JP4964648B2 - Toner binder and toner - Google Patents

Description

  The present invention relates to a toner binder and a toner.

  Conventionally, from the viewpoint of fixability, charging stability, and filming resistance, a crystalline polyester having a ratio of the softening point to the maximum peak temperature of heat of fusion (softening point / peak temperature) of 0.6 to 1.3 and softening The amorphous polyester having a ratio of the point to the maximum peak temperature of heat of fusion (softening point / peak temperature) of more than 1.3 and 4 or less, and the number average molecular weight of the crystalline polyester is 4,000 to A toner binder in which the acid value of the amorphous polyester is 10,000 mgKOH / g or less has been proposed (Patent Document 1).

JP 2004-226847 A

However, conventionally, since the crystalline polyester and the amorphous polyester are mixed at the time of forming the toner, the two kinds of polyesters which are difficult to mix cannot be sufficiently uniformly dispersed. There is a problem that the polyester becomes non-uniform. As a result, the toner using the conventional toner binder tends to cause image deterioration. In particular, when this toner is subjected to high-speed continuous printing, image deterioration is remarkable.
An object of the present invention is to provide a toner binder in which image deterioration is unlikely to occur.

The toner binder of the present invention is characterized in that the ratio {(1/2 drop temperature) / (melt temperature)} of the 1/2 drop temperature to the melting temperature by DSC is 0.9 or more and less than 1.1. At least one selected from the group consisting of a tetravalent polyhydric alcohol and a 3-4 tetravalent polycarboxylic acid is included as an essential constituent monomer, and the essential constituent monomer is added in an amount of 0.001 to 100 mol of the alcohol component. A non-linear crystalline polyester (A) containing 1 to 20 mol;
Formula (I):

(R is an alkylene having 2 or 3 carbon atoms, x and y are integers of 0 to 10, and the sum of x and y is 1 to 16). At least one amorphous resin selected from the group consisting of a polyester, a polyester polyamide, and a hybrid resin containing polyester, wherein the constituent monomer is a resin containing at least 40 mol% with respect to 100 mol of the alcohol component. B) and
Graft weight having a structure in which a polyolefin resin (C1) having a softening point of 100 to 170 ° C., a vinyl resin (C2) having an SP value of 10.6 to 12.6, and a vinyl monomer constituting (C2) are grafted to (C1) It consists of a resin dispersant (C) consisting of a coalescence (C3),
Based on the weight of the non-linear crystalline polyester (A), the amorphous resin (B) and the resin dispersant (C), the content of the non-linear crystalline polyester (A) is 1 to 49% by weight, The gist is that the content of the crystalline resin (B) is 50 to 98% by weight and the content of the resin dispersant (C) is 1 to 14% by weight.
Another feature of the toner of the present invention is that it contains the toner binder and a colorant.

The toner binder of the present invention tends to be uniformly dispersed in the toner at the time of toner formation. Therefore, when the toner binder of the present invention is used, a toner that hardly causes image deterioration can be easily obtained.

“Non-linear” means a chemical structure including a branched structure, a cyclic structure and / or a crosslinked structure, and does not include a chemical structure consisting only of a linear structure.
“Crystallinity” means that the ratio of {1/2 drop temperature to melting temperature by DSC {(1/2 drop temperature) / (melting temperature)} is 0.9 or more and less than 1.1, preferably 0.98 to It means having 1.05.
The term “amorphous” means that the ratio of {1/2 drop temperature to melting temperature} {(½ drop temperature) / (melting temperature)} is 1.1 to 4.0, preferably 1.5 to 3. It means having 0.
The melting temperature is measured by the method described later, and corresponds to the intersection of the baseline extension line below the maximum endothermic peak temperature and the tangent line indicating the maximum slope from the peak rising portion to the peak apex. It is.

<Non-linear crystalline polyester (A)>
The ½ drop temperature (° C.) of the non-linear crystalline polyester (A) is preferably 85 to 140, more preferably 100 to 140, and particularly preferably 100 to 130.
The ½ drop temperature 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 defined as a ½ drop temperature.

The melting temperature (° C.) of the non-linear crystalline polyester (A) is preferably 77 to 140, more preferably 90 to 140, particularly preferably 100 to 130.
The melting temperature is a value measured as follows.
Using a differential scanning calorimeter {for example, DSC210, manufactured by Seiko Denshi Kogyo Co., Ltd.], the sample to be measured was heated to 200 ° C., cooled to 0 ° C. at a cooling rate of 10 ° C./min, and then heated to 10 ° C. Measure the endothermic change by increasing the temperature at a minute / minute, draw a graph of “endothermic amount” and “temperature”, tangent line indicating the maximum slope from the peak of the maximum peak to the peak apex, and the maximum peak The temperature corresponding to the intersection with the extension of the baseline below the temperature is taken as the melting temperature.
The glass transition point is also measured in the same way (melting temperature is read as glass transition point).

  Ratio {(1/2 drop temperature) / (melt temperature)} of the 1/2 drop temperature of the non-linear crystalline polyester (A) and the melting temperature by DSC is 0.9 or more and less than 1.1, preferably 0.98 to 1.05, particularly preferably 1.00 to 1.03.

The non-linear crystalline polyester (A) comprises an alcohol component composed of a divalent to tetravalent polyhydric alcohol and a carboxylic acid component composed of a divalent to tetravalent polyvalent carboxylic acid as essential constituent monomers {2 to 4 May be abbreviated as a valence monomer}.
The non-linear crystalline polyester (A) includes an alcohol component composed of a divalent to tetravalent polyhydric alcohol and a carboxylic acid component composed of a divalent to tetravalent polyvalent carboxylic acid. At least one selected from the group consisting of a monohydric alcohol and a trivalent or tetravalent polyvalent carboxylic acid is included as an essential constituent monomer {may be abbreviated as a trivalent to tetravalent monomer}.
Content (mol) of a 3-4 valence monomer unit is 0.1-20 with respect to 100 mol of alcohol components, Preferably it is 0.5-15, More preferably, it is 1-13.

Examples of the dihydric alcohol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1, Examples include 8-octanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, 1,4-butenediol, diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. Among these, from the viewpoint of softening point and crystallinity, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexane Diol and neopentyl glycol are preferable, and 1,4-butanediol is more preferable.
The content (mol) of the dihydric alcohol unit is preferably 50 to 100, more preferably 70 to 100, per 100 mol of the alcohol component.

Examples of the trihydric alcohol include 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, Examples include methylolpropane and 1,3,5-trihydroxymethylbenzene.
Examples of the tetrahydric alcohol include diglycerin, 1,2,3,6-hexanetetraalcohol, 1,4-sorbitan, and pentaerythritol.
Of the trihydric alcohol and tetrahydric alcohol, glycerin is preferable from the viewpoint of softening point and crystallinity.

