ppm or less.
A surfactant is a compound having both a hydrophobic portion and a hydrophilic portion in the molecule, and when producing a chemical toner obtained by an emulsion aggregation method, granulation of particles in an aqueous phase, a suspension polymerization method, an emulsion polymerization, or the like. It is a surfactant generally used in. It is necessary to form stable oil droplets from the resin, monomer, polymerization initiator, colorant, release agent, etc. in the aqueous phase.
However, the toner of the present invention is not a chemical toner that requires the use of a surfactant, but a production method that does not use a surfactant, for example, a toner is preferably produced by a pulverization method. Does not substantially add a surfactant, so the content is 1000 ppm or less even if it is included. The content of the surfactant in the toner is preferably 500 ppm or less, more preferably 100 ppm or less, and particularly preferably 10 ppm or less.

The method for measuring the content of the toner binder and the surfactant in the toner is, for example, a high performance liquid chromatograph mass spectrometer (LC-MS) in which the surfactant in the toner is extracted into an organic solvent such as THF or methanol. , A method of identifying and quantifying the chemical composition by a nuclear magnetic resonance apparatus (NMR) or the like.

In the present invention, the content of the toner binder and the surfactant in the toner is a value measured by the following method.
(1) <Sample preparation> 200 mg of toner or toner binder is weighed in a screw tube, 25 ml of methanol is put therein, and ultrasonic waves are applied for 30 minutes to extract the surfactant. Then, centrifugation is performed, the supernatant is sampled, and filtered to prepare a measurement sample.

(2) The measurement conditions are as follows.
Analyzer: LCMS-8030 (manufactured by Shimadzu Corporation)
Column: InertSustainSwift (GL Science Co., Ltd.) particle diameter 1.9 μm, inner diameter 2.1 mm, length 50 mm
Mobile phase: A (10 mM ammonium acetate aqueous solution/methanol=80/20 [volume ratio])
B Methanol A/B=40/60 [volume ratio]
Flow rate: 0.3 mL/min Injection volume: 0.2 μl
Ion source: ESI (±)
In addition, in the above-mentioned quantitative analysis method of this time, since the amount of the surfactant was 5 ppm or less, the detection limit was set. Therefore, in Tables 3 and 4 in the examples, the case where the amount of the surfactant was 5 ppm or less was not detected.

The amount of carbon-carbon double bonds in the polyester (A1) is not particularly limited, but from the viewpoint that the cross-linking reaction effectively occurs and the hot offset resistance of the toner is improved, it is preferably based on the weight of (A1). 0.02-2.0 mmol/g, more preferably 0.06-1.9 mmol/g, particularly preferably 0.10-1.5 mmol/g, most preferably 0.15-1.0. It is mmol/g.

In the toner binder of the present invention, the amount of carbon-carbon double bond in the polyester (A1) means the carbon-carbon dibonding amount contained in 1 g of the total of raw materials such as alcohol component and carboxylic acid component constituting the polyester resin (A1). It is the number of millimoles of heavy bonds.
As an actual calculation method, for example, when fumaric acid (0.1 g) and a bisphenol A/PO2 mol adduct (0.9 g) are used as raw materials for the polyester resin, carbon-carbon dicarbonate is added to 1 g of the total raw materials. Since it has 0.1 g of fumaric acid containing one heavy bond and a molecular weight of 116,
0.1/116×1000=0.86 mmol/g.
For example, when fumaric acid (0.3 g) and bisphenol A/PO2 mole adduct (0.7 g) are used as raw materials for the polyester resin, one carbon-carbon double bond is contained per 1 g of the total raw materials. Since it has 0.3 g of fumaric acid having a molecular weight of 116,
0.3/116×1000=2.59 mmol/g.

The acid value of the polyester (A1) is preferably 0 to 30 mgKOH/g, more preferably 0 to 25 mgKOH/g, and particularly preferably 0 to 10 mgKOH/g, from the viewpoint of charge stability.
The acid value of polyester (A1) can be measured by the method specified in JIS K0070 (1992 version).

The glass transition temperature Tg _T of the toner binder of the present invention is preferably −35 to 80° C., more preferably 35 to 65° C. When the glass transition temperature Tg _T is −35° C. or higher, heat resistant storage stability becomes good, and when it is 80° C. or lower, fixability becomes good.
The glass transition temperature (Tg _T ) is measured by differential scanning calorimetry by the method (DSC method) specified in ASTM D3418-82, and the inflection point indicating the glass transition temperature (Tg) can be confirmed on the DSC chart. it can. For example, it can be measured using DSC20 and SSC/580 manufactured by Seiko Instruments Inc.

By the way, the toner binder of the present invention is preferably used in combination with the non-linear polyester resin (A) and the amorphous polyester resin (B) excluding (A) for the purpose of further improving the low temperature fixing property.
The amorphous polyester resin (B) used together for this purpose includes a saturated alcohol component (x) and a saturated carboxylic acid component (w) as constituent monomers, and an unsaturated carboxylic acid component (y) and an unsaturated alcohol component. Even if the resin does not contain (z) as a constituent monomer and has a crosslinked structure, the carbon atom contained in the polyester (A0) is directly bonded to the carbon atom contained in the polyester (A0). It is a resin that does not include a structure crosslinked by.

