JP2011242565A - Toner binder and toner composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner binder excellent in fixability and blocking resistance of toner.SOLUTION: The toner binder for electrophotography contains: a linear polyester resin (A) and a nonlinear polyester resin (B) which are mutually incompatible and are produced by poly-condensation of carboxylic acid component (x) and a polyol component (y); and a compatibilizer (C) which is a polyester resin produced by polycondensation of a carboxylic acid component (x') and a polyol component (y'), which is a single 2-20C aliphatic polyol or a single 2-20C alicyclic polyol, and has an SP value "(cal/cm)" between those of (A) and (B).

Description

  The present invention relates to a toner binder and a toner composition used for electrophotography, electrostatic recording, electrostatic printing and the like.

The toner binder for electrophotography, which is commonly used as an image fixing method in copying machines, printers, etc., does not fuse the toner to the heat roll even at a high fixing temperature (hot offset resistance), fixing. Toner can be fixed even at low temperatures (low temperature fixability), hard to absorb moisture under severe conditions of high temperature and high humidity, excellent charging stability, storage stability as fine particles (blocking resistance), etc. Is required.
In recent years, there is an increasing demand for color, high speed, high reliability, compactness, low cost, and energy savings in copiers and printers. In particular, in order to reduce the environmental load (energy saving), it is urgently necessary to cope with both low-temperature fixing property and blocking resistance of the toner.
For the purpose of improving the fixing performance of these toners, it has been conventionally known that incompatible resins specialized in low temperature range and high temperature range are used as a matrix phase and a domain phase. In addition, many methods for adding a compatibilizer for compatibilizing the incompatible resin have been proposed for vinyl resins such as styrene polymers (Patent Document 1).

JP-A-8-328303

However, conventional toners composed of a matrix phase and a domain phase do not sufficiently satisfy all of low-temperature fixability, hot offset resistance, and blocking resistance, and when using a recent high-speed machine or a small-sized electronic copying machine. In particular, a wide fixing temperature range is required.
An object of the present invention is to use a polyester resin that exhibits excellent fixing performance in a low temperature region and a high temperature region that are incompatible with each other in the sea-island structure {sea phase (matrix phase) and island phase (domain phase)}. Thus, an object of the present invention is to provide a toner composition having an increased fixing temperature range and excellent blocking resistance.

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 linear polyester resin (A) and a non-linear polyester resin (B) which are incompatible with each other, and a carboxylic acid component obtained by polycondensation of a carboxylic acid component (x) and a polyol component (y). A polyester resin obtained by polycondensation of (x ′) and a polyol component (y ′) which is a single aliphatic polyol or alicyclic polyol having 2 to 20 carbon atoms, and having an SP value of [(cal / cm ³ ) ^1/2 ] is an electrophotographic toner binder containing a compatibilizer (C) positioned between (A) and (B); and the toner binder and colorant, and if necessary, a release agent, a charge A toner composition containing one or more additives selected from a control agent, magnetic powder, and a fluidizing agent.

  By using the toner binder and the toner composition of the present invention, it becomes possible to obtain a toner having excellent fixing properties, and it is possible to provide a toner binder having excellent toner blocking resistance.

The present invention is described in detail below.
The linear polyester resin (A) in the present invention is obtained by polycondensation of a carboxylic acid component (x) and a polyol component (y). The carboxylic acid component (x) is preferably composed of a polycarboxylic acid (x2) and / or a monocarboxylic acid (x1) if necessary.

Among monocarboxylic acids (x1), as aliphatic (including alicyclic) monocarboxylic acids, alkane monocarboxylic acids having 1 to 30 carbon atoms (formic acid, acetic acid, propionic acid, butanoic acid, isobutanoic acid, caprylic acid) , Capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, serotic acid, monitoring acid, melicic acid, etc.), alkene monocarboxylic acid having 3 to 24 carbon atoms (acrylic acid, methacrylic acid, oleic acid, Linoleic acid and the like). Among the aromatic monocarboxylic acids in (x1), aromatic monocarboxylic acids having 7 to 36 carbon atoms (such as benzoic acid, methylbenzoic acid, Pt-butylbenzoic acid, phenylpropionic acid, and naphthoic acid) Is mentioned.
Among these (x1), an aromatic monocarboxylic acid having 7 to 36 carbon atoms is preferable, and benzoic acid, methylbenzoic acid, and Pt-butylbenzoic acid are more preferable.

  The monocarboxylic acid (x1) is preferably from 0 to 30 mol%, more preferably from 1 to 25 mol%, particularly preferably from 2 to 20 mol, based on the entire carboxylic acid component (x), from the viewpoint of storage stability. %.

  Examples of the polycarboxylic acid (x2) include dicarboxylic acid (x21) and trivalent to hexavalent or higher polycarboxylic acid (x22).

  Examples of the dicarboxylic acid (x21) include alkane dicarboxylic acids having 4 to 36 carbon atoms (for example, succinic acid, adipine, and sebacic acid); alicyclic dicarboxylic acids having 6 to 40 carbon atoms [for example, dimer acid (dimerized linoleic acid)] An alkene dicarboxylic acid having 4 to 36 carbon atoms (for example, alkenyl succinic acid such as dodecenyl succinic acid, malee, fumar, citracone, and mesaconic acid); an aromatic dicarboxylic acid having 8 to 36 carbon atoms (phthal, isophthal, terephthal, and Naphthalenedicarboxylic acid, etc.); and ester-forming derivatives thereof [lower alkyl (alkyl group having 1 to 4 carbon atoms: methyl, ethyl, n-propyl, etc.) ester, and acid anhydrides]; You may use the above together. Among these, preferred are alkene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms, and ester-forming derivatives thereof, and more preferred are terephthalic acid, isophthalic acid, and / or Alternatively, lower alkyl (alkyl group having 1 to 4 carbon atoms) ester (x211).

Examples of the tri- or hexavalent polycarboxylic acid (x22) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid), and aliphatic polycarboxylic acids having 6 to 36 carbon atoms. (Hexane tricarboxylic acid, etc.) and ester-forming derivatives thereof may be mentioned, and two or more of them may be used in combination.
Among these, trimellitic acid and pyromellitic acid, and ester-forming derivatives thereof are preferable.

