JP2007271789A - Toner binder and toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner binder hardly causing degradation in an image. <P>SOLUTION: The toner binder comprises: (A) crystalline polyester having a number average molecular weight of 5,000 to 10,000, a weight average molecular weight of 150,000 to 8,000,000, the maximum peak temperature of 70 to 140°C in heat of fusion, a ratio ä(half-fall temperature)/(peak temperature)} of the half-fall temperature to the maximum peak temperature of the heat of fusion ranging from 0.8 to 1.3; and (B) a dispersant comprising (B1) a polyolefin resin having a softening point of 100 to 160°C, (B2) a vinyl resin having a SP of 1.5 to 11.7, and (B3) a grafted polymer having a grafted structure of the vinyl monomers constituting (B2) to (B1). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

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

  Conventionally, from the viewpoint of low temperature fixability, storage stability and durability, the number average molecular weight is 5,000 to 10,000, the weight average molecular weight is 150,000 to 8,000,000, and the maximum peak temperature of heat of fusion is 60 to A crystalline polyester having a ratio between a softening point and a maximum peak temperature of heat of fusion (softening point / peak temperature) of 0.6 to 1.3, and a toner comprising the crystalline polyester as a binder resin It has been proposed (Patent Document 1).

JP 2004-61875 A

However, conventionally, the wax added at the time of tonerization for imparting releasability and the crystalline polyester are difficult to mix, so that the wax cannot be sufficiently dispersed, and the wax becomes non-uniform in the toner. is there. 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.

<Crystalline polyester (A)>
The number average molecular weight (Mn) of the crystalline polyester (A) is preferably from 5,000 to 10,000, more preferably from 5,500 to 9,000, particularly preferably from the viewpoints of storage stability and low-temperature fixability. 6,000 to 8,000.
From the viewpoint of durability, the weight average molecular weight (Mw) of the crystalline polyester (A) is preferably 150,000 to 8 million, more preferably 300,000 to 6 million, and particularly preferably 1,200,000 to 5,000,000.

  The number average molecular weight (Mn) and the weight average molecular weight (Mw) are measured by gel permeation chromatography (GPC) using polystyrene having a known molecular weight as a standard substance {JIS K0124: 2002 (general rule for high performance liquid chromatography), corresponding ISO: conforming to ISO 11843-1: 1997 (Capability of detection-Part1: Terms and definitions.)} (For example, measurement conditions are as follows).

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)

  The maximum peak temperature (° C.) of the heat of fusion of the crystalline polyester (A) is preferably from 70 to 140, more preferably from 90 to 140, particularly preferably from 100 to 130, from the viewpoints of fixability, storage stability and durability. It is.

<Maximum peak heat of fusion>
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. The temperature is increased at a time per minute and the change in endothermic heat is measured. A graph of “endothermic heat generation” and “temperature” is drawn, and the temperature corresponding to the maximum peak of the endothermic heat generation is the maximum peak temperature of the heat of fusion.

  75-160 is preferable, as for 1/2 fall temperature (degreeC) of crystalline polyester (A), More preferably, it is 95-150, Most preferably, it is 110-140. Within this range, the offset resistance is further improved.

<1/2 drop temperature>
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 ratio {(1/2 drop temperature) / (peak temperature)} of “1/2 drop temperature” and “maximum heat of fusion peak temperature” of the crystalline polyester (A) is 0.8 to 1.3. More preferably, it is 0.9 to 1.2, particularly preferably more than 1.0 and 1.2 or less.

In the present invention, “crystallinity” means that the ratio {(1/2 drop temperature) / (peak temperature)} of the 1/2 drop temperature to the maximum peak temperature of the heat of fusion is in the above range. .
On the other hand, the term “amorphous” means that the ratio {(1/2 drop temperature) / (peak temperature)} of the 1/2 drop temperature to the maximum peak temperature of the heat of fusion is greater than 1.3 and 4.0 or less { Preferably it means 1.5 to 3.0}.

