JP2019040184A - Toner binder, toner and method for manufacturing toner binder - Google Patents

Abstract

To provide a toner binder and toner excellent in low temperature fixability, hot offset resistance, heat resistant storage stability, moisture heat resistant storage stability, toner fluidity, charge stability and charge rising properties.SOLUTION: A toner binder includes a nonlinear polyester resin (A) and a saturated carboxylic acid. The nonlinear polyester resin (A) includes an alcohol component (x) including divalent or higher alcohol, a saturated carboxylic acid component (y) and an unsaturated carboxylic acid component (z). At least one of the (y) and the (z) is a nonlinear polyester resin obtained by directly combining carbon atoms included in a polyester resin (a) being the polycondensate of a carboxylic component including divalent or higher carboxylic acid. The saturated carboxylic acid is divalent or higher aromatic carboxylic acid, and the content of the saturated carboxylic acid is 10-10000 ppm on the basis of the weight of the toner binder.SELECTED DRAWING: None

Description

  The present invention relates to a toner binder and a toner used for developing an electrostatic charge image or a magnetic latent image in an electrophotographic method, an electrostatic recording method, an electrostatic printing method, and the like, and a method for producing the toner binder.

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

In order to pass through these processes without problems, the toner must first maintain a stable charge amount, and then it must have good fixability to paper. In addition, since the apparatus includes a heating body in the fixing unit, the temperature rises in the apparatus, and thus the toner is required not to block in the apparatus.
Further, there is a strong demand for improvement in low-temperature fixability of toner from the viewpoint of energy saving in that the electrophotographic apparatus is reduced in size, speeded up, and promotes higher image quality and energy consumption in the fixing process is reduced.

  Recently, many types of paper such as recycled paper with large surface irregularities and coated paper with a smooth surface are used as a 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, when 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. Therefore, it is assumed that offset resistance is required.

  Toner binders that have a great influence on toner properties are easily balanced between storage and fixability, and recently, polyester resins are the mainstream. Conventionally, carbon-carbon of polyester resins using radical polymerization reaction with peroxides. Toners that have both low-temperature fixability and hot-offset properties by cross-linking double bonds have been proposed, but they are still inadequate, and they are not sufficient for heat and heat resistance under severe conditions of high temperature and high humidity. (Patent Document 1). On the other hand, although a toner with improved wet heat resistance and fluidity under high temperature and high humidity has been proposed, the low temperature fixing property and hot offset property are insufficient (Patent Document 2).

  As described above, toner binders and toners having excellent low-temperature fixability and hot offset resistance, heat-resistant storage stability, wet heat storage resistance, toner fluidity, charge rising property and charging stability are I didn't.

International Publication No. 2007/034813 Japanese Patent Laying-Open No. 2015-179241

  The present invention provides a toner binder and a toner excellent in low-temperature fixability and hot offset resistance, excellent in heat-resistant storage, long-term wet heat storage, toner fluidity, charge rise and charge stability. For the purpose.

The inventors of the present invention have reached the present invention as a result of studies to achieve the above object.
That is, the present invention is a toner binder containing a non-linear polyester resin (A) and a saturated carboxylic acid, and the non-linear polyester resin (A) is an alcohol component (x) containing a divalent or higher alcohol and a saturated carboxylic acid component. Polyester resin (a) which is a polycondensate of a carboxylic acid component containing (y) and an unsaturated carboxylic acid component (z) and at least one of (y) and (z) containing a divalent or higher carboxylic acid Is a non-linear polyester resin in which carbon atoms are directly bonded to each other, the saturated carboxylic acid is a divalent or higher valent aromatic carboxylic acid, and the content of the saturated carboxylic acid is 10 ppm to 10,000 ppm based on the weight of the toner binder A binder; a toner containing the toner binder; and a method for producing the toner binder.

  According to the present invention, there are provided a toner binder and a toner excellent in low-temperature fixability and hot offset resistance, excellent in heat-resistant storage stability, long-term wet heat storage resistance, toner fluidity, charge rising property and charge stability. It became possible.

  The toner binder of the present invention includes an alcohol component (x) containing a divalent or higher alcohol, a saturated carboxylic acid component (y), and an unsaturated carboxylic acid component (z), and at least one of the above (y) and (z). One is a non-linear polyester resin (A) in which carbon atoms of the polyester resin (a), which is a polycondensate of a carboxylic acid component containing a divalent or higher carboxylic acid, and a divalent or higher aromatic carboxylic acid. The toner binder contains a saturated carboxylic acid, and the content of the saturated carboxylic acid is 10 ppm to 10,000 ppm based on the weight of the toner binder.

  The polyester resin (a) of the present invention contains an alcohol component (x) containing a divalent or higher alcohol, a saturated carboxylic acid component (y), and an unsaturated carboxylic acid component (z). At least one of these is a polycondensate of a carboxylic acid component containing a divalent or higher carboxylic acid, but the resin composition is not particularly limited as long as it is the above-described constituent component. Note that in this specification, the unsaturated bond contained in the aromatic ring structure and the heterocyclic structure is not considered in determining whether the component is an unsaturated carboxylic acid component or a saturated carboxylic acid component.

  Examples of the alcohol component (x) containing a divalent or higher alcohol include a diol (x1) and a trivalent or higher polyol (x2).

Examples of the diol (x1) include alkylene glycols having 2 to 36 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol. 1,9-nonanediol, 1,10-decanediol and 1,12-dodecanediol), alkylene ether glycols having 4 to 36 carbon atoms (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol and the like) Polytetramethylene ether glycol, etc.), C6-C36 alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.), (poly) alkylene oxide adducts of the above alicyclic diols Preferably the number of added moles is 1 to 30), aromatic diol [monocyclic dihydric phenol (eg hydroquinone etc.) and bisphenol etc.] and alkylene oxide adducts of the above aromatic diol (preferably added mole number 2 to 30), etc. Is mentioned.
Among these diols (x1), an alkylene oxide adduct of an aromatic diol is preferable and an alkylene oxide adduct of a bisphenol is more preferable from the viewpoint of low-temperature fixability and heat-resistant storage stability.
In the alkylene oxide, the alkylene group preferably has 2 to 4 carbon atoms, and examples of the alkylene oxide include ethylene oxide, 1,2- or 1,3-propylene oxide, 1,2-, 2,3-, 1, 3- or iso-butylene oxide and tetrahydrofuran are preferred.

  The alkylene oxide adduct of bisphenols can be obtained by adding alkylene oxide (hereinafter, alkylene oxyside may be abbreviated as AO) to bisphenols. Examples of bisphenols include those represented by the following general formula (1).

HO-Ar-P-Ar-OH (1)
[In the formula, P represents an alkylene group having 1 to 3 carbon atoms, —SO ₂ —, —O—, —S—, or a direct bond, and Ar represents a halogen atom or an alkyl having 1 to 30 carbon atoms. Represents a phenylene group which may be substituted with a group. ]

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

The alkylene oxide added to these bisphenols is preferably an alkylene oxide having 2 to 4 carbon atoms. Specifically, ethylene oxide (hereinafter, ethylene oxide may be abbreviated as EO), propylene oxide (hereinafter referred to as “EO”). , Propylene oxide may be abbreviated as PO), 1,2-, 2,3-, 1,3- or iso-butylene oxide, tetrahydrofuran, and combinations of two or more thereof.
Of these, EO and / or PO are preferred. The added mole number of AO is preferably 2 to 30 moles, more preferably 2 to 10 moles.