The content of terephthalic acid, isophthalic acid and / or their lower alkyl (carbon number of alkyl group: 1 to 4) ester (x211) in the polycarboxylic acid (x2) is preferably from the viewpoint of storage stability. It is 85-100 mol%, More preferably, it is 90-100 mol%.
The molar ratio of terephthalic acid and / or its lower alkyl ester to (x211) and isophthalic acid and / or its lower alkyl ester is preferably 20:80 to 100: 0 from the viewpoint of the mechanical strength of the resin. More preferably, it is 25: 75-80: 20.

Examples of the polyol component (y) constituting the linear polyester resin (A) include a diol (y1) and a tri- to octavalent or higher polyol (y2).
Examples of the diol (y1) include alkylene glycols having 2 to 36 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); C4-C36 alkylene ether glycol (diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); C6-C36 alicyclic diol ( 1,4-cyclohexanedimethanol and hydrogenated bisphenol A, etc.); (poly) oxyalkylene of the above alicyclic diol (alkylene having 2 to 4 carbon atoms, the same applies to the following polyoxyalkylene groups) ether [ Number 1 to 30 of xoxyalkylene units (hereinafter abbreviated as AO units); and polyoxy of dihydric phenol [monocyclic dihydric phenol (for example, hydroquinone) and bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.)] Examples include alkylene ethers (number of AO units 2 to 30), and two or more of them may be used in combination.

  Of these, preferred are polyoxyalkylene ethers of dihydric phenols and bisphenols.

  Examples of the polyol (y2) having 3 to 8 or more valences include 3 to 8 or more aliphatic polyhydric alcohols having 3 to 36 carbon atoms (an alkane polyol and an intramolecular or intermolecular dehydrate thereof such as glycerin, Trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, polyglycerin, and dipentaerythritol; sugars and derivatives thereof such as sucrose and methylglucoside); (poly) oxyalkylene ethers of the above aliphatic polyhydric alcohols ( Number of AO units 1-30); polyoxyalkylene ether of trisphenols (trisphenol PA, etc.) (number of AO units 2-30); novolac resin (phenol novolac, cresol novolac, etc., average degree of polymerization 3-60) Of the Etc. (the number 2 to 30 of AO units) oxyalkylene ether and the like, may be used in combination of two or more thereof.

  Of these, preferred are polyoxyalkylene ethers of novolak resins.

Polyol component (y) [In this section, it means a polyol component that is a constituent unit of the linear polyester resin (A) excluding those removed outside the system during the polycondensation reaction. ] The proportion of aromatic polyol (dihydric phenol, bisphenols and polyoxyalkylene ether of novolak resin) is preferably 85 to 100 mol%, more preferably 90 to 100 mol%, from the viewpoint of mechanical strength. is there.
In particular, the content of the polyoxyalkylene ether of bisphenols (number of AO units 2 to 30) in (y) is preferably 90 to 100 mol%, more preferably 95 to 100 mol, from the viewpoint of mechanical strength. %, Particularly preferably 100 mol%.

  Further, in the total of the carboxylic acid component (x) and the polyol component (y), the total of 3 to 8 or more polyol (y2) and 3 to 6 or more polycarboxylic acid (x22) The ratio is preferably 0.1 to 15 mol%, more preferably 0.2 to 12 mol%. When the amount is 0.1 mol% or more, the storage stability of the toner is good, and when the amount is 15 mol% or less, the charging characteristics of the toner are good.

As a method for producing a polyester resin (A) by polycondensation of a carboxylic acid component (x) composed of a polycarboxylic acid (x2) and / or a monocarboxylic acid (x1) if necessary, and a polyol component (y) Although not particularly limited, for example, a mixture of (x1) and (x2) and (y) can be polycondensed together, but at least a part of (x2) and (y) After polycondensation at an equivalent ratio such that the hydroxyl group of (y) is excessive, the hydroxyl group of the obtained polycondensate (A0) and the carboxyl group of (x1) may be reacted to further polycondense. . If necessary, after the polycondensation of (A0) and (x1), a polycarboxylic acid (x22) having 3 to 6 or more valences is added and reacted as a monofunctional or bifunctional group, and the remaining functional groups May be further polycondensed under the condition of leaving it unreacted.
The reaction ratio between the polyol component (y) and the polycarboxylic acid component (x) is preferably 2/1 to 1/2, more preferably 1. as the equivalent ratio [OH] / [COOH] of the hydroxyl group to the carboxyl group. 5/1 to 1 / 1.3, particularly preferably 1.3 / 1 to 1 / 1.2.

In the present invention, the polycondensation of the carboxylic acid component (x) and the polyol component (y) can be performed using a known esterification reaction. As a general method, for example, in the presence of a polymerization catalyst in an inert gas (nitrogen gas or the like) atmosphere, the reaction temperature is preferably 150 to 280 ° C, more preferably 180 to 270 ° C, and particularly preferably 200 to 260. It can carry out by making it react at ° C. The reaction time is preferably 30 minutes or longer, particularly 2 to 40 hours from the viewpoint of reliably performing the polycondensation reaction.
It is also effective to reduce the pressure in order to improve the reaction rate at the end of the reaction.

As the polymerization catalyst for obtaining the polyester resin (A), it is preferable to use a polymerization catalyst containing one or more metals selected from titanium, antimony, zirconium, nickel, and aluminum from the viewpoint of reactivity and environmental protection. More preferably, a titanium-containing catalyst is used.
Examples of the titanium-containing catalyst include titanium alkoxide, potassium oxalate titanate, titanium terephthalate, and catalysts described in JP-A-2006-243715 [titanium dihydroxybis (triethanolamate), titanium monohydroxytris (triethanolaminate). And their intramolecular polycondensates], and catalysts described in JP-A 2007-11307 (titanium tributoxy terephthalate, titanium triisopropoxy terephthalate, titanium diisopropoxy diterephthalate, etc.) and the like. .
Antimony trioxide etc. are mentioned as an antimony containing catalyst.
Zirconyl acetate etc. are mentioned as a zirconium containing catalyst.
Nickel acetylacetonate etc. are mentioned as a nickel containing catalyst.
Examples of the aluminum-containing catalyst include aluminum hydroxide and aluminum triisopropoxide.

