JP2003098726A - Electrostatic charge image developing toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a developer having high durability in which wax is uniformly dispersed in a binder resin even when a polyester resin is used as the binder resin and toner spent by the wax is suppressed while stable image density is obtained, to provide an electrophotographic toner which can form stable images for a long time without producing irregular image density or the like even when the toner is left to stand in a high temperature and high humidity environment and which does not decrease the fixing temperature range, and to provide a method for forming an image by using the above electrophotographic toner. SOLUTION: The electrophotographic toner contains at least a polyester resin as a binder resin, a coloring agent, carnauba wax which has <=5 KOH mg/g acid value and from which free fatty acids are removed, and a grafted polymer of a polyolefin resin and a vinyl monomer having the solubility parameter (SP value) ranging from 10.6 to 12.6.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic toner used in an electrophotographic method, an electrostatic recording method, an electrostatic printing method and the like, and an image forming method using the toner.

[0002]

2. Description of the Related Art Conventionally, in order to fix an image visualized with an electrophotographic toner (hereinafter sometimes simply referred to as "toner"), a heat fixing method using a heat roll is generally used, and particularly, In the case of black toner, a fixing method in which a release agent is contained in the toner and oil is not used for a heat roll is the mainstream recently. The image forming method includes a one-component developing method and a two-component developing method, and the two-component developing method is widely used. However, since only toner is consumed, the toner concentration ratio in the developer is Since it decreases, it is necessary to keep the mixing ratio with the carrier constant, which causes a drawback that the developing device becomes large. on the other hand,
The one-component developing method does not have the above-mentioned drawbacks and has an advantage of downsizing of the apparatus, etc. However, since the carrier having the charge imparting function is not contained, the toner charge amount is lower than that of the two-component method.

In both the one-component developing system and the two-component developing system, if the polyolefin wax contained as a release agent is poorly dispersed in the binder resin, the charge distribution tends to be broad and the developability is deteriorated. Will end up. In particular, when the toner is left under high temperature and high humidity, the charge of the toner further decreases, and particularly in the one-component developing method, low image density and uneven image density become a problem.

Regarding the fixability of the toner, it is desirable that the lower fixing lower limit temperature and the higher offset temperature to the heat roll have a wider fixing temperature range. From this viewpoint, it is preferable to use a polyester resin as the binder resin. Although it is more advantageous than using a styrene acrylic resin, there is a problem that the dispersion of the wax used as a release agent is particularly deteriorated with respect to the polyester resin. Further, in order to improve the dispersion of the polyolefin wax in the binder resin, JP-A 2000-305319 discloses that the solubility parameter (SP value) with polyolefin is 10.0 to 1
It has been proposed to contain a graft polymer composed of a vinyl-based monomer in the range of 5.0, but the polyolefin wax has a remarkably poor so-called carrier spent in long-term copying and is not suitable for a highly durable developer.

[0005]

SUMMARY OF THE INVENTION Therefore, it is an object of the present invention to solve the above problems in the prior art and achieve the following objects. That is, an object of the present invention is to achieve a highly durable development in which even when a polyester resin is used as a binder resin, the wax is uniformly dispersed in the binder resin to obtain a stable image density and the toner spent by the wax is small. To provide the agent. Another purpose is electrophotography that does not cause image density unevenness even when the toner is left under high temperature and high humidity, forms a stable image for a long time, and does not narrow the fixing temperature range. To provide toner for use. Still another object is to provide an image forming method using the electrophotographic toner.

[0006]

Means for Solving the Problems As a result of intensive investigations by the present inventors to improve the dispersibility of a polyolefin wax in a polyester resin, a polyester resin was used as a binder resin by adding a specific graft polymer. Even when it was present, it was found that the polyolefin wax was uniformly dispersed, troubles such as a decrease in image density did not occur for a long period of time, and the fixability was not deteriorated, and the present invention was completed. Means for solving the above problems are as follows.