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

  Examples of the trivalent or higher polyol (x2) include trivalent or higher aliphatic polyhydric alcohols having 3 to 36 carbon atoms (alkane polyols and intramolecular or intermolecular dehydrates such as glycerin, trimethylolethane, trimethylolpropane, Pentaerythritol, sorbitol, sorbitan, polyglycerin, dipentaerythritol, etc.), saccharides and derivatives thereof (such as sucrose and methylglucoside), and alkylene oxide adducts of aliphatic polyhydric alcohols (preferably 1-30 added moles) , Alkylene oxide adducts of trisphenols (trisphenol PA, etc.) (preferably an addition mole number of 2 to 30), novolak resins (phenol novolac and cresol novolac, etc., and an average degree of polymerization of preferably 3 to 60) Alkylene oxa De adduct (preferably addition molar number 2 to 30), and the like.

  Among these alcohol components (x), those which are preferable from the viewpoint of achieving both low-temperature fixability and hot offset resistance are alkylene glycols having 2 to 12 carbon atoms, EO and / or PO adducts of bisphenols (preferably additions). Mole number 2 to 30), trihydric or higher aliphatic polyhydric alcohol, and EO and / or PO adduct (preferably addition mole number 2 to 30) of novolak resin.

More preferable from the viewpoint of storage stability are alkylene glycols having 2 to 10 carbon atoms, EO and / or PO adducts of bisphenols (preferably 2 to 5 addition moles), 3 to 4 aliphatic polyvalents. EO and / or PO adducts (preferably 2-30 added moles) of alcohol and novolak resin.
Particularly preferred are alkylene glycols having 2 to 6 carbon atoms, trivalent aliphatic polyhydric alcohols, and EO and / or PO adducts of bisphenol A (preferably 2 to 5 moles added), most preferably ethylene. EO and / or PO adducts of glycol, propylene glycol, trimethylolpropane, and bisphenol A (preferably the number of added moles is 2 to 3).

  From the viewpoint of heat-resistant storage and toner fluidity, it is preferable that the alkylene oxide adduct of bisphenols is contained in an alcohol component in an amount of 10 mol% or more, more preferably 30 mol% or more, and more preferably 50 mol% or more. Most preferably.

  Examples of the saturated carboxylic acid component (y) include aromatic carboxylic acid (y1) and aliphatic carboxylic acid (y2). As the saturated carboxylic acid component (y), one type may be used, or two or more types may be used in combination.

Examples of the aromatic carboxylic acid (y1) include, for example, an aromatic dicarboxylic acid having 8 to 36 carbon atoms (phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc.) and a trivalent or higher aromatic having 9 to 20 carbon atoms. Examples thereof include polycarboxylic acids (trimellitic acid, pyromellitic acid, etc.).
Examples of the aliphatic carboxylic acid (y2) include aliphatic dicarboxylic acids having 2 to 50 carbon atoms (such as oxalic acid, malonic acid, succinic acid, adipic acid, repargic acid, and sebacic acid), and fatty acids having 6 to 36 carbon atoms. Vinyl tricarboxylic acid (hexane tricarboxylic acid, etc.) and unsaturated carboxylic acid vinyl polymer [Mn: 450-10,000] (styrene / maleic acid copolymer, styrene / acrylic acid copolymer, and styrene / fumaric acid copolymer) Polymer, etc.).

As the saturated carboxylic acid component (y), anhydrides of these carboxylic acids, lower alkyl (carbon number 1 to 4) esters (methyl esters, ethyl esters, isopropyl esters, etc.) may be used, and these carboxylic acids and You may use together.
Moreover, you may use monovalent saturated carboxylic acid, such as a benzoic acid, in the range which does not affect the physical property of a nonlinear polyester resin (A).

  Of these carboxylic acid components (y), a saturated carboxylic acid having a valence of 2 or more is preferable from the viewpoint of achieving both low-temperature fixability and hot offset resistance, more preferably an aliphatic dicarboxylic acid having 2 to 50 carbon atoms, An aromatic dicarboxylic acid having 8 to 36 carbon atoms and an aromatic polycarboxylic acid having 9 to 20 carbon atoms.

More preferable from the viewpoint of storage stability are adipic acid, terephthalic acid, isophthalic acid, maleic acid, trimellitic acid, pyromellitic acid, and combinations thereof.
Particularly preferred are adipic acid, terephthalic acid, trimellitic acid, and combinations thereof. Likewise preferred are anhydrides and lower alkyl esters of these acids.

The unsaturated carboxylic acid component (z) is an unsaturated carboxylic acid component having a polymerizable carbon-carbon double bond, for example, an unsaturated monocarboxylic acid having 2 to 30 carbon atoms (acrylic acid, methacrylic acid). And alkenedicarboxylic acids having 4 to 50 carbon atoms (alkenyl succinic acid such as dodecenyl succinic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid and glutaconic acid).
As unsaturated carboxylic acid component (z), anhydrides of these carboxylic acids, lower alkyl (1 to 4 carbon atoms) esters (methyl esters, ethyl esters, isopropyl esters, etc.) may be used, or these carboxylic acids. You may use together.

  Among these unsaturated carboxylic acid components (z), from the viewpoint of heat-resistant storage stability, it is preferably a divalent or higher unsaturated carboxylic acid, more preferably an alkenyl succinic acid having 16 to 50 carbon atoms, maleic acid, fumaric acid. It is an acid.

  At least one of the saturated carboxylic acid component (y) and the unsaturated carboxylic acid component (z) is a component containing a divalent or higher carboxylic acid.

  The weight average molecular weight (Mw) of the soluble portion of tetrahydrofuran (THF) in the polyester resin (a) of the present invention is preferably 15,000 to 100,000 from the viewpoint of hot offset resistance and charge rising property. More preferably, it is 20,000-100,000, Most preferably, it is 21,900-100,000.

  The ratio (Mw / Mn) of the weight average molecular weight (Mw) of the THF soluble component in the polyester resin (a) of the present invention to the number average molecular weight (Mn) of the THF soluble component in the polyester resin (a) is From the viewpoints of low-temperature fixability, hot offset resistance, wet heat storage resistance and charge rising property, it is preferably 4 to 15, more preferably 6 to 15, and particularly preferably 6.5 to 15.

In the present invention, the number average molecular weight (hereinafter sometimes abbreviated as Mn) and the weight average molecular weight (hereinafter sometimes abbreviated as Mw) of the polyester resin and the like are 0.25% by weight of the polyester resin and the like. It can be measured under the following conditions using GPC as a sample solution that is dissolved in THF so that the insoluble content is filtered off with a glass filter.
Device (example): HLC-8120 manufactured by Tosoh Corporation
Column (example): TSK GEL GMH6 2 [Tosoh Corp.]
Measurement temperature: 40 ° C
Sample solution: 0.25 wt% THF solution Solution injection amount: 100 μl
Detection device: Refractive index detector Reference material: Tosoh Co., Ltd. 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)

  The glass transition temperature (Tg) of the polyester resin (a) is preferably −35 ° C. to 80 ° C. More preferably, it is -15 degreeC-60 degreeC, More preferably, it is 30 degreeC-60 degreeC, Most preferably, it is 30 degreeC-45 degreeC. When the Tg is 80 ° C. or lower, the low-temperature fixability is improved, and when it is −35 ° C. or higher, the heat resistant storage stability is improved.

  The glass transition temperature (Tg) is a temperature at an inflection point measured by a differential scanning calorimetry by a method (DSC method) defined in ASTM D3418-82 and shown by a chart by differential scanning calorimetry (DSC). For example, it can be measured using Seiko Instruments Co., Ltd. DSC20, SSC / 580.

Specifically, 5 mg of a sample is put in a container of a DSC apparatus, heated at a temperature of about 20 ° C. per minute to a temperature about 30 ° C. higher than that at the end of the glass transition, and cooled at a temperature of about 60 ° C. per minute to a temperature about 50 ° C. lower than the glass transition temperature. Then, it is heated at 20 ° C. per minute up to a temperature of about 30 ° C. higher than that at the end of the glass transition.
From the above measurement, draw a graph of the amount of heat absorbed and generated and the temperature, and the slope of the curve of the stepwise change part of the glass transition and the straight line obtained by extending the base line on the low temperature side of the graph to the high temperature side is maximized. The temperature at the intersection with the drawn tangent is defined as the glass transition temperature (Tg).