The amount of the catalyst added is desirably determined as appropriate so as to maximize the reaction rate. The addition amount is preferably 10 ppm to 1.9%, more preferably 100 ppm to 1.7%, based on the total raw materials. The amount added is preferably 10 ppm or more, so that the reaction rate is increased.
In the above and the following, “%” means “% by weight” unless otherwise specified.

The SP value (solubility parameter) of the linear polyester resin (A) is preferably 10.0 to 11.5, more preferably 10.5 to 11.0.
When the SP value is 10.0 or more, the fixability (low temperature side) becomes good, and when it is 11.5 or less, it becomes difficult to be affected by the environmental conditions, Tg increases, and the blocking resistance becomes good.
The SP value in the present invention is calculated by the method described in the following document proposed by Fedors et al.
"POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1974, Vol. 14, No. 2, ROBERT F. FEDORS. (Pp. 147-154)"

  The acid value (mgKOH / g, hereinafter the same) of the linear polyester resin (A) is preferably 2 to 100, more preferably 5 to 80, and particularly preferably 15 to 60. When the acid value is 2 or more, the low-temperature fixability at the time of toner formation is good, and when it is 100 or less, the charging characteristics at the time of toner formation do not deteriorate.

The hydroxyl value (mgKOH / g, the same applies hereinafter) of the linear polyester resin (A) is preferably 0 to 125, more preferably 1 to 100. When the hydroxyl value is 125 or less, the hot offset resistance at the time of toner formation becomes better.
The acid value and hydroxyl value in the present invention are measured by the method defined in JIS K0070.

  As for the molecular weight of the linear polyester resin (A), the peak top molecular weight (hereinafter referred to as Mp) is preferably 1000 to 15000, more preferably 1500 to 13000, and particularly preferably 2000 to 12000. When Mp is 1000 or more, the resin strength necessary for fixing is expressed, and when it is 15000 or less, the low-temperature fixability at the time of toner formation is good.

Above and below, the molecular weight (Mp) of the polyester resin is measured under the following conditions using gel permeation chromatography (GPC).
Device (example): Tosoh HLC-8120
Column (example): TSKgelGMHXL (2)
TSKgelMultiporeHXL-M (1 pc.)
Measurement temperature: 40 ° C
Measurement solution: 0.25% THF solution Injection amount: 100 μl
Detector: Refractive index detector Reference material: TSK standard polystyrene (manufactured by Tosoh)
Molecular weight = 4480000, 2890000, 1090000, 355
000, 190000, 96400, 37900, 1810
The molecular weight showing the maximum peak height on the chromatogram obtained for a total of 12 points of 0, 9100, 2800, 1050 and 500 is referred to as peak top molecular weight (Mp). The molecular weight of the polyester resin for toner was measured by dissolving the polyester resin in a THF solvent and filtering the insoluble matter with a glass filter as a sample solution.

Further, the softening point [Tm] of the linear polyester resin (A) is preferably 70 to 120 ° C, more preferably 75 to 110 ° C, and particularly preferably 80 to 100 ° C. In this range, the balance between hot offset resistance and low-temperature fixability is good.
The softening point is a value measured as follows.
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 And this value (temperature when half of the measurement sample flows out) is taken as the softening point.

The glass transition temperature (Tg) of the linear polyester resin (A) used in the present invention is preferably 45 ° C. or higher from the viewpoint of storage stability. From the viewpoint of low temperature fixability, the low temperature fixability at the time of toner formation is good when the temperature is 75 ° C. or lower.
In addition, in the above and below, Tg is measured by the method (DSC method) prescribed | regulated to ASTM D3418-82 using Seiko Denshi Kogyo Co., Ltd. DSC20, SSC / 580.

  The tetrahydrofuran (THF) insoluble content in the linear polyester resin (A) is preferably 5% or less from the viewpoint of low-temperature fixability during toner formation. More preferably, it is 4% or less, and particularly preferably 3% or less.

The THF-insoluble matter in 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 insoluble matter is calculated from the weight of the dried resin content on the glass filter and the weight ratio of the sample.

  The nonlinear polyester resin (B) in the present invention is obtained by polycondensation of a carboxylic acid component (x) and a polyol component (y). The carboxylic acid component (x) is preferably composed of a monocarboxylic acid (x1) and a polycarboxylic acid (x2).

Examples of the monocarboxylic acid (x1) include those described above.
Among these (x1), an aromatic monocarboxylic acid having 7 to 36 carbon atoms is preferable, and benzoic acid, methylbenzoic acid, and Pt-butylbenzoic acid are more preferable.
The monocarboxylic acid (x1) is preferably from 1 to 30 mol%, more preferably from 1 to 25 mol%, particularly preferably from 2 to 20 mol, based on the entire carboxylic acid component (x) from the viewpoint of storage stability. %.

Examples of the polycarboxylic acid (x2) include those described above.
Among the dicarboxylic acids (x21), preferred are alkene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms and ester-forming derivatives thereof, and more preferred are terephthalic acid and isophthalic acid. And / or their lower alkyl (alkyl group having 1 to 4 carbon atoms) ester (x211).
Preferred among the tri- to hexavalent or higher polycarboxylic acids (x22) are trimellitic acid and pyromellitic acid, and ester-forming derivatives thereof.

The content of terephthalic acid, isophthalic acid and / or their lower alkyl (carbon number of alkyl group: 1 to 4) ester (x211) in the polycarboxylic acid (x2) is preferably from the viewpoint of storage stability. It is 85-100 mol%, More preferably, it is 90-100 mol%.
The molar ratio of terephthalic acid and / or its lower alkyl ester to (x211) and isophthalic acid and / or its lower alkyl ester is preferably 20:80 to 100: 0 from the viewpoint of the mechanical strength of the resin. More preferably, it is 25: 75-80: 20.

Examples of the polyol component (y) constituting the nonlinear polyester resin (B) include a diol (y1) and a tri- to octavalent or higher polyol (y2).
Examples of the diol (y1) include those described above.
Of these, alkylene glycols having 2 to 12 carbon atoms (y11), polyoxyalkylene ethers of bisphenols (number of AO units 2 to 30), and combinations thereof are preferable. More preferred is alkylene glycol having 2 to 12 carbon atoms (particularly ethylene glycol) (y11).

