JP2019095781A - Method for producing toner - Google Patents

Abstract

To provide a toner excellent in low temperature fixability and hot-offset resistance, micro offset resistance, glossiness, heat-resistant storage property and charge stability.SOLUTION: A method for producing a toner includes a step of mixing a polyester resin (A) having a carbon-carbon double bond amount of 0.02-2.00 millimole/g based on a weight of the polyester resin (A1), a polyester resin (B) having a carbon-carbon double bond amount of less than 0.02 millimole/g based on a weight of the polyester resin (B), a coloring agent, a release agent, and a crosslinking agent (c) capable of reacting with the carbon-carbon double bond of the (A1) at 50-200°C, in which viscosities at 120°C of (A1) and (B) satisfy Expression (1): 0.1≤ηA1/ηB≤125, in Expression (1), ηA1 represents viscosity ηPa s of the polyester resin (A1) at 120°C, and ηB represents viscosity ηPa s of the polyester resin (B) at 120°C.SELECTED DRAWING: None

Description

  The present invention relates to a method of producing a toner.

In recent years, with the development of electrophotographic systems, the demand for electrophotographic apparatuses such as copying machines and laser printers has been rapidly increasing, and the demand for their performance has also been advanced.
Conventionally, for electrophotography, a latent image based on image information is formed on a latent image carrier such as an electrophotographic photosensitive member, and the latent image is developed with a toner of a corresponding color, and then the toner image is transferred onto a transfer material There is known a method and apparatus for obtaining an image by heating and fixing a toner image on a transfer material after repeating an image forming process of transferring the image to the image.

In order to pass through these processes without problems, it is necessary for the toner to first maintain a stable charge, and then to have good fixability to paper. In addition, since the device has a heater at the fixing portion, the temperature in the device is increased, so that the toner is required not to be blocked in the device.
Further, from the viewpoint of energy saving in which the consumption energy in the fixing step is reduced while the miniaturization, speeding up and image quality enhancement of the electrophotographic apparatus are promoted, the improvement of the low temperature fixability of the toner is strongly demanded.

  Recently, as a transfer material to be used, many types of paper such as recycled paper with large surface irregularities and coated paper with a smooth surface are used. In order to cope with the surface properties of these transfer materials, a wide nip fixing device such as a soft roller or a belt roller is preferably used. However, when the nip width is increased, the contact area between the toner and the fixing roller is increased, and a so-called high temperature offset phenomenon occurs in which the molten toner adheres to the fixing roller, so it is premised that offset resistance is required.

In order to prevent the high temperature offset phenomenon, a method of mixing a high molecular weight resin and a low molecular weight resin is generally used, whereby the entire molecular weight distribution can be broadened and both the offset resistance and the low temperature fixability can be achieved. However, when resins having extremely different melt viscosities are mixed, uniform dispersion of the resins can not be obtained, and sufficient low temperature fixability and offset resistance can not be obtained.
Patent Documents 1 and 2 disclose a technique for improving the above-mentioned mixing property and improving low-temperature fixability and hot offset property by crosslinking unsaturated double bonds using a radical polymerization reaction with peroxide. ing. However, the dispersion of the release agent and the pigment is not sufficient, and there is a problem that the micro offset due to the dispersion between the particles and the release to the particle surface and the pigment occurs. Further, Patent Document 3 proposes a method in which a pigment, a release agent, a resin and a polymerization initiator are simultaneously mixed, but the dispersion of the release agent and the pigment is not sufficient. On the other hand, Patent Document 4 proposes a method of improving the hot offset property by improving the dispersibility of the release agent using a dispersant, but it is still insufficient.

  As described above, toner binders and toners excellent in low-temperature fixability and hot offset resistance, and further excellent in micro offset resistance, glossiness, heat resistant storage stability and charge stability have not been found.

International Publication No. 2007/034813 JP, 2017-45036, A JP-A-8-152743 JP 2011-13548 A

  An object of the present invention is to provide a toner which is excellent in low-temperature fixability and hot offset resistance, and further excellent in micro offset resistance, glossiness, heat resistant storage stability and charge stability.

The present inventors arrived at the present invention as a result of studying to achieve the above object.
That is, in the present invention, the polyester resin (A1) wherein the carbon-carbon double bond content is 0.02 to 2.00 mmol / g based on the weight of the polyester resin (A1), the carbon-carbon double bond content is Polyester resin (B), which is less than 0.02 mmol / g based on the weight of polyester resin (B), colorant, releasing agent, and crosslinking agent capable of reacting with carbon-carbon double bond possessed by (A1). (C) is mixed at 50 ° C. to 200 ° C., and it is a method for producing a toner in which the viscosities at 120 ° C. of the (A1) and the (B) satisfy the following formula (1).
0.1 ≦ ηA1 / ηB ≦ 125 (1)
[Η A1 is the viscosity η Pa · s of the polyester resin (A1) at 120 ° C., and η B is the viscosity η Pa · s of the polyester resin (B) at 120 ° C. ]

  The toner obtained by the production method of the present invention is excellent in low-temperature fixability and hot offset resistance, and further excellent in micro offset resistance, glossiness, heat resistant storage stability and charging stability.

Hereinafter, the present invention will be described in detail by showing embodiments of the present invention.
The method for producing a toner according to the present invention comprises a polyester resin (A1) having a carbon-carbon double bond content of 0.02 to 2.00 mmol / g based on the weight of the polyester resin (A1), a carbon-carbon double React with the polyester resin (B) having a binding amount of less than 0.02 mmol / g based on the weight of the polyester resin (B), the colorant, the mold release agent, and the carbon-carbon double bond possessed by the above (A1) A method of producing a toner including the step of mixing the obtained crosslinking agent (c) at 50 ° C. to 200 ° C., and the viscosities at 120 ° C. of the (A1) and the (B) satisfy the following formula (1) It is characterized by
0.1 ≦ ηA1 / ηB ≦ 125 (1)
[Η A1 is the viscosity η Pa · s of the polyester resin (A1) at 120 ° C., and η B is the viscosity η Pa · s of the polyester resin (B) at 120 ° C. ]
Hereinafter, the method for producing the toner of the present invention will be sequentially described.

The toner produced according to the present invention is produced using, as an essential component, a polyester resin (A1) having a carbon-carbon double bond content of 0.02 to 2.00 mmol / g based on the weight of the polyester resin (A1). Ru.
The polyester resin (A1) is a polyester resin obtained by polycondensing an alcohol component and a carboxylic acid component, and it may have a carbon-carbon double bond of 0.02 to 2.00 mmol / g. Alcohol components and carboxylic acid components may be used. In addition, the carbon-carbon double bond of the present invention does not include aromatic ring and heterocyclic ring bonds.
In order for the polyester resin (A1) to have a carbon-carbon double bond, an unsaturated carboxylic acid component (z) and / or an alcohol component having a carbon-carbon double bond and / or a carboxylic acid component may be used. Or the method of using unsaturated alcohol component (w), etc. are mentioned. Further, in the above method, a component having no carbon-carbon double bond can be used other than the above-mentioned essential component, and as a component having no carbon-carbon double bond, a saturated alcohol component (x) and Saturated carboxylic acid component (y) etc. are mentioned.
Among these components, as a component of the polyester resin (A1), from the viewpoint that (A1) has a carbon-carbon double bond, unsaturated carboxylic acid component (z) and / or unsaturated alcohol component (w) It is preferable to use
The polyester resin (A1) may have a carbon-carbon double bond of 0.02 to 2.00 mmol / g, and one of each of these components may be polycondensed. What polycondensed by using together multiple types as each component may be used.
In the present specification, bonding of an aromatic ring and a heterocyclic ring is not considered in determining whether it is the unsaturated carboxylic acid component (z) or the saturated carboxylic acid component (y). That is, a compound wherein the aromatic ring portion and the heterocyclic portion are unsaturated carboxylic acids is judged as the unsaturated carboxylic acid component (z), and a compound wherein the aromatic ring portion and the heterocyclic portion are saturated carboxylic acids is saturated Judged as carboxylic acid component (y).
Similarly, the combination of an aromatic ring and a heterocyclic ring is not considered in determining whether it is the unsaturated alcohol component (w) or the saturated alcohol component (x). That is, a compound in which the aromatic ring moiety and the heterocyclic moiety are unsaturated alcohols other than the aromatic ring moiety is judged as the unsaturated alcohol component (w), and a compound in which the aromatic ring moiety and the heterocyclic moiety are saturated alcohols is a saturated alcohol component ( Judge as x).

  As the unsaturated carboxylic acid component (z), unsaturated monocarboxylic acid (z1), unsaturated dicarboxylic acid (z2), unsaturated polycarboxylic acid (z3), anhydrides and lower alkyl esters of these acids, etc. may be mentioned. Be One type of unsaturated carboxylic acid component (z) may be used, or two or more types may be used in combination.

  Examples of the unsaturated monocarboxylic acid (z1) include unsaturated monocarboxylic acids having 2 to 30 carbon atoms, and specific examples thereof include acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, 3-butenoic acid, and angelic acid. , Tiglic acid, 4-pentenoic acid, 2-ethyl-2-butenoic acid, 10-undecenoic acid, 2,4-hexadienoic acid, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vacenic acid, gadeau Examples include acids, eicosenoic acids, erucic acid and nervonic acid.

  Examples of unsaturated dicarboxylic acids (z2) include alkene dicarboxylic acids having 4 to 50 carbon atoms. Specifically, alkenyl succinic acids such as dodecenyl succinic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid And acids such as glutaconic acid.