  The acid value of the polyester resin (a) is preferably from 5 mgKOH / g to 80 mgKOH / g, more preferably from 10 to 65 mgKOH / g, particularly preferably from 30 to 50% from the viewpoint of hot offset resistance, low-temperature fixability and gloss. 60 mg KOH / g.

The hydroxyl value of the polyester resin (a) is preferably 0 to 60 mgKOH / g, more preferably 3 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g from the viewpoints of chargeability and heat-resistant storage stability.
The acid value and hydroxyl value of the polyester resin (a) can be measured by a method specified in JIS K0070 (1992 edition).

In this invention, it does not restrict | limit especially as a method of manufacturing a polyester resin (a) and the linear polyester resin (B) mentioned later, A well-known method can be used. For example, it can be manufactured as follows.
The reaction can 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, and particularly preferably 170 to 235 ° C. The reaction time is preferably 30 minutes or more, particularly preferably 2 to 40 hours, from the viewpoint of reliably performing the polycondensation reaction.

  At this time, an esterification catalyst can be used as needed. Examples of the esterification catalyst include a tin-containing catalyst (for example, dibutyltin oxide), antimony trioxide, and a titanium-containing catalyst [for example, titanium alkoxide, potassium oxalate titanate, titanium terephthalate, titanium terephthalate alkoxide, Japanese Patent Application Laid-Open No. 2006-243715. Patent Documents [Titanium dihydroxybis (triethanolamate), titanium monohydroxytris (triethanolamate), titanylbis (triethanolaminate) and their intramolecular polycondensates, etc.], and JP2007- No. 11307 catalyst (titanium tributoxyterephthalate, titanium triisopropoxyterephthalate, titanium diisopropoxyditerephthalate, etc.)], zirconium-containing catalyst (for example, zirconyl acetate), and acetic acid Lead and the like. Among these, a titanium-containing catalyst is preferable. It is also effective to reduce the pressure in order to improve the reaction rate at the end of the reaction.

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

  The reaction ratio between the alcohol component (x) and the carboxylic acid component (the sum of the saturated carboxylic acid component (y) and the unsaturated carboxylic acid component (z)) is the equivalent ratio [OH] / [COOH] of the hydroxyl group to the carboxyl group. The ratio is preferably 2/1 to 1/2, more preferably 1.5 / 1 to 1 / 1.3, particularly preferably 1.4 / 1 to 1 / 1.2.

The nonlinear polyester resin (A) of the present invention includes an alcohol component (x) containing a divalent or higher alcohol, a saturated carboxylic acid component (y), and an unsaturated carboxylic acid component (z). It is a non-linear polyester resin in which the carbon atoms of the polyester resin (a), which is a polycondensate of a carboxylic acid component containing a divalent or higher carboxylic acid, is directly bonded to each other.
Here, the “non-linear” polyester resin is a polyester resin having a branch (crosslinking point) in the main chain.

  The non-linear polyester resin (A) forms a carbon-carbon bond by crosslinking all or at least a part of carbon-carbon double bonds derived from the unsaturated carboxylic acid component (z) constituting the polyester resin (a). To obtain. For example, a carbon-carbon double bond is introduced into the main chain or side chain of the polyester resin (a), and a cross-linking reaction is performed by a radical addition reaction, a cation addition reaction, an anion addition reaction, or the like to generate an intermolecular carbon-carbon bond. Reaction. The polyester resin having a network formed by the crosslinking reaction has a component that cannot be dissolved in tetrahydrofuran (hereinafter, “tetrahydrofuran” may be abbreviated as THF). Therefore, the polyester resin is “non-linear”. This can be confirmed by dissolving the polyester resin in THF and having a component insoluble in THF (sometimes abbreviated as THF insoluble matter).

Of the cross-linking reactions, radical addition reaction is preferable because of many choices of reaction conditions. In the case of a crosslinking reaction in which a carbon-carbon bond is generated between molecules by a radical addition reaction, a radical may be generated using a radical reaction initiator, or the radical may be generated by heat or light energy without using a radical reaction initiator. It may be generated.
The method for generating radicals is preferably a method using a radical reaction initiator (c) and / or an additive for living radical polymerization (d) from the viewpoint of effectively causing a bridge reaction in a short time. From the viewpoint of fixing properties, a method using a living radical polymerization additive is more preferable.

  The radical reaction initiator (c) used for the crosslinking reaction of the polyester resin (a) in the present invention is not particularly limited, and is exemplified by the following azo compounds or diazo compounds (c1) and inorganic peroxides ( c2-1) and organic peroxide (c2-2).

  The azo compound or diazo compound (c1) is not particularly limited, and examples thereof include 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,2′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile and the like.

  The inorganic peroxide (c2-1) is not particularly limited, and examples thereof include hydrogen peroxide, ammonium persulfate, potassium persulfate, and sodium persulfate.

  The organic peroxide (c2-2) is not particularly limited, and examples thereof include benzoyl peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, α, α-bis (t -Butylperoxy) diisopropylbenzene, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di- t-Butylperoxyhexine-3, acetyl peroxide, isobutyryl peroxide, octaninol peroxide, decanolyl peroxide, lauroyl peroxide, 3,3,5-trimethylhexanoyl peroxide, m-toluyl peroxide , T-butylperoxyisobutyrate, t-butylperoxyneodecanoate, cumene hydropero Side, succinic peroxide, di (2-ethoxyethyl) peroxydicarbonate, cumyl peroxyneodecanoate, t-butylperoxy 2-ethylhexanoate, t-butylperoxy 3,5,5- Examples include trimethylhexanoate, t-butyl peroxylaurate, t-butyl peroxybenzoate, t-butyl peroxyisopropyl carbonate, and t-butyl peroxyacetate.

Examples of the living radical polymerization additive (d) used for the crosslinking reaction of the polyester resin (a) in the present invention include additives used in the following three methods. In addition, although the above radical reaction initiator (c) may be used for living radical polymerization, the living radical polymerization additive (d) excludes the above radical reaction initiator (c). .
(1) "Atom Transfer Radical Polymerization" (ATRP) using organic halides as initiators and transition metal complexes as catalysts
This method is excellent as a method for producing a vinyl polymer having a halogen or the like that is relatively advantageous for a functional group conversion reaction at the terminal of the obtained living polymer and having a specific functional group.
Specific examples thereof include alkyl halides such as ethyl 2-bromoisobutyrate and 2-iodoisobutyric acid. Examples of the catalyst include metal salts such as copper (I) bromide, copper (II) bromide, copper (I) chloride and copper (II) chloride. Further, examples of the ligand include alkylpyridylmethanimines such as propylpyridylmethanimine.
(2) Living polymerization by nitrooxide radical (Nitroxide-mediated Polymerization: NMP)
Specifically, 2,2,5-trimethyl-4-phenyl-3-azahexane-3-nitroxide, N-tert-butyl-N- (2-methyl-1-phenylpropyl) -O- (1-phenyl) Ethyl) hydroxylamine and the like.
(3) Reversible Addition / Fragmentation Chain Transfer Polymerization: RAFT (Reversible Addition / Fragmentation Chain Transfer Polymerization: RAFT)
Specific examples include 4-cyano-4-[(dodecylsulfanylthiocarbonyl) sulfanyl] pentanoic acid.

