JP2020076954A - Method for manufacturing toner binder - Google Patents

Abstract

To provide an excellent toner binder that satisfies all of image intensity, heat-resistant storage properties, charge stability, glossiness, and durability, while maintaining low-temperature fixability and hot offset resistance.SOLUTION: There is provided a method for manufacturing a toner binder having a step of cross-linking polyester (A1) under the presence of a crystalline vinyl resin (B). The cross-linking method is preferably the following method (1), (2), or (3). The method (1): a method for reacting and cross-linking a carbon-carbon double bond; the method (2): a method for reacting and cross-linking a carboxyl group included in (A1) and a hydroxyl group in a tri- or more valent polyalcohol (s) or reacting and cross-linking a hydroxyl group included in (A1) and a tri- or more valent polycarboxylic acid or a carboxyl group and/of an acid anhydride group of an anhydride thereof (t); the method (3): a method for reacting and cross-linking a carboxyl group and/or a hydroxyl group included in (A1) and a polyfunctional epoxy compound (E).SELECTED DRAWING: None

Description

  The present invention relates to a method for manufacturing a toner binder.

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.
Conventionally, for full-color electrophotography, a latent image based on color image information is formed on a latent image carrier such as an electrophotographic photoreceptor, the latent image is developed with toner of a corresponding color, and then the toner image is transferred. There is known a method and apparatus for obtaining a multicolor image by repeating the image forming process such as transferring onto a material and then heating and fixing the toner image on the transfer material.

  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 reduces the energy consumption in the fixing process as well as miniaturization, high speed and high image quality of the electrophotographic apparatus, there is a strong demand for improvement of the low temperature fixing property of the toner.
Further, recently, many types of paper such as recycled paper having large surface irregularities and coated paper having a smooth surface are used as the transfer material. In order to cope with the surface properties of these transfer materials, a fixing device having a wide nip width such as a soft roller or a belt roller is preferably used. However, if the nip width is widened, the contact area between the toner and the fixing roller increases, and a so-called high temperature offset phenomenon occurs in which the molten toner adheres to the fixing roller, so that hot offset resistance is required.
In addition to the above, a multicolor image (full color) requires much higher gloss than a monochrome image (monochrome) due to reproduction of photographic images, etc., and it is necessary to make the toner layer of the obtained image smooth. There is.
Therefore, it is necessary to develop low-temperature fixability while maintaining high offset and anti-offset properties, and a high gloss toner image in a wide working range has been demanded.

  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 fixability.

As a method of expanding the fixing temperature range, a toner using a polyester resin containing an unsaturated carboxylic acid as a constituent component has been proposed (Patent Document 1). Moreover, a polyester-vinyl composite resin in which a polyester resin containing an unsaturated carboxylic acid as a constituent component and a vinyl resin are bonded has also been proposed (Patent Documents 2 and 3).
However, although these methods can prevent the offset phenomenon at a high temperature to some extent, the lower limit temperature of fixing is insufficient, and the demands for high speed and energy saving have not yet been sufficiently answered.

On the other hand, a toner using a crystalline vinyl resin as a material for lowering the low-temperature fixing temperature has been proposed (Patent Documents 4 and 5).
However, although this method also improves the low-temperature fixability, the hot offset resistance at high temperatures was insufficient.

  As described above, there has not been an excellent toner binder that satisfies all of image strength, heat resistant storage stability, charge stability, glossiness and durability while maintaining low-temperature fixability and hot offset resistance. It was

JP, 2017-003985, A JP, 2005-135485, A JP, 2008-054888, A JP, 2007-193069, A International Publication No. 2018/110593

  An object of the present invention is to provide an excellent toner binder which satisfies all of image strength, heat resistant storage stability, charge stability, glossiness and durability while maintaining low temperature fixing property and hot offset resistance. ..

The present inventors have arrived at the present invention as a result of intensive studies to solve these problems.
That is, the present invention is a method for producing a toner binder having a step of crosslinking the polyester (A1) in the presence of the crystalline vinyl resin (B).

  According to the present invention, it is possible to provide a toner binder excellent in image strength, heat resistant storage stability, charge stability, glossiness and durability while maintaining low temperature fixability and hot offset resistance. Further, the toner binder obtained by the production method of the present invention is also excellent in pulverizability.

The method for producing a toner binder of the present invention has a step of crosslinking the polyester (A1) in the presence of the crystalline vinyl resin (B).
The method for producing the toner binder of the present invention will be described below in sequence.

In the method for producing a toner binder of the present invention, since the polyester (A1) is crosslinked to form the polyester resin (A) in the presence of the crystalline vinyl resin (B), the viscosity difference and the solubility parameter that cannot be generally mixed uniformly are used. (Hereinafter, abbreviated as SP value) A crystalline vinyl resin (B) and a polyester resin (A) having a difference can be made into a uniform mixture, and a toner binder having a wide range of fixing temperature can be obtained.
Since the polyester resin (A) having a network formed by the above crosslinking reaction cannot be dissolved in tetrahydrofuran (hereinafter abbreviated as THF), it means that the polyester resin has a network formed by the crosslinking reaction. Can be confirmed by dissolving in THF and having a component insoluble in THF (THF insoluble component).

The method of crosslinking the polyester (A1) in the crosslinking step is preferably the following method (1), (2) or (3).
Method (1): a method in which the polyester (A1) is a polyester (A11) having a carbon-carbon double bond, and the carbon-carbon double bond is reacted to crosslink;
Method (2): The polyester (A1) is a polyester (A12) having a carboxyl group and / or a hydroxyl group, and the carboxyl group of (A1) is reacted with a hydroxyl group of a polyhydric alcohol (s) having a valence of 3 or more. A method of crosslinking or crosslinking by reacting a hydroxyl group of (A1) with a carboxyl group and / or an acid anhydride group of a polycarboxylic acid having a valence of 3 or more or its anhydride (t);
Method (3): Polyester (A1) is a polyester (A12) having a carboxyl group and / or a hydroxyl group, and the carboxyl group and / or hydroxyl group (A1) is reacted with a polyfunctional epoxy compound (E) to crosslink. how to.

The toner binder obtained by these methods is a toner binder in which the cross-linking reaction of the polyester (A1) is likely to form a uniform mixture in a short time, and which is excellent in all properties of low-temperature fixability, hot offset resistance and heat resistant storage stability. Is preferred, which is preferable.
Further, when the polyester (A1) is crosslinked in the presence of the crystalline vinyl resin (B), the polyester (A1) and the crystalline vinyl resin (B) may react, but they do not react from the viewpoint of low temperature fixability. Is preferred.

At least part of the cross-linking by the carbon-carbon bond of the polyester (A11) in the cross-linking method (1), the carbon atom constituting one carbon-carbon double bond existing in the polyester (A11) molecule is a polyester. (A11) It is preferably a carbon-carbon bond formed by bonding to a carbon atom that constitutes another carbon-carbon double bond existing in the molecule.
One carbon-carbon double bond and the other carbon-carbon double bond may be present in the same polyester (A11) molecule or may be present in different polyester (A11) molecules.

  As a form of the cross-linking reaction to form a carbon-carbon bond, for example, a carbon-carbon double bond is introduced into the main chain or side chain of the polyester (A11), and the radical reaction initiator (c) is allowed to act to generate a radical. It is preferable to bond the carbon-carbon double bonds in the polyester (A11) to each other by a crosslinking reaction by utilizing radicals generated from the reaction initiator (c). In addition to this reaction, a cation addition reaction or anion addition reaction may be performed to generate an intermolecular carbon-carbon bond.

Moreover, the polyester (A11) having a carbon-carbon double bond in the present invention contains an unsaturated carboxylic acid component (y) and / or an unsaturated alcohol component (z), and contains an unsaturated carboxylic acid component (y) and It is preferable that the polyester resin is obtained by polycondensing a constituent component containing one of the unsaturated alcohol components (z) as an essential component.
Furthermore, the polyester (A11) having a carbon-carbon double bond may contain a saturated alcohol component (x) and a saturated carboxylic acid component (w) as constituent components in addition to the above essential components.
Further, the polyester (A11) may be obtained by polycondensing each of these components one by one, or may be polycondensed by using plural kinds of each component in combination.
In the present specification, the bond between the aromatic ring and the heterocycle is not taken into consideration in determining whether the component is the unsaturated carboxylic acid component (y) or the saturated carboxylic acid component (w).
Similarly, the bond between the aromatic ring and the heterocycle is not considered in determining whether the unsaturated alcohol component (z) or the saturated alcohol component (x).

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

  Examples of unsaturated monools (z1) include unsaturated monools having 2 to 30 carbon atoms, and preferable examples include 2-propen-1-ol, palmitoleyl alcohol, elaidyl alcohol, oleyl alcohol, and erucyl alcohol. And 2-hydroxyethyl methacrylate and the like.

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

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

As the saturated monool (x1), a linear or branched alkyl alcohol having 1 to 30 carbon atoms (methanol, ethanol, isopropanol, 1-decanol, dodecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol and Lignoceryl alcohol, etc.) and the like.
Among these saturated monools, a linear or branched alkyl alcohol having 8 to 24 carbon atoms is preferable, and a linear alkyl alcohol having 8 to 24 carbon atoms is more preferable, from the viewpoint of image strength and heat resistant storage stability. And more preferred are dodecyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol and lignoceryl alcohol.

Examples of the saturated diol (x2) include alkylene glycols having 2 to 36 carbon atoms (ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentane. Diol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol and 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 fat. Cyclic diols (1,4-cyclohexanedimethanol and hydrogenated bisphenol A, etc.) (x23), alkylene oxide (hereinafter abbreviated as AO) adducts of the alicyclic diols (preferably average addition mole number 1 to 30) (X24), aromatic diol [monocyclic dihydric phenol (for example, hydroquinone, etc.) and bisphenols, etc.] (x25), and AO adduct of the above aromatic diol (preferably an average addition mole number of 2 to 30) (x26), etc. Is mentioned.
Among these saturated diols (x2), an alkylene glycol having 2 to 36 carbon atoms (x21) and an AO adduct (x26) of an aromatic diol are preferable from the viewpoint of low-temperature fixability and heat-resistant storage stability, and AO of bisphenols. Adducts are more preferred.
As the AO, those having an alkylene group with 2 to 4 carbon atoms (ethylene oxide, propylene oxide, 1,2-, 2,3- or iso-butylene oxide and tetrahydrofuran) are preferable. AO may be used alone or in combination of two or more.

Examples of the bisphenols include those represented by the following general formula (1).
HO-Ar-P-Ar-OH (1)
P in the general formula (1) represents an alkylene group having 1 to 3 carbon atoms, —SO ₂ —, —O—, —S— or a direct bond, and Ar has a hydrogen atom as a halogen atom or a C 1 to 30 carbon atom. It represents a phenylene group which may be substituted with an alkyl group.

  Specific examples of the bisphenols represented by the general formula (1) include, for example, bisphenol A, bisphenol F, bisphenol B, bisphenol AD, bisphenol S, trichlorobisphenol A, tetrachlorobisphenol A, dibromobisphenol F, 2-methyl. Examples thereof include bisphenol A, 2,6-dimethylbisphenol A and 2,2′-diethylbisphenol F, and these may be used alone or in combination of two or more.

From the viewpoint of heat-resistant storage stability and low-temperature fixability, EO and / or PO are preferable as the AO constituting the AO adduct of bisphenols.
The average addition mole number of AO is preferably 2 to 30 moles, more preferably 2 to 10 moles, and further preferably 2 to 5 moles.
Among the AO adducts of bisphenols, EO adducts of bisphenol A (the average number of moles added is preferably 2 to 4, more preferably 2 to 4) are preferable from the viewpoints of toner fixability, pulverizability and heat resistant storage stability. 3) and / or PO adduct (average number of moles added is preferably 2 to 4, more preferably 2 to 3).

  As the trivalent or higher saturated polyol (x3), a trivalent or higher aliphatic polyhydric alcohol (x31) having 3 to 36 carbon atoms, a saccharide or a derivative thereof (x32), an AO adduct of an aliphatic polyhydric alcohol (average) The number of moles added is preferably 1 to 30) (x33), AO adduct of trisphenols (trisphenol PA, etc.) (average number of moles added is preferably 2 to 30) (x34), novolac resin (phenol novolac and cresol). Examples thereof include novolac and the like, and the average degree of polymerization thereof is preferably 3 to 60) and an AO adduct (average added mole number is preferably 2 to 30) (x35).

Examples of the trihydric or higher aliphatic polyhydric alcohol (x31) having 3 to 36 carbon atoms include alkane polyol and its intramolecular or intermolecular dehydrated product, such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and the like. Examples thereof include sorbitol, sorbitan, polyglycerin and dipentaerythritol.
Examples of the saccharide and its derivative (x32) include sucrose and methyl glucoside.

  Among the saturated polyols (x3) having a valence of 3 or more, from the viewpoint of achieving both low-temperature fixability and hot offset resistance, an aliphatic polyhydric alcohol (x31) having 3 to 36 carbon atoms and a novolac resin (phenol) is used. Novolak, cresol novolac, etc. are included, and an AO adduct (average addition mole number is preferably 2 to 30) (x35) having an average degree of polymerization of preferably 3 to 60 is preferable.

  Among the saturated alcohol components (x), from the viewpoints of low temperature fixability, hot offset resistance and heat resistant storage stability, alkylene glycols (x21) having 2 to 36 carbon atoms and AO adducts of bisphenols (average addition moles) are preferable. The number is preferably 2 to 30), a trivalent or more aliphatic polyhydric alcohol (x31) having 3 to 36 carbon atoms and a novolac resin (phenol novolac, cresol novolac, etc. are included, and the average degree of polymerization is preferably 3 to 60) AO adduct (average added mole number is preferably 2 to 30) (x35).

  As the saturated alcohol component (x), more preferable from the viewpoint of heat resistant storage stability are alkylene glycols having 2 to 10 carbon atoms, AO adducts of bisphenols (average addition mole number is preferably 2 to 5), and 3 carbon atoms. To 36-trivalent aliphatic polyhydric alcohols and novolac resins (including phenol novolac and cresol novolac, etc., preferably having an average degree of polymerization of 3 to 60), AO adducts (average number of moles added is preferably 2 to 30), and more preferably, an alkylene glycol having 2 to 6 carbon atoms, an AO adduct of bisphenol A (average addition mole number is preferably 2 to 5), and a trivalent fat having 3 to 36 carbon atoms. Group polyhydric alcohols, particularly preferred are ethylene glycol, propylene glycol, AO adducts of bisphenol A (average number of moles added is preferably 2 to 3), and trimethylolpropane.

