JP2017003985A - Toner binder and toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an excellent toner binder which achieves all of low temperature fixability, glossiness and hot offset resistance, and satisfies all of flowability of a toner, heat-resistant storage property, charge stability, crushability and image intensity.SOLUTION: There is provided a toner binder which is a toner binder containing a polyester resin (A1) containing an alcohol component (y) and an unsaturated carboxylic acid component (z) as constituent materials and a nonlinear polyester modified resin (A) chemically bonded to a radical reaction initiator (c), where a peak top molecular weight of the polyester resin (A1) is 2,000-12,000, a fraction insoluble to tetrahydrofuran (THF) of the nonlinear polyester modified resin (A) is 50 wt.% or more, and the toner binder has at least one inflection point indicating a glass transition temperature Tgin a temperature range of -20°C to 80°C in a chart by differential scanning calorimetry (DSC).SELECTED DRAWING: None

Description

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

  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. In general, in an electrophotographic system, an electrostatic charge image (latent image) is formed on a photoreceptor, and then the latent image is developed using toner to form a toner image. The toner image is transferred onto a recording medium such as paper and then fixed by a method such as heating.

  In order to pass through these processes without problems, the toner must first 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 high image quality and energy consumption in the fixing process is reduced. In addition, when fixing a toner image by a hot roll fixing method, the hot roll and the molten toner are in direct contact at the time of fixing. At this time, the transfer paper to which the toner transferred onto the hot roll is sent next time, etc. Since the so-called offset phenomenon occurs, the anti-offset property is required. Therefore, it is necessary to develop low-temperature fixability while maintaining offset resistance, and a toner having a wider working range, for example, a fixing temperature range of 50 ° C. or more, has been demanded.

  The toner binder has a great influence on the toner characteristics as described above, and a polystyrene resin, a styrene-acrylic resin, a polyester resin, an epoxy resin, a polyurethane resin, a polyamide resin and the like are known. Polyester resin is especially attracting attention because it is easy to balance the fixing property and the fixing property.

  Conventionally, as a method for expanding the fixing temperature range of a polyester resin, a method using a non-linear polyester resin having a three-dimensional crosslinked structure using a tri- or higher functional monomer has been studied (for example, see Patent Document 1). However, although the non-linear polyester resin described in Patent Document 1 is excellent in hot offset resistance and can exhibit a high maximum fixing temperature, the level of low-temperature fixing property is not yet sufficient.

  Therefore, the use of a linear polyester resin composed of a divalent carboxylic acid compound and a divalent alcohol compound has been studied as a means for improving the low-temperature fixability. (For example, refer to Patent Document 2). However, a linear polyester resin having no three-dimensional structure is excellent in low-temperature fixability, but has a problem that a wide fixing temperature range cannot be obtained because of poor hot offset resistance.

Therefore, toners using a reaction product of a mixture of a polymerizing resin and a polyester resin and an isocyanate have been proposed (Patent Documents 3 to 5).
However, even with this method, offset phenomenon at high temperature can be prevented to some extent, but at the same time, the lower limit fixing temperature also increases, making it difficult to fix at low temperature, and due to the high cohesiveness of urea groups and urethane groups derived from isocyanates. The grindability of the resin is remarkably deteriorated. Furthermore, the uniformity of the resin is impaired and the heat-resistant storage stability is deteriorated, and the demands for speeding up and energy saving have not yet been fully satisfied.

Therefore, toners using products obtained by crosslinking a polyester resin having an unsaturated double bond with a radical reaction initiator have been proposed (Patent Documents 6 to 11).
However, even with this method, even if the offset phenomenon at high temperature can be prevented to some extent, the lower limit fixing temperature also rises at the same time, so that low-temperature fixing becomes difficult, and the demands for speeding up and energy saving have not yet been fully met.

  On the other hand, Patent Document 12 proposes a chemical toner obtained by a suspension polymerization method in which granulation is performed in an aqueous phase. In this method, a monomer, a polymerization initiator, a colorant, a release agent, etc. are added to an aqueous phase containing a dispersion stabilizer while stirring to form oil droplets, and then the temperature is raised to cause a polymerization reaction. This is a method for obtaining toner particles. According to this suspension polymerization method, the toner particles can be made smaller in size and the resin can be made uniform, so that low temperature fixability, hot offset resistance and heat resistant storage stability can be compatible. Agent) must be used, and there is a problem that the chargeability is lowered by the remaining of the agent.

  As described above, while satisfying both low-temperature fixability, glossiness and hot offset resistance, toner fluidity, heat resistant storage stability, charging stability, grindability, image strength, bending resistance and document offset resistance are improved. There has never been an excellent toner binder and toner that satisfy all of them.

JP-A-57-109825 Japanese Patent Laid-Open No. 4-12367 JP-A 63-56659 JP-A-4-211272 JP 2004-258627 A JP 2001-013726 A JP 2006-154625 A JP 2005-99428 A JP 2008-233531 A International Publication No. 2007/034813 JP 2010-204141 A JP 2007-212753 A

  The present invention provides an excellent toner binder and toner satisfying all of the fluidity, heat-resistant storage stability, charging stability, pulverization property and image strength of the toner while achieving both low-temperature fixability, glossiness and hot offset resistance. The purpose is to provide.

As a result of intensive studies to solve these problems, the present inventors have reached the present invention.
That is, the present invention relates to a non-linear polyester-modified resin (A) in which a polyester resin (A1) having an alcohol component (y) and an unsaturated carboxylic acid component (z) as constituent materials and a radical reaction initiator (c) are chemically bonded. The polyester resin (A1) has a peak top molecular weight of 2,000 to 12,000, and the non-linear polyester-modified resin (A) has an insoluble content of tetrahydrofuran (THF) of 50% by weight or more. A toner binder, wherein the toner binder has at least one inflection point indicating a glass transition temperature Tg _T on a chart by differential scanning calorimetry (DSC) in a temperature range of -20 ° C to 80 ° C; The toner binder is a toner containing a colorant.

  According to the present invention, it is possible to provide a toner binder and a toner excellent in fluidity, heat-resistant storage stability, charging stability, pulverization property and image strength of a toner while achieving both low-temperature fixability, glossiness and hot offset resistance. It became possible.

The toner binder of the present invention is a non-linear polyester-modified resin (C1) obtained by chemically bonding a polyester resin (A1) having an alcohol component (y) and an unsaturated carboxylic acid component (z) as constituent materials and a radical reaction initiator (c). A toner binder containing A).
Moreover, the peak top molecular weight of the polyester resin (A1) having a carbon-carbon unsaturated bond in the molecule is 2,000 to 12,000, and the tetrahydrofuran (THF) insoluble content of the non-linear polyester-modified resin (A) is 50. % By weight or more.
The toner binder has at least one inflection point indicating a glass transition temperature (Tg) in a temperature range of −20 ° C. to 80 ° C. of a chart obtained by differential scanning calorimetry (DSC) of the toner binder.
Below, the toner binder of this invention is demonstrated sequentially.

The toner binder of the present invention is a non-linear polyester-modified resin (C1) obtained by chemically bonding a polyester resin (A1) having an alcohol component (y) and an unsaturated carboxylic acid component (z) as constituent materials and a radical reaction initiator (c). A) is included as an essential component. Further, the polyester resin may be one kind or a mixture of two or more kinds of polyester resins. For example, a combination of the non-linear polyester-modified resin (A) defined in the present invention and the other polyester resin (B) described later. But you can.
Moreover, the polyester resin (A1) in the present invention is obtained by polycondensation of one or more kinds of alcohol components (y) and one or more kinds of unsaturated carboxylic acid components (z). ) In the molecule.
In addition to (y) and (z), (A1) may be polycondensed using one or more saturated carboxylic acid components (x) as a constituent material.