  Examples of the trivalent to octavalent or higher polyol (y2) include those described above. Among these, preferred are 3 to 8 or higher aliphatic polyhydric alcohols and polyoxyalkylene ethers of novolac resins (number of AO units 2 to 30), and more preferred are polyoxyalkylenes of novolac resins. Ether (number of AO units 2 to 30).

Polyol component (y) [In this section, it means a polyol component which is a constituent unit of the non-linear polyester resin (B) excluding those removed outside the system during the polycondensation reaction. The proportion of alkylene glycol having 2 to 12 carbon atoms (y11) is preferably 85 to 100 mol%, more preferably 90 to 100 mol%, from the viewpoint of mechanical strength.
In particular, the content of ethylene glycol in (y) is preferably 90 to 100 mol%, more preferably 95 to 100 mol%, and particularly preferably 100 mol% from the viewpoint of mechanical strength.

  Moreover, the sum total of 3-8 valence or more polyol (y2) and 3-6 valence or more polycarboxylic acid (x22) in the sum total of a carboxylic acid component (x) and a polyol component (y). Is preferably 0.1 to 15 mol%, more preferably 0.2 to 12 mol%. When the amount is 0.1 mol% or more, the storage stability of the toner is good, and when the amount is 15 mol% or less, the charging characteristics of the toner are good.

  As a method for producing a nonlinear polyester resin (B) by polycondensation of a carboxylic acid component (x) composed of a monocarboxylic acid (x1) and a polycarboxylic acid (x2) and a polyol component (y) Although not particularly limited, the mixture of (x1) and (x2) and (y) can be polycondensed together, but at least a part of (x2) and (y) are first converted to (y It is preferable that polycondensation is performed at an equivalent ratio such that the hydroxyl group of () is excessive, and then the hydroxyl group of the obtained polycondensate (B0) is reacted with the carboxyl group of (x1) to further polycondense. If necessary, after the polycondensation of (B0) and (x1), a polycarboxylic acid having 3 to 6 or more valences (x22) may be added and further polycondensed.

The polycondensation of the carboxylic acid component (x) and the polyol component (y) when producing the nonlinear polyester resin (B) can be performed using a known esterification reaction. As a general method, for example, in the presence of a polymerization catalyst in an inert gas (nitrogen gas or the like) atmosphere, the reaction temperature is preferably 150 to 280 ° C, more preferably 180 to 270 ° C, and particularly preferably 200 to 260. It can carry out by making it react at ° C. The reaction time is preferably 30 minutes or longer, particularly 2 to 40 hours from the viewpoint of reliably performing the polycondensation reaction.
It is also effective to reduce the pressure in order to improve the reaction rate at the end of the reaction.
The reaction ratio in the reaction of the polyol component (y) and at least a part of the polycarboxylic acid (x2) in the first stage is preferably 2 / as the equivalent ratio [OH] / [COOH] of the hydroxyl group to the carboxyl group. The ratio is 1-1 / 1, more preferably 1.5 / 1 to 1.01 / 1, and particularly preferably 1.3 / 1 to 1.02 / 1.
The ratio of all polyol components (y) and all carboxylic acid components (x) used in the production of (B) is preferably 2/1 as an equivalent ratio [OH] / [COOH] of hydroxyl groups to carboxyl groups. ½, more preferably 1.5 / 1 to 1 / 1.3, particularly preferably 1.3 / 1 to 1 / 1.2.

The SP value of the polyester resin (B) is usually 11.5 to 13.0, preferably 11.5 to 12.5.
When the SP value is 11.5 or more, the fixability (high temperature side) is good, and when it is 13.0 or less, the blocking resistance is good.

  The glass transition temperature [Tg] of the non-linear polyester resin (B) is preferably 45 ° C to 80 ° C, and more preferably 50 ° C to 70 ° C. When Tg is 80 ° C. or lower, the low-temperature fixability is improved. Moreover, blocking resistance is favorable in Tg being 45 degreeC or more.

  The softening point [Tm] of the non-linear polyester resin (B) is not particularly limited, but is preferably 90 ° C to 170 ° C, and more preferably 120 ° C to 160 ° C. When Tm is 90 ° C. or higher, the hot offset resistance is good, and when Tm is 170 ° C. or lower, the fixability is good.

  The Mp of the tetrahydrofuran (THF) soluble part of the nonlinear polyester resin (B) is preferably 2000 to 12000, and more preferably 3000 to 10,000.

  The THF insoluble content in the nonlinear polyester resin (B) is preferably 3 to 50% from the viewpoint of low temperature fixability. More preferably, it is 5 to 40%, and particularly preferably 10 to 35%. When the THF-insoluble content is 50% or less, the glossiness (gloss) of the image is good.

The sum of the acid value and the hydroxyl value of the nonlinear polyester resin (B) is preferably 3 to 40, more preferably 10 to 40, and particularly preferably 20 to 39. When the sum of the acid value and the hydroxyl value is 3 or more, the storage stability is good, and when it is 40 or less, the charging stability is improved.
The acid value of the non-linear polyester resin (B) is preferably 3 to 40, more preferably 10 to 38, and the hydroxyl value is preferably 0 to 30, more preferably 0 to 10.

  The weight ratio [(A) / (B)] of the linear polyester resin (A) and the non-linear polyester resin (B) is preferably 90/10 in terms of both low-temperature fixability, hot offset resistance and grindability. -20/80, more preferably 80 / 20-20 / 80.

The toner binder of the present invention may contain a resin other than (A) and (B) as long as the effects of the present invention are not impaired. Other resins include polyester resins other than (A) and (B), vinyl resins [copolymers of styrene and alkyl (meth) acrylate, copolymers of styrene and diene monomers, etc.], epoxy resins ( Bisphenol A diglycidyl ether ring-opening polymer), urethane resin (polyaddition product of the polyol component and diisocyanate, etc.) and the like.
Among these, polyester resins other than (A) and (B) are preferable. The Mp of other resins is preferably 300 to 100,000.

  The compatibilizing agent (C) in the present invention is obtained by polycondensing a carboxylic acid component (x ′) and a polyol component (y ′) which is a single aliphatic polyol or alicyclic polyol having 2 to 20 carbon atoms. can get. The carboxylic acid component (x ′) is preferably composed of a monocarboxylic acid (x′1) and / or a polycarboxylic acid (x′2).