"Amorphous" of the amorphous polyester resin (B) means that it does not have a maximum peak temperature (melting point) of heat of fusion measured by a differential scanning calorimeter (DSC) or is measured by a Koka type flow tester. The ratio of the softening temperature to the maximum peak temperature of melting heat (melting point) (softening temperature/maximum peak temperature of melting heat (melting point)) is outside the range of 0.80 to 1.55.
Further, the amorphous polyester resin (B) is preferably one that does not substantially contain a THF insoluble component, and as a preferable (B), for example, the THF insoluble component content is 1.0% by weight or less. It is a thing.

Of the saturated alcohol component (x) used for the amorphous polyester resin (B), from the viewpoint of low-temperature fixability and hot offset resistance, preferably an alkylene glycol having 2 to 10 carbon atoms or an alkylene oxide adduct of bisphenols. (Addition mole number 2 to 5) and polyoxyalkylene ether of novolac resin (number of oxyalkylene units 2 to 30), and particularly preferably, alkylene glycol having 2 to 6 carbon atoms and alkylene oxide adduct of bisphenol A ( The number of added moles is 2 to 5), and the most preferred is an alkylene oxide adduct of ethylene glycol, propylene glycol and bisphenol A (the number of added moles is 2 to 3).
In order to obtain an amorphous resin, the content of the linear diol is preferably 70 mol% or less, and more preferably 60 mol% or less of the diol component used. Further, in the saturated alcohol component (x) constituting the amorphous polyester resin (B), the diol (x2) is preferably 90 to 100 mol %.

The saturated carboxylic acid component (w) is preferably an aromatic dicarboxylic acid having 8 to 20 carbon atoms (phthalic acid, isophthalic acid, terephthalic acid, t-butyl) from the viewpoint of achieving both low temperature fixability and hot offset resistance. Isophthalic acid, 2,6-naphthalenedicarboxylic acid and 4,4′-biphenyldicarboxylic acid, etc.), aliphatic dicarboxylic acid having 2 to 50 carbon atoms (adipic acid, etc.), trivalent or more aromatic having 9 to 20 carbon atoms Polycarboxylic acids (such as trimellitic acid and pyromellitic acid) and combinations thereof. Further, it may be an anhydride or a lower alkyl ester of these acids.

Ratio of a considerable amount of the polyester (A1) having a carbon-carbon double bond used as a raw material of the non-linear polyester resin (A) and the weight of the amorphous polyester resin (B) [weight ratio (A1)/(B) ] Is preferably 5/95 to 50/50, more preferably 7/93 to 45/60, and particularly preferably 10/ in view of compatibility of low temperature fixability, hot offset resistance and heat resistant storage stability. 90-40/60.

Further, the amorphous polyester resin (B) may be linear or non-linear, but linear is preferable from the viewpoint of low temperature fixability and heat resistant storage stability.
Specifically, it is a polyester resin obtained by combining and condensing a saturated alcohol component (x) and a saturated carboxylic acid component (w).
Further, the amorphous polyester resin (B) may have a minute amount of cross-linking points which does not include a structure in which carbon atoms contained in the polyester (A0) are cross-linked by a direct bond between carbon atoms, and the molecular end thereof is poly It may be modified with trimellitic anhydride, phthalic anhydride, or the like, which is an anhydride of carboxylic acid (which may be trivalent or higher).

The Mn of the THF-soluble component of the amorphous polyester resin (B) is preferably 1,000 to 15,000, more preferably 1,200 to 10 from the viewpoint of achieving both heat-resistant storage stability and low-temperature fixability of the toner. 1,000, particularly preferably 1,500 to 5,000.

The Mw of the THF-soluble component of the amorphous polyester resin (B) is preferably from 2,000 to 30,000, and more preferably from the viewpoint of achieving both hot offset resistance, heat resistant storage stability and low temperature fixability of the toner. It is 2,500 to 20,000, particularly preferably 3,000 to 10,000.

When the amorphous polyester resin (B) is used, for example, in the state where the polyester (A1) having a carbon-carbon double bond in the molecule and the amorphous polyester resin (B) are mixed, (A1) At least a part of the carbon-carbon double bonds resulting from the unsaturated carboxylic acid component (y) and/or the unsaturated alcohol component (z) therein undergoes a cross-linking reaction to form a chemical bond to form a non-linear polyester resin (A). Is preferred, and it is a preferable method because the crosslinking reaction can be made uniform in a short time.

Further, in addition to the above, a method of producing a non-linear polyester resin (A) by crosslinking at least a part of carbon-carbon double bonds of the polyester (A1) using a radical reaction initiator (c) is a crosslinking reaction. Is effective, and the crosslinking reaction can be made uniform in a short time, which is a more preferable method.

Further, for the purpose of further improving low-temperature fixability and glossiness, the toner binder of the present invention preferably contains a crystalline resin (C) other than (A) in addition to the non-linear polyester resin (A). Further, when the crystalline resin (C) is used, like the amorphous polyester resin (B), for example, a polyester (A1) having a carbon-carbon double bond in the molecule and a crystalline resin (C) are used. In a mixed state, at least a part of the carbon-carbon double bonds resulting from the unsaturated carboxylic acid component (y) and/or the unsaturated alcohol component (z) in (A1) undergo a crosslinking reaction to form a chemical bond. Then, a method of producing the non-linear polyester resin (A) can be mentioned, which is a preferable method because the crosslinking reaction can be made uniform in a short time.

"Crystallinity" of the crystalline resin in the present invention means the ratio of the softening temperature measured by a high-performance flow tester and the maximum peak temperature (melting point) of heat of fusion measured by a differential scanning calorimeter (DSC). (Softening temperature/maximum peak temperature (melting point) of heat of fusion) is 0.80 to 1.55, which is a property of sharply softening by heat, and a resin having this property is referred to as a "crystalline resin". To do.