  Examples of the alcohol component (y) include monool (y1), diol (y2), trivalent to octavalent or higher polyol (y3), and the like.

As monool (y1), C1-C30 alkanol (Methanol, ethanol, isopropanol, dodecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, etc.) etc. are mentioned.
Among these monools, preferred are alkanols having 8 to 24 carbon atoms, and more preferred are dodecyl alcohol, myristyl alcohol, stearyl alcohol, behenyl alcohol, and combinations thereof.

Examples of the diol (y2) include alkylene glycols having 2 to 36 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 3-methyl-1, 5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, etc.);
C4-C36 alkylene ether glycol (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); C6-C36 alicyclic diol (1,4-cyclohexane) Dimethanol and hydrogenated bisphenol A, etc.);
(Poly) oxyalkylene of the above alicyclic diol [Alkylene group having 2 to 4 carbon atoms (oxyethylene, oxypropylene, etc.) or less] The ether [oxyalkylene unit (hereinafter abbreviated as AO unit)] 1 to 30];
Divalent phenols [monocyclic divalent phenols (for example, hydroquinone), polyoxyalkylene ethers of bisphenols (number of AO units 2 to 30)], and the like.

  Polyoxyalkylene ethers of bisphenols are usually obtained by adding alkylene oxide (hereinafter, “alkylene oxide” may be abbreviated as AO) to bisphenols. Examples of bisphenols include those represented by the following general formula (8).

OH-Ar-X-Ar-OH (8)
[Wherein X represents an alkylene group having 1 to 3 carbon atoms, —SO ₂ —, —O—, —S—, or a direct bond; Ar represents a halogen atom or an alkyl group having 1 to 30 carbon atoms; Represents an optionally substituted phenylene group. ]

  Specifically, for example, bisphenol A, bisphenol F, bisphenol B, bisphenol AD, bisphenol S, trichlorobisphenol A, tetrachlorobisphenol A, dibromobisphenol F, 2-methylbisphenol A, 2,6-dimethylbisphenol A and 2 , 2′-diethylbisphenol F, and two or more of these may be used in combination.

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, “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 the polyoxyalkylene ethers of bisphenols, EO and / or PO adducts of bisphenol A (average added mole number of 2 to 4, particularly 2 to 3) are preferable from the viewpoint of toner fixing properties.

Examples of the polyol (y3) having a valence of 3 to 8 or more include the following (y31) to (y35).
3 to 8 or more aliphatic polyhydric alcohol (y31) having 3 to 36 carbon atoms (alkane polyol and intramolecular or intermolecular dehydrated product thereof;
For example, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, polyglycerin and dipentaerythritol, etc. Sugars and derivatives thereof (y32);
For example, (poly) oxyalkylene ether (number of AO units 1 to 30) (y33) of the above aliphatic polyhydric alcohol such as sucrose and methyl glucoside;
Polyoxyalkylene ethers of trisphenols (such as trisphenol PA) (number of AO units 2 to 30) (y34);
Examples thereof include polyoxyalkylene ethers (number of AO units 2 to 30) (y35) of novolak resins (phenol novolak and cresol novolak, etc., average degree of polymerization 3 to 60).

  Among these alcohol components (y), those preferable from the viewpoint of achieving both low-temperature fixability and hot offset resistance are alkylene glycols having 2 to 12 carbon atoms, polyoxyalkylene ethers of bisphenols (number 2 to 2 of AO units). 30), an aliphatic polyhydric alcohol having 3 to 8 valences or more, and a polyoxyalkylene ether of a novolac resin (number of AO units: 2 to 30).

More preferable from the viewpoint of storage stability are alkylene glycols having 2 to 10 carbon atoms, polyoxyalkylene ethers of bisphenols (2 to 5 of AO units), polyoxyalkylene ethers of novolac resins (2 of AO units). ~ 30).
Particularly preferred are alkylene glycols having 2 to 6 carbon atoms and polyoxyalkylene ethers of bisphenol A (number of AO units 2 to 5), and most preferred are polyoxyalkylene ethers of ethylene glycol, propylene glycol and bisphenol A ( The number of AO units is 2-3).

  Examples of the unsaturated carboxylic acid component (z) include unsaturated monocarboxylic acids (z1), unsaturated dicarboxylic acids (z2), and anhydrides and lower alkyl esters of these acids.

  As unsaturated monocarboxylic acid (z1), C2-C30 unsaturated monocarboxylic acid is mentioned, Specifically, acrylic acid, methacrylic acid, propiolic acid, 2-butyric acid, crotonic acid, isocrotonic acid, 3-butenoic 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, Examples include elaidic acid, vaccenic acid, gadoleic acid, eicosenoic acid, erucic acid, and nervonic acid.

  Examples of the unsaturated dicarboxylic acid (z2) include alkene dicarboxylic acids having 4 to 50 carbon atoms, specifically, alkenyl succinic acid such as dodecenyl succinic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid and Glutaconic acid, etc.), vinyl polymer of unsaturated carboxylic acid [number average molecular weight (hereinafter referred to as Mn, according to gel permeation chromatography (GPC)): 450 to 10,000] (α-olefin / maleic acid copolymer) Etc.

Among these unsaturated carboxylic acids (z), preferred are alkenyl succinic acid such as acrylic acid, methacrylic acid, propiolic acid, dodecenyl succinic acid, maleic acid, fumaric acid from the viewpoint of compatibility between low-temperature fixability and hot offset resistance. It is an acid.
More preferred are acrylic acid, methacrylic acid, maleic acid, fumaric acid, and combinations thereof. Likewise preferred are anhydrides and lower alkyl esters of these acids.

  As the carboxylic acid component, the unsaturated carboxylic acid component (z) is essential, but the saturated carboxylic acid component (x) may be used in combination as a constituent raw material. Examples of such saturated carboxylic acid component (x) include alkanedicarboxylic acids having 2 to 50 carbon atoms (oxalic acid, malonic acid, succinic acid, adipic acid, repartic acid, sebacic acid, etc.), aromatics having 8 to 36 carbon atoms. Dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc.), aromatic polycarboxylic acids having 9-20 carbon atoms (trimellitic acid, pyromellitic acid, etc.), aliphatic tricarboxylic acids having 6-36 carbon atoms Acid (hexanetricarboxylic acid etc.), etc. are mentioned.

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

Among these saturated carboxylic acid components (x), preferred are both alkane dicarboxylic acids having 2 to 50 carbon atoms, alkenedicarboxylic acids having 4 to 50 carbon atoms, and carbon atoms from the viewpoint of achieving both low temperature fixability and hot offset resistance. An aromatic dicarboxylic acid having 8 to 20 carbon atoms and an aromatic polycarboxylic acid having 9 to 20 carbon atoms.
More preferable from the viewpoint of storage stability are adipic acid, alkenyl succinic acid having 16 to 50 carbon atoms, terephthalic acid, isophthalic acid, maleic acid, fumaric 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 polyester resin (A1) in the present invention is not particularly limited, but is preferably non-linear from the viewpoint of improving elasticity at high temperatures.
Moreover, although the manufacturing method of the polyester resin (A1) in this invention is not specifically limited, As mentioned above, an alcohol component (y) and an unsaturated carboxylic acid component (z) are used as a constituent raw material. Furthermore, when the polyester resin (A1) is nonlinear, for example, in addition to the unsaturated carboxylic acid component (z), a trivalent or higher polyol is used as the alcohol component (y) as a constituent raw material, or a saturated carboxylic acid component Examples of (x) include trivalent or higher carboxylic acids or acid anhydrides or lower alkyl esters. By being non-linear, heat resistant storage stability and hot offset resistance are improved.