  Further, as the saturated alcohol component (x), from the viewpoint of charge stability, AO adducts of bisphenols (average added mole number is preferably 2 to 5), 3 to 8 valent aliphatic polyhydric alcohols and novolaks are preferable. Resins (including phenol novolac and cresol novolac, etc., and having an average degree of polymerization of preferably 3 to 60) are AO adducts (average addition mole number is preferably 2 to 30), more preferably bisphenol A. AO adducts (average addition mole number is 2 to 5), and more preferred are AO adducts of bisphenol A (average addition mole number is 2 to 3).

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

As the unsaturated carboxylic acid component (y), unsaturated monocarboxylic acid (y1), unsaturated dicarboxylic acid (y2), unsaturated polycarboxylic acid (y3) having a valence of 3 or more, and anhydrides or lower alkyls of these acids are used. Examples thereof include esters.
These may be used alone or in combination of two or more.

  The unsaturated monocarboxylic acid (y1) includes an unsaturated monocarboxylic acid having 2 to 30 carbon atoms, such as acrylic acid, methacrylic acid, propiolic acid, 2-butyric acid, crotonic acid, isocrotonic acid, 3-butene. Acid, angelic 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, Examples include vaccenic acid, gadoleic acid, erucic acid and nervonic acid.

  The unsaturated dicarboxylic acid (y2) includes an alkene dicarboxylic acid having 4 to 50 carbon atoms, for example, alkenylsuccinic acid such as dodecenylsuccinic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, glutaconic acid and the like. Is mentioned.

  Examples of the trivalent or higher unsaturated polycarboxylic acid (y3) include trivalent or higher alkene polycarboxylic acids having 6 to 50 carbon atoms (specifically, aconitic acid, 3-butene-1,2,3-tricarboxylic acid). And alkene tricarboxylic acids such as 4-pentene-1,2,4-tricarboxylic acid; 1-pentene-1,1,4,4-tetracarboxylic acid, 4-pentene-1,2,3,4-tetracarboxylic acid And alkene tetracarboxylic acids such as 3-hexene-1,1,6,6-tetracarboxylic acid).

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

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

Examples of the aromatic carboxylic acid include aromatic monocarboxylic acids having 7 to 37 carbon atoms (benzoic acid, toluic acid, 4-ethylbenzoic acid, 4-propylbenzoic acid, etc.), aromatic dicarboxylic acids having 8 to 36 carbon atoms. Examples thereof include acids (phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc.), aromatic polycarboxylic acids having 9 to 20 carbon atoms and having a valence of 3 or more (trimellitic acid, pyromellitic acid, etc.), and the like.
Examples of the aliphatic carboxylic acid 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, myristin). 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, lepargic acid, sebacic acid, etc.), carbon number 6 To 36 aliphatic tricarboxylic acids (hexane tricarboxylic acid, etc.) and the like.
As the saturated carboxylic acid component (w), anhydrides of these carboxylic acids, lower alkyl (C1-4) esters (methyl ester, ethyl ester, isopropyl ester, etc.) may be used. You may use together with carboxylic acid.

  Among these saturated carboxylic acid components (w), from the viewpoint of low temperature fixability, hot offset resistance and heat resistant storage stability, aromatic monocarboxylic acids having 7 to 37 carbon atoms and fats having 2 to 50 carbon atoms are preferable. Benzoic acid is a group-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, and more preferable from the viewpoint of heat resistant storage stability and charge stability. , Adipic acid, alkyl succinic acid, terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid and combinations thereof, and more preferable are adipic acid, terephthalic acid, trimellitic acid and combinations thereof. Further, it may be an anhydride or a lower alkyl ester of these acids.

  Further, the method for producing the polyester (A11) in the present invention is not particularly limited, but as described above, a constituent component containing one or more kinds of the unsaturated carboxylic acid component (y) and / or the unsaturated alcohol component (z) is used. The method of polycondensation is preferred.

  The polyester (A11) having a carbon-carbon double bond in the present invention is not particularly limited, but is preferably a non-linear polyester from the viewpoint of improving elasticity at high temperature. When the polyester (A11) is a non-linear polyester, heat resistant storage stability and hot offset resistance are improved. The non-linear polyester can be obtained, for example, by using a saturated diol (x2) as the saturated alcohol component (x) and a trivalent or higher saturated polyol (x3) in the above proportions.

The content of the carbon-carbon double bond in the polyester (A11) is not particularly limited, but is preferably 0.02 to 2 mmol / g based on the weight of the polyester (A11), and more preferably 0.1. 06 to 1.9 mmol / g, more preferably 0.10 to 1.5 mmol / g, and particularly preferably 0.15 to 1.0 mmol / g.
When the content of the carbon-carbon double bond is 0.02 to 2.0 mmol / g based on the weight of the polyester (A11), a cross-linking reaction preferably occurs and the hot offset resistance of the toner becomes good. ..

The method for measuring the carbon-carbon double bond content in the polyester (A11) is not particularly limited, and it can be measured by ¹ H-NMR, ¹³ C-NMR, bromine number test method (JIS K2605) and the like. The carbon-carbon double bond content in the examples was measured by the following method.
<Sample adjustment>
Weigh 100 mg of sample into a ¹³ C-NMR tube, weigh 10 mg of sodium trimethylsilylpropane sulfonate as an internal standard substance, weigh 10 mg of Cr (AcAc) ₃ as a relaxation reagent, and add 0.45 ml of a deuterated solvent (heavy pyridine) to make a resin. Dissolve.
<Measurement conditions>
Device: Bruker BioSpin "AVANCE III HD400"
Accumulation number: 24000 times <Analysis and calculation>
For example, if the carbon-carbon double bond is an unsaturated carboxylic acid component (z) such as maleic acid and fumaric acid, the area of the carbon peak (164.6 ppm) of the double bond derived from the unsaturated carboxylic acid component (z). The double bond content (mmol / g) is calculated from the ratio and the area ratio of the carbon peak (0 ppm) of the internal standard substance.

  The radical reaction initiator (c) used for the crosslinking reaction of the polyester (A11) is not particularly limited, and examples thereof include an inorganic peroxide (c1), an organic peroxide (c2) and an azo compound (c3). Be done. Also, 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, cumyl peroxy neodecanoate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxy-3,5,5 -Trimethylhexanoate, t-butylperoxylaurate, t-butylperoxybenzoate, t-butylperoxyisopropyl monocarbonate and t-butylperoxyacetate.

  The azo compound (c3) is not particularly limited, but, for example, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis ( Cyclohexane-1-carbonitrile), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile and azobisisobutyronitrile.

Among these, the organic peroxide (c2) is preferable because it has a high initiator efficiency and does not generate a by-product such as a cyan compound.
Furthermore, since the crosslinking reaction proceeds efficiently and the amount used is small, a reaction initiator having a high hydrogen abstraction ability is more preferable, and benzoyl peroxide, di-t-butyl peroxide, t-butyl cumyl peroxide, Dicumyl peroxide, α, α-bis (t-butylperoxy) diisopropylbenzene, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, t-butylperoxyisopropyl monocarbonate and A radical reaction initiator having a high hydrogen abstraction ability such as di-t-hexyl peroxide is more preferable.

The amount of the radical reaction initiator (c) used is not particularly limited, but may be based on the total weight of the unsaturated carboxylic acid component (y) and the unsaturated alcohol component (z) used in the polymerization reaction to obtain the polyester (A11). Based on 0.1 to 50 parts by weight is preferred.
When the amount of the radical reaction initiator used is 0.1 parts by weight or more, the crosslinking reaction tends to proceed easily, and when it is 50 parts by weight or less, the odor tends to be good. The amount used is more preferably 30 parts by weight or less, further preferably 20 parts by weight or less, and particularly preferably 10 parts by weight or less.

  When radical polymerization is carried out with the above-mentioned type of radical reaction initiator (c) and the above-mentioned amount used, a cross-linking reaction between carbon-carbon double bonds in the polyester (A11) preferably occurs, resulting in hot offset resistance and heat resistance of the toner. It is preferable because the storage stability and the image strength are improved.

  The polyester (A12) in the crosslinking method (2) has a carboxyl group and / or a hydroxyl group, and when the polyester (A12) has a carboxyl group, a polyhydric alcohol (s) having a valence of 3 or more is used at a high temperature. By carrying out the esterification reaction below, a network structure is formed and a crosslinked polyester resin is obtained. When the polyester (A12) has a hydroxyl group, a polycarboxylic acid having a valence of 3 or more or its anhydride (t) is added and the esterification reaction is carried out at a high temperature to obtain a similarly crosslinked polyester resin. Be done.

  The polyester (A12) in the crosslinking method (3) has a carboxyl group and / or a hydroxyl group, and a polyaddition reaction is carried out using the polyfunctional epoxy compound (E) to form a network structure, which is crosslinked. A polyester resin is obtained.

  The polyester (12) includes a carboxylic acid component containing the saturated carboxylic acid component (w) and / or the unsaturated carboxylic acid component (y), the saturated alcohol component (x) and / or the unsaturated alcohol component (z). A polyester resin obtained by polycondensation with an alcohol component containing) is preferable, and preferable ones in each component are the same as in the case of the polyester (11).

By carrying out the reaction under the condition that the number of moles of the carboxyl group of the carboxylic acid component is more than the number of moles of the hydroxyl group of the alcohol component, a polyester (12) having more carboxyl groups than the hydroxyl groups as terminal functional groups can be obtained, and a polyester having a valence of 3 or more can be obtained. It is suitably used for a crosslinking reaction with a polyhydric alcohol (s).
In addition, a polyester (12) having more hydroxyl groups than carboxyl groups as terminal functional groups can be obtained by reacting under a condition in which the number of moles of hydroxyl groups of the alcohol component is in excess of the number of moles of carboxyl groups of the carboxylic acid component. It is preferably used for the crosslinking reaction with the polycarboxylic acid or its anhydride (t). The polyester (12) may have a carbon-carbon double bond like the polyester (11).

  The polyester (A12) is not particularly limited, but is preferably a non-linear polyester from the viewpoint of improving elasticity at high temperatures. When the polyester (A12) is a non-linear polyester, heat resistant storage stability and hot offset resistance are improved. The non-linear polyester can be obtained, for example, by using a saturated diol (x2) as a saturated alcohol component (x) and a saturated polyol (x3) having a valence of 3 or more in the proportions described in the description of the polyester (11). ..

The total value of the acid value and the hydroxyl value of the polyester (A12) having a carboxyl group and / or a hydroxyl group is not particularly limited, but is preferably 30 to 150 mgKOH / g, more preferably 30 to 150 mgKOH / g, and further The amount is preferably 30 to 150 mgKOH / g, particularly preferably 30 to 150 mgKOH / g.
When the total value of the acid value and the hydroxyl value of the polyester (A12) is 30 to 150 mgKOH / g, a crosslinking reaction preferably occurs and the hot offset resistance of the toner becomes good. When the total value of the acid value and the hydroxyl value is less than 30, the molecular weight between cross-linking points may be long and it may be difficult to obtain a network structure. On the other hand, when the total value of the acid value and the hydroxyl value is more than 150, the molecular weight between crosslinking points is short, which may result in non-uniform crosslinking.
The acid value and the hydroxyl value in the present invention can be measured by the method specified in JIS K0070 (1992).

  Examples of the trihydric or higher polyhydric alcohol (s) in the crosslinking method (2) include the trihydric or higher polyhydric saturated polyols (x3) and the like, and from the viewpoint of achieving both low temperature fixability and hot offset resistance, AO adducts (average addition moles) of trihydric or higher aliphatic polyhydric alcohols (x31) of number 3 to 36 and novolac resins (phenol novolac and cresol novolac, etc. are included, and preferably have an average degree of polymerization of 3 to 60). The number is preferably 2 to 30) (x35), and particularly preferred is trimethylolpropane.

  As the trivalent or higher polycarboxylic acid or its anhydride (t) in the crosslinking method (2), the trivalent or higher unsaturated polycarboxylic acid (y3), the trivalent or higher aromatic polycarboxylic acid having 9 to 20 carbon atoms is used. Examples thereof include carboxylic acids, the above-mentioned aliphatic tricarboxylic acids having 6 to 36 carbon atoms, and anhydrides thereof. From the viewpoint of low-temperature fixing property, hot offset resistance and heat resistant storage stability, 3 having 9 to 20 carbon atoms is preferable. Among the polyvalent aromatic polycarboxylic acids and their anhydrides, more preferred from the viewpoint of heat-resistant storage stability and charge stability are trimellitic acid, pyromellitic acid and their anhydrides, and more preferred are trimeric acids. Mellitic acid and trimellitic anhydride.

  Examples of the polyfunctional epoxy compound (E) in the crosslinking method (3) include aromatic polyepoxy compounds, heterocyclic polyepoxy compounds, alicyclic polyepoxy compounds and aliphatic polyepoxy compounds.

  Examples of aromatic polyepoxy compounds include polyhydric phenol glycidyl ether compounds, polyhydric phenol glycidyl ester compounds, glycidyl aromatic polyamines, and other aromatic polyepoxy compounds.

  Examples of the glycidyl ether of polyhydric phenol include bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol B diglycidyl ether, bisphenol AD diglycidyl ether, bisphenol S diglycidyl ether, halogenated bisphenol A diglycidyl, tetrachlorobisphenol A. Diglycidyl ether, catechin diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, pyrogallol triglycidyl ether, 1,5-dihydroxynaphthalene diglycidyl ether, dihydroxybiphenyl diglycidyl ether, octachloro-4,4′-dihydroxybiphenyldi Glycidyl ether, tetramethylbiphenyl diglycidyl ether, dihydroxynaphthylcresol triglycidyl ether, tris (hydroxyphenyl) methane triglycidyl ether, dinaphthyltriol triglycidyl ether, tetrakis (4-hydroxyphenyl) ethane tetraglycidyl ether, p-glycidylphenyl Dimethyltolyl bisphenol A glycidyl ether, trismethyl-t-butyl-butylhydroxymethane triglycidyl ether, 9,9'-bis (4-hydroxyphenyl) furo orange glycidyl ether, 4,4'-oxybis (1,4-phenyl) Ethyl) tetracresol glycidyl ether, 4,4'-oxybis (1,4-phenylethyl) phenyl glycidyl ether, bis (dihydroxynaphthalene) tetraglycidyl ether, novolac type epoxy resin (phenol novolac type epoxy resin, cresol novolac type epoxy resin) , Bisphenol A novolac type epoxy resin, limonene phenol novolac type epoxy resin), bisphenol A type epoxy resin, polyphenol polyglycidyl ether obtained by condensation reaction of phenol and glyoxal, glutaraldehyde or formaldehyde, and resorcinol and acetone. Examples thereof include polyglycidyl ethers of polyphenols obtained by condensation reaction.

  Examples of the glycidyl ester of polyhydric phenol include diglycidyl phthalate, diglycidyl isophthalate and diglycidyl terephthalate.