The ratio [weight ratio (A1)/(C)] of the amount of the polyester (A1) having a carbon-carbon double bond used as the raw material of the non-linear polyester resin (A) to the weight of the crystalline resin (C) is From the viewpoint of toner fluidity, heat-resistant storage stability, crushability, image strength after fixing, low-temperature fixing property and glossiness, 5/95 to 95/5 is preferable, and 15/85 to 85/15 is more preferable. Yes, and particularly preferably 40/60 to 60/40.

The crystalline resin (C) is not particularly limited in its chemical structure as long as it is compatible with the non-linear polyester resin (A) during fixing.
Examples thereof include resins such as crystalline polyester resin, crystalline polyurethane resin, crystalline polyurea resin, crystalline polyamide resin, and crystalline polyvinyl resin. Among them, the crystalline polyester resin is preferable from the viewpoint of compatibility.

Examples of the crystalline polyester resin include a polyester resin containing a diol component (X) and a dicarboxylic acid component (Y) as essential constituent monomers, and an alcohol component having a valence of 3 or more or a trivalent component as necessary. You may use together the said polycarboxylic acid component. Examples of the diol component (X) include those exemplified for the diol (x2). Examples of the dicarboxylic acid component (Y) include those exemplified as the dicarboxylic acid among those exemplified as the saturated carboxylic acid component (w).
As the diol of the diol component (X), a chain aliphatic diol is preferable from the viewpoint of crystallinity. The carbon number is preferably 2-36, more preferably 2-20. Specifically, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol and 1,20-eicosanediol etc. are mentioned. Of these, those having 2 to 12 carbon atoms (ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol and 1, 12-dodecanediol) is preferred.
From the viewpoint of crystallinity, low-temperature fixability and heat-resistant storage stability, the content of the linear aliphatic diol in the diol component is the total number of moles of the diol component (X) used as a monomer constituting the crystalline polyester resin. A crystalline polyester resin having a content of 80 mol% or more is preferable.
As the dicarboxylic acid of the dicarboxylic acid component (Y) that constitutes the crystalline polyester resin, an aliphatic dicarboxylic acid is preferable from the viewpoint of crystallinity, low temperature fixability and heat resistant storage stability, and a linear aliphatic dicarboxylic acid (adipic acid , Sebacic acid, azelaic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid and the like) are particularly preferable.

A method for manufacturing the toner binder will be described.
The toner binder is not particularly limited as long as it contains the non-linear polyester resin (A). For example, when two or more types of polyester resins and additives are mixed, a known mixing method may be used, such as powder mixing and melt mixing. Or solvent mixture may be used. Further, they may be mixed at the time of forming a toner. Among these methods, melt mixing which is homogeneously mixed and does not require solvent removal is preferable.

Examples of the mixing device for powder mixing include a Henschel mixer, a Nauter mixer, and a Banbury mixer. A Henschel mixer is preferred.
Examples of the mixing device for melt mixing include a batch-type mixing device such as a reaction tank and a continuous-type mixing device. A continuous mixer is preferred for uniform mixing at an appropriate temperature in a short time. Examples of the continuous mixing device include an extruder, a continuous kneader, and a triple roll.

As a method of solvent mixing, two or more types of polyester resins are dissolved in the above organic solvent and homogenized, followed by solvent removal and pulverization, or two or more types of polyester resins dissolved in the above organic solvents After the dispersion, the granules and the solvent are removed.

As a specific method for performing melt mixing, a mixture of polyester (A1) and, if necessary, an amorphous polyester resin (B) and/or a crystalline resin (C) is injected into a twin-screw extruder at a constant speed, At the same time, the radical reaction initiator (c) may be injected at a constant rate, and the reaction may be carried out while kneading and conveying at a temperature of 100 to 200°C.

At this time, the polyester (A1) and the amorphous polyester resin (B) and/or the crystalline resin (C), which are reaction raw materials to be charged or injected into the twin-screw extruder, do not need to be cooled from the resin reaction solution, respectively. It may be directly injected into the extruder as it is, or it may be carried out by cooling the resin once produced and pulverizing and supplying it to the twin-screw extruder.
Further, the method of melt mixing is not limited to these specifically exemplified methods, for example, a suitable method such as a method of charging raw materials into a reaction vessel, heating to a temperature at which they are in solution, and mixing. Of course, you can do it.

Further, at this time, as a method of desolvating the organic solvent derived from the decomposed product of the initiator, while reacting the raw materials in a twin-screw extruder, depressurizing from the vent port, cooling the resin once reacted, pulverized It is also possible to supply the product again to the twin-screw extruder and reduce the pressure from the vent port. Further, the resin which has once reacted may be cooled and pulverized, and the pressure may be reduced while stirring at an arbitrary temperature using a Nauta mixer or the like. When the raw materials are charged in a reaction vessel, heated to a temperature at which they are in a solution state, and mixed and reacted, the solvent may be desolvated by a depressurizing operation as it is after the reaction or by an appropriate method. Of course you can.

The toner of the present invention may contain the toner binder of the present invention, but may contain a colorant.

As the colorant, all of the dyes and pigments used as the colorant 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, Orazol Brown B, Oil Pink OP, etc., and these are used alone. Alternatively, two or more kinds can be mixed and used. If necessary, magnetic powder (a powder of a ferromagnetic metal such as iron, cobalt, 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 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.