By using these, the low-temperature fixability is improved. Since it is difficult to analyze the difference in structure and properties of organic solvent insoluble matter (gel content) with the current technology, the following is speculated, but compared with the case where the additive for living radical polymerization (d) is not used, polyester Since the cross-linked portion of the resin (a) forms a uniform gel structure, it is considered that there are no excessive cross-linked portions that inhibit low-temperature fixing.
In the living polymerization, a radical polymerization initiator (c) may be used in combination with the living radical polymerization additive (d).

Although it does not restrict | limit especially as a method of manufacturing a nonlinear polyester resin (A), For example, the method of the following (1)-(3) is mentioned, It can select arbitrarily.
(1) An alcohol component (x) containing a divalent or higher alcohol, a saturated carboxylic acid component (y), and an unsaturated carboxylic acid component (z) are added, and if necessary, a radical reaction initiator (c) and / or a living room Method for producing nonlinear polyester resin (A) by adding radical polymerization additive (d) and simultaneously performing polycondensation and addition polymerization (2) Once saturated with alcohol component (x) containing bivalent or higher alcohol After polycondensation of carboxylic acid component (y), unsaturated carboxylic acid component (z) and polyester resin (a), radical reaction initiator (c) and / or living radical polymerization additive (d) are added as necessary. (3) Unsaturated carboxylic acid component (z) is added and, if necessary, radical reaction initiator (c) and / or Ng radical polymerization additive (d) is added, and after addition polymerization, an alcohol component (x) containing a dihydric or higher alcohol and a saturated carboxylic acid component (y) are added, and polycondensation is performed for nonlinearity. Method for producing polyester resin (A)

  Among these, the method (2) is preferable from the viewpoints of reaction rate control and resin uniformity.

  The toner binder of the present invention contains a saturated carboxylic acid which is a divalent or higher valent aromatic carboxylic acid. Examples of the divalent or higher aromatic carboxylic acid include aromatic dicarboxylic acids having 8 to 36 carbon atoms and trivalent or higher aromatic polycarboxylic acids having 9 to 20 carbon atoms. Specific examples include phthalic acid, terephthalic acid, isophthalic acid, trimellitic acid, and pyromellitic acid.

From the viewpoint of chargeability, the toner binder of the present invention has a saturated carboxylic acid content of 10 ppm to 10000 ppm based on the weight of the toner binder.
When the content of the saturated carboxylic acid is less than 10 ppm, the charging property such as the rising property of charging and the charging stability is deteriorated, and when it exceeds 10,000 ppm, the wet heat resistance is deteriorated.
The content of the saturated carboxylic acid is preferably 50 ppm to 8000 ppm, more preferably 100 ppm to 5000 ppm, and most preferably 150 ppm to 2000 ppm.
The saturated carboxylic acid may be left as an unreacted product when producing (A) and (B), or may be added after producing (A) and (B), but remains as an unreacted product. It is preferable from the viewpoint of uniformity. When (A) is left as an unreacted product during production, the weight average molecular weight of the polyester resin (a) should be in the range of 21,900 to 100,000, and the weight average molecular weight of the polyester resin (a) ( The ratio (Mw / Mn) of Mw) to the number average molecular weight (Mn) is in the range of 6.5 to 15, and the alkylene oxide adduct of bisphenols of the polyester resin (a) is 50 mol% in the alcohol component. Non-linear polyester containing by cross-linking carbon-carbon double bonds derived from unsaturated carboxylic acid component (z) using radical reaction initiator (c) and / or living radical polymerization additive (d) It becomes controllable by manufacturing resin (A).

  When leaving the saturated carboxylic acid as an unreacted product when producing (A), the unreacted saturated carboxylic acid left in the polycondensation reaction to obtain the polyester resin (a) that is the precursor of (A) The weight ratio of the saturated carboxylic acid (divalent or higher aromatic carboxylic acid) as the component (y) is the polyester resin (a) contained in the non-linear polyester resin (A) from the viewpoint of low-temperature fixability and wet heat storage resistance. Is preferably 10 ppm to 1000 ppm, more preferably 10 ppm to 800 ppm, and particularly preferably 10 ppm to 600 ppm, based on the total weight of the structural unit derived from and the saturated carboxylic acid.

  Weight ratio of saturated carboxylic acid (divalent or higher aromatic carboxylic acid) which is an unreacted saturated carboxylic acid component (y) left in the polycondensation reaction for obtaining the linear polyester resin (B) of the present invention described later Is preferably 5000 ppm or less, more preferably 3500 ppm or less, and particularly preferably 10-2500 ppm, based on the total weight of the linear polyester resin (B) and saturated carboxylic acid, from the viewpoints of low-temperature fixability and wet heat resistance.

  In addition, the content rate of saturated carboxylic acid can be measured with a high performance liquid chromatograph mass spectrometer (LC / MS) or a liquid chromatograph (LC).

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

Examples of LC measurement conditions include the following conditions.
In addition, the content of trimellitic acid of the present invention was measured under the following conditions.
<Measurement conditions of LC>
LC measuring device: “ACQUITY UPLC H-Class” [manufactured by Waters]
Column: “CAPCEL PACK C18” (particle diameter: 5 μm, ID: 4.6 mmφ,
Length 250mm) [made by SHISEIDO]
Mobile phase: 0.05% phosphoric acid aqueous solution / methanol = 80/20 (volume%)
Injection volume: 10 μl
Flow rate: 0.6 ml / min
Column temperature: 40 ° C
Detector: “PDA detector” [manufactured by Shimadzu Corporation]
Detection wavelength: 230 nm

  In addition to the non-linear polyester resin (A) and the saturated carboxylic acid, the toner binder of the present invention preferably further contains a linear polyester resin (B) for the purpose of improving glossiness and grindability.

The linear polyester resin (B) contained for this purpose is a resin containing an alcohol component (x) and a saturated carboxylic acid component (y) as constituent components and not containing an unsaturated carboxylic acid component (z).
The linear polyester resin (B) may be any polyester resin that does not substantially contain THF-insoluble matter, for example, if the content is 1.0% by weight or less.

  The linear polyester resin (B) may have a trace amount of crosslinking points as long as it does not contain THF-insoluble matter, and the molecular terminal of the anhydride of polycarboxylic acid (which may be trivalent or higher) is anhydrous. It may be modified with trimellitic acid, phthalic anhydride, or the like.

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

The Mw content of the THF soluble portion of the linear polyester resin (B) is preferably from 2,000 to 30,000, more preferably from 2,500 to 20,000, particularly from the viewpoint of heat-resistant storage stability and low-temperature fixability of the toner. Preferably it is 3,000-10,000.
Mn and Mw of the THF soluble content of the linear polyester resin (B) can be measured by the same method as that for the polyester resin (a).

  The acid value of the linear polyester resin (B) is preferably 0 to 50 mgKOH / g, more preferably 5 to 40 mgKOH / g, and particularly preferably 10 to 30 mgKOH / g. When a polyester resin having an acid value of 50 mgKOH / g or less is used, low-temperature fixability and glossiness when used as a toner are improved.

The hydroxyl value of the linear polyester resin (B) is preferably 0 to 80 mgKOH / g, more preferably 5 to 70 mgKOH / g, and particularly preferably 10 to 60 mgKOH / g. When the hydroxyl value is 80 mgKOH / g or less, the heat resistant storage stability when used as a toner is good.
The acid value and hydroxyl value of the linear polyester resin (B) can be measured by the same method as for the polyester resin (a).

The glass transition temperature (Tg) of the linear polyester resin (B) is preferably 45 ° C. to 80 ° C. from the viewpoint of low temperature fixability and heat resistant storage stability.
The glass transition temperature (Tg) can be measured by the same method as for the polyester resin (a).

  When the linear polyester resin (B) is used in combination, the weight ratio (A) / (B) of the nonlinear polyester resin (A) of the present invention to the linear polyester resin (B) is low temperature fixability, hot offset resistance, and gloss. From the viewpoint of compatibility of the properties, the ratio is preferably 1/99 to 99/1, more preferably 3/97 to 50/50, and particularly preferably 5/95 to 30/70.