In order to set the number average molecular weight (Mn), the weight average molecular weight (Mw), the maximum peak temperature of the heat of fusion, the 1/2 drop temperature, and the ratio {(1/2 drop temperature) / (peak temperature)} to the above ranges, Easily carried out by adjusting the molar ratio (OH / COOH) of the divalent polyol and divalent polycarboxylic acid described later (OH / COOH), the content and type of the trivalent or higher polyol and / or polycarboxylic acid, or selecting the reaction conditions. Can do.
That is, when the molar ratio (OH / COOH) of the divalent monomer approaches 1, the number average molecular weight (Mn) increases, and the ½ drop temperature and the maximum peak temperature of the heat of fusion both increase and move away from 1. As the number average molecular weight (Mn) decreases, the ½ drop temperature and the maximum peak temperature of the heat of fusion both decrease. Further, when the content of the trivalent or higher monomer is increased, the weight average molecular weight (Mw) is increased and the ½ drop temperature is increased. Therefore, {(1/2 drop temperature) / (peak temperature)} can be increased by increasing the content of the trivalent or higher monomer.

The crystalline polyester (A) can be obtained by condensation polymerization of a 2-6 valent polyol and a 2-4 valent polycarboxylic acid.
Diols (dihydric polyols) include bis {4-hydroxypolyoxypropylenephenyl} propane, bis {4-hydroxypolyoxyethylenephenyl} propane, bis {4-hydroxypolyoxypropylene / polyoxyethylenephenyl} propane, ethylene Glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6 -Hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A and hydrogenated bisphenol Etc. The.
Among these, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol and 1,4-butanediol are preferable, and 1,4-butanediol is more preferable.

Examples of the trivalent to hexavalent polyol include sorbitol, 1,2,3,6-hexanetetraol, sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5. -Pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene and the like.
Of these, glycerin and trimethylolpropane are preferred.

  The content (mol%) of the diol unit is preferably 60 to 100, more preferably 80 to 100, and particularly preferably 90 to 100, based on the number of moles of the divalent to hexavalent polyol unit. Furthermore, the diol is preferably one kind of diol.

Dicarboxylic acids (divalent polycarboxylic acids) include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, malon Acid, n-dodecenyl succinic acid, isododecenyl succinic acid, n-dodecyl succinic acid, isododecyl succinic acid, n-octenyl succinic acid, n-octyl succinic acid, isooctenyl succinic acid, isooctyl succinic acid, and anhydrides thereof Or a lower alkyl ester etc. are mentioned.
Of these, maleic acid, fumaric acid, isophthalic acid, terephthalic acid, adipic acid and alkenyl succinic acid are preferred, and fumaric acid is more preferred.

Examples of the trivalent to tetravalent polycarboxylic acids (including acid anhydrides and lower alkyl esters) include 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, and 1,2,4-naphthalenetricarboxylic acid. Acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, tetra (Methylene carboxyl) Methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, emporic trimer acid, their acid anhydrides, lower alkyl esters and the like.
Of these, 1,2,4-benzenetricarboxylic acid (trimellitic acid) is preferred.

  The content (mol%) of the dicarboxylic acid unit is preferably 60 to 100, more preferably 80 to 100, and particularly preferably 90 to 100, based on the number of moles of the divalent to tetravalent polycarboxylic acid unit. Further, the dicarboxylic acid is preferably one kind of dicarboxylic acid.

  The molar ratio of polycarboxylic acid to polyol (polycarboxylic acid / polyol) is preferably from 0.9 to less than 1.0, more preferably from 0.95 to less than 1.0, particularly preferably from the viewpoint of storage stability. Is 0.97 or more and less than 1.0.