  As the unsaturated polycarboxylic acid (z3), trivalent or higher alkene polycarboxylic acids having 6 to 50 carbon atoms (specifically, aconitic acid, 3-butene-1,2,3-tricarboxylic acid and 4-pentene) Alkene tricarboxylic acids such as -1,2,4-tricarboxylic acid, 1-pentene-1,1,4,4-tetracarboxylic acid, 4-pentene-1,2,3,4-tetracarboxylic acid and 3-hexene Alkene tetracarboxylic acid such as -1,1,6,6-tetracarboxylic acid etc. may be mentioned.

Among these unsaturated carboxylic acid components (z), acrylic acid, methacrylic acid, alkenyl succinic acid, maleic acid and fumaric acid are preferable from the viewpoint of achieving both low temperature fixing ability and hot offset resistance.
More preferably, acrylic acid, methacrylic acid, maleic acid, fumaric acid and combinations thereof are used. Anhydrides and lower alkyl esters of these acids are also preferred.

  As unsaturated alcohol component (w), unsaturated monool (w1), unsaturated diol (w2), etc. are mentioned. The unsaturated alcohol component (w) may be used alone or in combination of two or more.

  Examples of unsaturated monools (w1) include unsaturated monools having 2 to 30 carbon atoms, and preferred examples thereof include 2-propen-1-ol, oleyl alcohol and 2-hydroxyethyl methacrylate. .

  As unsaturated diol (w2), C2-C30 unsaturated diol is mentioned, A preferable example is licinoleyl alcohol.

  Examples of the saturated alcohol component (x) include saturated monool (x1), saturated diol (x2), and trivalent or higher saturated polyol (x3). The saturated alcohol component (x) may be used alone or in combination of two or more.

As saturated monool (x1), C1-C30 linear or branched alkyl alcohol (A methanol, ethanol, isopropanol, dodecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol etc.) etc. are mentioned.
Among these saturated monools, preferred are linear or branched alkyl alcohols having 8 to 24 carbon atoms, and more preferred are dodecyl alcohol, myristyl alcohol, stearyl alcohol, behenyl alcohol and combinations thereof.

The saturated diol (x2) is an alkylene glycol having 2 to 36 carbon atoms (preferably an alkylene glycol having 2 to 12 carbon atoms, and specifically, ethylene glycol, 1,2-propylene glycol, 1,3-propylene) Glycol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol and 1,12-dodecanediol Etc.), C4-C36 alkylene ether glycols (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol and polytetramethylene ether glycol etc.), C6-C36 alicyclic diols (1, 4-Cyclohe Sundimethanol and hydrogenated bisphenol A etc.), (poly) alkylene oxide adducts of the above-mentioned alicyclic diols (preferably with an average added mole number of 1 to 30), aromatic diols [monocyclic dihydric phenols (eg hydroquinone etc.) and And the like, and alkylene oxide adducts of the above-mentioned aromatic diols (preferably, the average addition mole number is 2 to 30).
Among these, from the viewpoint of low-temperature fixability and heat resistant storage stability, alkylene oxide adducts of aromatic diols are preferable, and alkylene oxide adducts of bisphenols are more preferable.
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 and the like).

  The alkylene oxide adduct of bisphenols is generally obtained by adding an alkylene oxide (hereinafter, "alkylene oxide" may be abbreviated as AO) to bisphenols. As bisphenols, what is shown by following General formula (1) is mentioned.

HO-Ar-P-Ar-OH (1)
[Wherein, P represents an alkylene group having 1 to 3 carbon atoms, -SO _2- , -O-, -S- or a direct bond, and Ar represents a halogen atom or an alkyl having 1 to 30 carbon atoms] Represents a phenylene group which may be substituted by a group. ]

  Bisphenols include, for example, bisphenol A, bisphenol F, bisphenol B, bisphenol AD, bisphenol S, trichlorobisphenol A, tetrachlorobisphenol A, dibromobisphenol F, 2-methylbisphenol A, 2, 6-dimethylbisphenol A and 2 And 2'-diethyl bisphenol F, and two or more of these can be used in combination.

As the alkylene oxide to be 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), propylene oxide (It means “1,2-propylene oxide” and may be abbreviated as PO hereinafter), 1,2-, 2,3-, 1,3- or iso-butylene oxide, tetrahydrofuran and two of them Combinations of species or more may be mentioned.
In terms of heat resistant storage stability and low temperature fixability, AO constituting an AO adduct of bisphenols is preferably EO and PO. The average addition mole number of AO is preferably 2 to 30 moles, more preferably 2 to 10 moles, and still more preferably 2 to 5 moles from the viewpoint of heat resistant storage stability and low temperature fixability.
Among the alkylene oxide adducts of bisphenols, preferred from the viewpoint of toner fixability are EO adducts and PO adducts of bisphenol A (average addition mole number is preferably 2 to 4, more preferably 2 to 3) It is.

  The trivalent or higher saturated polyol (x3) includes a trivalent or higher aliphatic polyhydric alcohol having 3 to 36 carbon atoms (x31), saccharides and derivatives thereof (x32), and AO adducts of aliphatic polyhydric alcohols (average Addition mole number is preferably 1 to 30 (x 33), AO adduct of trisphenol (such as trisphenol PA) (average addition mole number is preferably 2 to 30) (x 34), novolak resin (phenol novolac and cresol Novolak and the like are included, and an AO adduct of which the average degree of polymerization is preferably 3 to 60 is preferable (the average addition mole number is preferably 2 to 30) (x 35) and the like.

  Examples of the trivalent or higher aliphatic polyhydric alcohol having 3 to 36 carbon atoms (x 31) include alkane polyols and intramolecular or intermolecular dehydrated products thereof, such as glycerin, trimethylol ethane, trimethylol propane, pentaerythritol, Sorbitol, sorbitan, polyglycerin and dipentaerythritol etc. may be mentioned.

  Examples of sugars and their derivatives (x32) include sucrose and methyl glucoside.

  Among the trivalent or higher saturated polyols (x3), trivalent or higher aliphatic polyhydric alcohol (x31) having 3 to 36 carbon atoms and novolak resin (phenol Novolak and cresol novolac and the like are included, and an AO adduct (average addition mole number is preferably 2 to 30) (x 35) is preferable as the average polymerization degree is preferably 3 to 60.

  It is preferable from the viewpoints of heat resistant storage stability and hot offset resistance that a combination of a divalent diol (x2) and a trivalent or higher polyol (x3) as the saturated alcohol component (x) is used.

  Among these saturated alcohol components (x), preferable ones from the viewpoint of coexistence of low temperature fixing ability and hot offset resistance are alkylene glycols having 2 to 12 carbon atoms, and AO adducts of bisphenols (the average addition mole number is preferably Is a trivalent or higher aliphatic polyhydric alcohol having 2 to 30 carbon atoms (x 31), and novolak resins (phenol novolak and cresol novolac etc. are included, and the average degree of polymerization is preferably 3 to 60) Of AO adducts (average added mole number is preferably 2 to 30) (x 35).

More preferable from the viewpoint of heat-resistant storage stability are alkylene glycols having 2 to 10 carbon atoms, AO adducts of bisphenols (the average addition mole number is preferably 2 to 5), and tri- to tetravalent compounds having 3 to 36 carbon atoms It is an AO adduct (average added mole number is preferably 2 to 30) containing aliphatic polyhydric alcohol and (phenol novolak and cresol novolac etc., preferably 3 to 60 as average polymerization degree).
More preferably, it is an alkylene glycol having 2 to 6 carbon atoms, a trivalent aliphatic polyhydric alcohol having 3 to 36 carbon atoms, and an AO adduct of bisphenol A (average addition mole number is preferably 2 to 5), particularly Preferably, ethylene glycol, propylene glycol, 3-methyl-1,5-pentanediol, trimethylolpropane and AO adduct of bisphenol A (preferably 2-3 as the number of AO units).

  As the saturated alcohol component (x), it is preferable to use a saturated diol (x2) and a trivalent or higher saturated polyol (x3) in combination. The molar ratio [(x2) / (x3)] of the saturated diol (x2) and the trivalent or higher saturated polyol (x3) when used in combination is preferably 99/1 to 80/20 from the viewpoint of hot offset resistance, 98 / 2 to 90/10 are more preferable.

As a saturated carboxylic acid component (y), aromatic carboxylic acid (y1) and aliphatic carboxylic acid (y2) are mentioned.
As the saturated carboxylic acid component (y), one type may be used, or two or more types may be used in combination.
As aliphatic carboxylic acid (y2), aliphatic monocarboxylic acid having 2 to 50 carbon atoms (acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthate, caprylic acid, pelargonic acid, capric acid, lauric acid, Myristic acid, palmitic acid, margaric acid, stearic acid and behenic acid etc.), aliphatic dicarboxylic acid having 2 to 50 carbon atoms (oxalic acid, malonic acid, succinic acid, adipic acid, repargic acid and sebacic acid etc.), carbon number 6-36 aliphatic tricarboxylic acid (hexane tricarboxylic acid etc.) etc. are mentioned.
As aromatic carboxylic acid (y1), aromatic monocarboxylic acid having 7 to 37 carbon atoms (benzoic acid, toluic acid, 4-ethylbenzoic acid, 4-propylbenzoic acid, etc.), aromatics having 8 to 36 carbon atoms Examples thereof include dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, etc.), and trivalent or higher aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, etc.), and the like.

  As the saturated carboxylic acid component (y), anhydrides of these carboxylic acids, lower alkyl (1 to 4 carbon atoms) esters (such as methyl ester, ethyl ester and isopropyl ester) may be used, and these carboxylic acids and You may use together.