In the present invention, each polyester resin can be produced in the same manner as a normal polyester production method.
For example, 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 total reaction ratio of the alcohol component (y) to the unsaturated carboxylic acid component (z) and / or the saturated carboxylic acid component (x) is preferably 2 as the equivalent ratio [OH] / [COOH] of the hydroxyl group to the carboxyl group. / 1/1/2, more preferably 1.5 / 1 to 1 / 1.3, particularly preferably 1.4 / 1 to 1 / 1.2.

The polyester resin (A1) needs to have a peak top molecular weight of 2,000 to 12,000 in gel permeation chromatography (GPC), and preferably has a peak top molecular weight of 3,000 to 11,500. It is.
When the peak top molecular weight is from 2,000 to 12,000, low temperature fixability and hot offset property are preferred.

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

In the present invention, GPC is used for the peak top molecular weight, number average molecular weight (hereinafter sometimes abbreviated as Mn), and weight average molecular weight (hereinafter sometimes abbreviated as Mw) of resins such as polyester resins. And can be measured under the following conditions.
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% tetrahydrofuran (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 molecular weight is measured by dissolving a polyester resin or the like in tetrahydrofuran (hereinafter sometimes abbreviated as THF) so as to be 0.25% by weight, and filtering out the insoluble matter with a glass filter.

  Here, the “non-linear” polyester-modified resin (A) is a polyester resin having a branch (crosslinking point) in the main chain.

By the way, for the purpose of improving the low-temperature fixability, the toner binder of the present invention is preferably used in combination with the polyester resin (B).
As the polyester resin (B) used in combination for this purpose, any polyester resin may be used as long as it does not substantially contain THF-insoluble matter. As long as it does not contain THF-insoluble matter, it may have a very small amount of crosslinking points, or may have a molecular end modified with an anhydride of saturated polycarboxylic acid (which may be trivalent or higher).

  The production method of the non-linear polyester-modified resin (A) is first a condensation polymerization of a polyester resin (A1) having a carbon-carbon double bond in the molecule using an alcohol component (y) and an unsaturated carboxylic acid component (z). Then, a crosslinking reaction occurs between the carbon-carbon double bonds resulting from the unsaturated carboxylic acid component (z) in (A1) using the radical generated from the radical reaction initiator (c). Then, a non-linear polyester-modified resin (A) is produced by chemical bonding.

  The radical reaction initiator (c) used for the crosslinking reaction in the present invention is not particularly limited, and an azo compound, a diazo compound (c1), or an organic peroxide (c2) is used.

  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 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- Butylperoxyhexine-3, acetyl peroxide, isobutyryl peroxide, octanonor peroxide, decanolyl peroxide, lauroyl peroxide, 3,3,5-trimethylhexanoyl peroxide, m-toluyl peroxide, t -Butyl peroxyisobutyrate, t-butyl peroxyneodecanoate, cumyl peroxyneode Noate, t-butyl peroxy 2-ethylhexanoate, t-butyl peroxy 3,5,5-trimethylhexanoate, t-butyl peroxylaurate, t-butyl peroxybenzoate, t-butyl Examples include peroxyisopropyl carbonate and t-butyl peroxyacetate.

Among these, the organic peroxide (c2) is preferable because it has high initiator efficiency and does not produce toxic byproducts such as cyanide.
Furthermore, since the crosslinking reaction proceeds efficiently and the amount used can be small, a reaction initiator having a high hydrogen abstraction ability is particularly preferable. 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 and A radical reaction initiator having a high hydrogen abstraction ability such as t-butylperoxyisopropyl carbonate is particularly preferred.

Although the usage-amount of a radical reaction initiator (c) is not restrict | limited in particular, 0.1-50 weight% is preferable based on the weight of an unsaturated carboxylic acid component (z).
When the amount of the radical reaction initiator used is 0.1% by weight or more, the crosslinking reaction tends to proceed, and when it is 50% by weight or less, the odor tends to be good. The amount used is more preferably 30% by weight or less, further preferably 20% by weight or less, and particularly preferably 10% by weight or less.

The unsaturated carboxylic acid component (z) in the polyester resin (A1) can be chemically bonded to the vinyl monomer (a) excluding the unsaturated carboxylic acid component (z). The polyester resin is preferably not chemically bonded because the low-temperature fixability deteriorates.
Examples of the vinyl monomer (a) include hydrocarbon monomers such as styrene and alkyl (meth) acrylates having 5 or more carbon atoms. In addition, (meth) acrylate means a methacrylate or an acrylate.
Alternatively, even when chemically bonded, the total amount of vinyl monomers bonded is preferably 4% by weight or less based on the weight of the toner binder. The smaller the content of (a), the better the balance between low temperature fixability, heat resistant storage stability and hot offset resistance.

  The non-linear polyester-modified resin (A) is a polyester-modified resin obtained by reacting the polyester resin (A1) with the radical reaction initiator (c), and effectively undergoes a cross-linking reaction, so that the toner has hot offset resistance and heat resistant storage stability. Is preferable because it becomes favorable.

  For example, in the case of a cross-linking reaction in which a carbon-carbon bond is generated between molecules by a radical addition reaction when producing a non-linear polyester-modified resin (A), carbon--in the main chain or side chain of the polyester resin (A1). In order to introduce a carbon double bond, a polycondensation reaction is performed using a carboxylic acid compound having an unsaturated double bond and / or an alcohol compound having an unsaturated double bond, and these compounds are converted into those of the polyester resin (A1). What is necessary is just to incorporate as a structural component.

The content of the carbon-carbon double bond in the polyester resin (A1) is not particularly limited, but in the case of an unsaturated carboxylic acid (z), the raw material mole number of the acid component constituting the polyester resin (A1). Is preferably 10 to 100 mol%, and when the constituent component having an unsaturated double bond is an alcohol component, it is based on the number of moles of the raw material of the alcohol component constituting the polyester resin (A1). The content is preferably 1 to 50 mol%.
Moreover, when using together the carboxylic acid raw material and alcohol raw material which have an unsaturated double bond, it is preferable that both total is 10-100 mol%. When the unsaturated double bond content is 10 mol% or more, the hot offset resistance of the toner tends to be good, and the crosslinking reaction tends to occur effectively.

The glass transition temperature (Tg _A1 ) of the polyester resin (A1) is preferably −35 ° C. to 45 ° C. When the Tg is 45 ° C. or lower, the low-temperature fixability is good, and when it is −35 ° C. or higher, the heat resistant storage stability is good.
In addition, glass transition temperature (Tg) can be measured by the method (DSC method) prescribed | regulated to ASTM D3418-82, for example using Seiko Instruments Co., Ltd. DSC20 and SSC / 580.