A known method or the like can be applied to the polycondensation reaction between the polyol and the polycarboxylic acid {for example, polycondensation can be performed using a reaction catalyst in an inert gas atmosphere}.
Known catalysts can be used as the reaction catalyst, and examples thereof include dibutyltin oxide, tetrabutyl titanate, potassium titanyl oxalate, and zirconium acetate.
When using a reaction catalyst, the amount used (% by weight) is preferably from 0.01 to 2, more preferably from 0.05 to 1, and particularly preferably from 0.1 to 2, based on the weight of the polyol and polycarboxylic acid. 0.5.
The reaction temperature for the polycondensation is preferably about 120 to 270 ° C, more preferably 190 to 230 ° C.

<Dispersant (B)>
Examples of the polyolefin resin (B1) include an olefin polymer (B11), an oxidized product (B12) obtained by oxidizing the olefin polymer (B11), a modified product (B13) obtained by modifying the olefin polymer (B11), and an olefin. A copolymer (B14) 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 (B11) include polyethylene, polypropylene, ethylene / propylene copolymer, ethylene / 1-butene copolymer, and propylene / 1-hexene copolymer. The olefin polymer (B11) has only to 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}.

Examples of the oxidant (B12) include an oxidant obtained by oxidizing the polymer (B11) with air, oxygen, and / or ozone by a known method (for example, US Pat. No. 3,692,877).
As the modified product (B13), a known method (for example, JP-A-2001-278985), the polymer (B11) 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.
The copolymer (B14) includes polyethylene / acrylic acid copolymer, polypropylene / maleic anhydride copolymer, ethylene / propylene / methyl acrylate copolymer, ethylene / methyl acrylate copolymer, and propylene / methyl acrylate copolymer. A polymer etc. are mentioned.

  Among these, a polymer (B11), an oxidant (B12), and a modified body (B13) are preferable, a polymer (B11) is more preferable, and polyethylene and polypropylene are particularly preferable.

The softening point (° C.) of the polyolefin resin (B1) is preferably 100 to 160, more preferably 110 to 160, and particularly preferably 125 to 155. Within this range, when applied to toner, the fluidity and release effect of the toner are further improved.
The softening point is measured in accordance with JIS K2207-1996.

The melt viscosity (160 ° C., mPa · s) of the polyolefin resin (B1) 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 (B1) 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 (B1) has high crystallinity Once melted, it is hard to solidify even when cooled below the softening point. }.

The number average molecular weight (Mn) of the polyolefin resin (B1) is preferably 500 to 20000, more preferably 1000 to 15000, and particularly preferably 1500 to 10,000 from the viewpoints of filming on a carrier and releasability. .
The weight average molecular weight (Mw) of the polyolefin resin (B1) is preferably from 800 to 100,000, more preferably from 1500 to 60000, particularly preferably from 2000 to 30000, from the viewpoints of filming on the carrier and the releasability. .

The penetration of the polyolefin resin (B1) 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 (B2) 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. The sum (V) of the sum (ΔH) and the molar volume (Δv _i ) can be used.

The vinyl resin (B2) may be a homopolymer, but is preferably a copolymer (copolymer), more preferably a homopolymer SP value of 11.0 to 18.0 {preferably 11.0 to 16. A copolymer (B22) of a vinyl monomer (b221) that becomes 0} and a vinyl monomer (b222) that has a homopolymer SP value of 8.0 or more and less than 11.0 {preferably 9.0 to 10.8} ).

The vinyl monomer (b221) is not limited as long as the SP value of the homopolymer of (b221) 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 (b222) is not limited as long as the SP value of the homopolymer of (b222) 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, benzylstyrene, etc.}; 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 (B3) has a structure in which the vinyl monomer {vinyl monomer (b211), vinyl monomer (b221), and vinyl monomer (b222)} constituting the vinyl resin (B2) is grafted to the olefin resin (B1). However, each preferable range is as described above.

The number average molecular weight of the dispersant (B) is preferably 1500 to 100,000, more preferably 2500 to 50000, and particularly preferably 2800 to 20000.
The weight average molecular weight of the dispersant (B) is preferably 5,000 to 200,000, more preferably 6,000 to 100,000, and particularly preferably 7,000 to 50,000.