Among these saturated carboxylic acid components (y), preferred are those having 7 to 37 carbon atoms, and 1 to 50 aliphatic dicarboxylic acids having 2 to 50 carbon atoms, from the viewpoint of achieving both low temperature fixing ability and hot offset resistance. It is an acid, a C8-C20 aromatic dicarboxylic acid, and a C9-C20 trivalent or more aromatic polycarboxylic acid.
From the viewpoint of storage stability, chargeability and charge stability, benzoic acid, adipic acid, terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid and combinations thereof are more preferable.
More preferable are adipic acid, terephthalic acid, trimellitic acid and combinations thereof. Anhydrides and lower alkyl esters of these acids are likewise preferred.

The polyester resin (A1) in the present invention is not particularly limited, but is preferably a non-linear polyester resin from the viewpoint of improving the elasticity at high temperature.
Further, the method for producing the polyester resin (A1) in the present invention is not particularly limited, but it is preferable to be a polyester resin obtained by polycondensing an alcohol component and a carboxylic acid component as described above. Furthermore, when the polyester resin (A1) is a non-linear polyester resin, the heat resistant storage stability and the hot offset resistance are improved. The non-linear polyester resin may be, for example, a trivalent or higher aromatic polycarboxylic acid having 9 to 20 carbon atoms or a saturated carboxylic acid component having a trivalent or higher saturated polyol (x3) as a component raw material or a saturated carboxylic acid component. An acid anhydride or lower alkyl ester may be used. By being non-linear, the heat resistant storage stability and the hot offset resistance are improved.

The polyester resin (A1) in the present invention is a polyester resin (A1) in which the carbon-carbon double bond content is 0.02 to 2.00 mmol / g based on the weight of the polyester resin (A1). The amount of carbon-carbon double bonds referred to herein is the number of millimoles of carbon-carbon double bonds contained in 1 g in total of raw materials such as alcohol components and carboxylic acid components constituting the polyester resin (A1).
For example, a polyester resin composed of fumaric acid (0.05 g) and bisphenol A bisphenol A · PO2 molar adduct (0.95 g) as a raw material of polyester resin is a fumaric acid having a molecular weight of 116 per 1 g in total of polyester resin Because it has 0.05g,
It becomes 0.05 / 116x1000 = 0.43 mmol / g.
The polyester resin in this case corresponds to the polyester resin (A1).
For example, when fumaric acid (0.3 g) and bisphenol A bisphenol A · PO2 molar adduct (0.7 g) are used as raw materials of polyester resin, fumaric acid having a molecular weight of 116 is 0. Because I have 3g,
0.3 / 116 × 1000 = 2.59 mmol / g.
The polyester resin in this case does not correspond to the polyester resin (A1).

The carbon-carbon double bond content of the polyester resin (A1) in the present invention is 0.02 mmol / g or more, preferably 0.10 mmol, from the viewpoints of hot offset resistance, micro offset resistance, and heat resistant storage stability. / G or more, more preferably 0.15 mmol / g or more. Further, it is 2.00 mmol / g or less, preferably 1.00 or less, more preferably 0.75 or less, and still more preferably 0. 50 or less.
A step of mixing a polyester resin (A1), a polyester resin (B), a colorant, a mold release agent and a crosslinking agent (c) capable of reacting with the carbon-carbon double bond of the above (A1) at 50 ° C. to 200 ° C. At that time, when the amount of carbon-carbon double bonds of the polyester resin (A1) is within the above range, the non-linear polyester having carbon-carbon bonds in which carbon-carbon double bonds of the polyester resin (A1) are crosslinked. The resin is easily formed uniformly in the polyester resin (B), and the colorant and the releasing agent are easily dispersed in the polyester resin in a uniformly dispersed state.

In the present invention, the polyester resin (A1) and the polyester resin (B) can be produced in the same manner as known polyesters.
For example, the reaction may be carried out by reacting the components at a reaction temperature of preferably 150 to 280 ° C., more preferably 160 to 250 ° C., still more preferably 170 to 235 ° C. in an inert gas (nitrogen gas etc.) atmosphere. it can. 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 be used as needed. Examples of esterification catalysts include tin-containing catalysts (eg, dibutyltin oxide etc.), antimony trioxide, titanium-containing catalysts [eg titanium alkoxide, potassium oxalate titanate, titanium terephthalate, titanium terephthalate alkoxide, JP-A-2006-243715 Catalysts {Titanium diisopropoxy bis (triethanol aminate), titanium dihydroxy bis (triethanol aminate), titanium monohydroxy tris (triethanol aminate), titanyl bis (triethanol aminate) and their Intramolecular polycondensate etc. and catalysts described in JP 2007-11307 A (titanium tributoxy terephthalate, titanium triisopropoxy terephthalate, titanium diisopropoxy diterephthalate, etc.) ], Zirconium-containing catalysts (e.g. zirconyl acetate, etc.), and zinc acetate, and the like. Among these, preferred is a titanium-containing catalyst. It is also effective to reduce the pressure 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. As the stabilizer, hydroquinone, methylhydroquinone and hindered phenol compounds may, for example, be mentioned.

  The charging ratio of the total of the alcohol component and the carboxylic acid component is preferably 2/1 to 1/2, more preferably 1.5 / 1 to 1/1, as the equivalent ratio [OH] / [COOH] of the hydroxyl group and the carboxyl group. It is 1.3, particularly preferably 1.4 / 1 to 1 / 1.2.

  The weight average molecular weight (Mw) in gel permeation chromatography (GPC) of the tetrahydrofuran (sometimes abbreviated as THF) solution in the polyester resin (A1) is micro offset resistance, hot offset resistance, heat resistance It is preferably 2,000 to 40,000, more preferably a weight average molecular weight of 7,000 to 38,000, and still more preferably a weight average, from the viewpoint of coexistence of storage stability, low temperature fixability and glossiness. The molecular weight is 12,000 to 25,000. In addition, the measurement conditions of GPC measurement are as follows.

In the present invention, the weight average molecular weight of the polyester resin (A1), the polyester resin (B) and the resin in the toner (hereinafter sometimes abbreviated as Mw), the number average molecular weight (hereinafter abbreviated as Mn) The peak top molecular weight (hereinafter sometimes abbreviated as Mp) can be measured using GPC under the following conditions.
Device (one example): HLC-8120 (manufactured by Tosoh Corporation)
Column (one example): Two TSK GEL GMH6 [Tosoh Corp.]
Measurement temperature: 40 ° C
Sample solution: 0.25 wt% THF solution Injection volume: 100 μL
Detector: Refractive index detector Reference material: Tosoh Co., Ltd. product standard polystyrene (TSK standard POLYSTYRENE) 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)
To measure 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 glass transition temperature (Tg) of the polyester resin (A1) is preferably −20 to 60 ° C., and the low temperature fixability becomes good when the Tg is 60 ° C. or less, and the heat resistance storage is −20 ° C. or more Sex is good. More preferably, it is −10 to 50 ° C., further preferably 0 to 40 ° C., and particularly preferably 15 to 38 ° C.
In addition, a glass transition temperature (Tg) can be measured by the method (DSC method) prescribed | regulated to ASTMD3418-82, for example using TA Instruments Co., Ltd. product and DSC Q20.

Specifically, 5 mg of a sample is placed in a container of a DSC device, heated at a temperature of 20 ° C./min to a temperature about 30 ° C. higher than the end of glass transition, and cooled at a temperature of about 50 ° C. lower than the glass transition temperature at 60 ° C./min. Then, it is heated at a temperature of 20 ° C./min to a temperature about 30 ° C. higher than the end of the glass transition.
Draw a graph of heat absorption and temperature from the above measurement, and extend the baseline on the low temperature side of the graph to the high temperature side, and the point where the slope of the curve of the step change part of the glass transition is maximized The temperature at the point of intersection with the drawn tangent is taken as the glass transition temperature (Tg).

The softening point (Tm) of the polyester resin (A1) measured by a flow tester is preferably 60 to 170 ° C., more preferably 70 to 150 ° C., and particularly preferably 80 to 130 ° from the viewpoint of low temperature fixability and heat resistant storage stability. ° C.

The softening point (Tm) is measured by the following method.
A plunger with a load of 1.96 MPa is applied while heating a 1 g measurement sample at a temperature elevation rate of 6 ° C./min using a high-rise flow tester {eg, CFT-500 D, manufactured by Shimadzu Corporation). , Extrude from a nozzle with a diameter of 1 mm and a length of 1 mm, draw a graph of “Plunger drop amount (flow value)” and “temperature”, and set the temperature corresponding to half of the maximum drop amount of the plunger. Read from the graph, and this value (temperature at which half of the measurement sample has flowed out) is taken as the softening point (Tm).

The acid value of the polyester resin (A1) is preferably 0 to 30 mg KOH / g, more preferably 0 to 25 mg KOH / g, and particularly preferably 0 to 10 mg KOH / g from the viewpoint of chargeability stability.
The acid value of the polyester resin (A1) can be measured by the method specified in JIS K 0070 (1992 version).

The hydroxyl value of the polyester resin (A1) is preferably from 1 to 100 mg KOH / g, more preferably from 5 to 70 mg KOH / g, still more preferably from 10 to 10, from the viewpoint of low temperature fixability, glossiness, heat resistant storage stability and micro offset resistance. It is 40 mg KOH / g or less.
In the present invention, the hydroxyl value can be measured by the method defined in JIS K 0070.

In the present invention, the viscosity ηA1, which is the viscosity ηPa · s at 120 ° C. of the polyester resin (A1), is the mixing property with the polyester resin (B), the colorant, the release agent and the charge control agent, low temperature fixability, resistance From the viewpoint of hot offset property, micro offset resistance and glossiness, 1 to 10,000 Pa · s is preferable, more preferably 30 to 5,000 Pa · s, and most preferably 100 to 3,000 Pa · s.