In addition to the toner binder and the colorant, the toner of the present invention may optionally contain one or more additives selected from a releasing agent, a charge control agent, a fluidizing agent and the like.

Examples of the release agent include low molecular weight polypropylene, low molecular weight polyethylene, low molecular weight polypropylene polyethylene copolymer, polyolefin wax, microcrystalline wax, paraffin wax, Fischer-Tropsch wax and other aliphatic hydrocarbon waxes and their oxides, carnauba wax. , Montan wax, sazol 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 the like.

The polyolefin waxes include those obtained by (co)polymerizing (co)polymers of olefins (for example, ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-dodecene, 1-octadecene and mixtures thereof). And heat-reduced polyolefins], oxides of olefin (co)polymers with oxygen and/or ozone, maleic acid modified products of olefin (co)polymers [eg maleic acid and its derivatives (maleic anhydride, Modified products of monomethyl maleate, monobutyl maleate and dimethyl maleate], olefins and unsaturated carboxylic acids [(meth)acrylic acid, itaconic acid and maleic anhydride] and/or unsaturated carboxylic acid alkyl esters [(meth ) Copolymers with alkyl acrylates (alkyl having 1 to 18 carbon atoms) and alkyl maleates (alkyl having 1 to 18 carbon atoms), and the like, and sazol wax and the like.

Among the above, microcrystalline wax, paraffin wax, Fischer-Tropsch wax, carnauba wax and ester wax are preferable from the viewpoint of low temperature fixability and hot offset resistance.

From the viewpoint of low-temperature fixability and hot offset resistance, the release agent preferably has a softening point [Tm] of 50 to 170° C. by a flow tester, a polyolefin wax, a natural wax, and an aliphatic having 30 to 50 carbon atoms. Examples thereof include alcohols, fatty acids having 30 to 50 carbon atoms, and mixtures thereof.

As the charge control agent, a nigrosine dye, a triphenylmethane dye containing a tertiary amine as a side chain, a quaternary ammonium salt, a polyamine resin, an imidazole derivative, a quaternary ammonium salt group-containing polymer, a metal-containing azo dye, a copper phthalocyanine dye, Examples thereof include salicylic acid metal salts, benzylic acid boron complexes, sulfonic acid group-containing polymers, fluorine-containing polymers and halogen-substituted aromatic ring-containing polymers.

Examples of the fluidizing agent include colloidal silica, alumina powder, titanium oxide powder, calcium carbonate powder, fatty acid metal salt, silicone resin particles and fluororesin particles, and two or more kinds may be used in combination.

The release agent is 0 to 30% by weight, preferably 0.5 to 20% by weight, particularly preferably 1 to 10% by weight, based on the weight of the toner.
The charge control agent is 0 to 20% by weight, preferably 0.1 to 10% by weight, and particularly preferably 0.5 to 7.5% by weight, based on the weight of the toner.
The fluidizing agent is 0 to 10% by weight, preferably 0 to 5% by weight, particularly preferably 0.1 to 4% by weight, based on the weight of the toner.
The total amount of additives is 3 to 70% by weight, preferably 4 to 58% by weight, particularly preferably 5 to 50% by weight, based on the weight of the toner. When the composition ratio of the toner is within the above range, it is possible to easily obtain a toner having good charging properties.

The toner of the present invention may be obtained by any known kneading and pulverizing method, emulsion phase inversion method, polymerization method, or the like.
For example, when a toner is obtained by a kneading and pulverizing method, 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, the fine particles having a volume average particle diameter (D50) of preferably 5 to 20 μm can be prepared and then mixed with a fluidizing agent.
The volume average particle diameter (D50) is measured using a Coulter counter [eg, trade name: Multisizer III (manufactured by Coulter Co.)].

Further, when a toner is obtained by an emulsion phase inversion method, it may be produced by dissolving or dispersing the components constituting the toner excluding the fluidizing agent in an organic solvent, adding water to form an emulsion, and then separating and classifying. it can. The volume average particle diameter of the toner is preferably 3 to 15 μm.
The content of the organic solvent in the toner is preferably 25 to 2000 ppm, more preferably 40 to 1700 ppm, and most preferably 50 to 400 ppm from the viewpoint of heat resistant storage stability, odor and hot offset resistance.

The toner of the present invention is 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, to obtain an electrical latent image. Used as an image developer. The weight ratio of the toner to the carrier particles is preferably 1/99 to 100/0. Further, instead of the carrier particles, it may be rubbed with a member such as a charging blade to form an electric latent image.

The toner of the present invention is used for developing an electrostatic charge image or a magnetic latent image in electrophotography, electrostatic recording, electrostatic printing, etc., and is used as a support (paper, polyester film, etc.) by a copying machine, printer, etc. It is fixed as a recording material. As a method for fixing to the support, a known hot 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. Hereinafter, unless otherwise specified,% means% by weight and part means part by weight.