Specifically, 5 mg of a sample was 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. below 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 (A1) is preferably 0 to 30 mgKOH / g, more preferably 0 to 25 mgKOH / g, and particularly preferably 0 to 10 mgKOH / g from the viewpoint of charging stability.
The acid value of the polyester resin (A1) can be measured by the method prescribed in JIS K0070 (1992 edition).

The THF-insoluble content of the nonlinear polyester-modified resin (A) needs to be 50% by weight or more based on the weight of the nonlinear polyester-modified resin (A), more preferably 55% by weight or more, and particularly preferably 60% by weight or more.
When the THF-insoluble content is 50% by weight or more, the heat resistant storage stability and the hot offset resistance are improved.
When adjusting the THF-insoluble content of the non-linear polyester-modified resin (A), for example, the amount of unsaturated carboxylic acid component (z) is increased, the peak top molecular weight is increased, polyester resin (A1) and polyester resin (B ) And the like.

In the present invention, the storage elastic modulus and softening point of the THF insoluble or dissolved content of the toner binder are measured, or the content of the insoluble content of the non-linear polyester-modified resin (A) is measured. By the way.
Add 50 ml of THF to 0.5 g of toner binder and stir to reflux for 3 hours. After cooling to room temperature, the insoluble content is filtered off with a glass filter, and the resin content on the glass filter is reduced in pressure at 80 ° C. for 3 hours, and dried until THF is completely removed. The resin obtained by drying was regarded as an insoluble matter in THF in the toner binder.
Next, the solution obtained by filtration with the glass filter is decompressed at 80 ° C. for 3 hours, and dried until THF is completely removed. The resin content obtained here was taken as the content dissolved in THF in the toner binder.
The content of the THF-insoluble matter in the non-linear polyester-modified resin (A) is also determined by the same operation. When the polyester resin (B) is used in combination, the nonlinear polyester-modified resin (A) is synthesized by radical polymerization of only the polyester resin (A1), and the content of THF insoluble matter is calculated.

The storage elastic modulus G ′ _x150 (unit Pa) at 150 ° C. of the _{insoluble matter} in THF in the toner binder of the present invention satisfies the following inequality (1) from the viewpoint of hot offset resistance at the time of toner _formation. preferable.
G ′ _x150 ≧ 10,000 (1)

Preferably, G ′ _{x150 on the} left side is 30,000 or more, more preferably 50,000 or more.
When G ′ _{× 150} is 10,000 or more, it is considered that the viscosity is not too low in a practical range even in a high temperature region, and the hot offset resistance when used as a toner is good.

When adjusting the storage elastic modulus G ′ of the _{insoluble matter} in THF in the toner binder, for example, to increase G ′ _{× 150} , increase the Tm of the polyester resin and increase the ratio of the trivalent or higher component. This can be achieved by increasing the number of crosslinking points, increasing the molecular weight, increasing the Tg, and the like.

The storage elastic modulus G ′ _x150 (unit Pa) at 150 ° C. of the insoluble portion in THF in the toner binder of the present invention and the storage elastic modulus G ′ _x180 (unit Pa) in 180 ° C. of the insoluble portion in THF are _converted into toner. From the viewpoint of hot offset resistance at the time, it is preferable to satisfy the following formula (2).

G ′ _x150 / G ′ _x180 ≦ 10 (2)
Preferably _G'x150 / _G'x180 is 9 or less, More preferably, it is 0.1-8.
When G ′ _x150 and G ′ _x180 are 10 or less, it is considered that the viscosity is not too low in a practical range even in a high temperature range, and the hot offset resistance when used as a toner is good.

When adjusting the storage elastic modulus G ′ of the _{insoluble matter} in THF in the toner binder, for example, when it is _desired to reduce G ′ _x150 / G ′ _x180 , the Tm of the polyester resin is increased, and the trivalent or higher component The ratio can be increased, the number of cross-linking points is increased, the molecular weight is increased, or the Tg is increased.

The storage elastic modulus G ′ _x150 (unit Pa) at 150 ° C. of the insoluble portion in THF in the toner binder of the present invention and the storage elastic modulus G ′ _y150 (unit Pa) in 150 ° C. of the dissolved portion in THF at the time of toner _formation. From the viewpoint of hot offset resistance and low temperature fixability, it is preferable to satisfy the following formula (3).

G ′ _x150 / G ′ _y150 ≧ 500 (3)
Preferably, G ′ _x150 / G ′ _{y150 on the} left side is 1,000 or more, more preferably 2,000 or more.
When G ′ _x150 and G ′ _y150 are 500 or more, it is considered that the viscosity does not become too low in the practical range even in the high temperature range, and the viscosity tends to be lowered in the low temperature range, and resistance to hot offset when used as a toner. And low-temperature fixability is also improved.

When adjusting the storage elastic modulus G ′ of the _{insoluble matter} in THF in the toner binder, for example, when _increasing G ′ _x150 / G ′ _y150 (when increasing G ′ _x150 ), nonlinear polyester-modified resin It can be achieved by increasing the Tm of (A), increasing the ratio of trivalent or higher constituents, increasing the number of crosslinking points, increasing the molecular weight, or increasing the Tg.

In order to adjust the storage elastic modulus G ′ of the dissolved component in THF in the toner binder, for example, when increasing G ′ _x150 / G ′ _y150 (when decreasing G ′ _y150 ), polyester resin (B) Can be achieved by lowering the Tm, lowering the molecular weight, or lowering the Tg.

The ratio of the storage elastic modulus G ′ _x150 (unit Pa) and the loss elastic modulus G ″ _x150 (unit Pa) at 150 ° C. of the insoluble content of THF in the toner binder of the present invention is determined by the glossiness and resistance to toner. From the viewpoint of hot offset properties, it is preferable to satisfy the following formula (4).
G ″ _x150 / G ′ _x150 ≧ 0.1 (4)

The left side is preferably 0.2 or more, more preferably 0.3 or more, and particularly preferably 0.5 or more.
If G ″ _x150 / G ′ _x150 is 0.1 or more, it is considered that the viscosity does not become too low in the practical range even in the high temperature region, and the viscosity tends to be lowered in the low temperature region. Hot offset property is improved, and low-temperature fixability and glossiness are also improved.

When adjusting the storage elastic modulus G ′ and the loss elastic modulus G ″ of the _{insoluble matter} in THF in the toner binder, for example, when increasing G ″ _x150 / G ′ _x150 (G ′ _x150 is increased). In the case), the Tm of the non-linear polyester-modified resin (A) is increased, the ratio of the trivalent or higher component is increased, the number of crosslinking points is increased, the molecular weight is increased, or the Tg is increased.

The ratio of the storage elastic modulus G ′ _x120 (unit Pa) and the loss elastic modulus G ″ _x120 (unit Pa) at 120 ° C. of the insoluble content of THF in the toner binder of the present invention is the resistance to hot offset during toner _formation . In view of the above, it is preferable to satisfy the following inequality (5).
G ″ _y120 / G ′ _y120 ≦ 15 (5)

The left side is preferably 10 or less, more preferably 11 to 12, particularly preferably 12 to 13, and most preferably 13 to 15 or less.
When G ″ _x120 / G ′ _x120 is 0.1 or more, it is considered that the viscosity does not become too low in the practical range even in the high temperature range, and the viscosity tends to be lowered in the low temperature range. Hot offset property is improved, and low-temperature fixability and glossiness are also improved.