In the present invention, the viscosity ηA1, which is the viscosity ηPa · s at 120 ° C. of the polyester resin (A1), is measured using the following viscoelasticity measuring device.
Device: ARES-24A (manufactured by Rheometrics)
Jig: 25 mm Parallel plate frequency: 1 Hz
Distortion rate: 5%
Heating rate: 5 ° C / min. Heating start: 100 ° C
Heating end: 200 ° C

The toner produced according to the present invention is produced using, as an essential component, a polyester resin (B) having a carbon-carbon double bond content of less than 0.02 mmol / g based on the weight of the polyester resin (B).
The polyester resin (B) is a polyester resin obtained by polycondensing an alcohol component and a carboxylic acid component, and as long as the carbon-carbon double bond is less than 0.02 mmol / g, any alcohol component and carbonic acid An acid component may be used.
As a component which has a carbon-carbon double bond, unsaturated carboxylic acid component (z) and unsaturated alcohol component (w) are mentioned. Moreover, as a component which does not have a carbon-carbon double bond, saturated alcohol component (x) and saturated carboxylic acid component (y) are mentioned.

Examples of the alcohol component of the polyester resin (B) include the same as the unsaturated alcohol component (w) and the saturated alcohol component (x) of (A1).
Among these alcohol components, an alkylene glycol having 2 to 12 carbon atoms and an AO adduct of bisphenols are preferable from the viewpoint of achieving both low temperature fixability and heat resistant storage stability (average added mole number is preferably 2 to 30) It is.
From the viewpoint of heat resistant storage stability, more preferably, alkylene glycols having 2 to 10 carbon atoms, and AO adducts of bisphenols (average added mole number is preferably 2 to 5).
More preferably, it is an AO adduct of alkylene glycol having 2 to 6 carbon atoms and bisphenol A (average addition mole number is preferably 2 to 5), and particularly preferably, an AO adduct of propylene glycol and bisphenol A (average addition The number of moles is preferably 2 to 3).

Examples of the carboxylic acid component of the polyester resin (B) include the same as the unsaturated carboxylic acid component (z) and the saturated carboxylic acid component (y) of (A1).
Among these carboxylic acid components, preferred are an aromatic monocarboxylic acid having 7 to 37 carbon atoms, an aliphatic dicarboxylic acid having 2 to 50 carbon atoms, and a carbon number, from the viewpoint of achieving both low temperature fixability and heat resistant storage stability. It is 8-20 aromatic dicarboxylic acid and C9-C20 aromatic polycarboxylic acid.
From the viewpoint of heat resistant storage stability, chargeability and charge stability, benzoic acid, adipic acid, terephthalic acid, isophthalic acid, trimellitic acid and combinations thereof are more preferable.
Particularly preferred are adipic acid, isophthalic acid, terephthalic acid, trimellitic acid and combinations thereof. Anhydrides and lower alkyl esters of these acids are likewise preferred.

The polyester resin (B) may be a linear polyester resin or a non-linear polyester resin, but a linear polyester resin is preferable from the viewpoint of low temperature fixability and heat resistant storage stability.
Moreover, as a polyester resin (B), what does not contain a tetrahydrofuran insoluble part substantially from a viewpoint of low temperature fixability is preferable. It is preferable that it has a trace amount of crosslinking points unless it contains a tetrahydrofuran insoluble matter, and trimellitic anhydride, phthalic anhydride and anhydride of anhydride of saturated polycarboxylic acid (may be trivalent or more) having molecular terminal is preferable. Those modified with maleic acid or the like are also preferred.

The polyester resin (B) in the present invention is a polyester resin (B) having a carbon-carbon double bond content of less than 0.02 mmol / g based on the weight of the polyester resin (B). The amount of carbon-carbon double bonds referred to herein is the number of millimoles of carbon-carbon double bonds contained in 1 g in total of the alcohol component constituting the polyester resin (B) and the raw material of the carboxylic acid component. The calculation method is the same as that of the polyester resin (A1).

The carbon-carbon double bond content of the polyester resin (B) in the present invention is less than 0.02 mmol / g, preferably 0.01 mmol / g, from the viewpoint of low-temperature fixability, glossiness, and micro offset resistance. Or less, more preferably 0 mmol / g.

  From the viewpoint of achieving both the heat resistant storage stability of the toner and the low temperature fixability, the Mn of the tetrahydrofuran solution of the polyester resin (B) is preferably 1,000 to 15,000, and more preferably 1,500 to 5,000, More preferably, it is 2,000-4,000.

  The tetrahydrofuran Mw of the polyester resin (B) is preferably 2,000 to 30,000, more preferably 3,000, from the viewpoint of achieving both the hot offset resistance of the toner, the heat resistant storage stability, and the low temperature fixability. It is -10,000, More preferably, it is 4,000-8,000.

The glass transition temperature (Tg) of the polyester resin (B) is preferably 30 to 100 ° C., and the low temperature fixing property becomes good if the Tg is 100 ° C. or less, and the heat resistance storage property is 30 ° C. or more It becomes good. More preferably, it is 40-80 degreeC, More preferably, it is 50-70 degreeC, Especially preferably, it is 55-65 degreeC.
In addition, a glass transition temperature (Tg) can be measured by the method (DSC method) prescribed | regulated to ASTMD3418-82, for example using TA Instruments Co., Ltd. product and DSC Q20.

The softening point (Tm) of the polyester resin (B) measured with a flow tester is preferably 60 to 170 ° C., more preferably 70 to 150 ° C., and still more preferably 80 to 130 ° from the viewpoint of low temperature fixability and heat resistant storage stability. ° C.

The acid value of the polyester resin (B) is preferably 0 to 50 mg KOH / g, more preferably 1 to 40 mg KOH / g, and particularly preferably 5 to 30 mg KOH / g from the viewpoint of chargeability stability.
The acid value of the polyester resin (B) can be measured by the method specified in JIS K 0070 (1992 version).

The hydroxyl value of the polyester resin (B) is preferably 1 to 100 mg KOH / g, more preferably 5 to 80 mg KOH / g, still more preferably 10 to 100 mg from the viewpoints of low temperature fixability, glossiness, heat resistant storage stability and micro offset resistance. It is 60 mg KOH / g or less.
In the present invention, the hydroxyl value can be measured by the method defined in JIS K 0070.

In the present invention, the viscosity η B, which is the viscosity η Pa · s at 120 ° C. of the polyester resin (B), is the mixing property with the polyester resin (A1), the colorant, the release agent and the charge control agent From the viewpoint of hot offset property, micro offset resistance and glossiness, 0.1 to 10,000 Pa · s is preferable, more preferably 1 to 5,000 Pa · s, and most preferably 10 to 1,000 Pa · s. is there.

In the present invention, the viscosity η B which is the viscosity η Pa · s at 120 ° C. of the polyester resin (B) is measured using the following viscoelasticity measuring device.
Device: ARES-24A (manufactured by Rheometrics)
Jig: 25 mm Parallel plate frequency: 1 Hz
Distortion rate: 5%
Heating rate: 5 ° C / min. Heating start: 100 ° C
Heating end: 200 ° C

  The weight ratio [(A1) / (B)] of the polyester resin (A1) to the polyester resin (B) with respect to the whole raw materials used is 5 from the point of coexistence of low temperature fixability, hot offset resistance and heat resistant storage stability. / 95 to 50/50 is preferable, more preferably 7/93 to 45/60, and particularly preferably 10/90 to 40/60.

The toner produced by the present invention is produced with the crosslinking agent (c) capable of reacting with the carbon-carbon double bond of the polyester resin (A1) as an essential component.
The cross-linking agent (c) may be any one as long as it reacts with the carbon-carbon double bond of the polyester resin (A1). For example, the radical reaction initiator (c1) and the additive for living radical polymerization (c2) Can be mentioned. A radical is generated from the radical reaction initiator (c1) and reacted with a carbon-carbon double bond possessed by the polyester resin (A1) to cause a crosslinking reaction between carbon-carbon double bonds to cause chemical bonding The method of producing the modified resin is a preferred method.
The radical reaction initiator (c1) is not particularly limited, and an azo compound, a diazo compound (c11) and an organic peroxide (c12) are used. (C) may use 1 type and may use 2 or more types together.

  The azo compound and the diazo compound (c11) are not particularly limited, and examples thereof include 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1. Examples include '-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile and the like.

  The organic peroxide (c12) is not particularly limited, and benzoyl peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, α, α-bis (t-butylperoxy) ) Diisopropylbenzene, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di-t-butylper Oxyhexyne-3, acetyl peroxide, isobutyryl peroxide, octaninor peroxide, decanolyl peroxide, lauroyl peroxide, 3,3,5-trimethylhexanoyl peroxide, m-toluyl peroxide, t-butyl Peroxyisobutyrate, t-butylperoxyneodecanoate, cumylperoxyneodecanoe , T-butylperoxy 2-ethylhexanoate, t-butylperoxy 3,5,5-trimethylhexanoate, t-butylperoxylaurate, t-butylperoxybenzoate, t-butylperoxy Isopropyl monocarbonate and t-butyl peroxy acetate etc. may be mentioned.

  The additive for living radical polymerization (c2) is not particularly limited, and specific examples thereof include alkyl halides such as ethyl 2-bromoisobutyrate and 2-iodoisobutyric acid. In addition, examples of the catalyst include metal salts such as copper (I) bromide, copper (II) bromide, copper (I) chloride and copper (II) chloride. Further, as a ligand, alkyl pyridyl methane imine such as propyl pyridyl methane imine can be mentioned.