<Production Example 1> [Production of polyester (A1-1)]
In a reaction tank equipped with a cooling pipe, a stirrer and a nitrogen introducing pipe, 739 parts (96.0 mol%) of a bisphenol A/EO 2 mol adduct, 13 parts (4.0 mol%) of trimethylolpropane, and 137 terephthalic acid. Parts (42.0 mol %), 147 parts of adipic acid (51.2 mol %), and 2.5 parts of titanium diisopropoxybistriethanolaminate as a condensation catalyst were added at 230° C. to 0.5-2.5 kPa. After reacting for 5 hours under reduced pressure, the temperature was lowered to 175°C. 1 part of tert-butylcatechol was added as a polymerization inhibitor, 40 parts (6.8 mol%) of fumaric acid was further added, and the reaction was carried out for 2 hours in a nitrogen gas stream while distilling off the produced water. Next, the mixture was reacted for 8 hours under a reduced pressure of 0.5 to 2.5 kPa and then taken out to obtain polyester (A1-1). Tg _A1 of polyester (A1-1) was 37° C., the peak top molecular weight was 10,600, and the amount of double bonds was 0.32 mmol/g.

<Production Examples 2 to 3> [Production of polyesters (A1-2) to (A1-3)]
Polyester (A1-2) was prepared by charging alcohol components and carboxylic acid components shown in Table 1 in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introducing pipe, and otherwise performing the same reaction as in Production Example 1. ~ (A1-3) were obtained. Table 1 shows the double bond amount, glass transition temperature, and peak top molecular weight of the obtained polyesters (A1-2) to (A1-3).

<Production Example 4> [Production of polyester (A1-4)]
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introducing pipe, 559 parts (96.8 mol%) of 3-methyl-1,5-pentanediol, 18 parts (3.2 mol%) of trimethylolpropane, 578 parts (86.6 mol%) of terephthalic acid, 45 parts (7.7 mol%) of adipic acid, and 2.5 parts of titanium diisopropoxybistriethanolaminate as a condensation catalyst were added, and a nitrogen stream was formed at 220°C. The reaction was carried out for 2 hours while distilling off the produced water. Next, the reaction was performed under a reduced pressure of 0.5 to 2.5 kPa for 5 hours, and then the temperature was lowered to 175°C. 1 part of tert-butyl catechol was added as a polymerization inhibitor, 27 parts (5.7 mol%) of fumaric acid was further added, and the reaction was carried out for 2 hours in a nitrogen gas stream while distilling off the produced water. Next, the reaction was performed under a reduced pressure of 0.5 to 2.5 kPa for 8 hours, and then the product was taken out to obtain a polyester (A1-4). The recovered amount of 3-methyl-1,5-pentanediol was 86 parts. Table 1 shows the double bond amount, glass transition temperature, and peak top molecular weight of the obtained polyester (A1-4).

<Comparative Production Example 1> [Production of polyester (A1'-1)]
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introducing pipe, the alcohol component and the carboxylic acid component shown in Table 1 were charged, and otherwise the reaction was carried out in the same manner as in Production Example 1 to produce a polyester (A1′-1). ) Got.
Since the polyester (A1′-1) does not contain the unsaturated carboxylic acid component (y), it does not correspond to the polyester (A1) of the present invention.

<Production Example 5> [Production of amorphous polyester resin (B-1)]
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introducing pipe, 389 parts (50.0 mol%) of the bisphenol A/PO2 mol adduct and 365 parts of the bisphenol A/EO2 mol adduct described in Table 2 (50 0.0 mol %), 266 parts terephthalic acid (84.1 mol %), 7 parts adipic acid (6.9 mol %), 0.6 part titanium diisopropoxybistriethanolaminate as a condensation catalyst, nitrogen at 220° C. The reaction was carried out for 4 hours while distilling off the produced water under a stream of air. Furthermore, the reaction was performed for 10 hours under a reduced pressure of 0.5 to 2.5 kPa. Then, the mixture was cooled to 180° C., 29 parts (9.0 mol %) of trimellitic anhydride was added, and the mixture was allowed to react for 1 hour under a normal pressure and then taken out to obtain an amorphous polyester resin (B-1). This (B-1) does not contain the unsaturated carboxylic acid component (y).

<Production Example 6> [Production of crystalline resin (C-1)]
716 parts of dodecanedioic acid and 394 parts of 1,6-hexanediol and 0.5 part of tetrabutoxy titanate as a condensation catalyst were placed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, and a nitrogen stream was supplied at 170°C. The reaction was carried out for 8 hours while distilling off the produced water. Then, while gradually raising the temperature to 220° C., the reaction is carried out for 4 hours under a nitrogen stream while distilling off the produced water, and further under a reduced pressure of 0.5 to 2.5 kPa to give an acid value of 0.5. When it became the following, it was taken out to obtain a crystalline resin (C-1). The crystalline resin (C-1) had a softening temperature of 78°C and a melting point of 72°C. Since it has a softening temperature/melting point of 1.08, it has a property of being sharply softened by heat, and is a crystalline resin.

<Example 1> [Production of toner binder (D-1)]
15 parts of polyester (A1-1) and 85 parts of amorphous polyester resin (B-1) were supplied to a twin-screw kneader (Kurimoto Iron Works Co., Ltd., S5KRC kneader) at 52 kg/hour, and radical reaction was started at the same time. 2.0 parts of t-butyl peroxyisopropyl monocarbonate (c-1) was supplied as an agent at 1 kg/hour, and kneaded and extruded at 160° C. for 6 minutes to carry out a crosslinking reaction. The obtained product was cooled, and the powder pulverized to a particle size of 3 mm or less was supplied to a biaxial kneader and supplied at 52 kg/hour for 6 minutes at 160° C., a shaft rotation speed of 90 rpm, and a pressure reduction degree of 90 kPa. The solvent was removed from the vent port to obtain the toner binder (D-1) of the invention.