The toner binder of the present invention preferably has at least one glass transition temperature (Tg) in the temperature range of −20 ° C. to 80 ° C. More preferably, it is the temperature range of 35-65 degreeC. When the only inflection point is −20 ° C. or higher, the heat resistant storage stability is good, and when it is 80 ° C. or lower, the fixability is good.
In addition, when two or more Tg exists, it is enough if one of them exists in this temperature range. The glass transition temperature (Tg) can be measured by the same method as for the polyester resin (a).

The ratio (Mw / Mn) of the weight average molecular weight (Mw) of the THF soluble component in the toner binder of the present invention to the number average molecular weight (Mn) of the THF soluble component in the toner binder is low temperature fixability, hot resistance From the viewpoint of offset property and wet heat resistance, it is preferably 1 to 15, more preferably 2 to 13, particularly preferably 3 to 10.
The weight average molecular weight (Mw) of the THF soluble component in the toner binder and the number average molecular weight (Mn) of the THF soluble component in the toner binder are measured using the GPC.

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

  The Mw content of the toner binder of the present invention is preferably from 4,000 to 120,000, more preferably from 6,000 to 100,000, from the viewpoint of achieving both hot offset resistance and low-temperature fixability of the toner. Especially preferably, it is 8,000-80,000.

The content of the THF-insoluble component of the present invention is preferably 1 to 40% by weight, more preferably 3 to 40% by weight based on the weight of the toner binder, from the viewpoint of compatibility with hot offset resistance, low-temperature fixability and glossiness. 40% by weight.
The content of the THF-insoluble matter can be adjusted by adjusting the degree of crosslinking of the nonlinear polyester resin (A), using a linear polyester resin (B) described later, or the like.

A method for producing the toner binder will be described.
The toner binder is not particularly limited as long as it contains the nonlinear polyester resin (A). For example, when two kinds of polyester resins and additives are mixed, the mixing method may be a known method, such as powder mixing, melt mixing, Any of solvent mixing may be used. Further, it may be mixed at the time of toner formation. Among these methods, melt mixing is preferred in which mixing is uniform and solvent removal is not necessary.

Examples of the mixing device for powder mixing include a Henschel mixer, a Nauter mixer, and a Banbury mixer. A Henschel mixer is preferable.
As a mixing apparatus in the case of melt-mixing, a batch type mixing apparatus such as a reaction tank and a continuous mixing apparatus can be mentioned. In order to uniformly mix at an appropriate temperature in a short time, a continuous mixing device is preferable. Examples of the continuous mixing device include a static mixer, an extruder, a continuous kneader, and a three roll.

  Solvent mixing methods include dissolving two types of polyester resin in a solvent (ethyl acetate, THF, acetone, etc.), homogenizing, and then removing the solvent and crushing. There are methods such as granulation and solvent removal after dissolving in ethyl, THF, acetone, etc.) and dispersing in water.

  As a specific method for carrying out this melt mixing, a mixture of the polyester resin (a) and, if necessary, the linear polyester resin (B) is injected into the twin-screw extruder at a constant speed, and at the same time, the radical reaction initiator (c) and If necessary, there is a method in which the living radical polymerization additive (d) is also injected at a constant rate and the reaction is carried out while kneading and conveying at a temperature of 50 to 200 ° C.

  At this time, the polyester resin (a) and linear polyester resin (B), which are reaction raw materials charged or injected into the twin-screw extruder, are directly injected into the extruder as they are without cooling from the resin reaction solution. Alternatively, the resin once produced may be cooled and pulverized and supplied to a twin screw extruder.

  In addition, the method of melt mixing is not limited to these specifically exemplified methods. For example, the raw materials are charged into a reaction vessel, heated to a temperature at which the solution is brought into a solution state, and mixed. Of course you can do it.

  The toner containing the toner binder of the present invention may contain a colorant, a release agent, a charge control agent, a fluidizing agent, and the like as necessary.

As the colorant, all of dyes and pigments used as toner colorants can be used. Specifically, carbon black, iron black, Sudan Black SM, First Yellow G, Benzidine Yellow, Pigment Yellow, Indian First Orange, Irgasin Red, Paranitroaniline Red, Toluidine Red, Carmine FB, Pigment Orange R, Lake Red 2G, rhodamine FB, rhodamine B lake, methyl violet B lake, phthalocyanine blue, pigment blue, brilliant green, phthalocyanine green, oil yellow GG, Kayaset YG, olazole brown B and oil pink OP, etc. It may be individual and 2 or more types may be mixed. Further, if necessary, magnetic powder (a powder of a ferromagnetic metal such as iron, cobalt, or nickel or a compound such as magnetite, hematite, or ferrite) can also be included 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 of the present invention. In addition, when using magnetic powder, Preferably it is 20-150 weight part, More preferably, it is 40-120 weight part.

  As the release agent, those having a softening point (also referred to as a flow softening point) [Tm] of 50 to 170 ° C. by a flow tester are preferable, and low molecular weight polypropylene, low molecular weight polyethylene, low molecular weight polypropylene polyethylene copolymer, polyolefin wax, Aliphatic hydrocarbon waxes such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax and their oxides, carnauba wax, montan wax, sazol wax and their deoxidized wax, ester wax such as fatty acid ester wax, fatty acid amide , Fatty acids, higher alcohols, fatty acid metal salts and mixtures thereof.

A method for measuring the flow softening point [Tm] will be described.
Using a Koka-type flow tester {for example, CFT-500D, manufactured by Shimadzu Corporation), a load of 1.96 MPa was applied by a plunger while heating a 1 g measurement sample at a heating rate of 6 ° C./min. Extrude from a nozzle with a diameter of 1 mm and a length of 1 mm, draw a graph of “plunger descent (flow value)” and “temperature”, and set the temperature corresponding to 1/2 of the maximum plunger descent Let it be the flow softening point [Tm].

  Polyolefin waxes include (co) polymers [obtained by (co) polymerization] of olefins (for example, ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-dodecene, 1-octadecene, and mixtures thereof). And olefin (co) polymer oxides by oxygen and / or ozone, maleic acid modifications of olefin (co) polymers [eg maleic acid and its derivatives (maleic anhydride, Modified products such as monomethyl maleate, monobutyl maleate and dimethyl maleate), olefins and unsaturated carboxylic acids [(meth) acrylic acid, itaconic acid and maleic anhydride, etc.] and / or unsaturated carboxylic acid alkyl esters [(meta ) Alkyl acrylate (alkyl of 1 to 18 carbon atoms) ester and Copolymers of maleic acid alkyl (having 1 to 18 carbon atoms in the alkyl) esters, etc.] or the like, and Sasol wax.

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

  As charge control agents, nigrosine dyes, triphenylmethane dyes containing tertiary amines as side chains, quaternary ammonium salts, polyamine resins, imidazole derivatives, quaternary ammonium base-containing polymers, metal-containing azo dyes, copper phthalocyanine dyes , Salicylic acid metal salts, boron complexes of benzylic acid, sulfonic acid group-containing polymers, fluorine-containing polymers, halogen-substituted aromatic ring-containing polymers, and the like.

The composition ratio of the toner in the present invention is preferably 30 to 97% by weight, more preferably 40 to 95% by weight, particularly preferably 45 to 92% by weight, based on the weight of the toner. The colorant is preferably 0.05 to 60% by weight, more preferably 0.1 to 55% by weight, particularly preferably 0.5 to 50% by weight, and a release agent, charge control agent and fluidizing agent. Among these additives, the release agent is preferably 0 to 30% by weight, more preferably 0.5 to 20% by weight, particularly preferably 1 to 10% by weight, and the charge control agent is preferably 0%. -20% by weight, more preferably 0.1-10% by weight, particularly preferably 0.5-7.5% by weight, and the fluidizing agent is preferably 0-10% by weight, more preferably 0-5%. % By weight, particularly preferably 0.1 to 4% by weight A. The total content of additives is preferably 3 to 70% by weight, more preferably 4 to 58% by weight, and particularly preferably 5 to 50% by weight.
When the composition ratio of the toner is within the above range, a toner having good hot offset resistance and charging stability can be obtained.