Examples of the monocarboxylic acid (x′1) include the same as the above (x1).
Among these (x′1), an aromatic monocarboxylic acid having 7 to 36 carbon atoms is preferable, and benzoic acid, methylbenzoic acid, and Pt-butylbenzoic acid are more preferable.
The monocarboxylic acid (x′1) is preferably 1 to 30 mol%, more preferably 1 to 25 mol%, particularly preferably 2 with respect to the total carboxylic acid component (x ′) from the viewpoint of storage stability. ~ 20 mol%.

Examples of the polycarboxylic acid (x′2) include dicarboxylic acid (x′21) and tri- or hexavalent or higher polycarboxylic acid (x′22). Examples of (x′21) and (x′22) are the same as the above (x21) and (x22).

Examples of the polycarboxylic acid (x′2) include the same as the above (x2),
Of the dicarboxylic acids (x′21), preferred are alkane dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms, and ester-forming derivatives thereof, more preferably terephthalic acid, Isophthalic acid and / or their lower alkyl (alkyl group having 1 to 4 carbon atoms) ester (x′211).

  Preferred among the tri- to hexavalent or higher polycarboxylic acids (x′22) are trimellitic acid and pyromellitic acid, and ester-forming derivatives thereof.

The content of terephthalic acid, isophthalic acid, and / or their lower alkyl (carbon number of alkyl group: 1 to 4) ester (x′211) in the polycarboxylic acid (x′2) is a viewpoint of storage stability. Therefore, it is preferably 60 to 100 mol%, more preferably 90 to 100 mol%.
The molar ratio of terephthalic acid and / or its lower alkyl ester to (x′211) and isophthalic acid and / or its lower alkyl ester is preferably 20:80 to 100 from the viewpoint of the mechanical strength of the resin. : 0, more preferably 25:75 to 80:20.

  The polyol component (y ′) constituting the compatibilizer (C) is a single aliphatic polyol or alicyclic polyol having 2 to 20 carbon atoms.

  Examples of the aliphatic polyol having 2 to 20 carbon atoms include aliphatic diols having 2 to 4 carbon atoms such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, and 1,4-butanediol; C5-C20 linear aliphatic diols such as 5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, and 1,10-decanediol; neopentyl glycol, 2,2-diethyl- 1,3-propanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexane glycol, 1,2-octyl glycol, and 2-n-butyl- C5-C20 branched aliphatic diol such as 2-ethyl-1,3-propanediol; glycerin, trimethylo 3 to 8 or more aliphatic polyhydric alcohols having 3 to 36 carbon atoms such as ethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, polyglycerol, and dipentaerythritol; sugars such as sucrose and methylglucoside And derivatives thereof; (poly) oxyalkylene ethers of the above aliphatic polyhydric alcohols.

  Examples of the alicyclic polyol having 2 to 20 carbon atoms include 1,4-cyclohexanedimethanol and hydrogenated bisphenol A.

  The polyol component (y ′) is an aliphatic polyol or alicyclic polyol having 2 to 20 carbon atoms, and among these, ethylene glycol, 1,2-propylene glycol, neopentyl glycol are preferable from the viewpoint of blocking resistance. 1,4-cyclohexanedimethanol and hydrogenated bisphenol A, more preferably 1,2-propylene glycol and neopentyl glycol.

(C) is preferably the above-mentioned monocarboxylic acid (x′1) and / or dicarboxylic acid (x′21), and the diol, together with the above-mentioned tri- or hexavalent polycarboxylic acid (x It is obtained by reacting '22).
When no polyol component (y ′) is distilled out of the system during the polycondensation reaction, the content (mol%) of each polyol in the polyol component constituting (C) and (y ') The content (mol%) of each polyol in the polyol component contained in it becomes equal. In the case where some of the polyol is distilled out of the system during the polycondensation reaction, the polyol is used in excess of the polyol constituting (C). When the polyol to be distilled is ethylene glycol and / or 1,2-propylene glycol, for example, 120 to 200 mol% is used in (y ′) with respect to the amount in (C).
The reaction ratio between the polyol component and the polycarboxylic acid component is preferably 2/1 to 1/2, more preferably 1.5 / 1 to the equivalent ratio [OH] / [COOH] of the hydroxyl group to the carboxyl group. 1 / 1.3, particularly preferably 1.3 / 1 to 1 / 1.2.

  A polyester resin (C) is produced by polycondensing a carboxylic acid component (x ′) composed of a monocarboxylic acid (x′1) and a polycarboxylic acid (x′2) and a polyol component (y ′). The method in this case is not particularly limited, and the mixture of (x′1) and (x′2) and (y ′) can be polycondensed in a lump. At least a portion of (y ′) is polycondensed at an equivalent ratio such that the hydroxyl group of (y ′) is excessive, and then the hydroxyl group of the obtained polycondensate (C0) and (x′1) It is preferable that the carboxyl group is reacted and further polycondensed. If necessary, after polycondensation of (C0) and (x′1), a polycarboxylic acid (x′22) having 3 to 6 or more valences may be added and further polycondensed.

The compatibilizing agent (C) is composed of a polyol component (y ′) composed of a single aliphatic polyol or alicyclic polyol having 2 to 20 carbon atoms, and the SP value is between incompatible resins. A positioned polyester resin is used.

  The reason for using the polyester resin is to reduce the interface free energy between the phases by using the resin showing the SP value between the sea and island phases, and further stabilize the diameter of the continuous phase of the sea-island structure. This has the effect of dramatically improving the interaction at the continuous phase interface, so that the low-temperature fixability, offset resistance, etc. can be dramatically improved.

The SP value of the polyester resin (C) is usually 10.5 to 12.5, preferably 10.6 to 12.0.
When the SP value is 10.5 or more and 12.5 or less, the compatibility of (A) and (B) is good, and both the blocking resistance and the fixing property (low temperature side) are good.

  The glass transition temperature [Tg] of (C) is preferably 45 to 70 ° C, more preferably 50 to 65 ° C. When Tg is 70 ° C. or lower, the low-temperature fixability is improved. Moreover, blocking resistance is favorable in Tg being 45 degreeC or more.

  The molecular weight of (C) is preferably such that the peak top molecular weight (hereinafter referred to as Mp) is 2000 to 15000, more preferably 2500 to 12000, and particularly preferably 3000 to 10,000. When the Mp is 2000 or more, the resin strength necessary for fixing is expressed, and when it is 15000 or less, the low-temperature fixability at the time of toner formation is good.