<Example 2> [Production of toner binder (D-2)]
Charge polyester (A1-1), amorphous polyester resin (B-1), crystalline resin (C-1) and t-butylperoxyisopropyl monocarbonate (c-1) in the parts by weight shown in Table 3. Then, the crosslinking reaction and the solvent removal were carried out in the same manner as in Example 1 to obtain the toner binder (D-2) of the invention.

<Example 3> [Production of toner binder (D-3)]
The polyester (A1-1) in the parts by weight shown in Table 3, the amorphous polyester resin (B-1) and t-butylperoxyisopropyl monocarbonate (c-1) were charged, and a crosslinking reaction was carried out in the same manner as in Example 1. The solvent removal time was changed to 20 minutes to obtain the toner binder (D-3) of the invention.

<Example 4> [Production of toner binder (D-4)]
The polyester (A1-1) in the parts by weight shown in Table 3, the amorphous polyester resin (B-1) and t-butylperoxyisopropyl monocarbonate (c-1) were charged, and a crosslinking reaction was carried out in the same manner as in Example 1. The desolvation depressurization degree was changed to 35 kPa to obtain the toner binder (D-4) of the invention.

<Example 5> [Production of toner binder (D-5)]
The polyester (A1-1) in the parts by weight shown in Table 3, the amorphous polyester resin (B-1) and t-butylperoxyisopropyl monocarbonate (c-1) were charged, and a crosslinking reaction was carried out in the same manner as in Example 1. Then, the solvent was removed in a reaction kettle at 40° C. for 1440 minutes with a stirring rotation speed of 180 rpm and a reduced pressure of 90 kPa to obtain a toner binder (D-5) of the invention.

<Example 6> [Production of toner binder (D-6)]
Polyester (A1-1), amorphous polyester resin (B-1), t-butylperoxyisopropyl monocarbonate (c-1), hydrogen peroxide (c-2), and ascorbin in the parts by weight shown in Table 3 The acid (d-1) was charged and the crosslinking reaction and solvent removal were carried out in the same manner as in Example 1 to obtain the toner binder (D-6) of the present invention.

<Example 7> [Production of toner binder (D-7)]
Polyester (A1-1) in the parts by weight shown in Table 3, amorphous polyester resin (B-1), t-butylperoxyisopropyl monocarbonate (c-1), ferric sulfate (d-2), Pyrophosphoric acid (d-3) was charged, and a crosslinking reaction and solvent removal were carried out in the same manner as in Example 1 to obtain a toner binder (D-7) of the present invention.

<Example 8> [Production of toner binder (D-8)]
The polyester (A1-1), the amorphous polyester resin (B-1) and the di-t-butyl peroxide (c-3) in the parts by weight shown in Table 3 were charged, and a crosslinking reaction was carried out in the same manner as in Example 1. The solvent was removed to obtain the toner binder (D-8) of the invention.

<Examples 9 to 13> [Production of toner binders (D-9) to (D-13)]
The polyesters (A1-1) to (A1-4) in the parts by weight shown in Table 4, the amorphous polyester resin (B-1), and t-butylperoxyisopropyl monocarbonate (c-1) were charged, and the examples were prepared. Cross-linking reaction and solvent removal were carried out in the same manner as in 1 to obtain toner binders (D-9) to (D-13) of the present invention.

<Example 14> [Production of toner binder (D-14)]
The polyester (A1), the crystalline resin (C-1), and t-butylperoxyisopropyl monocarbonate (c-1) in the parts by weight shown in Table 4 were charged, and the crosslinking reaction and solvent removal were carried out in the same manner as in Example 1. Then, a toner binder (D-14) of the invention was obtained.

<Comparative Example 1> [Production of Toner Binder (D'-1)]
The polyester (A1'-1), the amorphous polyester resin (B-1), and the t-butylperoxyisopropyl monocarbonate (c-1) in the parts by weight shown in Table 4 were charged, respectively, and the same procedure as in Example 1 was performed. The reaction and solvent removal were performed to obtain a toner binder (D'-1). Since (A1'-1) in the toner binder (D'-1) is not crosslinked by carbon-carbon bonds, it does not correspond to the toner binder of the present invention.

<Comparative Example 2> [Production of Toner Binder (D'-2)]
The polyester (A1-1), the amorphous polyester resin (B-1), and the t-butylperoxyisopropyl monocarbonate (c-1) in the parts by weight shown in Table 4 were charged and crosslinked in the same manner as in Example 1. A toner binder (D′-2) was obtained by performing a reaction and not performing a solvent removal step. The toner binder (D′-2) has an organic soluble content of 5000 ppm and does not correspond to the toner binder of the present invention.

<Comparative Example 3> [Production of Toner Binder (D'-3)]
The polyester (A1-1), the amorphous polyester resin (B-1), and the t-butylperoxyisopropyl monocarbonate (c-1) in the parts by weight shown in Table 4 were charged and crosslinked in the same manner as in Example 1. The reaction was carried out, the desolvation time was changed to 180 minutes, the desolvation decompression degree was changed to 35 kPa, and the desolvation temperature was changed to 180° C. to obtain a toner binder (D′-3). The toner binder (D′-3) has an organic soluble content of 48 ppm and does not correspond to the toner binder of the present invention.

The glass transition temperature, organic solvent content and surfactant content of each of the toner binders (D-1) to (D-14) and the comparative toner binders (D'-1) to (D'-3) are shown in Table 3. And Table 4.