The toner of the present invention may be obtained by any known method such as kneading and pulverization, emulsion phase inversion, and polymerization.
For example, when a toner is obtained by a kneading and pulverizing method, the components constituting the toner excluding the fluidizing agent are dry blended, and then melt-kneaded, then coarsely pulverized, and finally atomized using a jet mill pulverizer or the like. Further, by further classifying the toner particles (preferably particles having a volume average particle diameter (D50) of 5 to 20 μm), a fluidizing agent can be mixed and manufactured.
The volume average particle diameter (D50) is measured using a Coulter counter [for example, trade name: Multisizer III (manufactured by Coulter)].

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

The toner of the present invention is mixed with carrier particles such as iron powder, glass beads, nickel powder, ferrite, magnetite, and ferrite whose surface is coated with a resin (acrylic resin, silicone resin, etc.) as necessary to cause an electrical latent. Used as an image developer. The weight ratio of toner to carrier particles is 1/99 to 100/0. In addition, instead of carrier particles, it can be rubbed with a member such as a charging blade to form an electrical latent image.
Note that the toner containing the toner binder of the present invention may not contain carrier particles.

  The toner of the present invention is fixed on 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, or the like can be applied.

  Hereinafter, although an example and a comparative example explain the present invention further, the present invention is not limited to these. Hereinafter, unless otherwise specified, parts are parts by weight.

<Production Example 1> [Production of polyester resin (a-1)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 729 parts (96.0 mol%) of bisphenol A · EO 2 mol adduct, 12 parts (4.0 mol%) of trimethylolpropane, 152 of terephthalic acid Parts (41.6 mol%), 163 parts (50.9 mol%) adipic acid, 19 parts (7.5 mol%) fumaric acid, 2.5 parts titanium diisopropoxybistriethanolamate as a condensation catalyst, polymerization 1 part of tert-butylcatechol was added as an inhibitor, and the reaction was carried out at 180 ° C. under a nitrogen stream for 4 hours while distilling off the generated water. Furthermore, after making it react for 10 hours under reduced pressure of 0.5-2.5 kPa, it took out and obtained the polyester resin (a-1).
The weight average molecular weight Mw of the polyester resin (a-1) was 37742, the number average molecular weight Mn was 3922, Mw / Mn was 9.6, and the content of saturated carboxylic acid (terephthalic acid) was 460 ppm.

<Production Example 2> [Production of polyester resin (a-2)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 737 parts (96.0 mol%) of bisphenol A · EO 2 mol adduct, 13 parts of trimethylolpropane (4.0 mol%), 152 terephthalic acid Parts (41.6 mol%), 163 parts (50.9 mol%) adipic acid, 18 parts (7.5 mol%) fumaric acid, 2.5 parts titanium diisopropoxybistriethanolamate as a condensation catalyst, polymerization 1 part of tert-butylcatechol was added as an inhibitor, and the reaction was carried out at 180 ° C. under a nitrogen stream for 4 hours while distilling off the generated water. Furthermore, after making it react under reduced pressure of 0.5-2.5 kPa for 10 hours, it took out and obtained the polyester resin (a-2).
The weight average molecular weight Mw of the polyester resin (a-2) was 21,922, the number average molecular weight Mn was 3168, Mw / Mn was 6.9, and the content of saturated carboxylic acid (terephthalic acid) was 10 ppm.

<Production Example 3> [Production of polyester resin (a-3)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 729 parts (96.0 mol%) of bisphenol A · EO 2 mol adduct, 12 parts (4.0 mol%) of trimethylolpropane, 142 of terephthalic acid Parts (38.8 mol%), 163 parts (50.9 mol%) adipic acid, 19 parts (7.5 mol%) fumaric acid, 2.5 parts titanium diisopropoxybistriethanolamate as a condensation catalyst, polymerization 1 part of tert-butylcatechol was added as an inhibitor, and the reaction was carried out at 180 ° C. under a nitrogen stream for 4 hours while distilling off the generated water. Furthermore, it was made to react under reduced pressure of 0.5-2.5 kPa for 10 hours. Thereafter, 10 parts (2.8 mol%) of terephthalic acid was added and homogenized for 1 hour, and then taken out to obtain a polyester resin (a-3).
The weight average molecular weight Mw of the polyester resin (a-3) was 37652, the number average molecular weight Mn was 3933, Mw / Mn was 9.6, and the content of saturated carboxylic acid (terephthalic acid) was 10,000 ppm.

<Production Examples 4 to 5> [Production of polyester resins (a-4) to (a-5)]
Production Examples 4 to 5 were produced except that the designated weight parts were based on the compositions of the saturated carboxylic acid component (y), unsaturated carboxylic acid component (z), and alcohol component (x) shown in Table 1. In the same manner as in Example 1, polyester resins (a-4) to (a-5) were obtained. The analysis values were as shown in Table 1.

<Comparative Production Example 1> [Production of Polyester Resin (a′-1)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 724 parts (96.0 mol%) of bisphenol A · EO 2 mol adduct, 12 parts (4.0 mol%) of trimethylolpropane, 175 of terephthalic acid Parts (45.0 mol%), 163 parts of adipic acid (55.0 mol%), 2.5 parts of titanium diisopropoxybistriethanolamate as a condensation catalyst, 1 part of tert-butylcatechol as a polymerization inhibitor, The reaction was carried out for 4 hours while distilling off the water produced under a nitrogen stream at 180 ° C. Furthermore, after making it react under reduced pressure of 0.5-2.5 kPa for 10 hours, it took out and obtained the polyester resin (a'-1).
The weight average molecular weight Mw of the polyester resin (a′-1) was 37750, the number average molecular weight Mn was 3922, Mw / Mn was 9.6, and the content of saturated carboxylic acid (terephthalic acid) was 520 ppm.

<Production Example 6> [Production of linear polyester resin (B-1)]
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 428 parts (60 mol%) of bisphenol A · PO 2 mol adduct, 319 parts (40 mol%) of bisphenol A · PO 3 mol adduct, 316 parts of isophthalic acid 316 Part (100 mol%) and 2.5 parts of titanium diisopropoxybistriethanolamate as a condensation catalyst, and the generated water was distilled under a reduced pressure of 0.5 to 2.5 kPa under a nitrogen stream at 220 ° C. It was allowed to react while leaving. When the acid value became less than 20, it was taken out to obtain a linear polyester resin (B-1). The content of the saturated carboxylic acid (isophthalic acid) in (B-1) was 2189 ppm.

<Production Example 7> [Production of linear polyester resin (B-2)]
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 445 parts (60 mol%) of bisphenol A · PO 2 mol adduct, 332 parts (40 mol%) of bisphenol A · PO 3 mol adduct, 277 isophthalic acid Part (100 mol%) and 2.5 parts of titanium diisopropoxybistriethanolamate as a condensation catalyst, and the generated water was distilled under a reduced pressure of 0.5 to 2.5 kPa under a nitrogen stream at 220 ° C. It was allowed to react while leaving. The polyester resin (B-2) was obtained by taking out when the acid value was less than 0.3. The content of the saturated carboxylic acid (isophthalic acid) in (B-2) was 10 ppm.