When adjusting the storage elastic modulus G ′ and loss elastic modulus G ″ of the _{insoluble matter} in THF in the toner binder, for example, when G ″ _x120 / G ′ _{x120 is} to be reduced (G ′ _x120 is reduced). In the case of) lowering the Tm of the non-linear polyester-modified resin (A), increasing the ratio of the trivalent or higher component, increasing the number of crosslinking points, decreasing the molecular weight, decreasing the Tg, or the polyester resin (B). This can be achieved by increasing the ratio.

In the present invention, the storage modulus G ′ _x150 , G ′ _x180 , and G ′ _y150 of the insoluble component and the dissolved component in THF in the toner binder are measured using the following viscoelasticity measuring device.
Apparatus: ARES-24A (Rheometric)
Jig: 25 mm parallel plate Frequency: 1 Hz
Distortion rate: 5%
Temperature increase rate: 5 ° C / min Temperature increase start: 100 ° C
End of temperature increase: 200 ° C

In the present invention, the storage elastic modulus G ′ _x60 of the _{insoluble matter} in THF in the toner binder is measured using the following viscoelasticity measuring device.
Apparatus: ARES-24A (Rheometric)
Jig: 8mm parallel plate Frequency: 1Hz
Distortion rate: 5%
Temperature increase rate: 5 ° C / min Temperature increase start: 40 ° C
End of temperature rise: 130 ° C

The softening point Tm _x (unit: ° C) by the flow tester of the THF insoluble matter in the toner binder of the present invention preferably satisfies the following formula (6) from the viewpoint of hot offset resistance at the time of toner formation.

140 ≦ Tm _x ≦ 250 (6)
More preferably Tm _x is 150 to 245 or less, still more preferably more than 160 240 or less, particularly preferably at 165 or more 238 or less, and most preferably 170 or more 235 or less.
If tm _x is at 140 to 250 hereinafter, also maintained a high viscosity in the practical range in the high temperature region, hot offset resistance becomes excellent when used as a toner.

To adjust the softening point Tm _x by a flow tester of the THF-insoluble fraction in the toner binder, for example, to increase the Tm _x, raise the Tm of the non-linear polyester-modified resin (A), the trivalent or more components This can be achieved by increasing the ratio, increasing the number of crosslinking points, increasing the molecular weight, increasing the Tg, or increasing the ratio of the non-linear polyester-modified resin (A).

Softening point Tm x by a flow tester of the THF-insoluble fraction of the toner binder of the present invention _(unit ° C.) and a softening point Tm y _(Units ° C.) by a flow tester of the THF-soluble fraction is anti-hot offset property during toner preparation, From the viewpoint of low-temperature fixability, it is preferable to satisfy the following formula (7).

Tm _x -Tm _y ≧ 55 (7)
More preferably the left-hand side of _Tm x -Tm _y is not less than 70, still more preferably 80 or more, and particularly preferably 90 or more, and most preferably 100 or more.
If tm _x -Tm _y is 55 or more, not the viscosity becomes too low in the practical range even in the high temperature region, and even more in the low temperature region considered likely to lower viscosity, the hot offset resistance good when used as a toner Thus, the low-temperature fixability is also improved.

To adjust the softening point Tm _x by a flow tester of the THF-insoluble fraction in the toner binder, for _example, to increase the Tm x -Tm _y (if increasing the Tm _x), non-linear polyester modified resin (A) This can be achieved by increasing the Tm, increasing the ratio of the trivalent or higher component, increasing the number of crosslinking points, increasing the molecular weight, increasing the Tg, or increasing the ratio of the non-linear polyester-modified resin (A).
To adjust the softening point Tm _y by a flow tester of the THF-soluble matter in the toner binder, for _example, to increase the Tm x -Tm _y (case of decreasing the the Tm _y), the Tm of the polyester resin (B) It can be achieved by lowering the molecular weight, lowering the molecular weight, or lowering the Tg.

In the present invention, the softening point Tm _x (unit: ° C.) by the flow tester of the THF-insoluble matter in the toner binder and the softening point Tm _y (unit: ° C.) by the flow tester of the THF-soluble matter are measured by the following methods.
<Softening point [Tm]>
Using a descending flow tester {for example, CFT-500D, manufactured by Shimadzu Corporation), a load of 1.96 MPa was applied by a plunger while heating a measurement sample of 1 g 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 amount (flow value)” and “temperature”, and graph the temperature corresponding to 1/2 of the maximum plunger descent amount This value (temperature when half of the measurement sample flows out) is taken as the softening point [Tm].

  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 15,000 to 120,000, more preferably from 20,000 to 100,000, from the viewpoint of achieving both hot offset resistance and low-temperature fixability of the toner. Especially preferably, it is 22,000-90,000, Most preferably, it is 25,000-80,000.

  The molecular weight distribution Mw / Mn of the THF-soluble component of the toner binder of the present invention is preferably 5 to 30, more preferably 6 to 28, from the viewpoint of the compatibility of the toner with hot offset resistance, heat resistant storage stability and low temperature fixability. Especially preferably, it is 7-26.

  The weight ratio (A1) / (B) of the polyester resin (A1) to the polyester resin (B) is 5/95 to 50/50 in terms of compatibility between low-temperature fixability, hot offset resistance, and heat storage stability. It is preferably 7/93 to 45/60, more preferably 10/90 to 40/60.

  The weight ratio of the THF-insoluble component and the THF-soluble component in the toner binder of the present invention is preferably 5/95 to 50/50 from the viewpoint of compatibility with hot offset resistance, low-temperature fixability, and glossiness. The ratio is preferably 7/93 to 45/60, and particularly preferably 9/91 to 40/60.

The weight ratio of the THF-insoluble matter and the THF-soluble matter in the toner binder of the present invention is determined by the following method.
Add 50 ml of THF to 0.5 g of the sample and stir to reflux for 3 hours. After cooling, the insoluble content 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 dried resin on the glass filter is taken as the weight of the THF-insoluble matter, and the weight obtained by subtracting the weight of the THF-insoluble matter from the weight of the sample is taken as the weight of the THF-soluble matter. Calculate the weight ratio.

The polyester resin (B) that is preferably used in combination with the nonlinear polyester-modified resin (A) is a polyester resin that does not have the unsaturated carboxylic acid component (z) as a constituent raw material.
The polyester resin (B) may be linear or non-linear, but is preferably linear from the viewpoint of low-temperature fixability and heat-resistant storage stability.
Specifically, it is a polyester resin obtained by condensing an alcohol component (y) and a saturated carboxylic acid (x) in combination.
Further, the 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 is a tricarboxylic anhydride (which may be trivalent or higher). It may be modified with merit acid, phthalic anhydride, maleic anhydride or the like.

  For example, in the case of mixing two types of resins, a polyester resin (A1) and a polyester resin (B), the polyester resin (A1) is reacted with the radical reaction initiator (c) in the polyester resin (B). It is a preferred method.

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

  The Mw content of the THF soluble portion of the polyester resin (B) is preferably 2,000 to 30,000, more preferably 2,500, from the viewpoint of compatibility of the toner with hot offset resistance, heat resistant storage stability and low temperature fixability. 20,000, particularly preferably 3,000 to 10,000.

  The toner binder of the present invention must have at least one inflection point indicating a glass transition temperature (Tg) on a chart by differential scanning calorimetry (DSC) in a temperature range of −20 ° C. to 80 ° C. You may have two or more inflection points which show a glass transition point, and one of them should just be this temperature range.