<Example 15> [Production of toner (T-1)]
To 85 parts of the toner binder (D-1), 6 parts of pigment carbon black MA-100 [manufactured by Mitsubishi Chemical Corporation], 4 parts of release agent carnauba wax, charge control agent T-77 [Hodogaya Chemical Co., Ltd.] (Manufactured)] 4 parts were added to form a toner by the following method.
First, after premixing using a Henschel mixer [FM10B manufactured by Mitsui Miike Kakoki Co., Ltd.], kneading was performed by a biaxial kneader [PCM-30 manufactured by Ikegai Co., Ltd.]. Then, after finely pulverizing using a supersonic jet crusher Labo Jet [manufactured by Nippon Pneumatic Mfg. Co., Ltd.], it was classified by an air flow classifier [MDS-I manufactured by Nippon Pneumatic Mfg. Co., Ltd.] to obtain a volume average particle size. Toner particles having a D50 of 8 μm were obtained.
Then, 100 parts of the toner particles were mixed with 1 part of colloidal silica [Aerosil R972: manufactured by Nippon Aerosil] as a fluidizing agent in a sample mill to obtain a toner (T-1) of the present invention. Table 5 shows the evaluation results of Toner (T-1).

<Examples 16 to 28> [Production of Toners (T-2) to (T-14)]
Toners (T-2) to (T-14) of the present invention were obtained in the same manner as in Example 15 except that the raw material contents shown in Table 5 were used. The evaluation results of Toners (T-2) to (T-14) are shown in Table 5.

<Comparative Examples 4 to 6> [Production of Toners (T'-1) to (T'-3)]
Toners (T'-1) to (T'-3) were obtained in the same manner as in Example 15 except that the raw materials listed in Table 5 were used. The evaluation results of Toners (T'-1) to (T'-3) are shown in Table 5.

[Evaluation method]
The following are the measurement methods of low-temperature fixability, glossiness, hot offset resistance, heat resistant storage stability, charge stability, pulverizability, image strength, odor, fluidity, bending resistance, and document offset property of the obtained toner. The evaluation method will be described including the judgment criteria.

<Low temperature fixability>
The toner was uniformly placed on the paper surface so that the amount would be 1.00 mg/cm ² . At this time, as a method for placing the powder on the paper surface, a printer without a heat fixing device is used.
The temperature at which cold offset occurred (MFT) was measured when this paper was passed through a soft roller at a fixing speed (peripheral speed of the heating roller) of 213 mm/sec.
The lower the cold offset generation temperature, the better the low-temperature fixability.
Under this evaluation condition, generally 125° C. or lower is required.

<Glossiness>
The fixing evaluation is performed in the same manner as the low temperature fixing property.
Lay white thick paper under the image, and use a gloss meter (HORIBA, Ltd., “IG-330”) to measure the gloss level (%) of the printed image at an incident angle of 60 degrees and to measure the cold offset. From the temperature above the generation temperature (MFT) to the temperature where the hot offset occurred, the measurement was performed every 5° C., and the highest glossiness (%) in that range was used as an index of the glossiness of the toner.
For example, if 120° C. is 10%, 125° C. is 15%, 130° C. is 20%, and 135° C. is 18%, 20% of 130° C. is the highest value, so 20% is adopted.
The higher the glossiness, the better the glossiness. Under this evaluation condition, 20% or more is preferable.

<Hot offset resistance (hot offset generation temperature)>
The fixation was evaluated in the same manner as the low-temperature fixability, and the presence or absence of hot offset on the fixed image was visually evaluated. The temperature at which hot offset occurred after passing through the pressure roller was defined as hot offset resistance (°C). Under this evaluation condition, the preferable range is 180° C. or higher.

<Heat-resistant storage stability>
1 g of the toner was placed in a closed container and allowed to stand for 24 hours in an atmosphere of a temperature of 50° C. and a humidity of 50%, the degree of blocking was visually determined, and the heat-resistant storability was evaluated according to the following criteria.
[Criteria]
◯: No blocking occurred at all.
Δ: Blocking occurs in part.
X: Blocking occurs on the whole.

<Charging stability>
(1) 0.5 g of toner and 20 g of ferrite carrier (F-150, manufactured by Powder Tech Co., Ltd.) are put in a 50 ml glass bottle, and the humidity is adjusted at 23° C. and relative humidity of 50% for 8 hours or more. (2) Friction stirring was performed for 50 minutes at 50 rpm for 60 minutes with a Turbula shaker mixer, and the charge amount at each time was measured.
A blow-off charge amount measuring device [manufactured by Toshiba Chemical Co., Ltd.] was used for the measurement.
The "charge amount after 60 minutes of friction time/charge amount after 10 minutes of friction time" was calculated and used as an index of charge stability.

[Criteria]
○: 0.7 or more △: 0.6 or more and less than 0.7 ×: less than 0.6

<Crushability>
A coarse crushed product (8.6 mesh pass to 30 mesh on) kneaded and cooled by a twin-screw kneader is finely divided by a supersonic jet crusher Labjet [manufactured by Nippon Pneumatic Mfg. Co., Ltd.] under the following conditions. Crushed.
Grinding pressure: 0.5 MPa
Crushing time: 10 minutes Adjuster ring: 15 mm
Louver size: Medium The volume average particle diameter (μm) was measured by Coulter Counter-TAII (manufactured by Coulter Electronics Co., USA) without classifying, and the pulverizability was evaluated according to the following criteria.