<Production Example 8> [Production of linear polyester resin (B-3)]
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 428 parts (60 mol%) of bisphenol A · PO 2 mol adduct, 319 parts (40 mol%) of bisphenol A · PO 3 mol adduct, 316 parts of isophthalic acid 316 Part (100 mol%) and 2.5 parts of titanium diisopropoxybistriethanolamate as a condensation catalyst, and the generated water was distilled under a reduced pressure of 0.5 to 2.5 kPa under a nitrogen stream at 220 ° C. It was allowed to react while leaving. The polyester resin (B-3) was obtained by taking out the acid value when it became less than 33. The content of this saturated carboxylic acid (isophthalic acid) in (B-3) was 10,000 ppm.

<Production Example 9> [Production of linear polyester resin (B-4)]
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction tube, 386 parts (50 mol%) of bisphenol A · PO 2 mol adduct, 363 parts (50 mol%) of bisphenol A · EO 2 mol adduct, 273 of terephthalic acid Part (90 mol%), and 2.5 parts of titanium diisopropoxybistriethanolamate as a condensation catalyst were added, and the generated water was distilled under a reduced pressure of 0.5 to 2.5 kPa under a nitrogen stream at 220 ° C. It was allowed to react while leaving. When the acid value became less than 1, it was cooled to 180 ° C. Thereafter, 34 parts (10 mol%) of trimellitic anhydride was added, reacted for 1 hour at atmospheric pressure, and then taken out to obtain a polyester resin (B-4). The content of the saturated carboxylic acid (B-4) is 1800 ppm, and the content of the divalent aromatic carboxylic acid (terephthalic acid) and the trivalent or higher aromatic carboxylic acid (trimellitic acid) is 950 ppm, respectively. And 850 ppm.

<Comparative Production Example 2> [Production of Polyester Resin (B′-1)]
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 428 parts (60 mol%) of bisphenol A · PO 2 mol adduct, 319 parts (40 mol%) of bisphenol A · PO 3 mol adduct, 316 parts of isophthalic acid 316 Part (100 mol%) and 2.5 parts of titanium diisopropoxybistriethanolamate as a condensation catalyst, and the generated water was distilled under a reduced pressure of 0.5 to 2.5 kPa under a nitrogen stream at 220 ° C. It was allowed to react while leaving. When the acid value became less than 35, the polyester resin (B′-1) was obtained. The content of the saturated carboxylic acid (isophthalic acid) in (B′-1) was 15000 ppm.

<Example 1> [Production of toner binder (C-1)]
27 parts of a polyester resin (a-1) and 73 parts of a linear polyester resin (B-1) are mixed and supplied to a twin-screw kneader (Kurimoto Iron Works, S5KRC kneader) at 50 kg / hour, simultaneously with a radical reaction initiator. As (c), 1.0 part of t-butylperoxyisopropyl monocarbonate (c-1) was supplied at 0.50 kg / hour and kneaded and extruded at 160 ° C. for 15 minutes to carry out a crosslinking reaction. The resultant was cooled to obtain a toner binder (C-1) containing the nonlinear polyester resin (A) of the present invention. This (C-1) had a saturated carboxylic acid content of 1723 ppm and Mw / Mn of 11.9. The contents of (C-1) divalent aromatic carboxylic acid (total of phthalic acid, isophthalic acid and terephthalic acid) and trivalent or higher aromatic carboxylic acid were 1723 ppm and 0 ppm, respectively.

<Example 2> [Production of toner binder (C-2)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 1.0 part of copper bromide (I) (d-1), polyester (a-1) 27 as an additive (d) for living radical polymerization Parts, linear polyester resin (B-1) 73 parts, N-propyl-2-pyridylmethanimine (d-2) 2.0 parts, toluene 200 parts was degassed and heated to 90 ° C. with stirring. Next, 1.0 part of ethyl 2-bromoisobutyrate (d-3) was added, reacted at 90 ° C. for 5 hours, toluene was removed, and the toner binder (C-2) containing the nonlinear polyester resin (A) of the present invention was removed. ) This (C-2) had a saturated carboxylic acid content of 1500 ppm and Mw / Mn of 6.5. The contents of (C-2) divalent aromatic carboxylic acid (total of phthalic acid, isophthalic acid and terephthalic acid) and trivalent or higher aromatic carboxylic acid were 1500 ppm and 0 ppm, respectively.

<Example 3> [Production of toner binder (C-3)]
4-cyano-4-[(dodecylsulfanylthiocarbonyl) sulfanyl] pentanoic acid (d-4) as an additive for living radical polymerization (d) in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube 1.0 part, 27 parts of polyester (a-1), 73 parts of linear polyester resin (B-1), 200 parts of toluene were added and deaerated, and then the temperature was raised to 60 ° C. with stirring. Next, 1.0 part of 2,2′-azobisisobutyronitrile (c-2) is added as a reaction initiator (c), reacted at 60 ° C. for 15 hours, toluene is removed, and the non-linear polyester of the present invention Toner binder (C-3) containing resin (A) was obtained. This (C-3) had a saturated carboxylic acid content of 1600 ppm and Mw / Mn of 5.9. The contents of (C-3) divalent aromatic carboxylic acid (total of phthalic acid, isophthalic acid and terephthalic acid) and trivalent or higher aromatic carboxylic acid were 1600 ppm and 0 ppm, respectively.

<Example 4> [Production of toner binder (C-4)]
27 parts of polyester (a-1) and 73 parts of linear polyester resin (B-1) were mixed and supplied to a twin-screw kneader (Kurimoto Iron Works, S5KRC kneader) at 50 kg / hour, and simultaneously a radical reaction initiator ( 0.50 kg of a mixture of 0.9 part of t-butylperoxyisopropyl monocarbonate (c-1) as c) and 0.1 part of 2-iodoisobutyric acid (d-5) as an additive for living radical polymerization (d) The mixture was kneaded and extruded at 160 ° C. for 15 minutes to carry out a crosslinking reaction. The obtained product was cooled to obtain a toner binder (C-4) containing the nonlinear polyester resin (A) of the present invention. The saturated carboxylic acid content of (C-4) was 1650 ppm, and Mw / Mn was 5.0. The contents of (C-4) divalent aromatic carboxylic acid (total of phthalic acid, isophthalic acid and terephthalic acid) and trivalent or higher aromatic carboxylic acid were 1650 ppm and 0 ppm, respectively.

<Example 5> [Production of toner binder (C-5)]
2,2,5-trimethyl-4-phenyl-3-azahexane-3-nitroxide (d-6) as an additive (d) for living radical polymerization in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube ) 0.1 part, 27 parts of polyester (a-1), 73 parts of linear polyester resin (B-1), 200 parts of toluene, and after deaeration, the temperature was raised to 60 ° C. with stirring. Next, 1.0 part of N-tert-butyl-N- (2-methyl-1-phenylpropyl) -O- (1-phenylethyl) hydroxylamine (d-7) was added and reacted at 120 ° C. for 30 hours. Toluene was removed to obtain a toner binder (C-5) containing the nonlinear polyester resin (A) of the present invention. The saturated carboxylic acid content of (C-5) was 1800 ppm, and Mw / Mn was 6.2. The contents of (C-5) divalent aromatic carboxylic acid (total of phthalic acid, isophthalic acid and terephthalic acid) and trivalent or higher aromatic carboxylic acid were 1800 ppm and 0 ppm, respectively.

Examples 6 to 11 [Production of Toner Binders (C-6) to (C-11)]
For Examples 6 to 11, toners were obtained in the same manner as in Example 1 except that the polyester resin (a), the polyester resin (B), and the reaction initiator (c) shown in Table 3 were each designated by weight. Binders (C-6) to (C-11) were obtained. The analytical values were as shown in Table 3, respectively.

<Example 12> [Production of toner binder (C-12)]
Example 12 was carried out except that the polyester resin (a), polyester resin (B), reaction initiator (c), and living radical polymerization additive (d) listed in Table 3 were each designated by weight. In the same manner as in Example 4, a toner binder (C-12) was obtained. The analytical values were as shown in Table 3, respectively.