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

  Other aromatic polyepoxy compounds include triglycidyl ether of p-aminophenol, diglycidyl urethane compound obtained by addition reaction of tolylene diisocyanate or diphenylmethane diisocyanate and glycidol, and polyol obtained by reacting the two reaction products with polyol. Also included are polyurethane (pre) polymers containing glycidyl groups and diglycidyl ethers of AO adducts of bisphenol A.

  Examples of the heterocyclic polyepoxy compound include trisglycidyl melamine.

  Examples of the alicyclic polyepoxy compound include vinyl cyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl) ether, ethylene glycol bisepoxydicyclopentyl ale, 3,4-epoxycyclohexyl. Methyl-3 ', 4'-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3', 4'-epoxy-6'-methylcyclohexanecarboxylate, bis (3,4-epoxy-6) -Methylcyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) butylamine, 2,2-bis (hydroxymethyl) -1-butanol 1,2-epoxy-4- (2-oxiranyl) Examples thereof include cyclohexane adducts and dimer acid diglycidyl ester. The alicyclic system also includes a nuclear hydrogenated product of the aromatic polyepoxy compound.

  Examples of the aliphatic polyepoxy compound include polyglycidyl ether bodies of aliphatic polyhydric alcohols, polyglycidyl ester bodies of aliphatic polyhydric carboxylic acids, and glycidyl aliphatic amines.

  Examples of the polyglycidyl ether of aliphatic polyhydric alcohol include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol. Diglycidyl ether, polytetramethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, etc. Be done.

  Examples of the polyglycidyl ester of aliphatic polycarboxylic acid include diglycidyl oxalate, diglycidyl malate, diglycidyl succinate, diglycidyl glutarate, diglycidyl adipate and diglycidyl pimelate.

Examples of the glycidyl aliphatic amine include N, N, N ′, N′-tetraglycidylhexamethylenediamine and the like.
Further, examples of the aliphatic system include (co) polymers of diglycidyl ether and glycidyl (meth) acrylate.

  Of these polyfunctional epoxy compounds, from the viewpoint of hot offset resistance and heat resistant storage stability, preferably an aromatic polyepoxy compound, an alicyclic polyepoxy compound, an aliphatic polyepoxy compound, more preferably It is an aromatic polyepoxy compound, more preferably a novolac type epoxy resin and a bisphenol A type epoxy resin.

The weight ratio [(A12) :( s)] of the polyester (A12) and the polyhydric alcohol (s) having a valence of 3 or more at the time of crosslinking is 99.8: 0 from the viewpoint of low-temperature fixing property and hot offset resistance. 2 to 80:20 is preferable, more preferably 99.5: 0.5 to 85:15, further preferably 99.2: 0.8 to 88:12, and particularly preferably 99: 1 to 90:10. is there.
In addition, the weight ratio [(A12) :( t)] of the tricarboxylic or higher polycarboxylic acid or its anhydride (t) to be cross-linked with the polyester (A12) is from the viewpoint of low-temperature fixing property and hot offset resistance. It is preferably 99.8: 0.2 to 90:10, more preferably 99.7: 0.3 to 92: 8, further preferably 99.6: 0.4 to 94: 6, and particularly preferably 99.5. : 0.5 to 95: 5.

  The weight ratio [(A12) :( E)] of the polyester (A12) and the polyfunctional epoxy compound (E) at the time of crosslinking is 99.8: 0.2 or more from the viewpoint of low-temperature fixing property and hot offset resistance. It is preferably 80:20, more preferably 99.5: 0.5 to 85:15, further preferably 99.2: 0.8 to 88:12, and particularly preferably 97: 3 to 90:10.

The polyester (A1) in the present invention can be produced in the same manner as a known polyester.
For example, the reaction may be performed 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, still more preferably 170 to 235 ° C. it can. The reaction time is preferably 30 minutes or more, more preferably 2 to 40 hours, from the viewpoint of surely performing the polycondensation reaction. In order to improve the reaction rate, it is preferable to have a step of reducing the pressure in addition to the step of normal pressure (pressure is 80 to 120 kPa), and the degree of pressure reduction is preferably 20 kPa or less, more preferably 15 kPa or less, and further preferably Is 10 kPa or less, particularly preferably 5 kPa or less.

At this time, an esterification catalyst can be used if necessary.
Examples of the esterification catalyst include a tin-containing catalyst (for example, dibutyltin oxide), an antimony trioxide, a titanium-containing catalyst [for example, titanium alkoxide, potassium oxalate titanate, titanium terephthalate, titanium terephthalate alkoxide, and JP 2006-243715 A. Catalysts {titanium diisopropoxybis (triethanolaminate), titanium dihydroxybis (triethanolaminate), titanium monohydroxytris (triethanolaminate), titanylbis (triethanolaminate) and their Intramolecular polycondensates, etc.} and catalysts described in JP-A-2007-11307 (titanium tributoxy terephthalate, titanium triisopropoxy terephthalate, titanium diisopropoxy diterephthalate, etc.) ], Zirconium-containing catalysts (e.g. zirconyl acetate, etc.), and zinc acetate, and the like. Preferred among these are titanium-containing catalysts.

  A stabilizer may be added for the purpose of obtaining polyester polymerization stability. As the stabilizer, hydroquinone, methylhydroquinone, 4-tert-butylcatechol, 4-methoxyphenol, 2-tert-butyl-4-methoxyphenol, 2,6-di-tert-butyl-4-methoxyphenol and hindered Examples thereof include phenol compounds.

  The charging ratio of the alcohol component and the acid component of the polyester (A1) used in the reaction is preferably 1/2 to 2/1, more preferably 1 as the equivalent ratio of hydroxyl group to carboxyl group ([OH] / [COOH]). /1.3 to 1.5 / 1, and more preferably 1 / 1.2 to 1.4 / 1. When the polyester (A1) is the polyester (A11), it may contain either one or both of the unsaturated carboxylic acid component (y) and the unsaturated alcohol component (z).

The glass transition temperature (Tg _A1 ) of the polyester (A1) in the present invention is preferably −35 to 55 ° C.
When Tg _A1 is 55 ° C. or lower, low temperature fixability becomes good, and when Tg _A1 is −35 ° C. or higher, heat resistant storage stability becomes good. The glass transition temperature (Tg _A1 ) of the polyester (A1) is more preferably −30 to 52 ° C., further preferably −25 to 50 ° C., and particularly preferably −20 to 45 ° C.
The glass transition temperature (Tg) can be measured by a method (DSC method) specified in ASTM D3418-82 using, for example, DSC Q20 manufactured by TA Instruments.

The peak top molecular weight Mp of the polyester (A1) in the present invention in gel permeation chromatography (GPC) is preferably 2,000 to 30,000, more preferably 3,000 to 20,000, and further preferably Is 4,000 to 12,000.
When the peak top molecular weight Mp of the polyester (A1) is 2,000 to 30,000, glossiness, low temperature fixability and hot offset resistance are preferable.

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

The peak top molecular weight Mp, the number average molecular weight (hereinafter sometimes abbreviated as Mn), and the weight average molecular weight (hereinafter sometimes abbreviated as Mw) of the resin such as polyester in the present invention are measured by GPC. It can be measured under the following conditions.
Device (one 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 solution injection amount: 100 μL
Detector: Refractive index detector Reference substance: Tosoh Corporation 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)
For the measurement of the molecular weight, the sample 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 acid value of the polyester (A1) is preferably 0.1 to 30 mgKOH / g, more preferably 0.1 to 25 mgKOH / g, and still more preferably 0.1 from the viewpoint of charging stability and heat resistant storage stability. It is from 10 to 10 mgKOH / g, particularly preferably from 1 to 10 mgKOH / g. When the acid value is 0.1 mgKOH / g or more, the charging stability becomes good, and when the acid value is 30 mgKOH / g or less, the heat resistant storage stability becomes good.

  "Crystallinity" of the crystalline vinyl resin (B) in the present invention means that when measured in the same manner as the endothermic peak top temperature (Tm) of the toner binder using a differential scanning calorimeter described below, It means that there is a clear endothermic peak, not a change in endotherm.

  The crystalline vinyl resin (B) in the present invention is preferably a polymer having a chain hydrocarbon group-containing (meth) acrylate (a) having 21 to 40 carbon atoms as a constituent monomer. The crystalline vinyl resin (B) contains 15 to 99% by weight of the (meth) acrylate (a) having a chain hydrocarbon group having 21 to 40 carbon atoms based on the weight of all the constituent monomers of (B). It is preferable to contain. (B) has crystallinity by containing 15 to 99% by weight of (a) as a constituent monomer. Further, when the carbon number of (a) is 21 or more, the heat resistant storage stability becomes good, and when the carbon number is 40 or less, the low temperature fixing property becomes good.

As (a), a (meth) acrylate having a linear alkyl group (having 18 to 36 carbon atoms) [octadecyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate, heneicosanyl (meth) acrylate, behenyl ( [Meth) acrylate, lignoceryl (meth) acrylate, ceryl (meth) acrylate, montanyl (meth) acrylate, triaconta (meth) acrylate and dotriaconta (meth) acrylate] and a branched alkyl group (having 18 to 36 carbon atoms). Examples thereof include (meth) acrylate [2-decyltetradecyl (meth) acrylate and the like].
Of these, a (meth) acrylate having a linear alkyl group (having 18 to 36 carbon atoms) is preferable from the viewpoints of heat-resistant storage stability of toner, low-temperature fixing property, hot offset resistance, crushability and image strength. Yes, more preferred is a (meth) acrylate having a linear alkyl group (having 18 to 30 carbon atoms), and even more preferred is octadecyl (meth) acrylate, eicosyl (meth) acrylate, behenyl (meth) acrylate, lignoceryl. (Meth) acrylate, ceryl (meth) acrylate and triaconta (meth) acrylate, particularly preferred are octadecyl acrylate, eicosyl acrylate, behenyl acrylate and lignoceryl acrylate.
The C21 to C40 (meth) acrylate (a) having a chain hydrocarbon group may be used alone or in combination of two or more.

The crystalline vinyl resin (B) is a (meth) acrylate having 21 to 40 carbon atoms and having a chain hydrocarbon group as a constituent monomer from the viewpoint of hot offset resistance of toner, heat resistant storage stability, pulverizability and charge stability. In addition to (a), a monomer (b) having a vinyl group and having 6 or less carbon atoms may be contained as a constituent monomer.
As the monomer (b), a (meth) acrylic monomer having 6 or less carbon atoms [(meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl (meth ) Acrylate and ethyl-2- (hydroxymethyl) acrylate, etc.], vinyl ester monomers having 6 or less carbon atoms [vinyl acetate, vinyl propionate, isopropenyl acetate, etc.], aliphatic hydrocarbon vinyl monomers having 6 or less carbon atoms [] Ethylene, propylene, butene, butadiene, isoprene, 1,5-hexadiene, etc.] and a monomer having a nitrile group and having 6 or less carbon atoms [(meth) acrylonitrile, etc.] and the like.
Of these, preferred are (meth) acrylic acid, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, vinyl acetate, and (meth) acrylonitrile.
As the monomer (b), one type may be used alone, or two or more types may be used in combination.

  The crystalline vinyl resin (B) is a (meth) acrylate (a) having a chain hydrocarbon group having 21 to 40 carbon atoms and a monomer (b) as constituent monomers from the viewpoint of heat resistant storage stability and hot offset resistance. Other than the above), the monomer (d) may be contained, and as the monomer (d), a chain carbonization of a styrene monomer (d1) and a (meth) acrylic monomer having more than 6 carbon atoms is used. (Meth) acrylic monomer (d2) excluding (meth) acrylate (a) having a hydrogen group having 21 to 40 carbon atoms, vinyl ester monomer (d3) having more than 6 carbon atoms, and nitrile group, urethane group, urea group A monomer (d4) having at least one functional group selected from the group consisting of an amide group, an imide group, an allophanate group and a burette group and an ethylenically unsaturated bond and having more than 6 carbon atoms (d4). Those having as a monomer are preferable. As the monomer (d), one type may be used alone, or two or more types may be used in combination.

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

Examples of the (meth) acrylic monomer (d2) include an alkyl (meth) acrylate having an alkyl group having 4 to 17 carbon atoms [butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, etc.], Hydroxyalkyl (meth) acrylate in which the alkyl group has 4 to 17 carbon atoms, aminoalkyl group-containing (meth) acrylate in which the alkyl group has 4 to 17 carbon atoms [dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate Etc.] and esters of unsaturated carboxylic acids having 8 to 20 carbon atoms with polyhydric alcohols [ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (Me ) Acrylate, 1,6-hexanediol di (meth) acrylate and polyethylene glycol di (meth) acrylate, etc.] and the like.
Of these, preferred are butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dimethylaminoethyl (meth) acrylate and a mixture of two or more thereof.

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

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

  The urethane group-containing monomer (d41) is an alcohol having an ethylenically unsaturated bond and having 2 to 22 carbon atoms (2-hydroxyethyl methacrylate, vinyl alcohol, etc.) and an isocyanate having 1 to 30 carbon atoms. Examples thereof include a monomer reacted by a known method and a monomer reacted by a known method with an alcohol having 1 to 26 carbon atoms and an isocyanate having 1 to 30 carbon atoms having an ethylenically unsaturated bond.

  Examples of the isocyanate having 1 to 30 carbon atoms include monoisocyanate compounds (benzenesulfonyl isocyanate, tosyl isocyanate, phenyl isocyanate, p-chlorophenyl isocyanate, butyl isocyanate, hexyl isocyanate, t-butyl isocyanate, cyclohexyl isocyanate, octyl isocyanate, 2-ethylhexyl isocyanate. , Dodecyl isocyanate, adamantyl isocyanate, 2,6-dimethylphenyl isocyanate, 3,5-dimethylphenyl isocyanate and 2,6-dipropylphenyl isocyanate, etc.), aliphatic diisocyanate compounds (trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate) , Pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate), alicyclic diisocyanate compounds (1,3-cyclopentene diisocyanate, 1 , 3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate and hydrogenated tetramethyl xylylene diisocyanate, etc.) and aromatic diisocyanate compounds ( Phenylene diisocyanate, 2,4-tolylene diisosonate, 2,6-tolylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-toluidine diisocyanate, 4,4'- Diphenyl ether diisocyanate, 4,4′-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate and the like).