[Criteria]
◯: less than 10 μm Δ: 10 μm or more and less than 12 μm ×: 12 μm or more

<Image intensity>
According to JIS K5600, the image fixed by the low-temperature fixing property was subjected to a scratch test by applying a load of 10 g from directly above the pencil fixed at an angle of 45 degrees, and the image strength was evaluated from the pencil hardness without scratches. .. The higher the pencil hardness, the better the image strength. Generally, HB or higher is required.

[Criteria]
○: HB or more △: B
×: 2B or less

<Odor test>
1.0 g of the toner was put 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 the odor was confirmed by 10 people's monitors and evaluated according to the following criteria.
[Criteria]
○: 1 person answered that it did not smell or 1 person answered that it stood △: 2 to 6 persons answered that it stood ×: 7 or more persons answered that it stinks

<Toner fluidity>
The quietness density of the toner was measured with a powder tester manufactured by Hosokawa Micron, and the fluidity of the toner was judged according to the following criteria. The above is the practical range.
[Criteria]
◯: 36 g/100 ml or more Δ: 30 g/100 ml or more and less than 36 g/100 ml X: less than 30 g/100 ml

<Bending resistance>
The image fixed by the low temperature fixing property is bent so that the image surface is on the inner side, rubbed 3 times with a load of 30 g, spread the paper, and visually check for the presence of white streaks after bending on the image. did.
[Criteria]
○: No white streaks △: Slight white streaks ×: White streaks

<Document offset property>
Two sheets of A4 paper, on which the images obtained by the evaluation of low-temperature fixability are fixed, are overlapped on their fixing surfaces, a load of 420 g (0.68 g/cm ² ) is applied, and the mixture is allowed to stand at 50° C. for 30 minutes. .. With respect to the state in which the superposed papers were separated from each other, the document offset property was evaluated according to the following criteria.

[Criteria]
○: No resistance △: Crisp sound, but the image did not peel from the paper surface ×: The image peeled from the paper surface

As is clear from the evaluation results in Table 5, all of the example toners of the present invention have excellent performance evaluation results.
On the other hand, the toner of Comparative Example was inferior in at least one performance evaluation.

INDUSTRIAL APPLICABILITY The toner binder and toner of the present invention have excellent low-temperature fixability, pulverizability, image strength and heat-resistant storage stability while maintaining offset resistance while having a high level of gloss, and are suitable for electrophotography, electrostatic recording and electrostatic It can be suitably used as a toner for full-color electrostatic image development and a toner binder used for printing and the like.
Furthermore, it is suitable for use as an additive for paints, an additive for adhesives, and particles for electronic paper.

Claims (10)

A method for producing a toner binder containing a non-linear polyester resin (A) and an organic solvent that is a decomposition product of a radical reaction initiator (c), which is a decomposition product of the radical reaction initiator (c) in the toner binder. Including a step of desolvating an organic solvent by a reduced pressure operation , the (A) is a resin having a structure in which a polyester (A0) is crosslinked, and at least one bond forming the crosslinked structure is a radical reaction initiator ( The polyester (A0), which is obtained by directly bonding at least one carbon atom of the carbon atoms contained in the polyester (A0) and the carbon atom contained in the polyester (A0) by using c), and is crosslinked. Is a polyester containing a polyester (A1) having a carbon-carbon double bond, a glass transition temperature Tg _A1 of the polyester (A1) having a carbon-carbon double bond is -9 to 37°C, and a non-linear polyester The resin (A) is a resin in which at least a part of the carbon-carbon double bonds derived from the polyester (A1) having a carbon-carbon double bond is crosslinked, and the radical reaction initiator (c The method for producing a toner binder, wherein the content of the organic solvent, which is a decomposed product of 1), is 50 ppm or more and 2000 ppm or less. The method for producing a toner binder according to claim 1, wherein the organic solvent is a compound having a carbon number of 2 to 10, a melting point of less than 30° C., and a boiling point of higher than 30° C. and 300° C. or lower. The method for producing a toner binder according to claim 1, wherein the organic solvent is at least one selected from the group consisting of acetone, isopropyl alcohol, and t-butanol. The carbon-carbon double bond amount in the polyester (A1) having a carbon-carbon double bond is 0.02 to 2.00 mmol/g based on the weight of (A1). A method for producing the toner binder as described above. The amorphous polyester resin containing an amorphous polyester resin (B) excluding the non-linear polyester resin (A), wherein (B) is an amorphous polyester resin having a saturated carboxylic acid component and a saturated alcohol component as constituent monomers. 4. The method for producing the toner binder according to any one of 4 above. A non-linear polyester resin containing an amorphous polyester resin (B) excluding the non-linear polyester resin (A), wherein (B) is an amorphous polyester resin having a saturated carboxylic acid component and a saturated alcohol component as constituent monomers. The ratio [weight ratio (A1)/(B)] of the equivalent amount of the polyester (A1) having a carbon-carbon double bond used as the raw material of (A) and the weight of the amorphous polyester resin (B) is 5 / 95-50 / 50 a method for producing a toner binder according to any one of claims 1 to 5 is. Method of manufacturing a toner binder according to any one of claims 1 to 6 containing a crystalline resin except a non-linear polyester resin (A) (C). Method for producing a toner binder according to claim 1-7 or a glass transition temperature Tg _T of the toner binder is -35~80 ℃. The method of manufacturing a toner containing toner binder according to any one of claims 1-8. The non-linear polyester resin (A) is crosslinked by directly bonding at least one carbon atom contained in the polyester (A0) to the carbon atom contained in the polyester (A0) by using the reducing agent (d). method for producing a toner binder according to claim 1-8 were those that are.