A method for producing the toner binder will be described.
The toner binder is not particularly limited as long as it contains a polyester resin (A1). For example, when two kinds of polyester resins and additives are mixed, the mixing method may be a well-known conventional method, such as powder mixing and melting. Either mixing or 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 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 the melt mixing, a mixture of the polyester resin (A1) and the polyester resin (B) is injected into the twin-screw extruder at a constant speed, and at the same time, the radical reaction initiator (c) is also fixed at a constant speed. There are methods such as injecting and reacting while kneading and conveying at a temperature of 100 to 200 ° C.
At this time, the polyester resin (A1) and the polyester resin (B), which are reaction raw materials charged or injected into the twin screw extruder, may be 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 of the present invention contains the toner binder of the present invention and a colorant.

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, Orazole Brown B, Oil Pink OP, etc. Or 2 or more types can be mixed and used. 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.

  In addition to the toner binder and the colorant, the toner of the present invention contains one or more additives selected from a mold release agent, a charge control agent, a fluidizing agent, and the like as necessary.

  As the mold release agent, those having a softening point [Tm] of 50 to 170 ° C. by a flow tester are preferable, polyolefin wax, natural wax, aliphatic alcohol having 30 to 50 carbon atoms, fatty acid having 30 to 50 carbon atoms, and these A mixture etc. are mentioned.

  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 with 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 [such as (meth) acrylic acid, itaconic acid and maleic anhydride] and / or unsaturated carboxylic acid alkyl esters [(meta ) Alkyl acrylate (alkyl 1 to 1 carbon atoms) 8) esters and maleic acid alkyl (C1-18 alkyl) copolymers of an ester, etc.] or the like, and Sasol wax.

  Examples of natural waxes include carnauba wax, montan wax, paraffin wax, and rice wax. Examples of the aliphatic alcohol having 30 to 50 carbon atoms include triacontanol. Examples of the fatty acid having 30 to 50 carbon atoms include 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.

  Examples of the fluidizing agent include colloidal silica, alumina powder, titanium oxide powder, and calcium carbonate powder.

The release agent is 0 to 30% by weight, preferably 0.5 to 20% by weight, particularly preferably 1 to 10% by weight, based on the toner weight.
The charge control agent is 0 to 20% by weight, preferably 0.1 to 10% by weight, particularly preferably 0.5 to 7.5% by weight, based on the toner weight.
The fluidizing agent is 0 to 10% by weight, preferably 0 to 5% by weight, particularly preferably 0.1 to 4% by weight, based on the toner weight.
The total amount of additives is 3 to 70% by weight, preferably 4 to 58% by weight, particularly preferably 5 to 50% by weight, based on the toner weight. When the composition ratio of the toner is in the above range, a toner having good chargeability can be easily 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 volume average particle diameter (D50) is preferably 5 to 20 μm and then mixed with a fluidizing agent.
The particle size (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. 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 usually 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.

  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, “%” represents “% by weight” and “parts” represents “parts by weight”.

<Production Example 1> [Production of polyester resin (A1-1)]
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 556 parts (63.1 mol%) of bisphenol A · PO 2 mol adduct, 18 parts (5.4 mol%) of trimethylolpropane, 3-methyl -1,4-pentanediol 94 parts (31.5 mol%), terephthalic acid 265 parts (64.2 mol%), adipic acid 60 parts (16.5 mol%), fumaric acid 56 parts (19.3 mol) %), 0.6 parts of titanium diisopropoxybistriethanolamate as a condensation catalyst, 5 parts of tert-butylcatechol as a polymerization inhibitor, and 4 hours while distilling off the water produced at 180 ° C. in a nitrogen stream Reacted. Furthermore, it was made to react under reduced pressure of 0.5-2.5 kPa for 10 hours. Subsequently, 34 parts of trimellitic anhydride was added, taken out after reaction for 1 hour under normal pressure and sealed to obtain a polyester resin (A1-1).
The peak top molecular weight of the polyester resin (A1-1) was 8,000, and the Tg was 20 ° C.

<Production Example 2> [Production of polyester resin (A1-2)]
Into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, the alcohol component and the carboxylic acid component described in Table 1 were charged, and the reaction was performed in the same manner as in Production Example 1 except that the polyester resin (A1-2 )
Table 1 shows the peak top molecular weight and Tg.

<Production Example 3> [Production of polyester resin (A1-3)]
Into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, the alcohol component and the carboxylic acid component described in Table 1 were charged, and the reaction was conducted in the same manner as in Production Example 1 except that the polyester resin (A1-3 )
Table 1 shows the peak top molecular weight and Tg.

<Production Example 4> [Production of polyester resin (A1-4)]
Into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, the alcohol component and the carboxylic acid component described in Table 1 were charged, and the reaction was conducted in the same manner as in Production Example 1 except that the polyester resin (A1-4 )
Table 1 shows the peak top molecular weight and Tg.

<Production Example 5> [Production of polyester resin (A1-5)]
Into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, the alcohol component and the carboxylic acid component described in Table 1 were charged, and the reaction was conducted in the same manner as in Production Example 1 except that the polyester resin (A1-5 )
Table 1 shows the peak top molecular weight and Tg.

<Production Example 6> [Production of polyester resin (A1-6)]
A reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube was charged with the alcohol component and carboxylic acid component described in Table 1, and the other reactions were carried out in the same manner as in Production Example 1 to obtain a polyester resin (A1-6 )
Table 1 shows the peak top molecular weight and Tg.

<Comparative Production Example 1> [Production of polyester resin (A1′-1)]
Into a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, the alcohol component and carboxylic acid component described in Table 1 were charged, and the reaction was conducted in the same manner as in Production Example 1 except that the polyester resin (A1′- 1) was obtained.

<Comparative Production Example 2> [Production of polyester resin (A1′-2)]
Into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, the alcohol component and carboxylic acid component described in Table 1 were charged, and the reaction was conducted in the same manner as in Production Example 1 except that the polyester resin (A1′-2 )

<Comparative Production Example 3> [Production of polyester resin (A1′-3)]
Into a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, the alcohol component and carboxylic acid component described in Table 1 were charged, and the reaction was conducted in the same manner as in Production Example 1 except that the polyester resin (A1′- 3) was obtained.
<Comparative Production Example 4> [Production of polyester resin (A1′-4)]
Into a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, the alcohol component and carboxylic acid component described in Table 1 were charged, and the reaction was conducted in the same manner as in Production Example 1 except that the polyester resin (A1′- 4) was obtained.

<Production Example 7> [Production of polyester resin (B-1)]
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 678 parts (100 mol%) of bisphenol A · PO2 mol adduct, 280 parts (72.8 mol%) of terephthalic acid, 77 parts of benzoic acid (27 0.2 mol%), 0.6 parts of titanium diisopropoxybistriethanolamate as a condensation catalyst, and a reaction was carried out for 4 hours while distilling off the water produced at 220 ° C. under a nitrogen stream. Furthermore, it was made to react under reduced pressure of 0.5-2.5 kPa for 10 hours. Subsequently, it cooled to 180 degreeC, 34 parts of trimellitic anhydride was added, it took out after reaction for 1 hour under normal pressure sealing, and the polyester resin (B-1) was obtained.