  The acid value (C) of (C) is preferably 0 to 60 (mg KOH / g, the same shall apply hereinafter), more preferably 0 to 50, and particularly preferably 0 to 40. When the acid value is 60 or less, the charging characteristics at the time of toner formation do not deteriorate.

  The hydroxyl value of (C) (mgKOH / g, hereinafter the same) is preferably 0-100 (mgKOH / g, the same below), more preferably 0-70, particularly preferably 0-50. When the hydroxyl value is 100 or less, the hot offset resistance at the time of toner formation becomes better.

  The softening point [Tm] of (C) is preferably from 70 to 130 ° C, more preferably from 75 to 120 ° C, particularly preferably from 80 to 115 ° C. In this range, the balance between hot offset resistance and low-temperature fixability is good.

The compatibilizer (C) is a linear polyester (A) that forms a sea-island structure and a non-linear polyester (B) or a linear polyester containing a composition constituting (A) and (B). It can be produced by melt kneading in a mill or the like, or using a known esterification or exchange reaction in a polymerization tank or a glass tube oven.
As a general method, for example, in the presence of a polymerization catalyst in an inert gas (nitrogen gas or the like) atmosphere, the reaction temperature is preferably 150 to 280 ° C, more preferably 180 to 270 ° C, and particularly preferably 200 to 260. It can carry out by making it react at ° C. The reaction time is preferably 30 minutes or more, particularly 2 to 40 hours from the viewpoint of reliably performing the reaction.
It is also effective to reduce the pressure in order to improve the reaction rate.

  The weight ratio [(A) :( B) :( C)] of the linear polyester resin (A), the non-linear polyester resin (B), and the compatibilizer (C) is low temperature fixability, hot offset resistance, and grindability. (10 to 85): (10 to 80): (0.1 to 15), more preferably (20 to 80): (15 to 60): (0.5 to 10) It is.

For the evaluation of the mixing property, the diameter of the island phase of the sea-island structure in which the linear polyester (A) in the toner binder is composed of the sea phase and the non-linear polyester (B) is composed of the island phase is that of a phase contrast microscope and a digital microscope (high resolution optical microscope). Observation and evaluation are possible at 100 to 5000 magnifications. Since the toner particle size is usually about 5 to 10 μm, the mixing property is good when the maximum toner particle size is 5 μm or less, more preferably 3 μm or less, and particularly preferably 0.1 to 1.5 μm. When the dispersed particle diameter is 5 μm or less, the low-temperature fixability and the hot offset resistance are good.
In the above and below, the evaluation of the mixing property is performed using an IX71 phase contrast microscope (an inverted research microscope) manufactured by OLYMPUS or / and a digital microscope manufactured by Keyence (high resolution zoom lens VH-Z500R / Z500W).

  The toner composition of the present invention contains the toner binder of the present invention, a colorant, and, if necessary, one or more additives selected from a release agent, a charge control agent, a magnetic powder, and a fluidizing agent.

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, Orazol Brown B and 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, nickel, or a compound such as magnetite, hematite, ferrite) can also be included as a colorant.
The content of the colorant is preferably 1 to 40 parts, more preferably 3 to 10 parts, with respect to 100 parts of the toner binder of the present invention. In addition, when using magnetic powder, Preferably it is 20-150 parts, More preferably, it is 40-120 parts. Above and below, parts mean parts by weight.

  The release agent preferably has a softening point of 50 to 170 ° C., and examples thereof include polyolefin wax, natural wax, aliphatic alcohol having 30 to 50 carbon atoms, fatty acid having 30 to 50 carbon atoms, and a mixture thereof. 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 (C1-C1 of alkyl 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 composition ratio of the toner composition of the present invention is preferably 30 to 97%, more preferably 40 to 95%, particularly preferably 45 to 92% of the toner binder of the present invention based on the weight of the toner composition; However, it is preferably 0.05 to 60%, more preferably 0.1 to 55%, particularly preferably 0.5 to 50%; among the additives, the release agent is preferably 0 to 30%, more preferably 0.5 to 20%, particularly preferably 1 to 10%; charge control agent is preferably 0 to 20%, more preferably 0.1 to 10%, particularly preferably 0.5 to 7.5%; The fluidizing agent is preferably 0 to 10%, more preferably 0 to 5%, particularly preferably 0.1 to 4%. The total content of additives is preferably 3 to 70%, more preferably 4 to 58%, and particularly preferably 5 to 50%. When the composition ratio of the toner is in the above range, a toner having good chargeability can be easily obtained.

The toner composition of the present invention may be obtained by any conventionally known method such as a kneading and pulverizing method, an emulsion phase inversion method, or a polymerization method. 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. By further classifying, the particle size (D50) can be preferably made into fine particles having a particle size of 5 to 20 μm, and then mixed with a fluidizing agent. The average particle size (D50) (D50 is the particle size when the number larger than a certain particle size in the volume particle size distribution of powder represents 50% of the total number of powders) is Coulter counter [ For example, it is measured using a product 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 composition 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. Used as a developer for a latent image. The weight ratio of toner to carrier particles is preferably 1/99 to 100/0. Further, instead of the carrier particles, it can be rubbed with a member such as a charging blade to form an electric latent image.

  The toner composition of the present invention is fixed on a support (paper, polyester film, etc.) by a copying machine, a printer, or the like to form 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.

  EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. Hereinafter, a part shows a weight part.

Production Example 1
[Synthesis of Linear Polyester Resin (A-1)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 230 parts of terephthalic acid, propylene oxide of bisphenol A (hereinafter referred to as PO) adduct: Newpol BP-2P (manufactured by Sanyo Chemical Industries: 2 mol of PO) Product) 690 parts, 120 parts of benzoic acid, 3 parts of titanium diisopropoxy bistriethanolaminate as a polymerization catalyst, reacted at 210 ° C. for 5 hours while distilling off the water generated in a nitrogen stream, The reaction was performed under a reduced pressure of 20 mmHg until the acid value was 2 or less. Next, 20 parts of trimellitic anhydride was added and reacted under normal pressure for 1 hour, and then taken out. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as linear polyester resin (A-1).
Mp of (A-1) was 5000, Tg was 62 ° C., Tm was 98 ° C., acid value was 15, hydroxyl value was 1, and SP value was 10.9.