Examples of divalent carboxylic acids include aliphatic carboxylic acids {oxalic acid, fumaric acid, maleic acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, malonic acid, dodecenyl succinic acid and octyl succinic acid. Acid etc.}; aromatic carboxylic acid {phthalic acid, isophthalic acid, terephthalic acid etc.}; alicyclic carboxylic acid {cyclohexanedicarboxylic acid etc.}; and anhydrides of these acids, alkyl (C 1-3) esters, etc. Is mentioned.
Of these, aliphatic carboxylic acids are preferable from the viewpoint of softening point and crystallinity, and fumaric acid is more preferable.
70-100 are preferable with respect to 100 mol of carboxylic acid components, and, as for content (mol) of a bivalent carboxylic acid unit, More preferably, it is 80-100.

Examples of the trivalent carboxylic acid include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid. Acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid and acid anhydrides thereof, alkyl (carbon number 1 -3) An ester etc. are mentioned.
Examples of tetravalent carboxylic acids include tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, emporic trimer acid, and acid anhydrides thereof, alkyl (having 1 to 3 carbon atoms). ) Esters and the like.
Of the trivalent carboxylic acid and tetravalent carboxylic acid, trimellitic acid and its acid anhydride are preferable from the viewpoint of softening point and crystallinity.
The non-linear crystalline polyester (A) is obtained by subjecting an alcohol component and a carboxylic acid component to a known method {for example, JP-A No. 2000-75549, JP-A No. 2004-61875, JP-A No. 2004-226847, etc. } Or the like.

The number average molecular weight of the tetrahydrofuran-soluble component of the non-linear crystalline polyester (A) is preferably 500 to 6000, more preferably 500 to 1000, from the viewpoints of blocking resistance and fixability.
The number average molecular weight (Mn) is measured by gel permeation chromatography (GPC) using polystyrene having a known molecular weight as a standard substance {JIS K0124: 2002 (General Rules for High Performance Liquid Chromatography), Corresponding ISO; ISO 11843- 1: 1997 (capability of detection-Part1: Terms and definitions.)} (For example, measurement conditions are as follows). 40 mg of a measurement sample is dissolved in 10 ml of tetrahydrofuran, filtered through a membrane filter (Toyo Filter Paper Co., Ltd., 0.2 μm hole diameter), and the filtrate is used.

Apparatus: CO-8010 {manufactured by Tosoh Corporation}
Column: GMLX and G3000HXL (both manufactured by Tosoh Corporation) each connected in series Column injection amount: 100 μL
Eluent: Tetrahydrofuran eluent flow rate: 1 mL / min Detector: Differential refractive index detector (RID)
Reference material: 12 standard polystyrene (TSK standard POLYSTYRENE) manufactured by Tosoh (molecular weight 500 1050 2800 5970 9100 18100 37900 96400 190000 355000 1090000 2890000)

<Amorphous resin (B)>
Amorphous resin (B) comprises an essential constituent monomer {2 to 4 monovalent monomer and an alcohol component comprising 2 to 4 valent polyhydric alcohol and a carboxylic acid component comprising 2 to 4 valent polyvalent carboxylic acid. The resin may be abbreviated as a polymer}, and is at least one amorphous resin selected from the group consisting of polyester, polyester polyamide, and a hybrid resin containing polyester.
The amorphous resin (B) contains a diol represented by the formula (I) as an essential constituent monomer.
The content (mole) of the diol is at least 40, preferably 60 to 100, more preferably 80 to 100, per 100 mol of the alcohol component.

In the formula (I), the alkylene group (R) having 2 or 3 carbon atoms includes ethylene and propylene. Of these, propylene is preferred.
Moreover, x and y are the integers of 0-10, Preferably it is 1-5, More preferably, it is 1-3.
Moreover, the sum of x and y is 1-16, Preferably it is 1-10, More preferably, it is 2-5.

Diols represented by formula (I) include bis (4-hydroxypolyoxypropylenephenyl) propane, bis (4-hydroxypolyoxyethylenephenyl) propane and bis (4-hydroxypolyoxyethylene / polyoxypropylenephenyl). Examples include propane.

Examples of the alcohol component other than the diol represented by the formula (I) include the aforementioned divalent to tetravalent polyhydric alcohols.
Moreover, as a carboxylic acid component, the above-mentioned 2-4 valent polyhydric carboxylic acid etc. are contained.

The amorphous resin (B) may contain an amine component {amine, aminocarboxylic acid, aminoalcohol and the like} as a monomer in addition to the essential constituent monomers {alcohol component and carboxylic acid component}.
Examples of the amine include ethylenediamine, hexamethylenediamine, diethylenetriamine, and xylylenediamine.
Examples of aminocarboxylic acids include ε-caprolactam.
Examples of amino alcohols include propanolamine.
Of these, amines and aminocarboxylic acids are preferable, and hexamethylenediamine and ε-caprolactam are more preferable.

Among the amorphous resins (B), polyesters are obtained by converting an alcohol component and a carboxylic acid component into a known method {for example, JP-A No. 2000-75549, JP-A No. 2004-61875, JP-A No. 2004-226847. Etc.} and the like.
Further, polyester polyamide is obtained by combining an alcohol component, a carboxylic acid component, and an amine component with a known method {for example, JP 2000-75549 A, JP 2004-61875 A, JP 2004-226847 A, etc.), etc. Can be obtained by condensation polymerization.
In addition, the hybrid resin containing polyester is obtained by a known method (for example, JP-A-8-171231, JP-A-8-44108, JP-A-Heihei) by using an alcohol component, a carboxylic acid component, and optionally an amine component, and a vinyl monomer. 8-320593, JP-A No. 2004-275908, JP-A No. 2002-72557, etc.} and the like.
Examples of vinyl monomers include known documents {for example, JP-A-8-171231, JP-A-8-44108, JP-A-8-320593, JP-A-2004-275908, JP-A-2002-72557. Gazette} etc. are included. Of these, (meth) acrylate and styrene monomer are preferable, and methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate are more preferable. 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, α-methylstyrene and styrene, particularly preferably methyl (meth) acrylate and styrene.

As for 1/2 fall temperature (degreeC) of an amorphous resin (B), 70-180 are preferable, More preferably, it is 80-150.
50-85 are preferable and, as for the glass transition point (degreeC) of an amorphous resin (B), 50-70 are more preferable.
The amorphous resin (B) is preferably a mixed resin of two or more kinds of resins. In the case of a mixed resin, a resin having a ½ drop temperature of 70 to 110 ° C. (resin a) and a resin having a ½ drop temperature of 110 to 180 ° C. from the viewpoint of both fixing properties and blocking resistance. A mixture of (resin b) is preferred {weight ratio (a / b): 30/70 to 80/20 is preferred. }.