  The glass transition point (Tg; ° C) of the dispersant (B) 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.

The content (% by weight) of the olefin resin (B1) is preferably 0.5 to 70, more preferably 1 to 20, particularly preferably 1 to 10, based on the weight of the dispersant (B).
The content (% by weight) of the vinyl resin (B2) is preferably 29 to 98.5, more preferably 34 to 79, and particularly preferably 50 to 59, based on the weight of the dispersant (B).
The content (% by weight) of the graft polymer (B3) is preferably 1 to 70, more preferably 20 to 65, particularly preferably 40 to 60, based on the weight of the dispersant (B).

For example, the dispersant (B) is obtained by dissolving or dispersing the polyolefin resin (B1) in a solvent {toluene, xylene and the like}, heating to about 100 to 200 ° C., and then forming a vinyl monomer {constituent monomer of the vinyl resin (B2): Hereinafter, the same} is dropped and polymerized.
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 use amount (% by weight) of the olefin resin (B1) is preferably 1 to 90, more preferably 5 to 80, and particularly preferably 10 to 40, based on the weight of (B1) and the vinyl monomer. .
The use amount (% by weight) of the vinyl monomer is preferably 10 to 99, more preferably 20 to 95, and particularly preferably 60 to 90, based on the weight of (B1) 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 (B1) and the vinyl monomer. .8-3.

The content (% by weight) of the crystalline polyester (A) is preferably 80 to 99.5, more preferably 85 to 99, particularly preferably based on the weight of the crystalline polyester (A) and the dispersant (B). Is 92-98.
The content (% by weight) of the dispersant (B) is preferably 0.5 to 20, more preferably 1 to 15, particularly preferably based on the weight of the crystalline polyester (A) and the dispersant (B). 2-8.
Within these ranges, the low-temperature fixability, the smoothness of the fixing surface, the offset resistance and the blocking resistance are further improved.

The toner binder for developing an electrostatic charge image of the present invention may contain an amorphous resin (C) and / or a wax (D) in addition to the crystalline polyester (A) and the dispersant (B).
<Amorphous resin (C)>
As the amorphous resin (C), a known polyester resin {amorphous polyester and amorphous polyester polyamide, etc .; for example, Patent Document 1, JP-A-2001-265056, etc.}, a known vinyl resin {amorphous Styrene-acrylic resin etc .; for example, JP-A-7-146582 etc. and known hybrid resins {hybrid resins in which amorphous polyester and vinyl resin are chemically bonded, etc .; for example, JP-A-10-087839, JP-A-8-54753, etc.} are included.
Of these, amorphous polyesters and hybrid resins are preferable from the viewpoint of fixing properties and compatibility with crystalline polyesters, and amorphous polyesters are more preferable.
When the amorphous resin (C) is contained, the content (% by weight) of the amorphous resin (C) is preferably 1 to 30, more preferably 2 based on the weight of the crystalline polyester (A). -20, particularly preferably 5-15.

<Wax (D)>
Examples of the wax (D) include ester wax {carnauba wax, montan wax, rice wax and the like}, long-chain aliphatic alcohols having 30 to 50 carbon atoms, and long-chain fatty acids having 30 to 50 carbon atoms.
When the wax (D) is contained, the content (% by weight) of the wax (D) is preferably 0.1 to 8, more preferably 0.5 to 6, based on the weight of the crystalline polyester (A). Especially preferably, it is 0.8-5.

  The toner binder of the present invention is a method of melt-mixing or powder-mixing a crystalline polyester (A) and a dispersant (B), and if necessary, an amorphous resin (C) and / or a wax (D) <1> In addition, a method <2> in which the crystalline polyester (A) and the amorphous resin (C) are previously melt-mixed and then the dispersant (B) and, if necessary, the wax (D) are powder mixed, and the dispersant (B ) And if necessary, in the presence of the wax (D), the crystalline polyester (A) is polymerized, and if necessary, the amorphous resin (C) and / or the wax (D) is melt-mixed or powder-mixed <3> Etc.