<Production Example 8> [Production of polyester resin (B-2)]
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 710 parts (100 mol%) of propylene glycol, 775 parts (100 mol%) of terephthalic acid, and titanium diisopropoxybistriethanolamate as a condensation catalyst were added. The reaction was carried out for 4 hours while distilling off the produced water and excess propylene glycol under a nitrogen stream at 6 parts at 220 ° C. Furthermore, it took out after reacting under reduced pressure of 0.5 to 2.5 kPa for 10 hours to obtain a polyester resin (B-2). The recovered propylene glycol was 325 parts.

<Production Example 9> [Production of polyester resin (B-3)]
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, 362 parts (50 mol%) of bisphenol A · EO 2 mol adduct, 275 terephthalic acid Part (100 mol%), titanium diisopropoxybistriethanolamate 0.6 part as a condensation catalyst, and a reaction was carried out for 4 hours while distilling off the water produced at 220 ° C. under a nitrogen stream. Furthermore, it was made to react under reduced pressure of 0.5-2.5 kPa for 10 hours. Subsequently, it cooled to 180 degreeC, 34 parts trimellitic anhydride was added, it took out after reaction for 1 hour under normal pressure sealing, and polyester resin (B-3) was obtained.

<Example 1> [Production of toner binder (C-1)]
25 parts of the polyester resin (A1-1) and 75 parts of the polyester resin (B-1) were supplied to a twin-screw kneader (Kurimoto Iron Works, S5KRC kneader) at 10 kg / hour, and at the same time, di-t as a radical reaction initiator. -1.0 part of butyl peroxide (c-1) was supplied at 0.10 kg / hour and kneaded and extruded at 170 ° C for 15 minutes to carry out a crosslinking reaction. The obtained product was cooled to obtain a toner binder (C-1).
Moreover, the THF insoluble content of the nonlinear polyester-modified resin (A-1) was 52% by weight.

<Example 2> [Production of toner binder (C-2)]
A polyester resin (A1-2), a polyester resin (B-2) and perbutyl D (c-1) shown in Table 2 were charged, and a crosslinking reaction was performed in the same manner as in Example 1 to obtain a toner binder (C-2). Got.
Moreover, the THF insoluble content of the nonlinear polyester-modified resin (A-2) was 85% by weight.

<Example 3> [Production of toner binder (C-3)]
A polyester resin (A1-3), a polyester resin (B-3) and perbutyl I (c-3) shown in Table 2 were charged, and a crosslinking reaction was performed in the same manner as in Example 1 to obtain a toner binder (C-3). Got.
Moreover, the THF insoluble content of the nonlinear polyester-modified resin (A-3) was 60% by weight.

<Example 4> [Production of toner binder (C-4)]
A polyester resin (A1-4), a polyester resin (B-1) and perbutyl I (c-3) shown in Table 2 were charged, and a crosslinking reaction was performed in the same manner as in Example 1 to obtain a toner binder (C-4). Got.
Moreover, the THF insoluble content of the nonlinear polyester-modified resin (A-4) was 69% by weight.

<Example 5> [Production of toner binder (C-5)]
A polyester resin (A1-5), a polyester resin (B-2), and perbutyl D (c-1) shown in Table 2 were charged, and a crosslinking reaction was performed in the same manner as in Example 1 to obtain a toner binder (C-5). Got.
Moreover, the THF insoluble content of the nonlinear polyester-modified resin (A-5) was 58% by weight.

<Example 6> [Production of toner binder (C-6)]
A polyester resin (A1-6), a polyester resin (B-3), and perbutyl I (c-3) shown in Table 2 were charged, and a crosslinking reaction was performed in the same manner as in Example 1 to obtain a toner binder (C-6). Got.
Moreover, the THF insoluble content of the nonlinear polyester-modified resin (A-6) was 55% by weight.

Comparative Example 1 [Production of Toner Binder (C′-1)]
A polyester resin (A1′-1), a polyester resin (B-1) and di-t-butyl peroxide (c-1) shown in Table 2 were charged and kneaded and extruded in the same manner as in Example 1 to obtain a toner binder. (C′-1) was obtained.
Since the polyester resin (A1′-1) did not undergo a crosslinking reaction, the nonlinear polyester-modified resin (A) was not obtained.

Comparative Example 2 [Production of Toner Binder (C′-2)]
A polyester resin (A1′-2), a polyester resin (B-1) and a di-t-butyl peroxide (c-1) shown in Table 2 were charged, and a crosslinking reaction was performed in the same manner as in Example 1 to obtain a toner. A binder (C′-2) was obtained.
Moreover, the THF insoluble content of the non-linear polyester-modified resin (A′-2) was 2% by weight.

<Comparative Example 3> [Production of Toner Binder (C′-3)]
A polyester resin (A1-1) and a polyester resin (B-1) shown in Table 2 were charged and kneaded and extruded in the same manner as in Example 1 to obtain a toner binder (C′-3).
Since the polyester resin (A1-1) did not undergo a crosslinking reaction, the nonlinear polyester-modified resin (A) was not obtained.

  Comparative Example 4 [Production of Toner Binder (C′-4)]

20 parts of polyester resin (A1′-3) shown in Table 2 was dissolved at 140 ° C. by heating, and 22 parts of styrene, 6 parts of butyl acrylate, 2 parts of monobutyl maleate and 0.1 part of benzoyl peroxide as radical reaction polymerization. Was added dropwise from the dropping funnel over 8 hours. The toner was aged at 140 ° C. for 4 hours to obtain a toner binder (C′-4) containing a non-linear polyester-modified resin (A′-3). The THF-insoluble matter in the nonlinear polyester-modified resin (A′-3) was 10% by weight.
Comparative Example 5 [Production of Toner Binder (C′-5)]
A polyester resin (A1′-4), a polyester resin (B-2), and di-t-butyl peroxide (c-1) shown in Table 2 were charged and subjected to a crosslinking reaction in the same manner as in Example 1 to obtain a toner. A binder (C′-5) was obtained.
Moreover, the THF insoluble content of the nonlinear polyester-modified resin (A′-4) was 65% by weight.

<Example 7> [Production of toner (T-1)]
To 85 parts of toner binder (C-1), 8 parts of carbon black MA-100 (manufactured by Mitsubishi Chemical Corporation), 3 parts of release agent carnauba wax, charge control agent T-77 [Hodogaya Chemical (Manufactured)] 2 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.
Subsequently, 100 parts of toner particles were mixed with 1 part of colloidal silica (Aerosil R972: manufactured by Nippon Aerosil Co., Ltd.) as a fluidizing agent in a sample mill to obtain toner (T-1) of the present invention.

<Example 8> [Production of toner (T-2)]
A toner was produced in the same manner as in Example 7 with the blending of the raw materials shown in Table 3, and a toner (T-2) of the present invention was obtained.

<Example 9> [Production of toner (T-3)]
A toner was produced in the same manner as in Example 7 with the blending of the raw materials shown in Table 3, and a toner (T-3) of the present invention was obtained.

<Example 10> [Production of toner (T-4)]
A toner was produced in the same manner as in Example 7 with the blending of the raw materials shown in Table 3, and a toner (T-4) of the present invention was obtained.

<Example 11> [Production of toner (T-5)]
A toner was produced in the same manner as in Example 7 with the blending of raw materials shown in Table 3, and a toner (T-5) of the present invention was obtained.

<Example 12> [Production of toner (T-6)]
A toner was produced in the same manner as in Example 7 with the blending of raw materials shown in Table 3, and a toner (T-6) of the present invention was obtained.