<Resin dispersant (C)>
Examples of the polyolefin resin (C1) include an olefin polymer (C11), an oxidized product (C12) obtained by oxidizing the olefin polymer (C11), a modified product (C13) obtained by modifying the olefin polymer (C11), and an olefin. A copolymer (C14) with a comonomer is included.

Examples of the olefin include ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-dodecene and 1-octadecene.
Examples of the olefin polymer (C11) include polyethylene, polypropylene, ethylene / propylene copolymer, ethylene / 1-butene copolymer, and propylene / 1-hexene copolymer. The olefin polymer (C11) may have a polyolefin structure as a polymer structure, and the monomer is not necessarily an olefin {for example, polymethylene (such as sazol wax) can be used}.

The oxidant (C12) includes an oxidant obtained by oxidizing the polymer (C11) with air, oxygen, and / or ozone, etc. by a known method (for example, US Pat. No. 3,692,877).
The modified product (C13) is a known method (for example, JP-A-2001-278985), and the polymer (C11) is unsaturated carboxylic acid {maleic anhydride, monomethyl maleate, monobutyl maleate, dimethyl maleate, etc. } Modified | denatured etc. modified | denatured by.

As comonomer, unsaturated carboxylic acid {(meth) acrylic acid, itaconic acid, maleic anhydride, etc.}, and unsaturated carboxylic acid alkyl ester {(meth) acrylic acid alkyl ester and maleic acid alkyl ester (alkyl Or the like.
Examples of the copolymer (C14) include polyethylene / acrylic acid copolymers, polypropylene / maleic anhydride copolymers, ethylene / propylene / methyl acrylate copolymers, ethylene / methyl acrylate copolymers, and propylene / methyl acrylate copolymers. A polymer etc. are mentioned.

  Among these, a polymer (C11), an oxidant (C12) and a modified body (C13) are preferable, a polymer (C11) is more preferable, and polyethylene and polypropylene are particularly preferable.

100-170 are preferable, as for the softening point (degreeC) of polyolefin resin (C1), More preferably, it is 110-160, Most preferably, it is 125-155. Within this range, when applied to toner, the fluidity and release effect of the toner are further improved.
The softening point is measured according to JIS K2207-1996.

The melt viscosity (160 ° C., mPa · s) of the polyolefin resin (C1) is preferably 2 to 10,000, more preferably 3 to 7000, and particularly preferably 5 to 4500. Within this range, when applied to toner, the fluidity and release effect of the toner are further improved.
The melt viscosity is measured according to JIS K6862-1984 (change from 180 ° C. to 160 ° C.). When the softening point of the polyolefin resin (C1) exceeds 160 ° C., the melt is measured at a temperature equal to or higher than the softening point and then cooled to 160 ° C. {Because the polyolefin resin (C1) has high crystallinity Once melted, it is hard to solidify even when cooled below the softening point. }.

The number average molecular weight of the polyolefin resin (C1) is preferably from 500 to 20000, more preferably from 1000 to 15000, and particularly preferably from 1500 to 10,000, from the viewpoints of filming on the carrier and the releasability.
The weight average molecular weight of the polyolefin resin (C1) is preferably from 800 to 100,000, more preferably from 1500 to 60000, and particularly preferably from 2000 to 30000, from the viewpoints of filming on the carrier and the releasability.
The number average molecular weight and the weight average molecular weight are measured in the same manner as described above (hereinafter the same).

The penetration of the polyolefin resin (C1) is preferably 5.0 or less, more preferably 3.5 or less, and particularly preferably 1.0 or less.
The penetration is measured according to JIS K2207-1996.

The SP value {solubility parameter: (cal / cm ³ ) ^1/2 } of the vinyl resin (C2) is preferably 10.5 to 11.7, more preferably 10.7 to 11.5, and particularly preferably 10. .8 to 11.0. Within this range, the uniform dispersion is further improved.
The SP value can be expressed by the following equation.
SP value (δ) = (ΔH / V) ^1/2
In the formula, ΔH represents the heat of vaporization (cal), and V represents the molar volume (cm ³ ).
ΔH and V are the molar evaporation heat (Δe _i ) of the atomic group described in “POLYMER ENGINEERING AND FEBRUARY, 1974, Vol. 14, No. 2, ROBERT F. FEDORS. (Pages 151 to 153)”. Total (ΔH) and molar volume (△
The sum (V) of v _i ) can be used.

The vinyl resin (C2) may be a homopolymer of the vinyl monomer (c211) having a homopolymer SP value of 10.6 to 12.6, but is preferably a copolymer (copolymer), more preferably Copolymer.
That is, the vinyl monomer (c221) having an SP value of the homopolymer of 11.0 to 18.0 {preferably 11.0 to 16.0}, and the SP value of the homopolymer of 8.0 to less than 11.0 { Preferably, it is a copolymer (C22) with a vinyl monomer (c222) to be 9.0 to 10.8}.

The vinyl monomer (c221) is not limited as long as the SP value of the homopolymer of (c221) is 11.0 to 18.0 {preferably 11.0 to 16.0}. α, β-unsaturated carboxylic acids and the like are included.
Examples of unsaturated nitriles include (meth) acrylonitrile and cyanostyrene.
Examples of the α, β-unsaturated carboxylic acid include (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid and anhydrides thereof, and monomethyl maleate, monobutyl maleate and monomethyl itaconate.

The vinyl monomer (c222) is not limited as long as the SP value of the homopolymer of (c222) is 8.0 or more and less than 11.0 {preferably 9.0 to 10.8}, and the styrene monomer { Styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene, p-methoxystyrene, p-hydroxystyrene, p-acetoxystyrene, vinyltoluene, ethylstyrene, phenylstyrene and benzylstyrene}; unsaturated carboxylic acid Alkyl (carbon number 1 to 18) ester {methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate, etc.}; vinyl ester monomer {vinyl acetate etc.}; vinyl ether monomer {Vinyl methyl ether, etc.]; Element-containing vinyl monomers {vinyl chloride}; and include diene monomer {butadiene and isobutylene} like.
Of these, styrene monomer and unsaturated carboxylic acid alkyl ester, more preferably styrene and (meth) acrylic acid alkyl ester, particularly preferably styrene and (meth) acrylic acid alkyl ester are used in combination.

  The graft polymer (C3) has a structure in which the vinyl monomer {vinyl monomer (c211), vinyl monomer (c221) and vinyl monomer (c222)} constituting the vinyl resin (C2) is grafted to the olefin resin (C1). However, each preferable range is as described above.