The toner binder of the present invention can be mixed with a colorant and a charge control agent to form a toner. If necessary, a mold release agent (wax), a fluidizing agent, and the like can be further contained.
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.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to this. The number average molecular weight, weight average molecular weight, ratio {(1/2 drop temperature) / (peak temperature)}, glass transition point and softening point were measured by the methods described above. Unless otherwise specified, parts means parts by weight and% means% by weight.

<Example 1>
1,4-butanediol 1010 parts (11.2 mole parts), fumaric acid 1276 parts (11.0 mole parts), trimellitic anhydride 20 parts (0.1 mole parts), hydroquinone 2 parts and dibutyltin oxide 4 The parts were reacted at 160 ° C. for 5 hours under a nitrogen atmosphere, and then reacted at 8.3 kPa and 160 ° C. for 12 hours to obtain crystalline polyester (AA1).

  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 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. Next, the solvent was distilled off to obtain dispersant (BB1) {SP value of styrene-acrylonitrile-monobutyl maleate copolymer (vinyl resin B2) contained: 11.0}.

  80 parts of crystalline polyester (AA1) and 20 parts of dispersant (BB1) were mixed for 10 minutes with a Henschel mixer {FM10B manufactured by Mitsui Miike Chemical Co., Ltd.} to obtain toner binder (1) of the present invention.

<Example 2>
“1,4-butanediol 1010 parts (11.2 mole parts), fumaric acid 1276 parts (11.0 mole parts), trimellitic anhydride 20 parts (0.1 mole parts)” 812 parts (9.0 mole parts) of butanediol, 260 parts (2.2 mole parts) of 1,6-hexanediol, 760 parts (6.5 mole parts) of fumaric acid, 800 parts of trimellitic anhydride (4.2 parts) The crystalline polyester (AA2) was obtained in the same manner as in Example 1 except that the molar part was changed to “mol part)”.

  1020 parts of xylene, 2000 parts of low molecular weight polypropylene {Bicol 660P manufactured by Sanyo Chemical Industries, 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. Subsequently, the solvent was distilled off to obtain dispersant (BB2) {SP value of styrene-acrylonitrile-butyl acrylate-acrylic acid copolymer (vinyl resin B2) contained: 10.8}.

  85 parts of crystalline polyester (AA2) and 15 parts of dispersant (BB2) were premixed for 5 minutes with a Henschel mixer {FM10B manufactured by Mitsui Miike Chemical Co., Ltd.}, and then with a continuous kneader, a jacket temperature of 150 ° C, The toner binder (2) of the present invention was obtained by melt-mixing with a residence time of 3 minutes.

<Example 3>
“1,4-butanediol 1010 parts (11.2 mole parts), fumaric acid 1276 parts (11.0 mole parts), trimellitic anhydride 20 parts (0.1 mole parts)” Butanediol 911 parts (10.1 mole parts), 1,6-hexanediol 130 parts (1.1 mole parts), fumaric acid 810 parts (7.0 mole parts), adipic acid 238 parts (1.6 mole parts) ), Trimellitic anhydride 400 parts (2.1 mole parts) ”to obtain a crystalline polyester (AA3) in the same manner as in Example 1.

  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. Next, the solvent was distilled off to obtain dispersant (BB3) {SP value of styrene-acrylonitrile-butyl acrylate-acrylic acid copolymer (vinyl resin B2) contained: 10.7}.

  98 parts of crystalline polyester (AA3) and 2 parts of dispersant (BB3) were premixed for 5 minutes with a Henschel mixer {FM10B manufactured by Mitsui Miike Chemical Co., Ltd.}, and then with a continuous kneader, a jacket temperature of 150 ° C, The toner binder (3) of the present invention was obtained by melt-mixing with a residence time of 3 minutes.