As the alcohol having 1 to 26 carbon atoms, methanol, ethanol, propanol, isopropyl alcohol, butanol, t-butyl alcohol, pentanol, heptanol, octanol, 2-ethylhexanol, nonanol, decanol, undecyl alcohol, lauryl alcohol, dodecyl. Alcohol, myristyl alcohol, pentadecyl alcohol, cetanol, heptadecanol, stearyl alcohol, isostearyl alcohol, elaidyl alcohol, oleyl alcohol, linoleyl alcohol, linolenyl alcohol, nonadecyl alcohol, heneicosanol, behenyl alcohol, ell Examples include sil alcohol and the like.
Examples of the isocyanate having an ethylenically unsaturated bond and having 1 to 30 carbon atoms include 2-isocyanatoethyl (meth) acrylate and 2- [0- (1′-methylpropylideneamino) carboxyamino] ethyl (meth) acrylate. , 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl (meth) acrylate and 1,1- (bis (meth) acryloyloxymethyl) ethyl isocyanate.

  Examples of the monomer (d42) having a urea group include amines having 3 to 22 carbon atoms (for example, primary amines such as primary amines (normal butylamine, t-butylamine, propylamine and isopropylamine), secondary amines. (Diethylamine, dinormalpropylamine, dinormalbutylamine, etc.), aniline, cyclohexylamine, etc.], and a monomer obtained by reacting an isocyanate having an ethylenically unsaturated bond and having 1 to 30 carbon atoms by a known method. Be done.

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

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

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

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

By using the monomer (d4), at least one functional group selected from the group consisting of a urethane group, a urea group, an amide group, an imide group, an allophanate group and a buret group is added to the crystalline vinyl resin (B). Can be introduced inside.
As a method for introducing at least one functional group selected from the group consisting of a urethane group, a urea group, an amide group, an imide group, an allophanate group and a burette group into the crystalline vinyl resin (B), In addition to the method using the monomers (d41) to (d46), the following method can also be used.
First, of the two compounds (the compound having an ethylenically unsaturated bond and the other compound) for obtaining the monomers (d41) to (d46), the compound having an ethylenically unsaturated bond is a chain hydrocarbon group. With a (meth) acrylate (a) having 21 to 40 carbon atoms. Subsequently, the other compound is reacted with the polymer of the compound having an ethylenically unsaturated bond and (a). Through the above procedure, the "polymer of the compound having an ethylenically unsaturated bond and (a)" and the "other compound" are bonded to each other to obtain the crystalline vinyl resin (B). In this reaction, the “polymer of a compound having an ethylenically unsaturated bond and (a)” and the “other compound” are urethane group, urea group, amide group, imide group, allophanate group or burette. At least one functional group selected from the group consisting of a urethane group, a urea group, an amide group, an imide group, an allophanate group and a burette group is introduced into the crystalline vinyl resin (B) because it is bound by a group. be able to.
In the case of the above method, the monomer (d4) is not used as the monomer constituting the crystalline vinyl resin (B), but since the obtained compounds are the same, the monomer (d4 ) Or containing the monomer (d) as a constituent monomer.

  Among these monomers (d4), a reaction product of 2-isocyanatoethyl (meth) acrylate and methanol and a reaction product of 2-isocyanatoethyl (meth) acrylate and di-normal-butylamine are preferable.

  Among these monomers (d), styrene, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and 2-isocyanato are preferable from the viewpoints of low-temperature fixability, heat-resistant storage stability, pulverizability, and raw material cost. It is a reaction product of ethyl (meth) acrylate and methanol and a reaction product of 2-isocyanatoethyl (meth) acrylate and di-n-butylamine, and more preferred is styrene.

  The crystalline vinyl resin (B) is a monomer other than a (meth) acrylate (a) having a chain hydrocarbon group having 21 to 40 carbon atoms, a monomer (b) and a monomer (d) as a constituent monomer. May be included, and examples thereof include divinylbenzene and alkylallylsulfosuccinic acid sodium salt.

  The weight ratio of the (meth) acrylate (a) having a chain hydrocarbon group having 21 to 40 carbon atoms in the monomer constituting the crystalline vinyl resin (B) is, as described above, the crystalline vinyl resin (B It is preferably from 15 to 99% by weight based on the weight of). When the weight ratio of (a) is 15% by weight or more, the low temperature fixability is good, and when it is 99% by weight or less, the hot offset resistance is good. From the viewpoints of low-temperature fixability, hot offset resistance and heat resistant storage stability, the weight ratio of (a) is more preferably 30 to 99% by weight, further preferably 40 to 95% by weight, and particularly preferably 45 to 90%. %, Most preferably 50-85% by weight.

  From the viewpoint of heat resistant storage stability, the monomer constituting the crystalline vinyl resin (B) preferably further contains the monomer (b), more preferably further contains the monomer (d). More preferably, the total amount of the monomer (b) and the monomer (d) is 2 to 50% by weight based on the weight of the crystalline vinyl resin (B).

The crystalline vinyl resin (B) in the present invention preferably satisfies the following relational expression (1) from the viewpoint of heat resistant storage stability and charge stability.
1.1 ≦ | SP (x) −SP (a) | ≦ 8.0 (1)
SP (a) in the relational expression (1) is an SP value of a homopolymer of a (meth) acrylate (a) having a chain hydrocarbon group and having 21 to 40 carbon atoms, and SP (x) is (a). It is SP value of the polymer of all the monomers other than).
The SP value (cal / cm ³ ) ^0.5 in the present invention is a value at 25 ° C. calculated by the method described in Robert F Fedors et al., Polymer engineering and science, Volume 14, Pages 151-154. Is.
Further, from the viewpoint of heat resistant storage stability when used as a toner, it is more preferable that 1.5 ≦ | SP (x) −SP (a) | ≦ 6.0 is satisfied.

When the crystalline vinyl resin (B) contains a THF insoluble matter, the content of the THF insoluble matter is preferably 1.0% by weight or less, and 0.1 to 1.0% by weight. Is more preferable.
In addition, it is preferable that the crystalline vinyl resin (B) does not contain a THF insoluble component from the viewpoint of low temperature fixability.

The acid value of the crystalline vinyl resin (B) is preferably 40 or less, more preferably 0 to 20, and further preferably 0 to 5, from the viewpoint of heat resistant storage stability and chargeability.
The acid value of the crystalline vinyl resin (B) can be measured by the method specified in JIS K0070.

  The Mn of the crystalline vinyl resin (B) is preferably 1,000 to 300,000 from the viewpoint of both heat-resistant storage stability of the toner and low-temperature fixability.

The Mw of the crystalline vinyl resin (B) is preferably 1,000 to 300,000 from the viewpoint of hot offset resistance, heat resistant storage stability and low temperature fixability of the toner.
Mn and Mw of the crystalline vinyl resin (B) can be measured by the same method as the polyester resin.

  The crystalline vinyl resin (B) in the present invention comprises a chain hydrocarbon group-containing (meth) acrylate (a) having 21 to 40 carbon atoms, a monomer (b) and a monomer (d) which are optionally used. It can be produced by polymerizing a monomer composition containing a) by a known method (method described in JP-A-5-117330, etc.). For example, it can be produced by a solution polymerization method in which the above monomer is reacted with a radical reaction initiator (azobisisobutyronitrile or the like) in a solvent (toluene or the like).

As the radical reaction initiator, the radical reaction initiator (c) described above may be used. The preferred radical reaction initiator (c) is also the same as described above.
The toner binder obtained by the method of the present invention may contain the compound used during the polymerization of the crystalline vinyl resin (B) and the residue thereof, as long as the effects of the present invention are not impaired.
Further, a resin other than the polyester resin (A) and the crystalline vinyl resin (B) and a known additive (release agent, etc.) may be contained.

As described above, the method for producing the toner binder of the present invention has a step of crosslinking the polyester (A1) in the presence of the crystalline vinyl resin (B). The method of crosslinking the polyester (A1) in the crosslinking step is preferably the following method (1), (2) or (3).
Method (1): a method in which the polyester (A1) is a polyester (A11) having a carbon-carbon double bond, and the carbon-carbon double bond is reacted to crosslink;
Method (2): The polyester (A1) is a polyester (A12) having a carboxyl group and / or a hydroxyl group, and the carboxyl group of (A1) is reacted with a hydroxyl group of a polyhydric alcohol (s) having a valence of 3 or more. A method of crosslinking or crosslinking by reacting the hydroxyl group of (A1) with a carboxyl group and / or an acid anhydride group of a tricarboxylic or higher polycarboxylic acid or its anhydride (t);
Method (3): The polyester (A1) is a polyester (A12) having a carboxyl group and / or a hydroxyl group, and the carboxyl group and / or hydroxyl group (A1) is reacted with a polyfunctional epoxy compound (E). How to crosslink.

The method of mixing the polyester (A1) and the crystalline vinyl resin (B) in the cross-linking step may be a commonly known method or the like, and examples of the mixing method include melt mixing and solvent mixing.
Examples of the solvent used for solvent mixing include ethyl acetate, THF, methyl ethyl ketone, acetone and the like.

  Examples of the mixing device 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 mixer include a static mixer, an extruder, a continuous kneader, and a triple roll.

Among the melt mixing and the solvent mixing, the melt mixing which does not require removal of the solvent is preferred because the mixing is uniform.
Of these, a method of crosslinking the polyester (A1) while melt mixing the crystalline vinyl resin (B) and the polyester (A1) is preferable.

  As a method for crosslinking (A1) by the crosslinking method (1) while melt-mixing (A1) and (B), a mixture of polyester (A11) and crystalline vinyl resin (B) is fixed in a twin-screw extruder. A method of injecting at a speed and at the same time also injecting a radical reaction initiator (c) at a constant rate to carry out the reaction while kneading and conveying at a temperature of 100 to 200 ° C, or a polyester (A11) and a crystalline vinyl resin (B) And the like are charged in a batch type mixing apparatus such as a reaction tank, melted and uniformly mixed, and then the radical reaction initiator (c) is charged and crosslinked at a temperature of 100 to 200 ° C.

  When a twin-screw extruder is used, the reaction raw material polyester (A11) and crystalline vinyl resin (B) charged or injected into the twin-screw extruder are directly fed to the extruder without cooling from the resin reaction solution. The injection may be carried out, or the resin once produced may be cooled and pulverized and then supplied to a twin-screw extruder.

  As a method for crosslinking (A1) by the crosslinking method (2) while melt-mixing (A1) and (B), a polyester (A12) and a crystalline vinyl resin (B) are batch-type mixing devices such as a reaction tank. Then, the mixture is melted and uniformly mixed, and then a trihydric or higher polyhydric alcohol (s) or a trihydric or higher polycarboxylic acid or an anhydride thereof (t) is charged, and an esterification reaction is performed at a temperature of 100 to 200 ° C. And the like.

  As a method of crosslinking (A1) by the crosslinking method (3) while melt-mixing (A1) and (B), the polyester (A12) and the crystalline vinyl resin (B) are mixed in a twin-screw extruder at a constant speed. Injecting the polyfunctional epoxy compound (E) at a constant rate at the same time, and carrying out the reaction while kneading and conveying at a temperature of 100 to 200 ° C., or the polyester (A12) and the crystalline vinyl resin (B). Examples include a method of charging a batch-type mixing device such as a reaction tank, melting and uniformly mixing, and then charging the polyfunctional epoxy compound (E) and crosslinking at a temperature of 100 to 200 ° C.

  The weight ratio [(A1) :( B)] of the polyester (A1) and the crystalline vinyl resin (B) at the time of producing the toner binder (before the crosslinking reaction) in the present invention is low temperature fixability, hot offset resistance and heat resistance. From the viewpoint of storability, it is preferably 5:95 to 50:50, more preferably 10:90 to 45:55, further preferably 13:87 to 42:58, and particularly preferably 15:85 to 40. : 60.

  The temperature for crosslinking the polyester (A1) is preferably 100 to 200 ° C., more preferably 120 to 195 ° C., further preferably 130 to 190 ° C., particularly from the viewpoint of uniformity of cross-linking and productivity. It is preferably 140 to 190 ° C. When the crosslinking temperature exceeds 200 ° C., the crystalline vinyl resin is decomposed, and thus the heat resistant storage stability may be deteriorated. When the crosslinking temperature is lower than 100 ° C., the resin viscosity is high and the crosslinking uniformity is deteriorated. There are cases.

The time of the crosslinking step in the method of crosslinking using a continuous mixing device such as a twin-screw extruder is preferably 1 to 300 minutes, more preferably 2 to 240 minutes, from the viewpoint of the uniformity and productivity of crosslinking. It is more preferably 3 to 180 minutes, and particularly preferably 4 to 120 minutes.
The time of the crosslinking step in the method of crosslinking using a batch-type mixing device such as a reaction tank is preferably 30 to 600 minutes, more preferably 60 to 540 minutes, still more preferably from the viewpoint of uniformity of crosslinking and productivity. Is 90 to 480 minutes, particularly preferably 120 to 420 minutes.

  When the method (1) and the method (2) are used for crosslinking, it is preferable to have a step of reducing the pressure in the reaction system during and / or after the crosslinking of the polyester (A1). This is because when the crosslinking is carried out by the method (1), the organic solvent, the initiator decomposition residue and the like are removed as described above. Further, in the case of crosslinking by the method (2), it is preferable to reduce the pressure in order to promote the esterification of the polyester (A12). The depressurization step may be started at the same time as the start of the crosslinking reaction, during the crosslinking reaction, or at any time after the crosslinking reaction.

  The temperature of the depressurization step is preferably 100 to 200 ° C., more preferably 120 to 195 ° C., further preferably 130 to 190 ° C., and particularly preferably 140 to 190 from the viewpoint of devolatilization efficiency and productivity. ℃. If the temperature during depressurization exceeds 200 ° C, the crystalline vinyl resin may be decomposed to deteriorate the heat resistant storage stability, and if the temperature during depressurization is lower than 100 ° C, the resin viscosity may be high and the efficiency may be poor. is there.

The time of the depressurizing step in the crosslinking method (1) is preferably 1 to 300 minutes, more preferably 2 to 240 minutes, still more preferably 3 to 180 minutes, particularly preferably 4 to 4 from the viewpoint of heat resistant storage stability and productivity. 120 minutes.
The time of the depressurizing step in the crosslinking method (2) is preferably 30 to 600 minutes, more preferably 60 to 540 minutes, further preferably 90 to 480 minutes, from the viewpoint of heat resistant storage stability, hot offset resistance and productivity. Particularly preferably, it is 120 to 420 minutes.

  The degree of pressure reduction in the pressure reduction step is preferably 0.01 to 30 kPa, more preferably 0.05 to 20 kPa, still more preferably 0.08 to 10 kPa, and particularly preferably, from the viewpoint of heat resistant storage stability, hot offset resistance and productivity. Is 0.1 to 5 kPa.

In the present invention, steps other than the crosslinking step and the depressurizing step are not particularly limited, and a general toner binder manufacturing step can be adopted.
For example, it is possible to provide a step of taking out the toner binder when melt-mixing and carrying out the crosslinking step, and a step of taking out the toner binder after solvent removal and pulverizing it when carrying out the solvent mixing and carrying out the crosslinking step. When the solvent is mixed and the crosslinking step is performed, a step of granulating and removing the solvent after dispersing in water can be provided. Further, a step of mixing the obtained granular toner binder with an additive by a known method or the like can be provided.