The content (% by weight) of the olefin resin (C1) is preferably 0.5 to 70, more preferably 1 to 20, particularly preferably 1 to 10, based on the weight of the resin dispersant (C).
The content (% by weight) of the vinyl resin (C2) is preferably 29 to 98.5, more preferably 34 to 79, particularly preferably 50 to 59, based on the weight of the resin dispersant (C).
The content (% by weight) of the graft polymer (C3) is preferably 1 to 70, more preferably 20 to 65, particularly preferably 40 to 60, based on the weight of the resin dispersant (C).

The content of each of these components can be determined as follows.
The resin dispersant (C) is dissolved in 5 times by weight of toluene with respect to (C) at 20 ° C., the insoluble matter (C1) is separated by filtration and dried, and the weight is measured. A toluene soluble part is dripped in acetone of 10 times the weight with respect to toluene at 20 degreeC, the obtained precipitation (C3) is dried, and a weight is measured. Further, the remaining acetone-soluble component (C2) is desolvated and dried, the weight is measured, and the respective weight ratio (%) is obtained.

The number average molecular weight of the resin dispersant (C) is preferably 1500 to 100,000, more preferably 2500 to 50000, and particularly preferably 2800 to 20000.
5000-200000 are preferable, as for the weight average molecular weight of a resin dispersing agent (C), More preferably, it is 6000-100,000, Most preferably, it is 7000-50000.

  The glass transition point (Tg; ° C) of the resin dispersant (C) is preferably 40 to 90, more preferably 45 to 80, and particularly preferably 50 to 70. Within this range, storage stability and low-temperature fixability are further improved.

For example, the resin dispersant (C) is obtained by dissolving or dispersing the polyolefin resin (C1) in a solvent {toluene, xylene and the like} and heating to about 100 to 200 ° C., and then forming a vinyl monomer {constituent monomer of the vinyl resin (C2). : Same below) is obtained by dropping and polymerizing.
An initiator may be used for the polymerization. Examples of the initiator include peroxides {benzoyl peroxide, ditertiary butyl peroxide, tertiary butyl peroxide benzoate, etc.} and the like. Moreover, it is preferable to distill off a solvent after superposition | polymerization.

In this case, the used amount (% by weight) of the olefin resin (C1) is preferably 1 to 90, more preferably 5 to 80, and particularly preferably 10 to 40, based on the weight of (C1) and the vinyl monomer. .
The amount (% by weight) of the vinyl monomer used is preferably from 10 to 99, more preferably from 20 to 95, particularly preferably from 60 to 90, based on the weight of (C1) and the vinyl monomer.

  When used with an initiator, the amount used (% by weight) is preferably 0.2 to 10, more preferably 0.5 to 5, particularly preferably 0, based on the weight of the olefin resin (C1) and the vinyl monomer. .8-3.

The content (% by weight) of the non-linear crystalline polyester (A) is based on the weight of the non-linear crystalline polyester (A), the amorphous resin (B), and the resin dispersant (C). 49 is preferable, more preferably 5 to 38.5, and particularly preferably 10 to 28.
The content (% by weight) of the amorphous resin (B) is 50 to 98 based on the weight of the non-linear crystalline polyester (A), the amorphous resin (B), and the resin dispersant (C). More preferably, it is 60-93.5, Most preferably, it is 70-80.
The content (% by weight) of the resin dispersant (C) is preferably 1 to 14 based on the weight of the non-linear crystalline polyester (A), the amorphous resin (B) and the resin dispersant (C). More preferably, it is 1.5-12, Most preferably, it is 2-8.

In addition to the non-linear crystalline polyester (A), the amorphous resin (B), and the resin dispersant (C), the toner binder of the present invention can contain a wax or the like.
Examples of the wax include ester wax (carnauba wax, montan wax, rice wax, etc.), a long-chain aliphatic alcohol having 30 to 50 carbon atoms, and a long-chain fatty acid having 30 to 50 carbon atoms.
When the wax is contained, the content (% by weight) of the wax is 0.1 to 0.1 on the basis of the weight of the non-linear crystalline polyester (A), the amorphous resin (B), and the resin dispersant (C). 10 is preferable, more preferably 0.5 to 8, particularly preferably 0.5 to 3.

The toner binder of the present invention comprises a non-linear crystalline polyester (A), an amorphous resin (B), a resin dispersant (C), and a method of melt-mixing wax as necessary <1>, non-linear A method <2> in which the crystalline polyester (A) and the amorphous resin (B) are melt-mixed in advance and then the powder is mixed with the resin dispersant (C) and, if necessary, the resin dispersant (C) and A method of polymerizing the non-linear crystalline polyester (A) and / or the amorphous resin (B) in the presence of a wax if necessary {If any of (A) and (B) is polymerized, the remaining (A ) Or (B) is obtained by powder mixing or melt mixing after polymerization} <3> or the like.

The toner binder of the present invention can be mixed with a colorant and a charge control agent to form a toner. In addition, a mold release agent, a fluidizing agent, etc. can be further contained as needed.
Known dyes, pigments and magnetic powders can be used as the colorant. Specifically, carbon black, Sudan Black SM, First Yellow-G, Benzidine Yellow, Pigment Yellow, Indian First Orange, Irgasin Red, Rose Nitroaniline Red, Toluidine Red, Carmine FB, Pigment Orange R, Lake Red 2G, Examples include rhodamine FB, rhodamine B lake, methyl violet B lake, phthalocyanine blue, pigment blue, prilliant green, phthalocyanine green, oil yellow GG, kayaset YG, orazol brown B, oil pink OP, magnetite, iron black and the like.
The content of the colorant in the toner is preferably 2 to 15% by weight when using a dye or pigment, and preferably 20 to 70% by weight when using magnetic powder.
As the charge control agent, known ones, that is, nigrosine dye, quaternary ammonium salt compound, quaternary ammonium base-containing polymer, metal-containing azo dye, salicylic acid metal salt, sulfonic acid group-containing polymer, fluorine-containing polymer, halogen-substituted aromatic Examples thereof include a ring-containing polymer. The content of the charge control agent in the toner is usually 0.1 to 5% by weight.

Known release agents may be used, such as polyolefin waxes (polyethylene wax, polypropylene wax, etc.); long-chain hydrocarbons (paraffin wax, sazol wax, etc.); carbonyl group-containing waxes (carnauba wax, montan wax) , Distearyl ketone, etc.). The content of the release agent in the toner is usually 0 to 10% by weight, preferably 1 to 7% by weight.
As the fluidizing agent, known materials such as colloidal silica, alumina powder, titanium oxide powder, and calcium carbonate powder can be used.

If necessary, the toner is mixed with carrier particles {iron powder, glass beads, nickel powder, ferrite, magnetite, and ferrite (surface coated with acrylic resin, silicone resin, etc.)} to obtain an electric latent image. It can be used as a developer. Further, instead of the carrier particles, an electric latent image can be formed by friction with a charging blade or the like.
The electric latent image is fixed on a support (paper, polyester film, etc.) by a known hot roll fixing method or the like.