<Example 4>
“1,4-butanediol 1010 parts (11.2 mole parts), fumaric acid 1276 parts (11.0 mole parts), trimellitic anhydride 20 parts (0.1 mole parts)” Butanediol 911 parts (10.1 mole parts), 1,6-hexanediol 130 parts (1.1 mole parts), fumaric acid 957 parts (8.2 mole parts), adipic acid 396 parts (2.7 mole parts) The crystalline polyester (AA4) was obtained in the same manner as in Example 1 except that the change was changed to “)”.

  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. Then, the solvent was distilled off to obtain dispersant (BB4) {SP value of styrene-acrylonitrile-butyl acrylate-acrylic acid copolymer (vinyl resin B2) contained: 11.5}.

  Bis {4-hydroxypolyoxypropylene (2.2 mol) phenyl} propane 1575 parts (90 mol parts), bis {4-hydroxypolyoxyethylene (2.2 mol) phenyl} propane 163 parts (10 mol parts), 377 parts (65 parts by mole) of fumaric acid and 4 parts of dibutyltin oxide were reacted at 220 ° C. for 8 hours under a nitrogen atmosphere, further reacted at 8.3 kPa and 220 ° C. for 1 hour, 336 parts (35 mole parts) of merit acid was added and reacted at 210 ° C. for 24 hours to obtain an amorphous resin (CC1).

  92.5 parts of crystalline polyester (AA4), 0.5 part of dispersant (BB4) and 7 parts of amorphous resin (CC1) are premixed for 5 minutes with a Henschel mixer {FM10B manufactured by Mitsui Miike Chemical Co., Ltd.} Then, the mixture was melt-mixed with a continuous kneader at a jacket temperature of 150 ° C. and a residence time of 3 minutes to obtain a toner binder (4) of the present invention.

<Example 5>
“1,4-butanediol 1010 parts (11.2 mole parts), fumaric acid 1276 parts (11.0 mole parts), trimellitic anhydride 20 parts (0.1 mole parts)” Butanediol 911 parts (10.1 mole parts), 1,6-hexanediol 130 parts (1.1 mole parts), fumaric acid 638 parts (5.5 mole parts), adipic acid 792 parts (5.4 mole parts) The crystalline polyester (AA5) was obtained in the same manner as in Example 1 except that the change was changed to “)”.

  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. Next, the solvent was distilled off to obtain dispersant (BB5) {SP value of styrene-acrylonitrile-butyl acrylate-acrylic acid copolymer (vinyl resin B2) contained: 11.7}.

  "Bis {4-hydroxypolyoxypropylene (2.2 mol) phenyl} propane 1575 parts (90 mol parts), bis {4-hydroxypolyoxyethylene (2.2 mol) phenyl} propane 163 parts (10 mol parts) And 377 parts (65 mole parts) of fumaric acid ", 420 parts (24 mole parts) of bis {4-hydroxypolyoxypropylene (2.2 moles) phenyl} propane, bis {4-hydroxypolyoxyethylene (2. 2 mol) Phenyl} propane 1235 parts (76 mole parts) and terephthalic acid 714 parts (86 mole parts) "and" Trimellitic anhydride 336 parts (35 mole parts) "were not used In the same manner as in Example 4, an amorphous resin (CC2) was obtained.

  95 parts of crystalline polyester (AA5), 1 part of dispersant (BB5) and 4 parts of amorphous resin (CC2) were premixed for 5 minutes with a Henschel mixer {FM10B manufactured by Mitsui Miike Chemical Co., Ltd.} The toner binder (5) of the present invention was obtained by melt mixing with a near kneader at a jacket temperature of 150 ° C. and a residence time of 3 minutes.