The toner binder obtained by the method of the present invention has an endothermic peak top temperature (Tm) derived from the crystalline vinyl resin (B) of 40 to 100 in a differential scanning calorimetric curve obtained by differential scanning calorimetry (also referred to as DSC measurement). It is preferable to have at least one in the range of 0 ° C., and it is more preferable to have at least one of the above peak top temperatures (Tm) in the range of 45 to 80 ° C. When the peak top temperature (Tm) is in the above range, the low temperature fixability of the toner binder, the heat resistant storage stability and the glossiness are well balanced. This is because the crystalline vinyl resin (B) rapidly melts at the endothermic peak top temperature (Tm) derived from the crystalline vinyl resin (B) to lower the viscosity of the toner binder, and is necessary when the toner is made into a toner. This is because the storage stability is satisfied.
However, the endothermic peak top temperature (Tm) derived from the crystalline vinyl resin (B) was measured using a differential scanning calorimeter, and the toner binder was kept at 30 ° C. for 10 minutes under the conditions of 30 ° C. to 10 ° C./minute. The first temperature rise to 150 ° C. was carried out at 150 ° C., then it was kept at 150 ° C. for 10 minutes, then cooled to 0 ° C. under the condition of 10 ° C./min, then kept at 0 ° C. for 10 minutes, then The top of the endothermic peak derived from the crystalline vinyl resin (B) in the differential scanning calorimetric curve in the second heating process when the second heating is performed from 0 ° C. to 150 ° C. under the condition of 10 ° C./min. Is a temperature that indicates. When there are a plurality of endothermic peaks derived from the crystalline vinyl resin (B), (Tm) is the peak top temperature of the endothermic peak having the largest endothermic amount calculated from each endothermic peak.

  The endothermic peak top temperature (Tm) of the toner binder is adjusted by adjusting the carbon number of the (meth) acrylate (a) having a chain hydrocarbon group having a chain hydrocarbon group which constitutes the crystalline vinyl resin (B). By adjusting the weight ratio of (a) constituting the crystalline vinyl resin (B) and satisfying the above relational expression (1), the above preferable range can be adjusted. Generally, the endothermic peak top temperature (Tm) is increased by increasing the carbon number of (a), increasing the weight ratio of (a), and increasing the weight average molecular weight of the crystalline vinyl resin (B). When the content of the crystalline vinyl resin (B) is small, the endothermic peak top temperature (Tm) is less likely to decrease by increasing the SP value difference between the polyester (A1) and the crystalline vinyl resin (B). Become.

The endothermic peak top temperature (Tm) is a value measured under the following conditions using a differential scanning calorimeter. As the differential scanning calorimeter, for example, DSC Q20 manufactured by TA Instruments Co., Ltd. can be used.
<Measurement conditions>
(1) Hold at 30 ° C for 10 minutes (2) Heat up to 150 ° C at 10 ° C / minute (3) Hold at 150 ° C for 10 minutes (4) Cool to 0 ° C at 10 ° C / minute (5) 10 ° C at 10 ° C Each endothermic peak of the differential scanning calorimetric curve measured during the process of holding for 6 minutes (6) and rising to 150 ° C. at 10 ° C./minute (7) and (6) is analyzed.

The toner binder obtained by the method of the present invention has a glass transition temperature (Tg _T ) within a temperature range of −30 ° C. to 80 ° C. in a differential scanning calorimetric curve obtained when performing differential scanning calorimetry (DSC). It is preferable to have at least one inflection point indicating. The inflection point indicating the glass transition temperature (Tg _T ) is more preferably in the temperature range of 35 to 65 ° C. When the inflection point indicating the glass transition temperature (Tg _T ) is in the temperature range of −30 ° C. or higher, the heat-resistant storage stability becomes good, and in the temperature range of 80 ° C. or lower, the fixability becomes good.
The glass transition temperature (Tg _T ) can be determined by the method (DSC method) specified in ASTM D3418-82. As the glass transition temperature (Tg _T ), for example, DSC Q20 manufactured by TA Instruments Co., Ltd. can be used.
<Measurement conditions>
(1) Temperature rise from 30 ° C to 20 ° C / min to 150 ° C (2) Hold at 150 ° C for 10 minutes (3) Cool to 20 ° C / min to -35 ° C (4) Hold at -35 ° C for 10 minutes (5 ) The differential scanning calorimetric curve measured in the process of heating (6) and (5) at 20 ° C./min to 150 ° C. is analyzed.

The toner binder obtained by the method of the present invention may contain a THF insoluble matter.
The content (% by weight) of the THF insoluble component in the toner binder is preferably 50% by weight or less, more preferably 30% by weight or less, from the viewpoint of gloss, hot offset resistance and low temperature fixing property. Yes, more preferably 15% by weight or less, and particularly preferably 0.1 to 10% by weight.

The content (wt%) of the THF insoluble component in the toner binder is determined by the following method.
50 mL of THF is added to 0.5 g of the sample, and the mixture is stirred and refluxed for 3 hours. After cooling, the insoluble matter is filtered off with a glass filter, and the resin content on the glass filter is dried under reduced pressure at 80 ° C. for 3 hours. The weight of the dry resin on the glass filter was taken as the weight of the THF insoluble matter, and the weight of the sample minus the weight of the THF insoluble matter was taken as the weight of the THF soluble matter. Calculate the weight percent of minutes.

  The Mn of the toner binder obtained by the method of the present invention is preferably from 500 to 24,000, more preferably from 700 to 17,000, further preferably from 900, from the viewpoint of achieving both heat-resistant storage stability and low-temperature fixability of the toner. ~ 12,000.

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

  The molecular weight distribution Mw / Mn of the toner binder obtained by the method of the present invention is preferably 2 to 30, and more preferably 2.5 to 28, from the viewpoint of hot offset resistance, heat resistant storage stability and low temperature fixability of the toner. More preferably, it is 3 to 26.

The content of the organic solvent in the toner binder obtained by the method of the present invention is preferably 20 to 2000 ppm based on the weight of the toner binder. When the organic solvent content is 2000 ppm or less, heat-resistant storage stability and odor are good, and when it is 20 ppm or more, low temperature fixability and gloss are good. The content of the organic solvent in the toner binder is more preferably 20 to 1500 ppm, further preferably 30 to 1000 ppm, and particularly preferably 40 to 500 ppm.
In particular, when the reaction in which the polyester (A1) is cross-linked with the radical reaction initiator (c) to generate a decomposition product of the radical reaction initiator (c) is used, the content of the organic solvent which is the decomposition product is By setting the content in the range, a toner excellent in odor, hot offset resistance, pulverizability, image strength and fluidity can be obtained.

  As a method of controlling the content of the organic solvent, for example, (1) control of the amount of the organic solvent used in producing the polyester resin (A1), the crystalline vinyl resin (B) and the toner binder, (2) the amount of the initiator. (Controlling the decomposed product of the initiator), (3) controlling the organic solvent used in (1) and (2) and the residue of decomposition of the initiator by removing the solvent.

In (3), the method of removing the solvent from the organic solvent and the method of removing the solvent from the initiator decomposition residue are not particularly limited. Then, the melt is fed and the pressure is reduced from the vent port. 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. Also, by crushing the toner binder into a dryer in which the temperature and pressure (normal pressure or reduced pressure) are adjusted according to the type of organic solvent to be desolvated, the amount of organic solvent in the toner binder can be reduced. You can control. 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 of the solvent removal is preferably 20 to 200 ° C, more preferably 30 to 170 ° C, and further preferably 40 to 160 ° C. The degree of reduced pressure for solvent removal is preferably 0.01 to 100 kPa, more preferably 0.1 to 95 kPa, and further preferably 1 to 90 kPa.
Further, the method of removing the solvent in a short time is preferable because the transesterification reaction between the polyester resin (A) and the crystalline vinyl resin (B) hardly occurs, and the hot offset resistance and the low temperature fixing property are good.

The content (ppm) of the organic solvent can be measured, for example, under the following conditions such as gas chromatography analysis and gas chromatography mass spectrometry.
The content of the organic solvent in the toner binder in the examples was measured under the following conditions.
[Gas chromatograph analysis measurement conditions]
Gas chromatograph: Agilent 6890N
Mass spectrometer: Agilent 5973 inert
Column: ZB-WAX (liquid phase: (14% -cyanopropyl-phenyl) methylpolysiloxane) 0.25 mm × 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, compounds having 3 to 8 carbon atoms are more preferable, and acetone is more preferable. Isopropyl alcohol and t-butanol.

  When a toner is produced using the toner binder obtained by the method of the present invention, in addition to the toner binder of the present invention, if necessary, one selected from a colorant, a release agent, a charge control agent, a fluidizing agent, and the like. The above known additives and the like can be used.

As the colorant, all of the dyes and pigments used as the colorant for toner can be used. For example, carbon black, iron black, Sudan black SM, first yellow G, benzidine yellow, pigment yellow, India first orange, 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 and Oil Pink OP. Or a mixture of two or more kinds. Further, if necessary, magnetic powder (a powder of a ferromagnetic metal such as iron, cobalt, nickel or a compound such as magnetite, hematite, ferrite) can be contained also as a colorant.
The content of the colorant is preferably 1 to 40 parts by weight, more preferably 3 to 10 parts by weight with respect to 100 parts by weight of the toner binder. When magnetic powder is used, it is preferably 20 to 150 parts by weight, more preferably 40 to 120 parts by weight.

  As the release agent, those having a flow softening point (T1 / 2) of 50 to 170 ° C. by a flow tester are preferable, and aliphatic hydrocarbon waxes such as polyolefin wax, microcrystalline wax, paraffin wax, and Fischer-Tropsch wax, and those Oxides, carnauba wax, montan wax and deoxidized waxes thereof, ester waxes, fatty acid amides, fatty acids, higher alcohols, fatty acid metal salts and the like.

The flow softening point (T1 / 2) of the release agent is a value measured under the following conditions.
<Method of measuring flow softening point (T1 / 2)>
Using a drop-down flow tester [eg, CFT-500D manufactured by Shimadzu Corporation], a load of 1.96 MPa was applied by a plunger while heating 1 g of a measurement sample at a temperature rising rate of 6 ° C./min. Push out from a nozzle with a diameter of 1 mm and a length of 1 mm, draw a graph of "plunger drop (flow value)" and "temperature", and graph the temperature corresponding to 1/2 of the maximum plunger drop. This is read as the flow softening point (T1 / 2).

  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 those obtained by further subjecting it to thermal degradation] (eg low molecular weight polypropylene, low molecular weight polyethylene, low molecular weight polypropylene polyethylene copolymer), oxidation of olefin (co) polymers by oxygen and / or ozone. And olefins (maleic acid modified products of (co) polymers [eg, maleic acid and its derivatives (maleic anhydride, monomethyl maleate, monobutyl maleate, dimethyl maleate, etc.) modified products]], olefins and unsaturated carboxylic acids [ (Meth) acrylic acid, itaconic acid, maleic anhydride and the like] and / or unsaturated carboxylic acid alkyl ester [(meth) acrylic acid alkyl (alkyl having 1 to 18 carbon atoms) ester and maleic acid alkyl (alkyl having 1 carbon) To 18) ester, etc.] and the like.

  Examples of the microcrystalline wax include Hi-Mic-2095, Hi-Mic-1090, Hi-Mic-1080, Hi-Mic-1070, Hi-Mic-2065, and Hi-Mic-manufactured by Nippon Seiro Co., Ltd. 1045, Hi-Mic-2045 and the like.

  Examples of the paraffin wax include Paraffin WAX-155, Paraffin WAX-150, Paraffin WAX-145, Paraffin WAX-140, Paraffin WAX-135, HNP-3, HNP-5, and HNP-made by Nippon Seiro Co., Ltd. 9, HNP-10, HNP-11, HNP-12, HNP-51 and the like.

  Examples of the Fischer-Tropsch wax include Sasolwax C80 manufactured by Sazol.

  Examples of carnauba wax include refined carnauba wax No. 1 manufactured by Kato Yoko Co., Ltd.

  Examples of the ester wax include fatty acid ester wax (for example, Nissan Electol WEP-2, WEP-3, WEP-4, WEP-5 and WEP-8 manufactured by NOF CORPORATION) and the like.

  The higher alcohols include aliphatic alcohols having 30 to 50 carbon atoms, such as triacontanol. The fatty acids include fatty acids having 30 to 50 carbon atoms, such as triacontanecarboxylic acid.

  Examples of fatty acid amides include DIAMIC Y and DIAmid 200 manufactured by Mitsubishi Chemical Corporation.

  Of the above, polyolefin wax, microcrystalline wax, paraffin wax, Fischer-Tropsch wax, carnauba wax and ester wax are preferable from the viewpoint of low-temperature fixability.

  The charge control agent may contain any of a positively chargeable charge control agent and a negatively chargeable charge control agent, a nigrosine dye, a triphenylmethane dye containing a tertiary amine as a side chain, and a quaternary ammonium salt. , Polyamine resins, imidazole derivatives, quaternary ammonium base-containing polymers, metal-containing azo dyes, copper phthalocyanine dyes, salicylic acid metal salts, benzylic acid boron complexes, sulfonic acid group-containing polymers, fluorine-containing polymers and halogen-substituted aromatic ring-containing polymers, etc. Is mentioned.

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

The content of the toner binder in the toner is preferably 30 to 97% by weight, more preferably 40 to 95% by weight, still more preferably 45 to 92% by weight, based on the weight of the toner.
The content of the colorant is preferably 0.05 to 60% by weight, more preferably 0.1 to 55% by weight, still more preferably 0.5 to 50% by weight, based on the weight of the toner.
The content of the release agent is preferably 0 to 30% by weight, more preferably 0.5 to 20% by weight, further preferably 1 to 10% by weight based on the weight of the toner.
The content of the charge control agent is preferably 0 to 20% by weight, more preferably 0.1 to 10% by weight, further preferably 0.5 to 7.5% by weight based on the weight of the toner.
The content of the fluidizing agent is preferably 0 to 10% by weight, more preferably 0 to 5% by weight, further preferably 0.1 to 4% by weight, based on the weight of the toner.
The total content of the additives is preferably 3 to 70% by weight, more preferably 4 to 58% by weight, and further preferably 5 to 50% by weight based on the weight of the toner.
By setting the composition ratio of the toner within the above range, it is possible to easily obtain a toner having good hot offset resistance, image strength, heat resistant storage stability, fluidity, charging stability, bending resistance and document offset property. .