<Comparative Examples 1 and 2> [Production of toner binders (C′-1) to (C′-2)]
For Comparative Examples 1 and 2, the polyester resin (a), the polyester resin (a ′), the polyester resin (B), and the reaction initiator (c) described in Table 3 were produced except that the weight parts were designated as respective parts. Toner binders ((C′-1) to (C′-2) were obtained in the same manner as in Example 1. The analytical values were as shown in Table 3, respectively.

<Example 13> [Production of toner (T-1)]
To 85 parts of toner binder (C-1), 6 parts of pigment carbon black MA-100 [manufactured by Mitsubishi Chemical Co., Ltd.], 4 parts of release agent carnauba wax, charge control agent T-77 [Hodogaya Chemical Co., Ltd.] (Manufactured)] 4 parts were added to form a toner by the following method.
First, after pre-mixing using a Henschel mixer [FM10B manufactured by Mitsui Miike Chemical Co., Ltd.], the mixture was kneaded using a twin-screw kneader [PCM-30 manufactured by Ikegai Co., Ltd.]. Next, the mixture was finely pulverized using a supersonic jet crusher lab jet [manufactured by Nippon Pneumatic Industry Co., Ltd.] and then classified by an airflow classifier [MDS-I made by Nippon Pneumatic Industry Co., Ltd.] Toner particles having a D50 of 8 μm were obtained.
Next, 99 parts of toner particles and 1 part of colloidal silica [Aerosil R972: manufactured by Nippon Aerosil Co., Ltd.] as a fluidizing agent were mixed in a sample mill to obtain toner (T-1) of the present invention.

Examples 14 to 24 [Production of Toners (T-2) to (T-12)]
Toners (T-2) to (T-12) of the present invention were obtained in the same manner as in Example 13 with the number of parts of the raw materials listed in Table 4.

<Comparative Examples 3 to 4> [Production of Toners (T′-1) to (T′-2)]
Toners (T′-1) to (T′-2) of the present invention were obtained in the same manner as in Example 13 with the number of ingredients blended in Table 4.

[Evaluation method]
Below are the methods for measuring and evaluating the low-temperature fixability, hot-offset resistance, heat-resistant storage stability, moist-and-heat storage resistance, fluidity, charging start-up property, and charging stability of the obtained toner, including criteria. explain.

<Low temperature fixability>
The toner was uniformly placed on the paper surface so as to be 0.6 mg / cm ² . At this time, as a method of placing the powder on the paper surface, a printer from which the heat fixing machine was removed was used. Other methods may be used as long as the powder can be uniformly loaded with the above-described weight density.
Measures the low temperature fixing temperature, which is the temperature at which cold offset occurs when this paper is passed through a pressure roller under conditions of a fixing speed (heating roller peripheral speed) of 213 mm / sec and a fixing pressure (pressure roller pressure) of 10 kg / cm ^2. did.
The lower the low temperature fixing temperature, the better the low temperature fixing property. The low temperature fixing temperature (° C.) of the toner is shown in Table 4 as the low temperature fixing property (° C.).

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

<Heat resistant storage stability>
The toner was allowed to stand in an atmosphere of 50 ° C. for 24 hours, the degree of blocking was judged visually, and the heat resistant storage stability was evaluated according to the following criteria.
[Criteria]
○: Blocking has not occurred.
X: Blocking has occurred.

<Moisture and heat storage stability>
The toner was allowed to stand for 360 hours in an atmosphere of 40 ° C. and a relative humidity of 80%, the degree of blocking was judged visually, and evaluated according to the following criteria.
[Evaluation criteria]
(Double-circle): Blocking has not generate | occur | produced.
○: Blocking does not occur until 24 hours, but blocking occurs at 360 hours.
X: Blocking has occurred at 24 hours.

<Fluidity>
The toner bulk density (g / 100 mL) was measured with a powder tester manufactured by Hosokawa Micron, and the fluidity was determined according to the following criteria. Δ or more (30 g / 100 mL or more) is a practical range.

[Criteria]
○: 33 or more Δ: 30 or more and less than 33 ×: less than 30

<Rise of charging>
(1) 0.5 g of toner and 20 g of ferrite carrier (P-Tech, F-150) were placed in a 50 mL glass bottle and conditioned at 23 ° C. and 50% relative humidity for 8 hours or more.
(2) Friction stirring was performed at 50 rpm × 6 seconds and 600 seconds with a tumbler shaker mixer, and the charge amount at each time was measured.
For the measurement, a blow-off charge measuring device [manufactured by Toshiba Chemical Co., Ltd.] was used.
“Charging amount at a friction time of 6 seconds / Charging amount at a friction time of 600 seconds” was calculated, and this was used as an index of charge rising property.

[Criteria]
○: 0.6 or more Δ: 0.4 or more and less than 0.6 ×: less than 0.4

<Charging stability>
(1) 0.5 g of toner and 20 g of ferrite carrier (P-Tech, F-150) were placed in a 50 mL glass bottle and conditioned at 23 ° C. and 50% relative humidity for 8 hours or more.
(2) Friction stirring was performed at 50 rpm for 10 minutes and 60 minutes with a tumbler shaker mixer, and the charge amount at each time was measured.
For the measurement, a blow-off charge measuring device [manufactured by Toshiba Chemical Co., Ltd.] was used.
“Charging amount of 60 minutes friction time / charging amount of 10 minutes friction time” was calculated and used as an index of charging stability.

[Criteria]
○: 0.8 or more △: 0.6 or more and less than 0.8 ×: Less than 0.6

  As is apparent from the evaluation results in Table 4, all the toners of Examples 13 to 24 of the present invention were excellent in performance evaluation.

The toner binder and toner of the present invention are excellent in low-temperature fixability and hot offset resistance, excellent in heat-resistant storage property, wet heat-resistant storage property, toner fluidity, charge rising property and charging stability, electrophotographic, electrostatic It can be suitably used as an electrostatic charge image developing toner and toner binder used for recording, electrostatic printing and the like.
Furthermore, it is suitable as a photosensitive resin composition for uses such as paint additives, adhesive additives, and electronic paper particles.

Claims (6)

A toner binder containing a non-linear polyester resin (A) and a saturated carboxylic acid,
The nonlinear polyester resin (A) includes a saturated carboxylic acid component (y) and an unsaturated carboxylic acid component (z), and at least one of the (y) and the (z) includes a divalent or higher carboxylic acid. A non-linear polyester resin in which carbon atoms of the polyester resin (a), which is a polycondensate of an alcohol component (x) containing a component and a divalent or higher alcohol, are directly bonded;
A toner binder in which the saturated carboxylic acid is a divalent or higher valent aromatic carboxylic acid, and the content of the saturated carboxylic acid is 10 ppm to 10,000 ppm based on the weight of the toner binder.   2. The toner binder according to claim 1, wherein a ratio (Mw / Mn) of a weight average molecular weight (Mw) and a number average molecular weight (Mn) of a tetrahydrofuran-soluble component in the toner binder is 1 to 15. 3.   The toner binder according to claim 1, further comprising a linear polyester resin (B).   The weight average molecular weight (Mw) of the tetrahydrofuran-soluble component in the polyester resin (a) is 15,000 to 100,000, and the ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) The toner binder according to claim 1, wherein the toner binder is 4 to 15.   A toner containing the toner binder according to claim 1.   Nonlinear polyester resin (A) crosslinks carbon-carbon double bonds derived from unsaturated carboxylic acid component (z) using radical reaction initiator (c) and / or living radical polymerization additive (d). The method for producing a toner binder according to any one of claims 1 to 4, wherein the toner binder is a resin obtained by causing the toner binder to be obtained.