Hereinafter, unless otherwise specified, parts means parts by weight and% means% by weight.
<Example 1>
1,4-butanediol 1350 parts (100 mole parts), fumaric acid 1566 parts (90 mole parts), trimellitic anhydride 345.6 parts (12 mole parts), dibutyltin oxide 1.5 parts and hydroquinone 1.5 The part was heated and stirred at 160 ° C. for 5 hours, then heated to 200 ° C. and stirred for 1 hour, and further stirred at 200 ° C. and 8.3 kPa for 1 hour to obtain the nonlinear crystalline polyester (a1). Obtained.

  1400 parts (80 mole parts) of propylene oxide adduct of bisphenol A (average addition mole number 2.2), 325 parts (20 mole parts) of ethylene oxide adduct of bisphenol A (average addition mole number 2.2), 166 isophthalic acid Parts (20 mol parts), fumaric acid 406 parts (70 mol parts), trimellitic anhydride 96 parts (10 mol parts), dibutyltin oxide 1.5 parts and hydroquinone 1.5 parts are stirred at 220 ° C. for 8 hours. After that, the mixture was stirred at 220 ° C. and 8.3 kPa for 5 hours to obtain an amorphous resin (b1).

  600 parts of xylene, low molecular weight polypropylene {Viscol 440P manufactured by Sanyo Chemical Industries, Ltd .: softening point 153 ° C} 480 parts and low molecular weight polyethylene {Sanwax LEL-400, manufactured by Sanyo Chemical Industries Co., Ltd .: softening point 128 ° C} 120 parts In an autoclave reaction vessel, uniformly dissolved, purged with nitrogen, heated to 175 ° C., and at this temperature, mixed solution {1992 parts of styrene, 186 parts of acrylonitrile, 240 parts of monobutyl maleate, di-t-butyl per 78 parts of oxyhexahydroterephthalate and 455 parts of xylene} were added dropwise over 3 hours and further stirred at this temperature for 30 minutes. Subsequently, the solvent was distilled off to obtain a resin dispersant (c1) {SP value of the contained styrene-acrylonitrile-monobutyl maleate copolymer (vinyl resin C2): 11.0}.

  After premixing 10 parts of the non-linear crystalline polyester (a1), 980 parts of the amorphous resin (b1) and 10 parts of the resin dispersant (c1) with a Henschel mixer {FM10B manufactured by Mitsui Miike Chemical Co., Ltd.} Then, the toner binder (1) of the present invention was obtained by melt mixing with a continuous kneader at a jacket temperature of 150 ° C. and a residence time of 3 minutes.

<Example 2>
1,350 parts (100 moles) of 1,4-butanediol, 1566 parts (90 moles) of fumaric acid and 345.6 parts (12 moles) of trimellitic anhydride, 930 parts (100 moles) of ethylene glycol, A nonlinear crystalline polyester (a2) was obtained in the same manner as in Example 1 except that the acid was changed to 1734.6 parts (98 mol parts) and trimellitic acid 129.6 parts (4.5 mol parts).

  1020 parts of xylene, 2000 parts of low molecular weight polypropylene {Bicol 660P manufactured by Sanyo Chemical Industries Co., Ltd .: softening point 145 ° C} are placed in an autoclave reaction vessel, uniformly dissolved, purged with nitrogen, and heated to 175 ° C. Then, a mixed solution {styrene 2385 parts, acrylonitrile 264 parts, butyl acrylate 330 parts, acrylic acid 21 parts, di-t-butylperoxyhexahydroterephthalate 32.5 parts and xylene 570 parts} is dropped over 3 hours. The mixture was further stirred at this temperature for 30 minutes. Next, the solvent was distilled off to obtain resin dispersant (c2) {SP value of styrene-acrylonitrile-butyl acrylate-acrylic acid copolymer (vinyl resin C2) contained: 10.8}.

  10 parts of non-linear crystalline polyester (a1), 980 parts of amorphous resin (b1) and 10 parts of resin dispersant (c1), 50 parts of non-linear crystalline polyester (a2), amorphous resin (b1 ) Toner binder (2) of the present invention was obtained in the same manner as in Example 1 except that the content was changed to 935 parts and resin dispersant (c2) 15 parts.

<Example 3>
1,350 parts (100 mole parts) of 1,4-butanediol, 1566 parts (90 mole parts) of fumaric acid and 345.6 parts (12 mole parts) of trimellitic anhydride were added to 1134 parts (84 moles) of 1,4-butanediol. Parts), hydrogenated bisphenol A 324 parts (9 mole parts), glycerin 96.6 parts (7 mole parts), oxalic acid 176 parts (13 mole parts) and succinic acid 1487 parts (84 mole parts) In the same manner as in Example 1, a non-linear crystalline polyester (a3) was obtained.

340 parts of xylene, low molecular weight polypropylene {Sanyo Chemical Industries Co., Ltd., Viscol 440P: softening point 153 ° C} 200 parts, low molecular weight polyethylene {Sanyo Chemical Industries, Ltd. Sun Wax LEL-400: softening point 128 ° C} 50 parts In an autoclave reaction vessel, uniformly dissolved, purged with nitrogen, heated to 175 ° C., and at this temperature, mixed solution {styrene 839 parts, acrylonitrile 44 parts, butyl acrylate 110 parts, acrylic acid 7 parts, diacid -32.5 parts of t-butylperoxyhexahydroterephthalate and 148 parts of xylene} were added dropwise over 3 hours, and further stirred at this temperature for 30 minutes. Subsequently, the solvent was distilled off to obtain a resin dispersant (c3) {SP value of the contained styrene-acrylonitrile-butyl acrylate-acrylic acid copolymer (vinyl resin C2): 10.7}.

  10 parts of non-linear crystalline polyester (a1), 980 parts of amorphous resin (b1) and 10 parts of resin dispersant (c1) were mixed with 490 parts of non-linear crystalline polyester (a3) and amorphous resin (b1 ) A toner binder (3) of the present invention was obtained in the same manner as in Example 1 except that 500 parts and 10 parts of the resin dispersant (c3) were changed.

<Example 4>
1,350 parts (100 moles) of 1,4-butanediol, 1566 parts (90 moles) of fumaric acid and 345.6 parts (12 moles) of trimellitic anhydride were added to 1350 parts (100 moles) of 1,4-butanediol. Part), 1444.2 parts (83 mole parts) of fumaric acid, and 518.4 parts (18 mole parts) of trimellitic anhydride, the non-linear crystalline polyester (a4) was obtained in the same manner as in Example 1. Obtained.