The toner containing the toner binder obtained by the method 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 except a fluidizing agent are dry-blended, melt-kneaded, then coarsely pulverized, and finally atomized by using a jet mill pulverizer or the like. By further classifying, the fine particles having a volume average particle diameter (D50) of 5 to 20 μm can be prepared, and then mixed with a fluidizing agent to be produced.
The volume average particle diameter (D50) is measured using a Coulter counter {for example, trade name: Multisizer III [Beckman Coulter, Inc.]}.

  When the toner is obtained by the emulsion phase inversion method, the components constituting the toner except the fluidizing agent may be dissolved or dispersed in an organic solvent, and then water may be added to form an emulsion, followed by separation and classification. it can. The volume average particle diameter of the toner is preferably 3 to 15 μm.

  The toner containing the toner binder obtained by the method of the present invention is a carrier such as ferrite whose surface is coated with iron powder, glass beads, nickel powder, ferrite, magnetite and a resin (acrylic resin, silicone resin, etc.) as required. It is mixed with the particles and used as a developer for the electric latent image. When carrier particles are used, the weight ratio of toner to carrier particles is preferably 1/99 to 99/1. 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 containing the toner binder obtained by the method of the present invention is fixed to a support (paper, polyester film, etc.) by a copying machine, a printer or the like to be used as a recording material. As a method for fixing to the support, a known hot roll fixing method, flash fixing method and the like can be applied.

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

  Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Hereinafter, “part” means part by weight.

<Production Example 1> [Production of polyester (A11-1)]
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 741 parts of a bisphenol A / EO 2.0 mol adduct as a saturated alcohol component (x), 13 parts of trimethylolpropane and a saturated carboxylic acid component (w) Terephthalic acid (124 parts) and adipic acid (115 parts) and titanium diisopropoxybis (triethanolaminate) (2.5 parts) as a catalyst were added, and the produced water was distilled off under a nitrogen stream at 230 ° C. Reacted for hours. 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 180 ° C. 1 part of tert-butyl catechol as a polymerization inhibitor was added, and 86 parts of fumaric acid as an unsaturated carboxylic acid component (y) was further added, reacted under a reduced pressure of 0.5 to 2.5 kPa for 8 hours, and then taken out. , Polyester (A11-1) was obtained.
The glass transition temperature of the polyester (A11-1) measured by the above method is 38 ° C., the peak top molecular weight is 11,000, the acid value is 2 mgKOH / g, the hydroxyl value is 18 mgKOH / g, and the double bond amount is 0.69 mmol / It was g.

<Production Examples 2 to 8> [Production of polyesters (A11-2) to (A11-8)]
A saturated alcohol component (x), a saturated carboxylic acid component (w) and an unsaturated carboxylic acid component (y) described in Table 1 were charged into a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introducing pipe, and other than that. Reacted in the same manner as in Production Example 1 to obtain polyesters (A11-2) to (A11-8). The glass transition temperature, peak top molecular weight, acid value, hydroxyl value and double bond amount of the obtained polyesters (A11-2) to (A11-8) are shown in Table 1.

<Production Example 9> [Production of polyester (A12-1)]
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introducing pipe, 813 parts of a bisphenol A / EO 2.0 mol adduct as a saturated alcohol component (x) and 70 parts of terephthalic acid as a saturated carboxylic acid component (w). , 147 parts of adipic acid, 24 parts of trimellitic anhydride, and 2.5 parts of titanium diisopropoxybis (triethanolaminate) as a catalyst were added, and the produced water was distilled off under a nitrogen stream at 230 ° C. The reaction was carried out for 2 hours. Next, after reacting under reduced pressure of 0.5 to 2.5 kPa for 5 hours, the temperature was lowered to 180 ° C. and then taken out to obtain polyester (A12-1). Table 1 shows the glass transition temperature, peak top molecular weight, acid value, hydroxyl value and double bond amount of the obtained polyester (A12-1).

<Production Examples 10 to 12> [Production of polyesters (A12-2) to (A12-4)]
A saturated alcohol component (x), a saturated carboxylic acid component (w) and an unsaturated carboxylic acid component (y) described in Table 1 were charged into a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introducing pipe, and other than that. Reacted in the same manner as in Production Example 9 to obtain polyesters (A12-2) to (A12-4). Table 1 shows the glass transition temperature, peak top molecular weight, acid value, hydroxyl value and double bond amount of the obtained polyesters (A12-2) to (A12-4).

<Production Example 13> [Production of polyester resin (A12-5)]
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introducing pipe, 717 parts of bisphenol A / PO3.0 mol adduct as a saturated alcohol component (x), 10 parts of trimethylolpropane and a saturated carboxylic acid component (w) 236 parts of terephthalic acid as described above and 2.5 parts of titanium diisopropoxybistriethanolaminate as a condensation catalyst were added, and the mixture was reacted at 230 ° C. under a nitrogen stream 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 after confirming that the acid value was less than 1 mgKOH / g, the temperature was lowered to 180 ° C. After adding 113 parts of adipic acid and reacting for 2 hours, the mixture was reacted for 3 hours under a reduced pressure of 0.5 to 2.5 kPa, and after confirming that the acid value was 30 mgKOH / g, it was taken out and polyester (A12-5) was obtained. Obtained. Table 1 shows the glass transition temperature, peak top molecular weight, acid value, hydroxyl value and double bond amount of the obtained polyester (A12-5).

<Production Example 14> [Production of polyester resin (A12-6)]
In a reaction tank equipped with a cooling pipe, a stirrer and a nitrogen introducing pipe, 695 parts of bisphenol A / EO 2.0 mol adduct as a saturated alcohol component (x), 12 parts of trimethylolpropane, and a saturated carboxylic acid component (w) Terephthalic acid (182 parts) and titanium diisopropoxybistriethanolaminate (2.5 parts) as a condensation catalyst were added, and the reaction was carried out at 230 ° C. under a nitrogen stream 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 after confirming that the acid value was less than 1 mgKOH / g, the temperature was lowered to 180 ° C. After adding 195 parts of adipic acid and reacting for 2 hours, it was reacted for 3 hours under a reduced pressure of 0.5 to 2.5 kPa, and after confirming that the acid value was 28 mgKOH / g, it was taken out and polyester (A12-6) was obtained. Obtained. Table 1 shows the glass transition temperature, peak top molecular weight, acid value, hydroxyl value and double bond amount of the obtained polyester (A12-6).

<Comparative Production Example 1> [Production of polyester (A11'-1)]
The alcohol component (x) and the saturated carboxylic acid component (w) described in Table 1 were charged in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introducing pipe, and the reaction was performed in the same manner as in Production Example 1 except for the above. A polyester (A11′-1) having no carbon-carbon double bond used in Comparative Example was obtained. Table 1 shows the glass transition temperature, peak top molecular weight, acid value and double bond amount of the obtained polyester (A11′-1).

<Comparative Production Example 2> [Production of polyester (A11'-2)]
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introducing pipe, 710 parts of propylene glycol as a saturated alcohol component (x), 775 parts of terephthalic acid as a saturated carboxylic acid component (w), and titanium diiso as a catalyst. 0.6 part of propoxybis (triethanolaminate) was added, and the mixture was reacted at 220 ° C. under a nitrogen stream for 4 hours while distilling off the produced water and excess propylene glycol. Furthermore, after reacting under reduced pressure of 0.5 to 2.5 kPa for 10 hours, the product was taken out to obtain a polyester (A11′-2) having no carbon-carbon double bond used in Comparative Examples. The unreacted propylene glycol recovered was 325 parts (therefore, the amount of propylene glycol in Table 1 is described as 385 parts). Table 1 shows the glass transition temperature, peak top molecular weight, acid value and double bond amount of the obtained polyester (A11′-2).

<Production Example 15> [Production of crystalline vinyl resin (B-1)]
After charging 138 parts of xylene into the autoclave and purging with nitrogen, the temperature was raised to 170 ° C. in a sealed state with stirring. Behenyl acrylate [abbreviated as C22 acrylate in the following, manufactured by NOF CORPORATION, the same applies hereinafter] 450 parts, styrene [manufactured by Idemitsu Kosan Co., Ltd. applies in the same way] 150 parts, acrylonitrile [manufactured by Nacalai Tex Co., Ltd., and so on] 150 parts of di-t-butyl peroxide [Perbutyl D, manufactured by NOF Corporation, the same applies hereinafter] and 100 parts of xylene were mixed with a mixed solution of 3 parts while controlling the internal temperature of the autoclave at 170 ° C. Polymerization was carried out by dropping over time. After the dropping, the dropping line was washed with 12 parts of xylene. Furthermore, the same temperature was maintained for 4 hours to complete the polymerization. The solvent was removed under reduced pressure of 0.5 to 2.5 kPa at 100 ° C. for 3 hours to obtain a crystalline vinyl resin (B-1). The composition is described in Table 2.
The endothermic peak top temperature of the crystalline vinyl resin (B-1) measured by the above method is 60 ° C., the acid value is 0 mgKOH / g, the weight average molecular weight is 14000, and | SP (x) -SP (a) | is 3 It was 0.6 (cal / cm ³ ) ^0.5 .

<Production Example 16> [Production of crystalline vinyl resin (B-2)]
After charging 138 parts of xylene into the autoclave and purging with nitrogen, the temperature was raised to 170 ° C. in a sealed state with stirring. The raw materials listed in Table 2 were dropped into an autoclave together with 100 parts of xylene, and otherwise the reaction was performed in the same manner as in Production Example 15 to obtain a crystalline vinyl resin (B-2). Table 2 shows the endothermic peak top temperature, acid value, weight average molecular weight and | SP (x) -SP (a) | of the obtained crystalline vinyl resin (B-2).
The C18 acrylate (a-2) in Table 2 is stearyl acrylate (octadecyl acrylate) manufactured by Kyoeisha Chemical Co., Ltd.

<Production Example 17> [Production of crystalline vinyl resin (B-3)]
After charging 470 parts of toluene in the autoclave and purging with nitrogen, the temperature was raised to 105 ° C. in a sealed state with stirring. 500 parts of C22 acrylate, 250 parts of styrene, 250 parts of acrylonitrile, 20 parts of methacrylic acid [manufactured by Tokyo Kasei Kogyo Co., Ltd.], 5 parts of sodium salt of alkylallyl sulfosuccinate [Eleminol JS-2, manufactured by Sanyo Kasei Co., Ltd.], 2-Isocyanatoethylmethacrylate [Karenzu MOI, Showa Denko KK] 19 parts, t-butyl peroxy-2-ethylhexanoate [Perbutyl O, NOF KK] 3.7 parts, and toluene 240 parts of the mixed solution was added dropwise over 2 hours for polymerization while controlling the internal temperature of the autoclave at 105 ° C. After maintaining at the same temperature for 4 hours to complete the polymerization, 16 parts of dinormal butylamine and 5 parts of bismuth catalyst [Neostan U-600 manufactured by Nitto Kasei Kogyo Co., Ltd.] were added, and the reaction was carried out at 90 ° C. for 6 hours. went. Then, the solvent was removed at 100 ° C. to obtain a crystalline vinyl resin (B-3). Table 2 shows the endothermic peak top temperature, acid value, weight average molecular weight and | SP (x) -SP (a) | of the obtained crystalline vinyl resin (B-3).

<Production Example 18> [Production of triacontaacrylate]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, an air introduction pipe, a pressure reducing device, and a water reducing device, 50 parts of 1-triacontanol [Tokyo Chemical Industry Co., Ltd.], 50 parts of toluene, 12 acrylic acids. Parts (manufactured by Mitsubishi Chemical Co., Ltd.) and 0.05 parts of hydroquinone were added and stirred to homogenize. Then, 2 parts of paratoluenesulfonic acid was added, and the mixture was stirred for 30 minutes, and then allowed to react for 5 hours while blowing water at a flow rate of 30 mL / min to remove water produced at 100 ° C. Then, the pressure in the reaction vessel was adjusted to 300 mmHg, and the reaction was further continued for 3 hours while removing the produced water. After cooling the reaction solution to room temperature, 30 parts of a 10 wt% sodium hydroxide aqueous solution was added, and the mixture was stirred for 1 hour and then left to stand to separate an organic phase and an aqueous phase. The organic phase was collected by liquid separation and centrifugation, and 0.01 part of hydroquinone was added, and the solvent was removed under reduced pressure while blowing air to obtain triacontaacrylate (abbreviated as C30 acrylate in Table 2).

<Production Examples 19 to 22 and Comparative Production Examples 3 to 4> [Production of crystalline vinyl resins (B-4) to (B-7), (B'-1) and (B'-2)]
After charging 138 parts of xylene into the autoclave and purging with nitrogen, the temperature was raised to 170 ° C. in a sealed state with stirring. The raw materials shown in Table 2 were dropped into an autoclave together with 100 parts of xylene, and otherwise the reaction was carried out in the same manner as in Production Example 15 to obtain crystalline vinyl resins (B-4) to (B-7) and (B′-1) ), And (B'-2) were obtained. The endothermic peak top temperature, acid value, weight average molecular weight and | SP of the crystalline vinyl resins (B-4) to (B-7), (B'-1) and (B'-2) obtained in Table 2 (X) -SP (a) | is described. The crystalline vinyl resins (B'-1) and (B'-2) contain less than 15% by weight of (meth) acrylate (a) having a chain hydrocarbon group and having 21 to 40 carbon atoms. Therefore, there is no clear endothermic peak and it does not correspond to the crystalline vinyl resin (B).
The following vinyl acetate (b-2) and butyl acrylate (d-3) were used.
Vinyl acetate: Nippon Viet Nam Poval Co., Ltd. Butyl acrylate: Tokyo Chemical Industry Co., Ltd., abbreviated as C4 acrylate in Table 2.

<Production Example 23> [Production of crystalline vinyl resin (B-8)]
After 250 parts of xylene was charged into the autoclave and purged with nitrogen, the temperature was raised to 105 ° C. in a sealed state with stirring. C22 acrylate 600 parts, styrene 75 parts, acrylonitrile 225 parts, 2-hydroxyethyl methacrylate [manufactured by Mitsubishi Gas Chemical Co., Inc.] 100 parts, t-butyl peroxy-2-ethylhexanoate [perbutyl O, NOF ( Co., Ltd.] and 10 parts of xylene and 700 parts of xylene were added dropwise over 3 hours while controlling the internal temperature of the autoclave at 105 ° C. to carry out polymerization. After the dropping, the dropping line was washed with 50 parts of xylene. Furthermore, the same temperature was maintained for 4 hours to complete the polymerization. The solvent was removed under reduced pressure of 0.5 to 2.5 kPa at 170 ° C. for 3 hours to obtain a crystalline vinyl resin (B-8). Table 2 shows the endothermic peak top temperature, acid value, weight average molecular weight and | SP (x) -SP (a) | of the obtained crystalline vinyl resin (B-8).