Among these crosslinking agents (c), an organic peroxide (c12) is preferable from the viewpoint of reactivity, hot offset resistance, and micro hot offset resistance. More preferred are t-butylperoxyisopropyl monocarbonate and di-t-butylperoxide t-butylperoxybensoate.
From the viewpoint of odor, preferred are azo compounds or diazo compounds (c11), and specific examples include 2,2′-azobis- (2,4-dimethylvaleronitrile).

Although the usage-amount in particular of a crosslinking agent (c) is not restrict | limited, 0.01-30 weight part is preferable with respect to 100 weight part of the sum total of polyester resin (A1) and polyester resin (B).
When the amount of the crosslinking agent used is 0.01 parts by weight or more, the crosslinking reaction tends to proceed easily, and when it is 30 parts by weight or less, the odor tends to be good. The amount used is more preferably 15 parts by weight or less, still more preferably 10 parts by weight or less, and particularly preferably 5 parts by weight or less.

  When the polyester (A1) is crosslinked by the crosslinking agent (c) of the type described above and the amount used, a crosslinking reaction suitably occurs to improve the hot offset resistance of the toner, the heat resistant storage stability and the image strength. It is preferable from

  As a coloring agent used by the manufacturing method of this invention, 1 type of coloring agents may be used and 2 or more types may be used together.

As colorants, all dyes and pigments used as colorants for toners can be used. Specifically, carbon black, iron black, sudan black SM, fast yellow G, benzidine yellow, pigment yellow, indofirst orange, irgasine 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. Or 2 or more types can be mixed and used. If necessary, magnetic powder (powder of a ferromagnetic metal such as iron, cobalt, nickel or the like or a compound such as magnetite, hematite or ferrite) can be contained as well as the function as a colorant.
The content of the coloring agent is preferably 1 to 40 parts by weight, more preferably 3 to 10 parts by weight with respect to 100 parts by weight of the toner obtained by the production method of the present invention from the viewpoint of toner image density and low temperature fixability. It is. When magnetic powder is used, it is preferably 20 to 70 parts by weight, more preferably 40 to 60 parts by weight.

The toner produced by the present invention is produced with a release agent as an essential component.
The release agent may be used alone or in combination of two or more.

  As a mold release agent, aliphatic hydrocarbon waxes such as low molecular weight polypropylene, low molecular weight polyethylene, low molecular weight polypropylene polyethylene copolymer, polyolefin wax, microcrystalline wax, paraffin wax, Fischer-Tropsch wax, and oxides thereof, carnauba Wax, montan wax, sazole wax and their deacidified waxes, ester waxes such as fatty acid ester waxes, fatty acid amides, fatty acids, higher alcohols, fatty acid metal salts and the like.

  Examples of polyolefin waxes include those obtained by (co) polymerization of olefins (such as ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-dodecene, 1-octadecene and mixtures thereof, etc.) And thermally-deformed polyolefins], oxides of (co) polymers of olefins with oxygen and / or ozone, maleic acid-modified products of (co) polymers of olefins [eg maleic acid and its derivatives (maleic anhydride, Monomethyl maleate, monobutyl maleate and dimethyl maleate etc.), olefins and unsaturated carboxylic acids [(meth) acrylic acid, itaconic acid and maleic anhydride etc] and / or unsaturated carboxylic acid alkyl esters [(meth ) Alkyl acrylate (alkyl carbon having 1 to 18 carbon) ester and Copolymers of maleic acid alkyl esters (number 1 to 18 carbon atoms in the alkyl)] or the like, and Sasol wax.

  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.

  The release agent preferably has a softening point [Tm] of 50 to 170 ° C. by a flow tester, more preferably 50 to 140 ° C., and further preferably 50 from the viewpoint of low temperature fixability and hot offset resistance. It is ~ 120 ° C.

  The content of the releasing agent is preferably 1 to 20 parts by weight, and more preferably 2 to 10 parts by weight with respect to 100 parts by weight of the toner obtained by the production method of the present invention, from the viewpoint of low temperature fixability and hot offset resistance. It is a weight part.

  The toner produced by the present invention is not limited to polyester resin, colorant, releasing agent and crosslinking agent (c), and, if necessary, at least one known member selected from the group consisting of charge control agents and fluidizing agents. Additives may be used.

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

  As a fluidizing agent, colloidal silica, alumina powder, titanium oxide powder, calcium carbonate powder, barium titanate, magnesium titanate, calcium titanate, calcium titanate, strontium titanate, zinc oxide, silica sand, clay, mica, wollastonite, Examples thereof include diatomaceous earth, chromium oxide, cerium oxide, bengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate and barium carbonate.

The charge control agent is contained in an amount of 0 to 20% by weight, preferably 0.1 to 10% by weight, and more preferably 0.5 to 5% by weight, based on 100 parts by weight of the toner.
The fluidizing agent is 0 to 10% by weight, preferably 0 to 5% by weight, and more preferably 0.1 to 4% by weight, based on 100 parts by weight of the toner.
The total amount of the colorant, the release agent and the additive is 3 to 70% by weight, preferably 4 to 58% by weight, more preferably 5 to 50% by weight, based on the weight of the toner. When the total amount of the coloring agent, the releasing agent and the additive in the toner is in the above range, the toner having good hot offset resistance, chargeability, toner flowability, heat resistant storage stability and charge stability can be easily used. You can get it.

  The toner obtained by the production method of the present invention is mixed with carrier particles such as iron powder, glass beads, nickel powder, ferrite, magnetite and ferrite coated on the surface with resin (such as acrylic resin and silicone resin) as necessary. It is used as a developer for electric latent images. The weight ratio of toner to carrier particles is preferably 1/99 to 100/0. Also, instead of the carrier particles, they can be rubbed with a member such as a charging blade to form an electric latent image.

  In the production method of the present invention, the viscosities at 120 ° C. of the polyester resin (A1) and the polyester resin (B) are from the viewpoints of micro offset resistance, low temperature fixability, hot offset resistance, glossiness and charge stability. It is necessary to satisfy the following relational expression (1).

0.1 ≦ ηA1 / ηB ≦ 125 (1)
Preferably, the relational expression (2) is satisfied, more preferably, the relational expression (3) is satisfied, and still more preferably, the relational expression (4) is satisfied.

1 ≦ ηA1 / ηB ≦ 110 (2)
5 ≦ ηA1 / ηB ≦ 95 (3)
10 ≦ ηA1 / ηB ≦ 70 (4)

  In order to adjust ηA1 / ηB, for example, when ηA1 / ηB is decreased (when ηA1 is decreased), the molecular weight of polyester (A1) is decreased, the glass transition temperature is decreased, the softening point is decreased, etc. Can be achieved by

  In order to adjust ηA1 / ηB, for example, when ηA1 / ηB is decreased (when ηB is increased), the molecular weight of polyester (B) is increased, or the glass transition temperature is increased, the softening point is increased, etc. Can be achieved by

  In order to adjust ηA1 / ηB, for example, when ηA1 / ηB is increased (when ηA1 is increased), the molecular weight of polyester (A1) is increased, or the glass transition temperature is increased, the softening point is increased, etc. Can be achieved by

  In order to adjust ηA1 / ηB, for example, when ηA1 / ηB is increased (when ηB is decreased), the molecular weight of polyester (B) is decreased, the glass transition temperature is decreased, the softening point is decreased, etc. Can be achieved by

The value of AA1 / ηB can be easily adjusted within the target range by using the alcohol component and the carboxylic acid component constituting the polyester resin (A1) and the polyester resin (B) as the preferable components described above.

  A cross-linking agent (c) capable of reacting with the polyester resin (A1), the polyester resin (B), the coloring agent, the releasing agent and the carbon-carbon double bond possessed by the above (A1) by satisfying the above relational expression (1) C. to 200.degree. C., the difference in viscosity between the polyester resin (A1) and the polyester resin (B) decreases, and carbon-carbon double bonds of the polyester resin (A1) are crosslinked. Since the non-linear polyester resin having a different carbon-carbon bond is easily formed uniformly in the polyester resin (B) and the micro offset property is easily improved, the coloring agent and the releasing agent are uniformly made in the polyester resin. It is estimated that it becomes easy to be fixed in a dispersed state.

  The toner obtained by the production method of the present invention is a polyester resin obtained by polycondensation of a component containing the aromatic carboxylic acid (y1) with the polyester resin (A1) and / or the polyester resin (B) used. In this case, the content of the aromatic carboxylic acid (y1) in the toner is preferably 10 ppm to 10000 ppm based on the weight of the toner from the viewpoint of charge stability, and the content of the saturated carboxylic acid (y1) is more preferable Is 50 ppm to 8000 ppm, more preferably 70 ppm to 7000 ppm, and particularly preferably 100 ppm to 3000 ppm.

  The content of the aromatic carboxylic acid (y1) in the toner can be measured by a high performance liquid chromatograph mass spectrometer (LC / MS) or a liquid chromatograph (LC).