340 parts of xylene, 60 parts of low molecular weight polyethylene {Sanwa Kasei Kogyo Co., Ltd. sun wax E-330: softening point 104 ° C} are placed in an autoclave reaction vessel, uniformly dissolved, purged with nitrogen, and heated to 175 ° C. At this temperature, a mixed solution {839 parts of styrene, 310 parts of acrylonitrile, 110 parts of butyl acrylate, 21 parts of acrylic acid, 32.5 parts of di-t-butylperoxyhexahydroterephthalate and 148 parts of xylene} is taken over 3 hours. Then, the mixture was further stirred at this temperature for 30 minutes. Next, the solvent was distilled off to obtain a resin dispersant (c4) {SP value of contained styrene-acrylonitrile-butyl acrylate-acrylic acid copolymer (vinyl resin C2): 11.5}.

  10 parts of non-linear crystalline polyester (a1), 980 parts of amorphous resin (b1) and 10 parts of resin dispersant (c1), 250 parts of non-linear crystalline polyester (a4), amorphous resin (b1 ) Toner binder (4) of the present invention was obtained in the same manner as in Example 1 except that 690 parts and resin dispersant (c4) were changed to 60 parts.

<Example 5>
1350 parts (100 mole parts) of 1,4-butanediol, 1566 parts (90 mole parts) of fumaric acid and 345.6 parts (12 mole parts) of trimellitic anhydride were added to 742.5 parts of 1,4-butanediol ( 55 mol parts), hydrogenated bisphenol A 1620 parts (45 mol parts), fumaric acid 1444.2 parts (83 mol parts) and trimellitic anhydride 158.4 parts (5.5 mol parts) In the same manner as in Example 1, a non-linear crystalline polyester (a5) was obtained.

  340 parts of xylene, 140 parts of low molecular weight polyethylene {Sanwax 161-P: softening point 111 ° C} manufactured by Sanyo Chemical Industries Co., Ltd.] are placed in an autoclave reaction vessel, uniformly dissolved, purged with nitrogen, and heated to 175 ° C. At this temperature, a mixed solution {839 parts of styrene, 310 parts of acrylonitrile, 20 parts of butyl acrylate, 40 parts of acrylic acid, 32.5 parts of di-t-butylperoxyhexahydroterephthalate and 148 parts of xylene} takes 3 hours. Then, the mixture was further stirred at this temperature for 30 minutes. Subsequently, the solvent was distilled off to obtain resin dispersant (c5) {SP value of styrene-acrylonitrile-butyl acrylate-acrylic acid copolymer (vinyl resin C2) contained: 11.7}.

  10 parts of non-linear crystalline polyester (a1), 980 parts of amorphous resin (b1) and 10 parts of resin dispersant (c1), 250 parts of non-linear crystalline polyester (a5), amorphous resin (b1 ) Toner binder (5) of the present invention was obtained in the same manner as in Example 1 except that 630 parts and resin dispersant (c5) were changed to 100 parts.

<Example 6>
1,350 parts (100 mole parts) of 1,4-butanediol, 1566 parts (90 mole parts) of fumaric acid and 345.6 parts (12 mole parts) of trimellitic anhydride,
Example 1 with the exception of 1594.4 parts (90 moles) of 1,6-hexanediol, 219 parts (10 moles) of 1,8-octanediol and 1681.5 parts (95 moles) of succinic acid In the same manner, a non-linear crystalline polyester (a6) was obtained.

  340 parts of xylene, 60 parts of low molecular weight polypropylene {Biscol 440P manufactured by Sanyo Chemical Industries Co., Ltd .: softening point 153 ° C} are placed in an autoclave reaction vessel, uniformly dissolved, purged with nitrogen, and heated to 175 ° C. Then, a mixed solution {styrene 839 parts, acrylonitrile 20 parts, butyl acrylate 154 parts, acrylic acid 10 parts, di-t-butylperoxyhexahydroterephthalate 32.5 parts and xylene 148 parts} is dropped over 3 hours. The mixture was further stirred at this temperature for 30 minutes. Subsequently, the solvent was distilled off to obtain a resin dispersant (c6) {SP value of contained styrene-acrylonitrile-butyl acrylate-acrylic acid copolymer (vinyl resin C2): 10.5}.

10 parts of non-linear crystalline polyester (a1), 980 parts of amorphous resin (b1) and 10 parts of resin dispersant (c1), 250 parts of non-linear crystalline polyester (a6), amorphous resin (b1 ) Toner binder (6) of the present invention was obtained in the same manner as in Example 1 except that 670 parts and resin dispersant (c6) were changed to 80 parts.

<Example 7>
1400 parts (80 mole parts) of propylene oxide adduct of bisphenol A (average addition mole number 2.2), 325 parts (20 mole parts) of ethylene oxide adduct of bisphenol A (average addition mole number 2.2), 166 isophthalic acid Parts (20 mole parts), fumaric acid 406 parts (70 mole parts) and trimellitic anhydride 96 parts (10 mole parts), bisphenol A propylene oxide adduct (average addition mole number 2.2) 1400 parts (80 Mole part), 78 parts (15 mole parts) neopentyl glycol, 26.5 parts (5 mole parts) diethylene glycol, 581 parts (70 mole parts) isophthalic acid, 134 parts (10 mole parts) dodecenyl succinic anhydride and tri An amorphous resin (b2) was obtained in the same manner as in Example 1 except that the merit acid was changed to 192 parts (20 mole parts).
10 parts of non-linear crystalline polyester (a1), 980 parts of amorphous resin (b1) and 10 parts of resin dispersant (c1), 250 parts of non-linear crystalline polyester (a1), amorphous resin (b2 ) Toner binder (7) of the present invention was obtained in the same manner as in Example 1, except that 730 parts and resin dispersant (c1) were changed to 20 parts.

<Example 8>
1400 parts (80 mole parts) of propylene oxide adduct of bisphenol A (average addition mole number 2.2), 325 parts (20 mole parts) of ethylene oxide adduct of bisphenol A (average addition mole number 2.2), 166 isophthalic acid Parts (20 mole parts), fumaric acid 406 parts (70 mole parts) and trimellitic anhydride 96 parts (10 mole parts) bisphenol A propylene oxide adduct (average number of moles added 2.2) 875 parts (50 Mole part), ethylene oxide adduct of bisphenol A (average addition mole number 2.2) 325 parts (20 mole parts), 156 parts (30 mole parts) neopentyl glycol, 664 parts (80 mole parts) isophthalic acid, dodecenyl anhydride Same as Example 1 except for changing to 67 parts (5 mole parts) of succinic acid and 144 parts (15 mole parts) of trimellitic anhydride To obtain an amorphous resin (b3) and.
10 parts of non-linear crystalline polyester (a1), 980 parts of amorphous resin (b1) and 10 parts of resin dispersant (c1), 250 parts of non-linear crystalline polyester (a2), amorphous resin (b3 ) Toner binder (8) of the present invention was obtained in the same manner as in Example 1 except that 690 parts and resin dispersant (c1) were changed to 60 parts.