Production Example 2
[Synthesis of Linear Polyester Resin (A-2)]
265 parts of terephthalic acid, PO adduct of bisphenol A: Newpol BP-2P (manufactured by Sanyo Chemical Industries: PO2 mol adduct), 765 parts, polymerization catalyst in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe 3 parts of titanium diisopropoxy bistriethanolaminate was added and reacted at 210 ° C. for 5 hours while distilling off the water produced in a nitrogen stream, followed by reaction under reduced pressure of 5 to 20 mmHg to give an acid value of 2 The reaction was continued until: Next, 25 parts of trimellitic anhydride was added and reacted for 1 hour under normal pressure, and then taken out. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as linear polyester resin (A-2).
Mp of (A-2) was 3500, Tg was 58 ° C., Tm was 95 ° C., acid value was 15, hydroxyl value was 65, and SP value was 10.9.

Production Example 3
[Synthesis of Nonlinear Polyester Resin (B-1)]
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 388 parts of terephthalic acid, 388 parts of isophthalic acid, 21 parts of adipic acid, 600 parts of ethylene glycol, titanium diisopropoxybistriethanolamate as a polymerization catalyst 5 parts was added and reacted for 5 hours while distilling off the water generated at 210 ° C. under a nitrogen stream, and then reacted for 1 hour under reduced pressure of 5 to 20 mmHg. Next, 17 parts of benzoic acid was added and reacted under normal pressure for 3 hours (linear polyester (B-1a)). Further, 57 parts of trimellitic anhydride was added and reacted under normal pressure for 1 hour, and then reacted under reduced pressure of 20 to 40 mmHg and taken out at a predetermined softening point. The recovered ethylene glycol was 280 parts. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (B-1).
Mp of (B-1) was 8000, Tg was 60 ° C., Tm was 145 ° C., the acid value was 26, the hydroxyl value was 1, and the SP value was 12.5.

Production Example 4
[Synthesis of Non-Linear Polyester Resin (B-2)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 530 parts of terephthalic acid, 130 parts of isophthalic acid, 5 parts of adipic acid, 650 parts of ethylene glycol, titanium diisopropoxybistriethanolamate as a polymerization catalyst 5 parts was added and reacted for 5 hours while distilling off the water generated at 210 ° C. under a nitrogen stream, and then reacted for 1 hour under reduced pressure of 5 to 20 mmHg. Subsequently, 55 parts of benzoic acid was added and reacted under normal pressure for 3 hours (linear polyester (B-2a)). Further, 85 parts of trimellitic anhydride was added and reacted under normal pressure for 1 hour, and then reacted under reduced pressure of 20 to 40 mmHg and taken out at a predetermined softening point. The recovered ethylene glycol was 280 parts. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (B-2).
Mp of (B-2) was 4500, Tg was 60 ° C., Tm was 145 ° C., acid value was 25, hydroxyl value was 10, and SP value was 12.3.

Production Example 5
[Synthesis of Compatibilizer (C-1)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, 715 parts of 1,2-propylene glycol, 740 parts of terephthalic acid, 35 parts of adipic acid, and 0.5 part of tetrabutoxy titanate as a polymerization catalyst were added. It was made to react for 12 hours, distilling off the water produced | generated under nitrogen stream at ° C. Next, while gradually raising the temperature to 230 ° C., the mixture is reacted for 4 hours while removing generated water under a nitrogen stream, further reacted under reduced pressure of 5 to 20 mmHg, and cooled when the softening point reaches 88 ° C. did. The recovered 1,2-propylene glycol was 325 parts. Next, the mixture was cooled to 180 ° C., 50 parts of trimellitic anhydride was added, reacted for 2 hours in a sealed state, reacted at 220 ° C. under reduced pressure of 20 to 40 mmHg, and taken out at a predetermined softening point. The obtained resin was cooled to room temperature and then pulverized into particles. Let this be the polyester resin (C-1) which is a compatibilizing agent.
Tg of (C-1) was 61 ° C., Tm was 101 ° C., Mp was 4,500, acid value was 29, hydroxyl value was 30, and SP value was 11.8.

Production Example 6
[Synthesis of Compatibilizer (C-2)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 700 parts of 1,2-propylene recall, 685 parts of terephthalic acid, 65 parts of adipic acid, and 0.5 part of tetrabutoxy titanate as a polymerization catalyst were added. It was made to react for 12 hours, distilling off the water produced | generated under nitrogen stream at ° C. Next, while gradually raising the temperature to 230 ° C., the mixture is reacted for 4 hours while removing generated water under a nitrogen stream, and further reacted under reduced pressure of 5 to 20 mmHg, and cooled when the softening point reaches 99 ° C. did. The recovered 1,2-propylene glycol was 315 parts. Next, the mixture was cooled to 180 ° C., 35 parts of trimellitic anhydride was added, reacted for 2 hours in a sealed state, reacted at 220 ° C. under reduced pressure of 20 to 40 mmHg, and taken out at a predetermined softening point. The obtained resin was cooled to room temperature and then pulverized into particles. Let this be the polyester resin (C-2) which is a compatibilizing agent.
Tg of (C-2) was 63 ° C., Tm was 115 ° C., Mp was 9500, acid value was 15, hydroxyl value was 40, and SP value was 11.7.

Production Example 7
[Synthesis of Compatibilizer (C-3)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 710 parts of hydrogenated bisphenol A, 235 parts of terephthalic acid, 140 parts of adipic acid, 0.5 part of tetrabutoxy titanate as a polymerization catalyst, and nitrogen at 180 ° C. It was made to react for 12 hours, distilling off the water produced | generated under airflow. Next, while gradually raising the temperature to 230 ° C., the reaction is carried out for 4 hours while removing the water produced under a nitrogen stream, and the reaction is further carried out under a reduced pressure of 5 to 20 mmHg, until the acid value becomes 2 or less. I took it out. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (C-3) as a compatibilizing agent.
Tg of (C-3) was 65 ° C., Tm was 100 ° C., Mp was 6500, acid value was 1, hydroxyl value was 35, and SP value was 11.0.