As the measurement conditions of LC / MS, for example, the following conditions may be mentioned.
Further, the measurement of the contents of phthalic acid, isophthalic acid and terephthalic acid according to the present invention was carried out under the following conditions.
<Measurement conditions for LC / MS>
LC / MS measuring apparatus: "LCMS- 8030" [manufactured by Shimadzu Corporation]
Column: "InertSustain C18" (particle diameter: 2.0 μm, inner diameter: 2.1 mm, length: 100 mm) [manufactured by GL Sciences Inc.]
Mobile phase: 10 mM aqueous ammonium acetate solution / methanol = 48/52 (vol%)
Injection volume: 0.4 μl
Flow rate: 0.2 ml / min
Column temperature: 40 ° C
Ionization method: ESI (-)
Measurement mode: SIM 165

As the measurement conditions of LC, for example, the following conditions may be mentioned.
Moreover, the measurement of the content of trimellitic acid of the present invention was carried out under the following conditions.
<Measurement conditions of LC>
LC measuring device: "ACQUITY UPLC H-Class" [made by Waters]
Column: “CAPCEL PACK C 18” (particle diameter: 5 μm, ID: 4.6 mmφ,
Length 250 mm [made by SHISEIDO]
Mobile phase: 0.05% phosphoric acid aqueous solution / methanol = 80/20 (volume%)
Injection volume: 10 μl
Flow rate: 0.6 ml / min
Column temperature: 40 ° C
Detector: "PDA Detector" [manufactured by Shimadzu Corporation]
Detection wavelength: 230 nm

The toner obtained by the production method of the present invention has heat resistance as it has at least one inflection point showing a glass transition temperature (Tg) in a chart by differential scanning calorimetry (DSC) in a temperature range of -20 ° C to 80 ° C. The temperature is preferably 30 to 70 ° C., more preferably 40 to 65 ° C. from the viewpoints of the properties and low-temperature fixability. There may be two or more inflection points indicating a glass transition point, and it is sufficient if one of them is in this temperature range.
The glass transition temperature (Tg) of the toner can be measured by the same method as the polyester resin (A1).

The acid value of the toner obtained by the production method of the present invention is preferably 1 to 50 mg KOH / g, more preferably 5 to 25 mg KOH / g, still more preferably 10 to 20 mg KOH / g from the viewpoint of chargeability stability.
The acid value of the toner can be measured by the method specified in JIS K 0070 (1992 version).

The hydroxyl value of the toner obtained by the production method of the present invention is preferably 2 to 100 mg KOH / g, more preferably 10 to 70 mg KOH / g, and further preferably from the viewpoint of low temperature fixability, glossiness, heat resistant storage stability and micro offset resistance. Preferably it is 20-40 mgKOH / g or less.
In the present invention, the hydroxyl value can be measured by the method defined in JIS K 0070.

  The weight average molecular weight (Mw) in the gel permeation chromatography (GPC) of the tetrahydrofuran solution in the toner obtained by the production method of the present invention is micro offset resistance, hot offset resistance, heat resistant storage stability, low temperature fixability and It is preferable that it is 2,000-100,000 from the point of coexistence of glossiness, More preferably, a weight average molecular weight is 6,000-70,000, More preferably, a weight average molecular weight is 10,000-40. , 000. The measurement conditions for GPC measurement are as described above.

The softening point (Tm) of the toner obtained by the production method of the present invention measured by a flow tester is preferably 60 to 170 ° C., more preferably 75 to 150 ° C., from the viewpoint of low temperature fixability and heat resistant storage stability. Preferably it is 90-135 degreeC. The measurement conditions of the flow tester are as described in the polyester resin (A1).

  The amount of tetrahydrofuran insoluble matter (gel amount) in the toner obtained by the manufacturing method of the present invention is preferably 1 to 70% by weight from the viewpoint of coexistence of hot offset resistance, low temperature fixing ability and glossiness. More preferably, it is 2-40 weight%, More preferably, it is 5-25 weight%.

The THF insoluble matter in the toner obtained by the production method of the present invention is determined by the following method.
50 ml of THF is added to 0.5 g of sample and stirred at reflux for 3 hours. After cooling, the insolubles are filtered off with a glass filter, and the resin on the glass filter is dried under reduced pressure at 80 ° C. for 3 hours. The weight of the dried solid on the glass filter is the weight of the THF insolubles.

The method of manufacturing the toner will be described.
It is essential to include the step of mixing the temperature of the polyester resin (A1), the polyester resin (B), the colorant, the release agent and the crosslinking agent (c) at 50 ° C. to 200 ° C. The temperature of the raw material at the time of mixing is preferably 90 to 180 ° C., more preferably 120 to 160 ° C., from the viewpoints of dispersibility, low temperature fixability, hot offset resistance and micro offset resistance. If the temperature is less than 50 ° C., the viscosity of the polyester resin (A1) and the polyester resin (B) is high and it is difficult to mix the resins uniformly. If the temperature exceeds 200 ° C., the viscosity of the polyester resin (A1) and the polyester resin (B) is low. It becomes difficult to mix the resin and the colorant uniformly.
Moreover, the mixing method in the case of mixing polyester resin (A1), polyester resin (B), a coloring agent, a mold release agent, and a crosslinking agent (c) may be a well-known method generally implemented, and as a mixing method, Powder mixing, melt mixing, solvent mixing and the like can be mentioned. Among the methods, melt mixing is preferred, as it mixes uniformly and does not require solvent removal. Moreover, in order to mix more uniformly, it may melt-mix after powder mixing, and it is a preferable method. Also, charge control agents and / or fluidizing agents other than the above components may be mixed simultaneously.

Examples of mixing devices for powder mixing include Henschel mixers, Nauta mixers and Banbury mixers. Preferably, it is a Henschel mixer.

As a mixing apparatus in the case of melt-mixing, batch type mixing apparatuses, such as a reaction tank, and a continuous type mixing apparatus are mentioned. In order to achieve uniform mixing in a short time in the temperature range of the present invention, a continuous mixing apparatus is preferred. As a continuous mixing apparatus, a twin-screw kneader, a static mixer, an extruder, a continuous kneader, a triple roll, etc. may be mentioned.

As a method of solvent mixing, polyester resin (A1), polyester resin (B), coloring agent, releasing agent and crosslinking agent (c) are dissolved or dispersed in solvent (ethyl acetate, THF, acetone etc.) and homogenized There is a method of removing the solvent if necessary after the reaction.

Among them, polyester resin (A1), polyester resin (B), colorant and release agent are powder mixed in advance, and then polyester resin (A1), polyester resin (B), colorant, release agent and crosslinker A preferred method is to crosslink the polyester resin (A1) while melt-mixing (c), and specific methods for carrying out such mixing include polyester resin (A1), polyester resin (B), coloring agent and mold release The powder is mixed using a Henschel mixer, then the polyester resin (A1), polyester resin (B), colorant and release agent are injected into the twin-screw kneader at c) is also injected at a constant speed, and there is a method such as performing reaction while kneading and conveying at a temperature of 50 to 200 ° C.

At this time, the polyester resin (A1) and the polyester resin (B) charged or injected into the twin-screw kneader are directly injected directly into the extruder without cooling from the resin reaction solution without powder mixing in advance. Alternatively, the resin once produced may be cooled and pulverized to be supplied to a twin-screw kneader.
Further, the method of melting and mixing is not limited to the methods specifically exemplified above. For example, the raw material is charged in a reaction vessel, heated to a temperature at which it becomes a solution, and mixed by an appropriate method such as mixing Of course what can be done.

The subsequent steps of the method for producing the toner of the present invention may be obtained by any of known methods such as kneading and pulverizing method, emulsion phase inversion method and polymerization method.
For example, in the case of obtaining the toner by the kneading and pulverizing method, after the mixing step, it is roughly pulverized and finally finely pulverized using a jet mill pulverizer etc. and further classified to obtain a volume average particle diameter (Dv 50) After forming into fine particles of preferably 5 to 20 μm, a fluidizing agent can be mixed and manufactured.
The particle size (Dv50) is measured using Coulter Counter [eg, trade name: Multisizer III (manufactured by Coulter, Inc.)].

When the toner is obtained by the emulsion phase inversion method, the mixture may be dissolved or dispersed in an organic solvent after the mixing step, and then emulsified by adding water or the like, and then separated and classified. The volume average particle diameter (Dv50) of the toner is preferably 3 to 15 μm.

  The toner obtained by the production method of the present invention is fixed on a support (paper, polyester film or the like) by a copying machine, a printer or the like to be used as a recording material. As a method of fixing on a support, a known heat roll fixing method and a flash fixing method can be applied.

The toner obtained by the production method of the present invention is used to develop an electrostatic charge image or a magnetic latent image in electrophotography, electrostatic recording, electrostatic printing, and the like. More particularly, the present invention relates to a toner used for developing an electrostatic charge image or magnetic latent image particularly suitable for full color.

Hereinafter, the present invention will be further described by way of examples and comparative examples, but the present invention is not limited thereto. Hereinafter, parts indicate parts by weight unless otherwise specified.

<Production Example 1> [Production of Polyester Resin (A1-1)]
733 parts of bisphenol A · EO adduct, 132 parts of terephthalic acid, 142 parts of adipic acid, 21 parts of trimethylolpropane, titanium diisopropoxy as a condensation catalyst in a reaction vessel equipped with a condenser, stirrer and nitrogen introduction pipe 2.5 parts of bistriethanolaminate was added, and reaction was performed for 2 hours while distilling off generated water under a nitrogen stream at 230 ° C. Next, after making it react under pressure reduction of 0.5-2.5 kPa for 5 hours, it cooled to 180 degreeC. As a polymerization inhibitor, 1 part of tert-butyl catechol was added, 48 parts of fumaric acid was further added, reacted under a reduced pressure of 0.5 to 2.5 kPa for 8 hours, and then taken out to obtain a polyester (A1-1).
The carbon-carbon double bond content of the polyester (A1-1) in the above method is 0.38 mmol / g, the weight average molecular weight (Mw) of the THF solution is 21100, and the viscosity ηA1 at 120 ° C. is 321 Pa · s. The The glass transition temperature, the softening point, the acid value and the hydroxyl value are described in Table 1.