<Comparative Examples 6 to 10> [Production of Toners (T′-1) to (T′-5)]
Toners (T′-1) to (T′-5) were obtained in the same manner as in Example 7 with the blending of raw materials shown in Table 3.

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

<Low temperature fixability>
The toner is uniformly placed on the paper so as to be 0.85 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 is removed is used. Other methods may be used as long as the powder can be uniformly loaded with the above-described weight density.
A cold offset generation temperature (MFT) was measured when this paper was 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 .
The lower the temperature at which cold offset occurs, the better the low-temperature fixability.
Under this evaluation condition, generally 120 ° C. or lower is required.

<Glossiness>
Fixation evaluation is performed in the same manner as low-temperature fixability. White cardboard was laid under the image, and the glossiness (%) of the printed image was measured at an incident angle of 60 degrees using a gloss meter (“IG-330” manufactured by Horiba, Ltd.). Higher gloss means better gloss. Under this evaluation condition, the preferable range is usually 10 or more, and 5 or less is not preferable.

<Hot offset resistance (hot offset temperature)>
Fixation was evaluated in the same manner as the low-temperature fixability, and the presence or absence of hot offset on the fixed image was visually evaluated. The temperature at which hot offset occurred after passing through the pressure roller was defined as hot offset resistance (° C.). Under these evaluation conditions, the preferred range is usually 180 ° C. or higher, and the preferred range is 160 ° C. or lower.

<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.

[Criteria]
○: 33 or more Δ: 25 or more and less than 33 ×: less than 25

<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.
Δ: Blocking occurs in part.
X: Blocking has occurred throughout.

<Charging stability>
(1) 0.5 g of toner and 20 g of a ferrite carrier (F-150, manufactured by Powdertech) are placed in a 50 ml glass bottle, and the humidity is adjusted at 23 ° C. and a relative humidity of 50% for 8 hours or more.
(2) Friction stirring was performed at 50 rpm × 20 minutes and 60 minutes with a tumbler shaker mixer, and the charge amount at each time was measured.
For the measurement, a blow-off charge 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]
○: 0.7 or more △: 0.6 or more and less than 0.7 ×: less than 0.6

<Crushability>
A coarsely pulverized product (8.6 mesh pass to 30 mesh on) kneaded and cooled by a twin-screw kneader is finely pulverized under the following conditions by a supersonic jet pulverizer, Labo Jet (manufactured by Nippon Pneumatic Industry Co., Ltd.). Crushed.
Crushing pressure: 0.5 MPa
Grinding time: 10 minutes Adjuster ring: 15 mm
Size of louver: Medium Without classification, volume average particle size (μm) was measured by Coulter Counter-TAII (manufactured by Coulter Electronics, USA), and grindability was evaluated according to the following criteria.

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

<Image intensity>
The image fixed in the evaluation of the low temperature fixability was subjected to a scratch test by applying a load of 10 g from right above the pencil fixed at an angle of 45 degrees according to JIS K5600, and the image strength was evaluated from the pencil hardness without scratches. . Higher pencil hardness means better image strength. Generally, H or higher is required.

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

As is clear from the evaluation results in Table 3, all the toners of Examples 7 to 12 of the present invention were excellent in performance evaluation.
On the other hand, the toner of Comparative Example 6, which does not contain an unsaturated carboxylic acid component (z), Comparative Examples 7, 8, and 9 in which the THF-insoluble content is out of the range, and Comparative Example 10 in which the peak top molecular weight is out of the range, The performance item was bad.

The toner binder and toner of the present invention are excellent in toner fluidity, heat storage stability, charging stability, pulverization property and image strength, while achieving both low-temperature fixability and glossiness and hot offset resistance. It can be suitably used as an electrostatic image developing toner and toner binder used for electrorecording, electrostatic printing and the like.
Furthermore, it is suitable for applications such as paint additives, adhesive additives, and electronic paper particles.

Claims (10)

Nonlinear polyester modification in which a polyester resin (A1) comprising an alcohol component (y) and an unsaturated carboxylic acid component (z) as a constituent raw material is crosslinked with carbon-carbon double bonds derived from (z) in (A1). A toner binder containing a resin (A), the polyester resin (A1) has a peak top molecular weight of 2,000 to 12,000, and the non-linear polyester-modified resin (A) has a tetrahydrofuran (THF) insoluble content of 50. And a toner binder having at least one inflection point indicating a glass transition temperature Tg _T on a chart by differential scanning calorimetry (DSC) in a temperature range of −20 ° C. to 80 ° C. binder.   Even if the unsaturated carboxylic acid component (z) in the polyester resin (A1) is not chemically bonded or chemically bonded to the vinyl monomer (a) excluding the unsaturated carboxylic acid component (z), The toner binder according to claim 1, wherein the binding amount is 4% by weight or less based on the weight of the toner binder.   Furthermore, a toner binder containing a polyester resin (B) that does not contain an unsaturated carboxylic acid component (z) as a constituent raw material.   The toner binder according to claim 3, wherein the weight ratio (A1) / (B) of the polyester resin (A1) to the polyester resin (B) is 5/95 to 50/50. The toner binder according to claim 1, wherein the toner satisfies the following relational expressions (1) to (3).
G ′ _x150 ≧ 10,000 (1)
G ′ _x150 / G ′ _x180 ≦ 10 (2)
G ′ _x150 / G ′ _y150 ≧ 500 (3)
[In the relational expression, G ′ _x150 is the storage elastic modulus (unit Pa) of the _{insoluble matter} in tetrahydrofuran (THF) in the toner binder at 150 ° C., and G ′ _x180 is the insoluble content in THF at 180 ° C. The storage elastic modulus (unit Pa) and G ′ _y150 represents the storage elastic modulus (unit Pa) at 150 ° C. of the dissolved part in THF in the toner binder. ] The toner binder according to claim 1, which satisfies the following relational expression (4) and relational expression (5).
G ″ _x150 / G ′ _x150 ≧ 0.1 (4)
G ″ _y120 / G ′ _y120 ≦ 15 (5)
[In the relational expression, G ″ _x150 represents the loss elastic modulus (unit Pa) at 150 ° C. of the insoluble _matter in tetrahydrofuran (THF) in the toner binder, and G ″ _y120 represents THF in the toner binder. _{Represents a} loss elastic modulus (unit Pa) at 120 ° C. of a dissolved portion of the toner, G ′ _x150 represents a storage elastic modulus (unit Pa) at 150 ° C. of an insoluble portion of THF in the toner binder, and G ′ _y120 represents The storage elastic modulus (unit Pa) at 120 ° C. of the dissolved amount of THF in the toner binder is represented. ] The toner binder according to claim 1, wherein the toner satisfies the following relational expression (6) and relational expression (7).
140 ≦ Tm _x ≦ 250 (6)
Tm _x -Tm _y ≧ 55 (7)
[However, in relation, Tm _x is the toner binder in tetrahydrofuran (THF) and softening point (℃) by a flow tester of the insoluble component, Tm _y a softening point measured by a flow tester of the THF-soluble component of the toner binder (℃) Represents. ] The toner binder according to claim 1, wherein the polyester resin (A1) has a glass transition temperature Tg _A1 of −35 to 45 ° C.   The toner binder according to any one of claims 1 to 8, wherein a weight ratio of tetrahydrofuran (THF) insoluble matter and THF soluble matter in the toner binder is 5/95 to 50/50.   A toner in which the toner binder according to claim 1 contains a colorant.