<Example 9>
1400 parts (80 mole parts) of propylene oxide adduct of bisphenol A (average addition mole number 2.2), 325 parts (20 mole parts) of ethylene oxide adduct of bisphenol A (average addition mole number 2.2), 166 isophthalic acid Parts (20 mole parts), fumaric acid 406 parts (70 mole parts) and trimellitic anhydride 96 parts (10 mole parts) bisphenol A propylene oxide adduct (average number of moles added 2.2) 875 parts (50 Mol parts), ethylene oxide adduct of bisphenol A (average addition mole number 2.2) 813 parts (50 mole parts), isophthalic acid 456.5 parts (55 mole parts), dodecenyl succinic anhydride 536 parts (40 mole parts) And an amorphous resin (b4) was obtained in the same manner as in Example 1 except that the amount was changed to 144 parts (15 parts by mole) of trimellitic anhydride.
10 parts of non-linear crystalline polyester (a1), 980 parts of amorphous resin (b1) and 10 parts of resin dispersant (c1) were mixed with 260 parts of non-linear crystalline polyester (a3) and amorphous resin (b4). ) A toner binder (9) of the present invention was obtained in the same manner as in Example 1, except that the amount was changed to 600 parts and 140 parts of the resin dispersant (c1).

<Example 10>
1400 parts (80 mole parts) of propylene oxide adduct of bisphenol A (average addition mole number 2.2), ethylene oxide adduct of bisphenol A (average addition mole number 2.2) 3
25 parts (20 mole parts), 166 parts (20 mole parts) isophthalic acid, 406 parts (70 mole parts) fumaric acid and 96 parts (10 mole parts) trimellitic anhydride were added to a propylene oxide adduct of bisphenol A (average) Addition mol number 2.2) 175 parts (10 mole parts), ethylene glycol 155 parts (50 mole parts), neopentyl glycol 156 parts (30 mole parts), diethylene glycol 53 parts (10 mole parts), isophthalic acid 581 parts ( 70 mol parts), amorphous resin (b5) was obtained in the same manner as in Example 1 except that it was changed to dodecenyl succinic anhydride 268 parts (20 mol parts) and trimellitic anhydride 96 parts (10 mol parts). .
10 parts of the non-linear crystalline polyester (a1), 980 parts of the amorphous resin (b1) and 10 parts of the resin dispersant (c1), 385 parts of the non-linear crystalline polyester (a4) and the amorphous resin (b5 The toner binder (10) of the present invention was obtained in the same manner as in Example 1 except that 555 parts and the resin dispersant (c1) were changed to 60 parts.

<Example 11>
875 parts (50 mole parts) of propylene oxide adduct of bisphenol A (average addition mole number 2.2), 813 parts (50 mole parts) of ethylene oxide adduct of bisphenol A (average addition mole number 2.2), isophthalic acid 456 5 parts (55 moles), 536 parts dodecenyl succinic anhydride (40 moles), 144 parts trimellitic anhydride (15 moles), 11 parts acrylic acid, 1.5 parts dibutyltin oxide under nitrogen atmosphere While stirring uniformly at a temperature of 135 ° C., a mixed solution of 270 parts of styrene, 30 parts of 2-ethylhexyl acrylate, and 20 parts of azobisisobutyronitrile was dropped at 135 ° C. over 4 hours and maintained at 135 ° C. Aged for 5 hours. Subsequently, the temperature was further raised to 230 ° C. and stirring was continued. When the ½ drop temperature reached a predetermined value (Table 2), the reaction was terminated, the reaction product was taken out of the container, cooled, and then pulverized. Thus, an amorphous resin (b6) was obtained.
10 parts of non-linear crystalline polyester (a1), 980 parts of amorphous resin (b1) and 10 parts of resin dispersant (c1) are combined with 100 parts of non-linear crystalline polyester (a5) and amorphous resin (b6). ) A toner binder (11) of the present invention was obtained in the same manner as in Example 1 except that 800 parts and 100 parts of the resin dispersant (c1) were changed.

<Example 12>
875 parts (50 mole parts) of propylene oxide adduct of bisphenol A (average addition mole number 2.2), 813 parts (50 mole parts) of ethylene oxide adduct of bisphenol A (average addition mole number 2.2), isophthalic acid 456 5 parts (55 mole parts), 536 parts dodecenyl succinic anhydride (40 mole parts), 144 parts trimellitic anhydride (15 mole parts), 11 parts acrylic acid, 270 parts styrene and 30 parts 2-ethylhexyl acrylate, azo 20 parts of bisisobutyronitrile, 1400 parts (80 mole parts) of a propylene oxide adduct of bisphenol A (average addition mole number 2.2), 78 parts (15 mole parts) neopentyl glycol, 26.5 parts diethylene glycol ( 5 mol parts), isophthalic acid 581 parts (70 mol parts), dodecenyl succinic anhydride 134 parts ( 0 parts by mole), 192 parts (20 parts by mole) of trimellitic anhydride, 10 parts of acrylic acid, 300 parts of styrene, 40 parts of 2-ethylhexyl acrylate, 18 parts of azobisisobutyronitrile, and Example 11 In the same manner, an amorphous resin (b7) was obtained.
Next, 10 parts of the non-linear crystalline polyester (a1), 980 parts of the amorphous resin (b1) and 10 parts of the resin dispersant (c1) were added to 280 parts of the non-linear crystalline polyester (a6), and the amorphous resin. (B7) A toner binder (12) of the present invention was obtained in the same manner as in Example 1 except that 660 parts and resin dispersant (c1) were changed to 60 parts.

<Example 13>
10 parts of non-linear crystalline polyester (a1), 980 parts of amorphous resin (b1) and 10 parts of resin dispersant (c1) are mixed with 240 parts of non-linear crystalline polyester (a1) and amorphous resin (b2 ) Toner binder (13) of the present invention was obtained in the same manner as in Example 1 except that 700 parts and resin dispersant (c2) were changed to 60 parts.

<Example 14>
10 parts of non-linear crystalline polyester (a1), 980 parts of amorphous resin (b1) and 10 parts of resin dispersing agent (c1), 240 parts of non-linear crystalline polyester (a2), amorphous resin (b3 ) Toner binder (14) of the present invention was obtained in the same manner as in Example 1 except that 700 parts and resin dispersant (c3) were changed to 60 parts.