<Production Examples 2 to 9> [Production of Polyester (A1-2) to (A1-9)]
The alcohol component and the carboxylic acid component described in Table 1 are charged into a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introducing pipe, and the reaction is carried out in the same manner as in Production Example 1 except for that, polyester (A1-2) To (A1-9) were obtained. Physical properties, such as the amount of carbon-carbon double bonds of polyester (A1-2) to (A1-9), the weight average molecular weight (Mw) of THF solution and the viscosity AA1 at 120 ° C, are listed in Table 1.

<Comparative Production Example 1> [Production of Polyester (A1′-1)]
The alcohol component and the carboxylic acid component described in Table 1 are charged into a reaction vessel provided with a cooling pipe, a stirrer and a nitrogen introducing pipe, and the reaction is carried out in the same manner as in Production Example 1 except for that, polyester (A1'-1 Got). Physical properties such as carbon-carbon double bond amount, weight-average molecular weight (Mw) of THF solution and viscosity ηA1 at 120 ° C. of polyester (A1′-1) obtained in Table 1 are described.
In addition, polyester (A1'-1) is a thing which does not satisfy | fill the reference | standard of (A1) carbon-carbon double bond amount is larger than 2.00 mmol / g.

Production Example 10 [Production of Polyester Resin (B-1)]
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, 428 parts of bisphenol A · PO2 molar adduct, 319 parts of bisphenol A · PO3 molar adduct, 316 parts of isophthalic acid, titanium diisopropoxy bis trioxide as a condensation catalyst 2.5 parts of ethanolaminate was added, and reaction was carried out for 4 hours while distilling off generated water under a nitrogen stream at 220 ° C. Furthermore, it reacted under pressure reduction of 0.5-2.5 kPa, and when the acid value became about 15 was taken out, polyester resin (B-1) was obtained.
The carbon-carbon double bond content of the polyester resin (B-1) in the above method was 0 mmol / g, and the viscosity η B at 120 ° C. was 73 Pa · s. In addition, the weight average molecular weight, glass transition temperature, softening point, acid value and hydroxyl value of the THF soluble matter are described in Table 2.

<Production Example 11> [Production of Polyester Resin (B-2)]
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 428 parts of bisphenol A · PO2 molar adduct, 320 parts of bisphenol A · PO3 molar adduct, 315 parts of isophthalic acid, titanium diisopropoxy bis trioxide as a condensation catalyst 2.5 parts of ethanolaminate was added, and reaction was carried out for 4 hours while distilling off generated water under a nitrogen stream at 220 ° C. Furthermore, it reacted under pressure reduction of 0.5-2.5 kPa, and when the acid value became about 21 was taken out, polyester resin (B-2) was obtained.
The amount of carbon-carbon double bonds of polyester (B-2) in the above method was 0 mmol / g, and the viscosity η B at 120 ° C. was 23 Pa · s. In addition, the weight average molecular weight, glass transition temperature, softening point, acid value and hydroxyl value of the THF soluble matter are described in Table 2.

<Production Example 12> [Production of Polyester Resin (B-3)]
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, 742 parts of bisphenol A • PO2 molar adduct, 282 parts of terephthalic acid, and 2.5 parts of titanium diisopropoxy bis triethanolaminate as a condensation catalyst, The mixture was reacted for 4 hours while distilling off generated water under a nitrogen stream at 220 ° C. Furthermore, after making it react under reduced pressure of 0.5 to 2.5 kPa for 10 hours, the temperature is lowered to 180 ° C., 34 parts of trimellitic anhydride is added, and after reaction for 1 hour under normal pressure sealing, it is taken out. I got 3).
The amount of carbon-carbon double bonds of polyester (B-3) in the above method was 0 mmol / g, and the viscosity η B at 120 ° C. was 298 Pa · s. In addition, the weight average molecular weight, glass transition temperature, softening point, acid value and hydroxyl value of the THF soluble matter are described in Table 2.

<Production Example 13> [Production of Polyester Resin (B-4)]
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, 742 parts of bisphenol A · PO2 molar adduct, 282 parts of terephthalic acid, 1 part of fumaric acid, titanium diisopropoxy bis triethanolaminate as a condensation catalyst. Five parts were added, and reaction was performed for 4 hours while distilling off generated water under a nitrogen stream at 220 ° C. Furthermore, after making it react under reduced pressure of 0.5 to 2.5 kPa for 10 hours, the temperature is lowered to 180 ° C., 34 parts of trimellitic anhydride is added, and after reaction for 1 hour under normal pressure sealing, it is taken out. I got 4).
The amount of carbon-carbon double bonds of polyester (B-4) in the above method was 0.01 mmol / g, and the viscosity η B at 120 ° C. was 320 Pa · s. In addition, the weight average molecular weight, glass transition temperature, softening point, acid value and hydroxyl value of the THF soluble matter are described in Table 2.

Example 1 [Production of Toner (T-1)]
27 parts of polyester resin (A1-1), 73 parts of polyester resin (B-1), 8 parts of carbon black MA-100 (manufactured by Mitsubishi Chemical Corporation) as a colorant, 3 parts of carnauba wax as a release agent, charge control First, 2 parts of the agent T-77 (made by Hodogaya Chemical Co., Ltd.) are pre-mixed using a Henschel mixer [FM10B made by Mitsui Miike Kako Co., Ltd.], and then a biaxial kneader [PCM-30 made by Ikegai Co., Ltd.] The above pre-mixture is fed at 30 kg / hour, and at the same time, 2 parts of t-butylperoxyisopropyl monocarbonate (c1-1), which is a crosslinking agent, is fed at 0.60 kg / hour to 150 ° C. for 20 minutes at 250 rpm. The kneading reaction was carried out by kneading and extrusion. Next, the mixture is finely pulverized using a supersonic jet crusher Rabojet (manufactured by Nippon Pneumatic Mfg. Co., Ltd.), and then classified with an air flow classifier (MDS-I manufactured by Japan Pneumatic Mfg. Co., Ltd.) to obtain volume average particle size. Toner particles having a particle diameter of (Dv 50) of 8 μm were obtained.
Next, 100 parts of toner particles were mixed with 1 part of colloidal silica (Aerosil R972: manufactured by Nippon Aerosil Co., Ltd.) as a fluidizing agent using a sample mill to obtain a toner (T-1) of the present invention.

Examples 2 to 12, 15, 17 Production of Toners (T-2) to (T-12), (T-15), and (T-17)
After preliminary mixing of polyester (A1), polyester resin (B), coloring agent, releasing agent, charge control agent in parts by weight described in Table 3 using a Henschel mixer [FM10B manufactured by Mitsui Miike Kako Co., Ltd.] , And the crosslinking agent (c) is supplied simultaneously to carry out the crosslinking reaction in the same manner as in Example 1. Thereafter, the toner is produced in the same manner as in Example 1, and the toner of the present invention (T -2) to (T-12), (T-15) and (T-17) were obtained.
In addition, the crosslinking agent (c) in Tables 3 and 4 is as follows.
(C1-1): t-butylperoxyisopropyl monocarbonate (c1-2): 2,2′-azobis- (2,4-dimethylvaleronitrile)

Example 13 [Manufacture of Toner (T-13)]
After preliminary mixing of polyester (A1), polyester resin (B), coloring agent, releasing agent, charge control agent in parts by weight described in Table 3 using a Henschel mixer [FM10B manufactured by Mitsui Miike Kako Co., Ltd.] The crosslinking reaction is carried out in the same manner as in Example 1 except that the temperature is changed from 150 ° C. to 120 ° C. by supplying the crosslinking agent (c) to the twin screw kneader and simultaneously supplying the crosslinking agent (c). The toner was manufactured to obtain a toner (T-13) of the present invention.

Example 14 [Manufacture of Toner (T-14)]
After preliminary mixing of polyester (A1), polyester resin (B), coloring agent, releasing agent, charge control agent in parts by weight described in Table 3 using a Henschel mixer [FM10B manufactured by Mitsui Miike Kako Co., Ltd.] The crosslinking reaction is carried out in the same manner as in Example 1 except that the temperature is changed from 150 ° C. to 90 ° C. by supplying the crosslinking agent (c) described in Table 3 simultaneously to the two-screw kneader. A toner was produced in the same manner as in Example 1 to obtain a toner (T-14) of the present invention.

Example 16 [Manufacture of Toner (T-16)]
27 parts of polyester resin (A1-9), 73 parts of polyester resin (B-1), 6 parts of Regal 400R (manufactured by Cabot Co., Ltd.) as carbon black as a coloring agent, HNP-9 (Nippon Seiwa Co., Ltd.) as paraffin wax as a releasing agent First, after pre-mixing 5 parts of charge- making agent and 2 parts of charge control agent T-77 (made by Hodogaya Chemical) using a Henschel mixer [FM10B made by Mitsui Miike Kako Co., Ltd.], a twin-screw kneader [( Co., Ltd. made by Ikegai PCM-30] at 30 kg / hour, and at the same time 0.5 parts of t-butylperoxyisopropyl monocarbonate (c1-1) as a crosslinking agent at 0.15 kg / hour Then, the crosslinking reaction was carried out by kneading and extruding at 150 ° C. for 20 minutes at 250 rpm. Next, the mixture is finely pulverized using a supersonic jet crusher Rabojet (manufactured by Nippon Pneumatic Mfg. Co., Ltd.), and then classified with an air flow classifier (MDS-I manufactured by Japan Pneumatic Mfg. Co., Ltd.) to obtain volume average particle size. Toner particles having a particle diameter of (Dv 50) of 8 μm were obtained.
Next, 100 parts of toner particles were mixed with 1 part of colloidal silica (Aerosil R972: manufactured by Nippon Aerosil Co., Ltd.) as a fluidizing agent using a sample mill to obtain a toner (T-16) of the present invention.