<Production Example 24> [Production of crystalline vinyl resin (B-9)]
After charging 138 parts of xylene into the autoclave and purging with nitrogen, the temperature was raised to 120 ° C. in a sealed state with stirring. A mixed solution of 450 parts of C22 acrylate, 75 parts of styrene, 225 parts of acrylonitrile, 225 parts of t-butyl peroxyisopropyl monocarbonate [Perbutyl I, manufactured by NOF CORPORATION] and 100 parts of xylene was used at an autoclave temperature of 120. While controlling the temperature to be 0 ° C, the mixture was added dropwise over 3 hours to carry out polymerization. After the dropping, the dropping line was washed with 50 parts of xylene. Further, after maintaining at the same temperature for 1 hour, the temperature was raised to 130 ° C. over 1 hour. Further, the temperature was kept at the same temperature for 2 hours to complete the polymerization. The solvent was removed at 170 ° C. for 3 hours under reduced pressure of 0.5 to 2.5 kPa to obtain a crystalline vinyl resin (B-9). Table 2 shows the endothermic peak top temperature, acid value, weight average molecular weight and | SP (x) -SP (a) | of the obtained crystalline vinyl resin (B-9).

<Production Example 25> [Production of crystalline vinyl resin (B-10)]
The autoclave was charged with 150 parts of toluene and 75 parts of vinyl acetate, purged with nitrogen, and then heated to 60 ° C. in a sealed state with stirring. C22 acrylate 300 parts, styrene 51 parts, acrylonitrile 25 parts, vinyl acetate 100 parts, acrylic acid 24 parts, 2,2'-azobis (2,4-dimethylvaleronitrile) [V-65, FUJIFILM Wako Pure Chemical Industries, Ltd. A)] 5.0 parts and a mixed solution of 325 parts of toluene were added dropwise over 3 hours while controlling the internal temperature of the autoclave at 60 ° C. to carry out polymerization. After the dropping, the dropping line was washed with 50 parts of toluene. Further, the temperature was maintained at the same temperature for 1 hour, and then the temperature was raised to 80 ° C. over 1 hour. Further, the temperature was kept for 1 hour to complete the polymerization. The solvent was removed at 120 ° C. for 5 hours under a reduced pressure of 0.5 to 2.5 kPa to obtain a crystalline vinyl resin (B-10). Table 2 shows the endothermic peak top temperature, acid value, weight average molecular weight and | SP (x) -SP (a) | of the obtained crystalline vinyl resin (B-10).

<Example 1> [Production of toner binder (C-1)]
32 parts of polyester (A11-1) and 68 parts of crystalline vinyl resin (B-1) are mixed and supplied to a twin-screw kneader [S5KRC Kneader manufactured by Kurimoto Iron Works Co., Ltd.] at 52 kg / hour, and at the same time, radicals are supplied. 1.0 part of t-butylperoxyisopropyl monocarbonate (c-3) as a reaction initiator (c) was supplied at 0.52 kg / hour, and kneaded and extruded at 90 rpm for 7 minutes at 160 ° C. to perform a crosslinking reaction, Furthermore, the pressure was reduced from the vent port to 5 kPa, and the mixture was mixed while removing the organic solvent. The toner obtained by mixing was cooled to obtain the toner binder (C-1) according to Example 1.

<Examples 2 to 12> [Production of Toner Binders (C-2) to (C-12)]
The polyester (A11) and the crystalline vinyl resin (B) in the parts by weight shown in Table 3 were mixed and supplied to a twin-screw kneader, and at the same time, the radical reaction initiator (c) was supplied, and the results are shown in Table 3. The crosslinking reaction and the removal of the organic solvent were performed at the crosslinking temperature in the same manner as in Example 1 to obtain toner binders (C-2) to (C-12) according to Examples 2 to 12.
The radical reaction initiators (c) in Tables 2 to 4 are as follows.
(C-1): di-t-butylperoxide (c-2): t-butylperoxy-2-ethylhexanoate (c-3): t-butylperoxyisopropyl monocarbonate (c-4) : T-butyl peroxybenzoate (c-5): 2,2′-azobis (2,4-dimethylvaleronitrile)

<Example 13> [Production of toner binder (C-13)]
20 parts of polyester (A11-2) and 80 parts of crystalline vinyl resin (B-8) were mixed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, and homogenized at 160 ° C. After that, 1 part of di-t-butyl peroxide was added and a crosslinking reaction was carried out at 160 ° C. for 3 hours. Then, the pressure was reduced under the condition of 0.5 to 2.5 kPa at 160 ° C. for 4 hours to remove the decomposition product derived from the initiator. The toner binder (C-13) according to Example 13 was obtained by cooling the obtained product.

<Example 14> [Production of toner binder (C-14)]
30 parts of polyester (A11-5) and 70 parts of crystalline vinyl resin (B-8) were mixed in a reaction tank equipped with a cooling tube, a stirrer and a nitrogen introducing tube, and homogenized at 175 ° C. Then, 2 parts of di-t-butyl peroxide was added and a crosslinking reaction was carried out at 175 ° C. for 1 hour. Thereafter, the pressure was reduced under the condition of 0.5 to 2.5 kPa at 175 ° C. for 2 hours to remove the decomposition product derived from the initiator. The toner binder (C-14) according to Example 14 was obtained by cooling the obtained product.

<Example 15> [Production of toner binder (C-15)]
20 parts of polyester (A11-1) and 80 parts of crystalline vinyl resin (B-1) were mixed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, and homogenized at 150 ° C. After that, 3 parts of di-t-butyl peroxide was added and a crosslinking reaction was carried out at 150 ° C. for 5 hours. Then, the pressure was reduced under the condition of 0.5 to 2.5 kPa at 150 ° C. for 6 hours to remove the decomposition product derived from the initiator. The toner binder (C-15) according to Example 15 was obtained by cooling the obtained product.

<Example 16> [Production of toner binder (C-16)]
In a reaction tank equipped with a cooling tube, a stirrer and a nitrogen introducing tube, 19.5 parts of polyester (A12-1) and 80 parts of crystalline vinyl resin (B-1) were mixed and homogenized at 180 ° C. After that, 0.5 part of trimellitic anhydride was added and homogenized for 30 minutes, and then esterification under reduced pressure was carried out under conditions of 0.5 to 2.5 kPa for 5 hours to carry out a crosslinking reaction. By cooling the obtained product, a toner binder (C-16) according to Example 16 was obtained.

<Example 17> [Production of toner binder (C-17)]
29 parts of polyester (A12-2) and 70 parts of crystalline vinyl resin (B-1) were mixed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, and homogenized at 190 ° C. Then, 1 part of trimellitic anhydride was added and homogenized for 30 minutes, and then esterification under reduced pressure was carried out under conditions of 0.5 to 2.5 kPa for 5 hours to carry out a crosslinking reaction. By cooling the obtained product, a toner binder (C-17) according to Example 17 was obtained.

<Example 18> [Production of toner binder (C-18)]
18 parts of polyester (A12-3) and 80 parts of crystalline vinyl resin (B-1) were mixed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, and homogenized at 170 ° C. Then, 2 parts of trimethylolpropane was added and homogenized for 30 minutes, and then esterification under reduced pressure was carried out under the condition of 0.5 to 2.5 kPa for 3 hours to carry out a crosslinking reaction. By cooling the obtained product, a toner binder (C-18) according to Example 18 was obtained.

<Example 19> [Production of toner binder (C-19)]
29.5 parts of polyester (A12-4) and 70 parts of crystalline vinyl resin (B-1) were mixed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introducing pipe, and homogenized at 175 ° C. After that, 0.5 part of trimellitic anhydride was added and homogenized for 30 minutes, and then esterification under reduced pressure was carried out under conditions of 0.5 to 2.5 kPa for 7 hours to carry out a crosslinking reaction. The toner binder (C-19) according to Example 19 was obtained by cooling the obtained product.

<Example 20> [Production of toner binder (C-20)]
39 parts of polyester (A12-4) and 60 parts of crystalline vinyl resin (B-5) were mixed and homogenized at 195 ° C. in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube. Then, 1 part of trimellitic anhydride was added and homogenized for 30 minutes, and then esterification under reduced pressure was carried out under conditions of 0.5 to 2.5 kPa for 7 hours to carry out a crosslinking reaction. By cooling the obtained product, a toner binder (C-20) according to Example 20 was obtained.

<Example 21> [Production of toner binder (C-21)]
14 parts of polyester (A12-3) and 85 parts of crystalline vinyl resin (B-6) were mixed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introducing pipe, and homogenized at 160 ° C. After that, 1 part of trimethylolpropane was added and homogenized for 30 minutes, and then esterification under reduced pressure was carried out under the condition of 0.5 to 2.5 kPa for 6 hours to carry out a crosslinking reaction. The toner binder (C-21) according to Example 21 was obtained by cooling the obtained product.

<Example 22> [Production of toner binder (C-22)]
14 parts of polyester (A12-1) and 85 parts of crystalline vinyl resin (B-4) were mixed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introducing pipe, and homogenized at 185 ° C. After that, 1 part of trimellitic anhydride was added and homogenized for 30 minutes, and then esterification under reduced pressure was carried out under conditions of 0.5 to 2.5 kPa for 4 hours to carry out a crosslinking reaction. The toner binder (C-22) according to Example 22 was obtained by cooling the obtained product.

<Example 23> [Production of toner binder (C-23)]
23 parts of polyester (A12-2) and 75 parts of crystalline vinyl resin (B-7) were mixed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, and homogenized at 190 ° C. Then, 2 parts of trimellitic anhydride was added and homogenized for 30 minutes, and then esterification under reduced pressure was carried out under conditions of 0.5 to 2.5 kPa for 2 hours to carry out a crosslinking reaction. By cooling the obtained product, a toner binder (C-23) according to Example 23 was obtained.

<Example 24> [Production of toner binder (C-24)]
40 parts of polyester (A12-5), 60 parts of crystalline vinyl resin (B-9), jER157S70 [bisphenol A novolac type epoxy resin, manufactured by Mitsubishi Chemical Corporation, the same applies hereinafter, epoxy equivalent 209] (E-1) 1 0.1 part of imidazole [manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., the same applies hereinafter] as an epoxidation catalyst is mixed and supplied to a twin-screw kneader at 80 kg / hour for 90 minutes at 180 ° C. and 90 rpm. Was kneaded and extruded to carry out a crosslinking reaction. The toner obtained by mixing was cooled to obtain a toner binder (C-24) containing a polyester resin in which the polyester (A12-5) was modified with an epoxy compound.

<Example 25> [Production of toner binder (C-25)]
60 parts of polyester (A12-5), 40 parts of crystalline vinyl resin (B-9), 2.1 parts of jER157S70 (E-1) and 0.1 part of imidazole which is an epoxidation catalyst are mixed, and a twin-screw kneader is used. At 80 kg / hour, and kneaded and extruded at 180 ° C. for 5 minutes at 90 rpm to carry out a crosslinking reaction. The toner obtained by mixing was cooled to obtain a toner binder (C-25) containing a polyester resin in which the polyester (A12-5) was modified with an epoxy compound.

<Example 26> [Production of toner binder (C-26)]
40 parts of polyester (A12-5), 60 parts of crystalline vinyl resin (B-10), 4.0 parts of jER157S70 (E-1) and 0.1 part of imidazole which is an epoxidation catalyst are mixed, and a biaxial kneader is used. At 80 kg / hour, and kneaded and extruded at 180 ° C. for 5 minutes at 90 rpm to carry out a crosslinking reaction. The toner obtained by the mixing was cooled to obtain a toner binder (C-26) containing a polyester resin in which the polyester (A12-5) was modified with an epoxy compound.

<Example 27> [Production of toner binder (C-27)]
60 parts of polyester (A12-5), 40 parts of crystalline vinyl resin (B-10), 6.5 parts of jER157S70 (E-1) and 0.1 part of imidazole which is an epoxidation catalyst are mixed, and a biaxial kneader is used. At 80 kg / hr, and kneaded and extruded at 180 ° C. for 5 minutes at 90 rpm to carry out a crosslinking reaction. The toner obtained by mixing was cooled to obtain a toner binder (C-27) containing a polyester resin in which the polyester (A12-5) was modified with an epoxy compound.

<Example 28> [Production of toner binder (C-28)]
40 parts of polyester (A12-5), 60 parts of crystalline vinyl resin (B-9), jER1001 [bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Co., Ltd., hereinafter, epoxy equivalent 470] (E-2) 3. 0 part and 0.1 part of imidazole which is an epoxidation catalyst were mixed and supplied to a biaxial kneader at 80 kg / hour, and kneaded and extruded at 180 ° C. for 5 minutes at 90 rpm to carry out a crosslinking reaction. The toner obtained by mixing was cooled to obtain a toner binder (C-28) containing a polyester resin in which the polyester (A12-5) was modified with an epoxy compound.

<Example 29> [Production of toner binder (C-29)]
60 parts of polyester (A12-5), 40 parts of crystalline vinyl resin (B-9), 6.0 parts of jER1001 (E-2) and 0.1 part of imidazole which is an epoxidation catalyst are mixed, and a biaxial kneader is used. At 80 kg / hour, and kneaded and extruded at 180 ° C. for 5 minutes at 90 rpm to carry out a crosslinking reaction. The toner obtained by mixing was cooled to obtain a toner binder (C-29) containing a polyester resin in which the polyester (A12-5) was modified with an epoxy compound.

<Example 30> [Production of toner binder (C-30)]
40 parts of polyester (A12-6), 60 parts of crystalline vinyl resin (B-9), 1.2 parts of jER157S70 (E-1) and 0.1 part of imidazole which is an epoxidation catalyst are mixed, and a biaxial kneader is used. At 80 kg / hr, and kneaded and extruded at 180 ° C. for 5 minutes at 90 rpm to carry out a crosslinking reaction. The toner obtained by mixing was cooled to obtain a toner binder (C-30) containing a polyester resin in which the polyester (A12-6) was modified with an epoxy compound.

<Example 31> [Production of toner binder (C-31)]
60 parts of polyester (A12-6), 40 parts of crystalline vinyl resin (B-9), 2.0 parts of jER157S70 (E-1) and 0.1 part of imidazole which is an epoxidation catalyst are mixed, and a twin-screw kneader is used. At 80 kg / hour, and kneaded and extruded at 180 ° C. for 5 minutes at 90 rpm to carry out a crosslinking reaction. The toner obtained by mixing was cooled to obtain a toner binder (C-31) containing a polyester resin in which the polyester (A12-6) was modified with an epoxy compound.