<Example 6>
“1,4-butanediol 1010 parts (11.2 mole parts), fumaric acid 1276 parts (11.0 mole parts), trimellitic anhydride 20 parts (0.1 mole parts)” 812 parts (9.0 mole parts) of butanediol, 260 parts (2.2 mole parts) of 1,6-hexanediol, 1060 parts (9.1 mole parts) of fumaric acid, 190 parts of trimellitic anhydride (1.0 parts) A crystalline polyester (AA6) was obtained in the same manner as in Example 1 except that the molar part was changed to "mol part)".

  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. Next, the solvent was distilled off to obtain dispersant (BB6) {SP value of styrene-acrylonitrile-butyl acrylate-acrylic acid copolymer (vinyl resin B2) contained: 10.5}.

  81 parts of crystalline polyester (AA6), 7 parts of dispersant (BB6) and 12 parts of amorphous resin (CC1) were premixed for 5 minutes with a Henschel mixer {FM10B manufactured by Mitsui Miike Chemical Co., Ltd.} The toner binder (6) of the present invention was obtained by melt mixing with a near kneader at a jacket temperature of 150 ° C. and a residence time of 3 minutes.

<Examples 7 to 12>
Toner binder for evaluation {toner binder of any one of Examples 1 to 6}, carbon black {8 parts MA100 manufactured by Mitsubishi Chemical Co., Ltd.), charge control agent {Spiron black TRH manufactured by Hodogaya Chemical Co., Ltd.} 1 Parts, 3 parts of low molecular weight polypropylene {Sanyo Chemical Industries Co., Ltd. Viscol 440P}, and 1 part of low molecular weight polyethylene {Sanwa Kasei Kogyo Co., Ltd. Sun Wax LEL-400} FM10B}, and premixed, and melt-kneaded with a biaxial kneader {PCM-30, manufactured by Ikegai Co., Ltd.) set at 130 ° C. 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 1-6>
100 parts of the toner binder for evaluation {the toner binder of any one of Examples 1 to 6} are added to crystalline polyesters (AA1) to (AA6) and amorphous resins (CC1) to (CC2) {in Examples 1 to 6 Crystalline polyesters (AA1) to (AA6) and amorphous resins (CC1) to (CC2) were used so that the corresponding ratios totaled 100 parts. A comparative toner was obtained in the same manner as in the above (1) except that the dispersants (BB1) to (BB6) were changed to a total of 100 parts, {corresponding to Examples 1 to 6 respectively. And it was set as Comparative Examples 1-6.

<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 these results are shown in Tables 4 and 5.

<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 7 to 12) were significantly better in image deterioration than the comparative toners. Further, the fixing characteristics (minimum fixing temperature, offset occurrence temperature) were improved, and the fluidity was greatly improved.

Claims (5)

Number average molecular weight 5,000-10,000, weight average molecular weight 150,000-8 million, maximum peak temperature of heat of fusion 70-140 ° C., ratio of 1/2 drop temperature to maximum peak temperature of heat of fusion {(1 / 2 temperature drop) / (peak temperature)} 0.8 to 1.3 crystalline polyester (A),
Graft weight having a structure in which a polyolefin resin (B1) having a softening point of 100 to 160 ° C., a vinyl resin (B2) having an SP value of 10.5 to 11.7, and a vinyl monomer constituting (B2) are grafted to (B1) A toner binder for developing an electrostatic charge image, comprising a dispersant (B) comprising a combination (B3). 2. The toner binder according to claim 1, wherein the molar ratio of the polycarboxylic acid unit to the polyol unit (polycarboxylic acid unit / polyol unit) of the crystalline polyester (A) is 0.9 or more and less than 1.0. The toner binder according to claim 2, comprising 60 to 100 mol% of a dicarboxylic acid unit as the polycarboxylic acid unit. Based on the total weight of the crystalline polyester (A) and the dispersant (B), the content of the crystalline polyester (A) is 80 to 99.5% by weight, and the content of the dispersant (B) is 0.5 to The toner binder according to claim 1, wherein the toner binder is 20% by weight.  A toner comprising the toner binder according to claim 1 and a colorant.