The characteristic values of the non-linear crystalline polyesters (a1) to (a6), the amorphous resins (b1) to (b7) and the resin dispersants (c1) to (c6) obtained in the examples are shown in Tables 1 to 3. Summarized in

<Examples 15 to 28>
Toner binder for evaluation {toner binder of any of Examples 1-14}, carbon black {8 parts MA100 manufactured by Mitsubishi Chemical Co., Ltd.), charge control agent {Spiron black TRH manufactured by Hodogaya Chemical Co., Ltd.} 1 Henshell mixer {FM made by Mitsui Miike Chemicals Co., Ltd.
10B}, and premixed at 130 ° C., twin-screw kneader {PCM- manufactured by Ikegai Co., Ltd.
30} to obtain a molten mixture.
The melt-kneaded product is cooled to about 25 ° C., then coarsely pulverized, and further finely pulverized using a supersonic jet pulverizer, Labojet {manufactured by Nippon Pneumatic Industry Co., Ltd.}, and then an air classifier {Nippon Pneumatic The toner particles were obtained by classification with MDS-I} manufactured by Kogyo Co., Ltd. Subsequently, 100 parts of toner particles and 0.3 part of colloidal silica {Aerosil R972 manufactured by Nippon Aerosil Co., Ltd.} were uniformly mixed to obtain the toner of the present invention.

<Comparative Examples 1-14>
100 parts of the toner binder for evaluation {the toner binder of any one of Examples 1 to 14} and the non-linear crystalline polyester and the amorphous resins (b1) to (b7) {in proportions corresponding to Examples 1 to 14 Nonlinear crystalline polyesters (a1) to (a6) and amorphous resins (b1) to (b7) were used so that the total amount would be 100 parts. A comparative toner was obtained in the same manner as in Examples 15 to 28 except that the total amount of the resin dispersants (c1) to (c6) was not changed} was 100 parts. Correspondingly, Comparative Examples 1 to 14 were used.

<Evaluation>
The obtained toner was evaluated for wax dispersion particle size, wax dispersion state, fluidity, minimum fixing temperature, hot offset occurrence temperature, and image deterioration, and Table 4 shows the results.

<Wax dispersion particle size>
Images taken with a transmission electron microscope (H-7100, manufactured by Hitachi, Ltd., 10,000 times) were analyzed with commercially available image processing software (WinROOF, manufactured by Mitani Corporation), and the average dispersed particle size of the wax was calculated.

<Wax dispersion state>
It observed with the transmission electron microscope (Hitachi Ltd. H-7100 type, 5000 times), and determined with the following reference | standard.
○: Wax is uniformly dispersed throughout and the particle size of the wax is uniform (no wax having a large particle size exists)
Δ: A small amount of wax with a large particle size exists x: Many waxes with a large particle size exist

<Fluidity>
The fluidity index was measured and evaluated using a powder tester manufactured by Hosokawa Micron. The larger the value, the better the fluidity.

<Minimum fixing temperature (MFT)>
30 parts of evaluation toner and 800 parts of ferrite carrier (F-150; manufactured by Powdertech) are uniformly mixed to form a two-component developer for evaluation. Using this developer, a developing machine {copier (AR5030; sharp) Unfixed image developed with the product excluding the fixing unit} manufactured by the fixing unit {the copier (SF8400A; manufactured by Sharp) with the fixing unit of the copying machine modified to make the heat roller temperature variable} the process speed 145 mm / sec. To obtain a fixed image {the heat roller temperature was changed from 110 ° C. to 230 ° C. every 10 ° C.}. Subsequently, the minimum temperature of the hot roller at which the residual ratio of the image density after rubbing the fixed image 5 times with a PPC pad paper to which a load of 300 g was applied was 70% or more was defined as the minimum fixing temperature.

<Hot offset generation temperature (HOT)>
While obtaining a fixed image in the same manner as the minimum fixing temperature (MFT), the minimum temperature of the hot roller when hot offset (visual observation) occurred was defined as the hot offset generation temperature.

<Image degradation>
Continuous development was performed in the same manner as the minimum fixing temperature (MFT) to obtain an unfixed image, and the 1000th unfixed image was determined according to the following criteria.
○: Image deterioration (density unevenness, etc.) cannot be confirmed visually Δ: Image deterioration (density unevenness) can be confirmed visually x: There are undeveloped locations

The toners using the toner binder of the present invention (Examples 15 to 27) were significantly better in image deterioration than the comparative toner. Further, the fixing characteristics (minimum fixing temperature, offset occurrence temperature) were improved, and the fluidity was greatly improved.

Claims (7)

The ratio of the 1/2 drop temperature to the melting temperature by DSC {(1/2 drop temperature) / (melting temperature)} is 0.9 or more and less than 1.1, and 3 to 4 polyhydric alcohols and 3 to 3 A non-containing composition comprising at least one selected from the group consisting of tetravalent polyvalent carboxylic acids as an essential constituent monomer, the essential constituent monomer being contained in an amount of 0.1 to 20 moles per 100 moles of the alcohol component. Linear crystalline polyester (A);
Formula (I):

(R is an alkylene having 2 or 3 carbon atoms, x and y are integers of 0 to 10, and the sum of x and y is 1 to 16). At least one amorphous resin selected from the group consisting of a polyester, a polyester polyamide, and a hybrid resin containing polyester, wherein the constituent monomer is a resin containing at least 40 mol% with respect to 100 mol of the alcohol component. B) and
Graft weight having a structure in which a polyolefin resin (C1) having a softening point of 100 to 170 ° C., a vinyl resin (C2) having an SP value of 10.6 to 12.6, and a vinyl monomer constituting (C2) are grafted to (C1) It consists of a resin dispersant (C) consisting of a coalescence (C3),
Based on the weight of the non-linear crystalline polyester (A), the amorphous resin (B) and the resin dispersant (C), the content of the non-linear crystalline polyester (A) is 1 to 49% by weight, A toner binder, wherein the content of the crystalline resin (B) is 50 to 98% by weight and the content of the resin dispersant (C) is 1 to 14% by weight. Non-linear crystalline polyester (A) is obtained by polycondensing an alcohol component containing at least 50 mol% of a diol having 2 to 6 carbon atoms and a carboxylic acid component containing at least 70 mol% of an aliphatic carboxylic acid. The toner binder according to claim 1, which is a resin. The toner binder according to claim 1 or 2, wherein the non-linear crystalline polyester (A) has a ½ drop temperature of 85 to 140 ° C. The toner binder according to any one of claims 1 to 3, wherein the amorphous resin (B) has a ½ drop temperature of 70 to 180 ° C and a glass transition point of 50 to 85 ° C. The vinyl resin (C2) is a monomer having an SP value of at least 11.0, and at least one selected from the group consisting of (meth) acrylonitrile monomers and α, β-unsaturated carboxylic acids as an essential constituent monomer The toner binder according to claim 1. The vinyl resin (C2) is a monomer having an SP value of at least 11.0, and at least one selected from the group consisting of (meth) acrylonitrile monomers and α, β-unsaturated carboxylic acids, and a styrene monomer The toner binder according to claim 1, wherein the toner binder is an essential constituent monomer. A toner comprising the toner binder according to claim 1 and a colorant.