<Example 32> [Production of toner binder (C-32)]
40 parts of polyester (A12-5), 60 parts of crystalline vinyl resin (B-9), EPPN-201 [phenol novolac type epoxy resin, manufactured by Nippon Kayaku Co., Ltd., hereinafter the same as epoxy equivalent 193] (E-3 ) 1.1 parts and 0.1 part of imidazole which is an epoxidation catalyst were mixed and supplied to a twin-screw kneader at 80 kg / hour, and kneaded and extruded at 160 ° C. for 5 minutes at 90 rpm to carry out a crosslinking reaction. The toner obtained by mixing was cooled to obtain a toner binder (C-32) containing a polyester resin in which the polyester (A12-5) was modified with an epoxy compound.

<Example 33> [Production of toner binder (C-33)]
60 parts of polyester (A12-5), 40 parts of crystalline vinyl resin (B-9), 2.2 parts of EPPN-201 (E-3) and 0.1 part of imidazole, which is an epoxidation catalyst, are mixed, and biaxial. The mixture was supplied to the kneader at 80 kg / hour, and kneaded and extruded at 160 ° C. for 5 minutes at 90 rpm to carry out a crosslinking reaction. The toner obtained by mixing was cooled to obtain a toner binder (C-33) containing a polyester resin in which the polyester (A12-5) was modified with an epoxy compound.

<Example 34> [Production of toner binder (C-34)]
20 parts of polyester (A12-5), 80 parts of crystalline vinyl resin (B-10), 1.9 parts of jER157S70 (E-1) and 0.1 part of imidazole which is an epoxidation catalyst are mixed, and a biaxial kneader is used. At 80 kg / hr, and kneaded and extruded at 180 ° C. for 5 minutes at 90 rpm to carry out a crosslinking reaction. The toner obtained by mixing was cooled to obtain a toner binder (C-34) containing a polyester resin in which the polyester (A12-5) was modified with an epoxy compound.

<Comparative Examples 1 to 5> [Production of Toner Binders (C'-1) to (C'-5)]
Polyester (A11) or (A11 ') in the number of parts by weight shown in Table 4 and crystalline vinyl resin (B) or crystalline vinyl resin (B') are mixed and mixed in a biaxial kneader in the same manner as in Example 1. Are supplied, and at the same time, the radical reaction initiator (c) is supplied to carry out the crosslinking reaction in the same manner as in Example 1 to obtain the toner binders (C′-1) to (C′-5) according to Comparative Examples 1 to 5. Obtained.

<Comparative Example 6> [Production of Toner Binder (C'-6)]
32 parts of polyester (A11-1) was supplied to a twin-screw kneader at 52 kg / hour, and at the same time, 1.0 part of t-butylperoxyisopropylmonocarbonate (c-3) as a radical reaction initiator (c) was added to 0. The mixture was supplied at 0.52 kg / hour and kneaded and extruded at 90 ° C. for 7 minutes at 160 ° C. to perform a crosslinking reaction. Further, the pressure was reduced from the vent port to 10 kPa to remove the organic solvent while mixing and cooling. According to Comparative Example 6, 32 parts of the obtained resin and 68 parts of the crystalline vinyl resin (B-1) were again fed to the twin-screw kneader at 52 kg / hour to melt-knead and cool the obtained product. A toner binder (C'-6) was obtained.

<Comparative Example 7> [Production of Toner Binder (C'-7)]
29 parts of polyester (A12-2) and 1 part of trimellitic anhydride were mixed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, and homogenized at 190 ° C. After that, the esterification under reduced pressure was carried out under the condition of 0.5 to 2.5 kPa for 5 hours to carry out a crosslinking reaction. 70 parts of the crystalline vinyl resin (B-1) was added thereto, melt-kneaded, and then the obtained product was cooled to obtain a toner binder (C′-7) according to Comparative Example 7.

By the above method, the content of the organic solvent in the toner binder according to each of the examples and the comparative examples, the endothermic peak top temperature derived from the crystalline vinyl resin (B) (in Table 3, Table 4, and Table 5, simply, Endothermic peak top temperature), glass transition temperature, and THF insoluble matter were measured. The results are shown in Tables 3, 4 and 5. In Examples 1 to 34 and Comparative Examples 1 and 3, there was only one endothermic peak derived from (B). Further, it was confirmed that the endothermic peak top temperature derived from (B) obtained by DSC measurement of the toner binder corresponds to the endothermic peak top temperature derived from vinyl resin shown in Table 2.
Since Comparative Example 2, Comparative Example 4, and Comparative Example 5 did not contain (B), the value of the endothermic peak top temperature (Tm) derived from (B) could not be observed (indicated by "-" in Table 2). Exist). Further, in Comparative Example 3, the glass transition temperature was −35 ° C. or lower, so the glass transition temperature is described as “−”.

<Example 35> [Production of toner (T-1)]
To 85 parts of the toner binder (C-1) according to Example 1, 8 parts of pigment carbon black [MA-100 manufactured by Mitsubishi Chemical Co., Ltd.], 4 parts of carnauba wax as release agent, charge control agent [ 2 parts of T-77 manufactured by Hodogaya Chemical Co., Ltd. was added to make a toner by the following method.
First, a Henschel mixer [FM10B manufactured by Nippon Coke Industry Co., Ltd.] was premixed and then kneaded by a twin-screw kneader [PCM-30 manufactured by Ikegai Co., Ltd.]. Then, after finely pulverizing using a supersonic jet crusher Labjet [KJ-25 manufactured by Kurimoto Iron Works Co., Ltd.], elbow jet classifier [Matsubo manufactured by EJ-L-3 (LABO) type] ] To obtain toner particles having a volume average particle diameter D50 of 8 μm.
Next, 100 parts of the 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-1) according to Example 35. .

<Examples 36 to 68> [Production of Toners (T-2) to (T-34)]
Toners (T-2) to (T-34) according to Examples 36 to 68 were obtained in the same manner as in Example 35, except that the toners were blended with the raw materials shown in Tables 6 to 8.

<Comparative Examples 8 to 14> [Production of Toners (T'-1) to (T'-7)]
Toners were produced in the same manner as in Example 35 with the compounding parts of the raw materials shown in Table 8 to obtain toners (T'-1) to (T'-7) according to Comparative Examples 8 to 14.

  With respect to the obtained toners (T-1) to (T-34) and (T'-1) to (T'-7), low temperature fixability, hot offset resistance, image strength, and heat resistant storage stability were measured by the following methods. The results of measuring or evaluating the charging stability, glossiness, durability and pulverizability are shown in Tables 6 to 8.

[Evaluation methods]
<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 of placing the powder on the paper surface, a printer without a heat fixing device was used.
This paper was passed through a soft roller at a fixing speed (peripheral speed of the heating roller) of 213 mm / sec and a heating roller temperature of 90 to 200 ° C. in steps of 5 ° C.
Next, the presence or absence of cold offset on the fixed image was visually observed, and the temperature at which cold offset occurred (MFT) was measured.
The lower the cold offset generation temperature, the better the low temperature fixability.
Under this evaluation condition, the MFT is generally preferably 125 ° C. or lower.

<Hot offset resistance>
By the same method as described in the low-temperature fixing property, the toner is placed on the paper surface, and the fixing speed (peripheral speed of the heating roller) of the paper is 213 mm / sec. It was passed at 5 ° C intervals.
Next, the presence or absence of hot offset on the fixed image was visually observed, and the hot offset generation temperature was measured.
The higher the hot offset generation temperature, the better the hot offset resistance. Under this evaluation condition, it is preferably 180 ° C. or higher.

<Image intensity>
According to JIS K5600-5-4 (1999), the image fixed by the above-mentioned evaluation of low-temperature fixability 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 scratched. The image strength was evaluated from the pencil hardness. The higher the pencil hardness, the better the image strength. Generally, it is preferably B or more.

<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 and excellent in heat resistant storage stability.
Δ: Blocking occurs in part, and heat resistant storage stability is poor.
X: Blocking occurred on the whole, and the heat-resistant storage stability was greatly deteriorated.

<Charging stability>
(1) 0.5 g of toner and 20 g of ferrite carrier (F-150 manufactured by Powder Tech Co., Ltd.) were put in a 50 mL glass bottle, and the humidity was adjusted at 23 ° C. and relative humidity of 50% for 8 hours or more.
(2) Friction stirring was carried out at 50 rpm for 10 minutes and 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 Kyocera 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 the charge stability index. The larger the charge stability index, the better the charge stability. Under this evaluation condition, it is preferably 0.7 or more.

<Glossiness>
The toner was fixed on the paper by placing the toner on the surface of the paper by the same method as described in the low-temperature fixability.
Next, a white thick paper is laid under the surface of the paper on which the toner is fixed, and a gloss meter (“IG-330” manufactured by Horiba, Ltd.) is used to measure the glossiness of the printed image ( %) Is measured every 5 ° C from the temperature above the cold offset occurrence temperature (MFT) to the temperature where the hot offset occurs, and the highest glossiness (maximum glossiness) (%) in that range is determined as the glossiness of the toner. Use as an index of sex.
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, 10% or more is preferable.

<Durability>
Continuous copying was performed using a commercially available monochrome copying machine [AR5030, manufactured by Sharp Corporation] with the toner as a two-component developer, and the durability was evaluated according to the following criteria.
[Criteria]
A: No change in image quality and no fog after copying 10,000 sheets.
A: Fog occurred after copying 10,000 sheets.
Δ: Fogging occurred after copying 6,000 sheets.
×: Fogging occurred after copying 2,000 sheets.

<Crushability>
To 85 parts of each of the toner binders used in the toners (T-1) to (T-34) and (T'-1) to (T'-7), a carbon black pigment [manufactured by Mitsubishi Chemical Corporation]. , MA-100] 8 parts, release agent carnauba wax 4 parts, charge control agent [Hodogaya Chemical Co., Ltd., T-77] 2 parts, Henschel Mixer Nippon Coke Industry Co., Ltd., FM10B. ], And the mixture obtained by kneading with a twin-screw kneader [PCM-30 manufactured by Ikegai Co., Ltd.] was cooled and then pulverized and classified to a size of 8.6 mesh pass to 30 mesh on. The particles were used as particles for evaluation of grindability, and the particles for evaluation of grindability were finely pulverized by a supersonic jet pulverizer Labo Jet [KJ-25 manufactured by Kurimoto Iron Works Co., Ltd.] under the following conditions.
Grinding pressure: 0.64 MPa
Crushing time: 15 minutes Separator frequency: 150Hz
Adjuster ring: 15mm
Size of louver: Medium As the particles for evaluation of pulverizability, finely pulverized products were used as they were without classification, and the volume average particle size (μm) was used as a Coulter counter [trade name: Multisizer III (Beckman Coulter )))].
The smaller the volume average particle size, the more excellent the pulverizability. Under this evaluation condition, it is preferably 8.0 μm or less.

As is clear from the evaluation results of Tables 6 to 8, all the toners (T-1) to (T-34) according to Examples 35 to 68 were excellent in all performance evaluations.
On the other hand, the toners (T'-1) to (T'-7) according to Comparative Examples 8 to 14 were defective in some performance items.

The toner binder obtained by the production method of the present invention and the toner using the toner binder have pulverizability, image strength, heat resistant storage stability, charge stability, glossiness and durability while maintaining low-temperature fixability and hot offset resistance. It has excellent properties and can be suitably used as a toner binder and a toner for developing an electrostatic charge image used in electrophotography, electrostatic recording, electrostatic printing and the like.
Furthermore, it is also suitable for applications such as paint additives, adhesive additives, and particles for electronic paper.

Claims (12)

  A method for producing a toner binder, which comprises a step of crosslinking a polyester (A1) in the presence of a crystalline vinyl resin (B). The method for producing a toner binder according to claim 1, wherein the method of crosslinking the polyester (A1) is the following method (1), (2), or (3).
Method (1): a method in which the polyester (A1) is a polyester (A11) having a carbon-carbon double bond, and the carbon-carbon double bond is reacted to crosslink;
Method (2): The polyester (A1) is a polyester (A12) having a carboxyl group and / or a hydroxyl group, and the carboxyl group of (A1) is reacted with a hydroxyl group of a polyhydric alcohol (s) having a valence of 3 or more. Or a method in which a hydroxyl group contained in (A1) is reacted with a polycarboxylic acid having a valence of 3 or more or a carboxyl group and / or an acid anhydride group of its anhydride (t) to crosslink;
Method (3): The polyester (A1) is a polyester (A12) having a carboxyl group and / or a hydroxyl group, and the carboxyl group and / or hydroxyl group (A1) is reacted with a polyfunctional epoxy compound (E). How to crosslink.   The toner binder according to claim 2, wherein the amount of double bonds in the polyester (A11) having a carbon-carbon double bond is 0.02 to 2 mmol / g based on the weight of the polyester (A11). Production method.   The method for producing a toner binder according to claim 2, wherein the total value of the acid value and the hydroxyl value of the polyester (A12) having a carboxyl group and / or a hydroxyl group is 30 to 150 mgKOH / g.   The method for producing a toner binder according to any one of claims 2 to 4, wherein the polyfunctional epoxy compound (E) is a polyfunctional epoxy compound having an epoxy equivalent of 140 to 500.   The method for producing a toner binder according to claim 1, wherein the temperature of the cross-linking reaction is 100 to 200 ° C. 6.   The method for producing a toner binder according to claim 1, further comprising the step of reducing the pressure in the reaction system during and / or after the crosslinking of the polyester (A1).   In the crystalline vinyl resin (B), the (meth) acrylate (a) having a chain hydrocarbon group having 21 to 40 carbon atoms as an essential constituent monomer is used as a basis based on the weight of all constituent monomers of (B). 15. The method for producing a toner binder according to claim 1, wherein the content is 15 to 99% by weight.   The method for producing a toner binder according to claim 8, wherein the crystalline vinyl resin (B) is a polymer having a monomer (b) having a vinyl group and having 6 or less carbon atoms as an essential constituent monomer.   The weight ratio [(A1) :( B)] of the polyester (A1) and the crystalline vinyl resin (B) before crosslinking is 5:95 to 60:40. Item 6. A method for producing a toner binder according to item. The method for producing a toner binder according to claim 1, wherein the polyester (A1) has a glass transition temperature (Tg _A1 ) of −35 to 55 ° C. 11. The differential scanning calorimetric curve of the obtained toner binder in the second heating process under the following measurement conditions shows that the endothermic peak top temperature (Tm) derived from the crystalline vinyl resin (B) is at least 1 in the range of 40 to 100 ° C. The method for producing a toner binder according to claim 1, wherein the toner binder has one piece.
[Measurement condition]
Using a differential scanning calorimeter, the toner binder was held at 30 ° C. for 10 minutes, the first temperature increase was carried out from 30 ° C. to 150 ° C. under the condition of 10 ° C./minute, and then held at 150 ° C. for 10 minutes. Then, the temperature is cooled to 0 ° C. under the condition of 10 ° C./min, the temperature is maintained at 0 ° C. for 10 minutes, and then the second heating is performed from 0 ° C. to 150 ° C. under the condition of 10 ° C./min.