Comparative production example 1
[Compatibilizer for comparison (RC-1)]
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 585 parts of terephthalic acid, 250 parts of isophthalic acid, 5 parts of adipic acid, 625 parts of ethylene glycol, and 0.5 part of tetrabutoxy titanate as a polymerization catalyst were added. It was made to react for 12 hours, distilling off the water produced | generated under nitrogen stream at 180 degreeC. Next, while gradually raising the temperature to 230 ° C., the mixture is reacted for 4 hours while removing generated water under a nitrogen stream, and further reacted under a reduced pressure of 5 to 20 mmHg, and cooled when the softening point reaches 98 ° C. did. The recovered ethylene glycol was 300 parts. Next, the mixture was cooled to 180 ° C., added with 17 parts of trimellitic anhydride, reacted for 2 hours under sealed conditions, reacted at 220 ° C. under reduced pressure of 20 to 40 mmHg, and taken out at a predetermined softening point. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (RC-1) which is a compatibilizing agent.
(RC-1) had a Tg of 58 ° C., a Tm of 103 ° C., an Mp of 7700, an acid value of 12, a hydroxyl value of 26, and an SP value of 12.4.

In Table 1 below, polyester resins (A1), (A2), (B1), (B2), compatibilizers (C-1), (C-2) (C-) obtained in Production Examples 1 to 7 The analytical values of the compatibilizer (RC-1) obtained in 3) and Production Comparative Example 1 were summarized.

Examples 1-7, Comparative Examples 1-3
Linear polyester resins (A-1, A-2) and nonlinear polyester resins (B-1, B-2) and compatibilizers (C-1, C) obtained in Production Examples 1 to 7 and Comparative Production Example 1 -2, C-3) and the comparative compatibilizing agent (RC-1) are put in a plastmill at the ratio shown in Table 2, and stirred and mixed at 140 ° C. for 10 minutes to obtain the toner binder (a-1) of the present invention. ) To (a-12) and comparative toner binders (a′-1) to (a′-3). To 100 parts of each toner binder, 8 parts of cyanine blue KRO (manufactured by Sanyo Dye) and 5 parts of carnauba wax are added. The toner was made 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 (D50) of 8 μm were obtained. Next, 100 parts of the toner particles were mixed with 0.5 part of colloidal silica (Aerosil R972: manufactured by Nippon Aerosil Co., Ltd.) using a sample mill, and the toner compositions (T-1) to (T-12) of the present invention and a comparison were made. Toner compositions (T′-1) to (T′-3) were obtained.
Table 2 shows the evaluation results evaluated by the following evaluation methods.

[Evaluation methods]
[1] Minimum fixing temperature (MFT)
An unfixed image developed using a commercial copying machine (AR5030; manufactured by Sharp) was evaluated using a fixing machine of a commercial copying machine (AR5030; manufactured by Sharp). The fixing roll temperature at which the residual ratio of the image density after rubbing the fixed image with a pad becomes 70% or more was set as the minimum fixing temperature.
[2] Hot offset generation temperature (HOT)
The fixing was evaluated in the same manner as the MFT, and the presence or absence of hot offset on the fixed image was visually evaluated. The fixing roll temperature at which hot offset occurred was defined as the hot offset occurrence temperature.
Regarding the minimum fixing temperature (MFT) and hot offset occurrence temperature (HOT), it is important that the fixing temperature range (difference between HOT and MFT) is wide.
[3] Blocking resistance Each toner composition was put in a polyethylene bottle, held in a constant temperature water bath at 45 ° C. for 8 hours, transferred to a 42 mesh sieve, and vibration strength was measured using a powder tester manufactured by Hosokawa Micron Corporation. The sample was shaken at 5 for 10 seconds, the weight percentage of the toner remaining on the sieve was measured, and judged according to the following criteria to evaluate the storage stability.
Residual toner weight%
A: 0% or more and less than 15% B: 15% or more and less than 25% Δ: 25% or more and less than 30% ×: 30% or more [4] Mixability evaluation Use a phase contrast microscope or a digital microscope (optical microscope).
The domain diameter of the island phase is measured at 400 to 5000 times.

Since the toner composition of the present invention using the toner binder of the present invention is excellent in charging stability, fixing temperature range, storage stability, etc., it is useful as a toner used in electrophotography, electrostatic recording, electrostatic printing and the like. is there.

Claims (9)

A linear polyester resin (A) and a non-linear polyester resin (B) that are incompatible with each other, and a carboxylic acid component (x ′) and a carboxylic acid component (x) and a polyol component (y) that are polycondensed A polyester resin obtained by polycondensation with a polyol component (y ′) which is a single aliphatic polyol or alicyclic polyol having 2 to 20 carbon atoms, and having an SP value of [(cal / cm ³ ) ^1/2 ] Contains a compatibilizing agent (C) located between (A) and (B).   The toner bander according to claim 1, wherein the carboxylic acid component (x) constituting the nonlinear polyester resin (B) is a monocarboxylic acid (x1) and a polycarboxylic acid (x2). The toner bander according to claim 1, wherein the carboxylic acid component (x) constituting the linear polyester resin (A) is a polycarboxylic acid (x2) and / or a monocarboxylic acid (x1) if necessary.   85-100 mol% of the polyol component (y) constituting the linear polyester resin (A) is an aromatic polyol, and 85-100 mol% of the polyol component (y) constituting the nonlinear polyester resin (B) is carbon number. The toner bander according to claim 1, which is 2 to 12 alkylene glycol (y11). The toner bander according to claim 1, wherein the SP value of the compatibilizing agent (C) is 10.5 to 12.5 (cal / cm ³ ) ^1/2 .   The toner bander according to any one of claims 1 to 5, wherein the compatibilizing agent (C) has a glass transition temperature of 45 to 70 ° C.   The weight ratio of the linear polyester resin (A), the nonlinear polyester resin (B), and the compatibilizer (C) is (10-85) :( 10-80) :( 0.1-15). The toner bander according to any one of 6.   The toner bander according to any one of claims 1 to 7, wherein the linear polyester resin (A) has a sea-island structure where the non-linear polyester resin (B) is an island phase, and the island phase has a diameter of 5 µm or less. A toner composition comprising the toner binder according to any one of claims 1 to 8, a colorant, and, if necessary, one or more additives selected from a release agent, a charge control agent, a magnetic powder, and a fluidizing agent.