<Comparative Examples 1 to 4> [Production of Toners (T'-1) to (T'-4)]
Henschel mixer [FM10B manufactured by Mitsui Miike Koki Co., Ltd.] using polyester (A1) or (A1 '), polyester resin (B), coloring agent, release agent, charge control agent of parts by weight described in Table 4 After pre-mixing, the mixture is supplied to a twin-screw kneader, and at the same time, a crosslinking agent (c) is supplied to carry out a crosslinking reaction in the same manner as in Example 1. Thereafter, a toner is produced in the same manner as in Example 1. (T'-1) to (T'-4) were obtained. In addition, (T'-1) and (T'-2) is a polyester resin (A1) whose carbon-carbon double bond content is 0.02 to 2.00 mmol / g based on the weight of the polyester resin (A1) Not using Moreover, the range of (eta) A1 / (eta) B does not satisfy | fill Formula (1) in (T'-3) and (T'-4).

Comparative Example 5 [Production of Toner (T′-5)]
After preliminary mixing of polyester (A1), polyester resin (B), coloring agent, releasing agent, charge control agent in parts by weight described in Table 4 using a Henschel mixer [FM10B manufactured by Mitsui Miike Kako Co., Ltd.] The crosslinking reaction is carried out in the same manner as in Example 1 except that the temperature is changed from 150 ° C. to 45 ° C. by supplying the crosslinking agent (c) described in Table 3 simultaneously to the two-screw kneader. A toner was produced in the same manner as in Example 1 to obtain a toner (T'-5). In addition, the temperature at the time of mixing at the time of manufacturing a toner is 45 degreeC, and (T'-5) does not correspond to the manufacturing method of the toner of this invention.

Comparative Example 6 [Manufacture of Toner (T′-6)]
27 parts of polyester resin (A1-3) and 73 parts of polyester resin (B-1) are mixed and supplied to a twin-screw kneader (S5 KRC kneader manufactured by Kurimoto Iron Works Ltd.) at a rate of 52 kg / hour, and simultaneously a crosslinking agent (c) 2.0g of t-butylperoxyisopropyl monocarbonate (c-1) was fed at 1.04 kg / hour, and the mixture was kneaded and extruded at 90 ° rpm for 7 minutes at 160 ° C. for a crosslinking reaction to obtain a mixture. The toner binder was cooled to obtain a toner binder.
Furthermore, 8 parts of carbon black MA-100 (manufactured by Mitsubishi Chemical Corporation) as a colorant, 4 parts of carnauba wax as a releasing agent, and 100 parts of a toner binder, and a charge control agent T-77 (manufactured by Hodogaya Chemical Co., Ltd.) 2 The mixture was pre-mixed using a Henschel mixer [FM10B manufactured by Mitsui Miike Kako Co., Ltd.], and then kneaded at 120 ° C. with a twin-screw kneader [PCM-30 manufactured by Ikegai Co., Ltd.]. Next, the mixture is finely pulverized using a supersonic jet crusher Rabojet (manufactured by Nippon Pneumatic Mfg. Co., Ltd.), and then classified with an air flow classifier (MDS-I manufactured by Japan Pneumatic Mfg. Co., Ltd.) to obtain volume average particle size. Toner particles having a particle diameter of (Dv 50) of 8 μm were obtained.
Next, 100 parts of toner particles were mixed with 1 part of colloidal silica (Aerosil R972: manufactured by Nippon Aerosil Co., Ltd.) as a fluidizing agent in a sample mill to obtain a toner (T′-6). The toner (T'-6) is subjected to a crosslinking reaction by reacting the polyester resin (A1) and the crosslinking agent (c) in the polyester resin (B) when producing the toner binder. The polyester resin (A1) and the crosslinking agent (c) are substantially absent, and do not fall under the method for producing a toner of the present invention.

[Evaluation method]
In the following, measurement methods and evaluation methods of the low temperature fixability, glossiness, hot offset resistance, micro offset resistance, heat resistant storage stability, and charge stability of the obtained toner will be described including the judgment criteria.

<Low temperature fixability>
The toner was uniformly loaded on the paper so as to be 0.85 mg / cm ² . At this time, the powder is put on the paper by using a printer from which the heat fixing device is removed.
The minimum fixing temperature (MFT) when this paper was passed through a pressure roller under the conditions of a fixing speed (heat roller circumferential speed) of 213 mm / sec and a fixing pressure (pressure roller pressure) of 10 kg / cm ² was measured.
The lower the minimum fixing temperature, the better the low-temperature fixability.

<Glossy>
Fixing evaluation is performed in the same manner as low temperature fixing. A white cardboard was laid under the image, and the glossiness (%) of the printed image was measured at an incident angle of 60 degrees using a gloss meter ("IG-330" manufactured by Horiba, Ltd.). The higher the degree of gloss, the better the gloss.

<Hot offset resistance (hot offset occurrence temperature)>
The fixation was evaluated in the same manner as the low temperature fixation, and the presence or absence of the hot offset to the fixed image was visually evaluated. After passing through the pressure roller, the temperature at which the hot offset occurred was taken as the hot offset resistance (° C.). In this evaluation condition, it means that the offset is less likely to occur as the temperature is higher, and if the temperature is 180 ° C. or more, the occurrence of the offset can be suppressed in an actual use mode.

<Micro offset resistance (micro offset occurrence temperature)>
In the same evaluation as fixing at low temperature, immediately after passing the paper loaded with toner through an external pressure roller, pass through a new paper not loaded with toner and visually evaluate the presence or absence of the colorant derived attached matter attached to the paper. And the following judgment criteria.

Judgment criteria
A: No micro offset generation in the fixing area B: Micro offset generation from temperature above MFT + 50 ° C to hot offset temperature C: Micro offset generation from temperature below MFT + 50 ° C to hot offset temperature

<Heat resistant storage stability>
1 g of the toner was placed in a closed container and allowed to stand in an atmosphere of temperature 50 ° C. and humidity 50% for 24 hours, the degree of blocking was visually judged, and heat resistance storage stability was evaluated according to the following judgment criteria.
Judgment criteria
A: No blocking has occurred at all.
B: Blocking has occurred in part.
C: Blocking has occurred 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.) were placed in a 50 ml glass bottle, and conditioned at 23 ° C. and 50% relative humidity for 8 hours or more.
(2) Friction stirring was carried out at 50 rpm × 20 minutes and 60 minutes with a Tumbler shaker mixer, and the charge amount at each time was measured.
For the measurement, a blow-off charge amount measuring apparatus [manufactured by Toshiba Chemical Co., Ltd.] was used.
The “charge amount for 60 minutes of friction time / charge amount for 10 minutes of friction time” was calculated and used as an indicator of charge stability.

Judgment criteria
○: 0.7 or more Δ: 0.6 or more and less than 0.7 ×: less than 0.6

As is clear from the evaluation results in Tables 3 and 4, all the toners of Examples 1 to 17 of the present invention obtained excellent results in all the performance evaluations.
On the other hand, the toners of Comparative Examples 1 and 2 which do not use the polyester resin (A1) having a carbon-carbon double bond amount of 0.02 to 2.00 mmol / g based on the weight of the polyester resin (A1), The toners of Comparative Examples 3 and 4 in which the range of AA1 / ηB does not satisfy Formula (1), and the toner and toner of Comparative Example 5 in which the temperature during mixing when producing the toner is as low as 45 ° C. In addition, the toner of Comparative Example 6 in which the polyester resin (A1) and the radical reaction initiator (c) were not present was poor in any of the performance items.

The toner obtained by the production method of the present invention is excellent in low-temperature fixability, hot offset resistance, micro offset resistance, glossiness, heat resistant storage stability, charge stability, and is suitable for electrophotography, electrostatic recording, electrostatic printing, etc. It can be suitably used as an electrostatic charge image developing toner to be used.
Furthermore, it is suitable as a photosensitive resin composition for applications such as additives for paints, additives for adhesives, and particles for electronic paper.

Claims (4)

Polyester resin (A1) having a carbon-carbon double bond content of 0.02 to 2.00 mmol / g based on the weight of the polyester resin (A1), and polyester resin (B) having a carbon-carbon double bond content The polyester resin (B), which is less than 0.02 mmol / g based on weight, the colorant, the mold release agent, and the crosslinker (c) capable of reacting with the carbon-carbon double bond possessed by the above (A1) at 50 ° C. A method for producing a toner, comprising the step of mixing at ~ 200 ° C, wherein the viscosities at 120 ° C of (A1) and (B) satisfy the following formula (1).
0.1 ≦ ηA1 / ηB ≦ 125 (1)
[Η A1 is the viscosity η Pa · s of the polyester resin (A1) at 120 ° C., and η B is the viscosity η Pa · s of the polyester resin (B) at 120 ° C. ]   The method for producing a toner according to claim 1, wherein a weight ratio [(A1) / (B)] of polyester resin (A1) to polyester resin (B) with respect to the whole used raw material is 5/95 to 50/50.   The method for producing a toner according to claim 1 or 2, wherein the weight average molecular weight (Mw) of the tetrahydrofuran solution in the polyester resin (A1) is 2,000 to 40,000. The polyester resin (A1) and / or the polyester resin (B) is a polyester resin obtained by polycondensing a component containing an aromatic carboxylic acid (y1), containing the aromatic carboxylic acid (y1) in the toner The method according to any one of claims 1 to 3, wherein the amount is 10 ppm to 10000 ppm based on the weight of the toner.