That is, the above-mentioned problem is (1) "at least a polyester resin as a binder resin, a colorant, a free fatty acid type carnauba wax having an acid value of 5 KOHmg / g or less, and a polyolefin resin and a solubility parameter. An electrophotographic toner containing a graft polymer composed of a vinyl monomer having a (SP value) in the range of 10.6 to 12.6, (2) "at least a polyester resin as a binder resin" , Colorant, acid number 30KOH
Oxidized rice wax of mg / g or less, and polyolefin resin and solubility parameter (SP value) of 10.6-1
(3) "at least polyester resin as binder resin, coloring agent, dipentaerythritol fatty acid ester, containing a graft polymer composed of a vinyl-based monomer in the range of 2.6" An electrophotographic toner containing wax and a graft polymer composed of a polyolefin resin and a vinyl monomer having a solubility parameter (SP value) in the range of 10.6 to 12.6 ", ( 4) "At least polyester resin as binder resin, colorant, acid value 30KO
Montane wax with Hmg / g or less, and polyolefin resin and solubility parameter (SP value) 10.6-1
An electrophotographic toner characterized by containing a graft polymer composed of a vinyl-based monomer in the range of 2.6, (5) "The average dispersed particle diameter of the wax contained in the toner is 0.05 to 0. The electrophotographic toner according to any one of the above items (1) to (4), characterized in that it is within a range of 0.8 μm.
Let B be the average dispersed particle diameter of the wax contained in the toner.
In any one of the above items (1) to (5), the wax dispersion ratio (a) represented by / A × 100 is in the range of 0.7 to 7.5. And the toner for electrophotography described above.

Further, means for solving the above problems are as follows:
The following modes are more preferable. <1> The graft polymer further contains a styrene monomer and / or a (meth) acrylic monomer as a constituent component. <2> Free fatty acid type carnauba wax has an acid value of 5KO
The acid value of the oxidized rice wax and montan wax is 30 or less. <3> The graft polymer has a softening point of 85 to 175 ° C.
A graft polymer composed of a vinyl monomer. <4> The electrophotographic toner according to any one of <1> to <3>, wherein the content of the graft polymer is 0.3 to 20% by weight based on the toner.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The electrophotographic toner of the present invention contains a binder resin, a colorant, a wax, and a specific graft polymer, and further contains other components, if necessary.

(Graft Polymer) The above-mentioned graft polymer is sometimes referred to as a "specific vinyl monomer" (hereinafter, referred to as "specific vinyl monomer") having at least a polyolefin resin and a solubility parameter (SP value) within a predetermined range. ), And preferably a styrene-based monomer and / or a (meth) acrylic-based monomer as a constituent component. That is, in the graft polymer, the main chain is the polyolefin, and the side chain has a vinyl polymer chain made of the specific vinyl monomer. Furthermore, it is preferable to have a styrene polymer chain composed of the styrene monomer and a (meth) acrylic polymer chain composed of the (meth) acrylic monomer in the side chains.

The olefins constituting the polyolefin resin of the present invention include ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-dodecene, 1-
Examples include octadecene. Examples of the polyolefin resin (1) include olefin polymers (1-1), olefin polymer oxides (1-2), modified olefin polymers (1-3) and olefins. Examples thereof include copolymers (1-4) with other polymerizable monomers. Examples of (1-1) include polyethylene, polypropylene, ethylene / propylene copolymers, ethylene / 1-butene copolymers and propylene / 1-hexene copolymers. Further, in the present invention, it suffices that the polymer structure has a polyolefin structure, and the monomer does not necessarily have to have an olefin structure. For example, polymethylene (such as Sazol wax) can be used. For (1-2), the above (1-1)
And the like. Examples of (1-3) include adducts of the maleic acid derivative (maleic anhydride, monomethyl maleate, monobutyl maleate, dimethyl maleate, etc.) of the above (1-1). As (1-4), unsaturated carboxylic acid [(meth) acrylic acid, itaconic acid, maleic anhydride, etc.], unsaturated carboxylic acid alkyl ester [(meth) acrylic acid alkyl (C1-C1
8) Ester, alkyl maleic acid (C1-C18) ester and the like] and copolymers of olefins and the like. Of these polyolefin resins (1),
Preferred are (1-1), (1-2), (1-3)
And more preferably polyethylene, polymethylene, polypropylene, ethylene / propylene polymer, oxidized polyethylene, oxidized polypropylene and maleated polypropylene, and particularly preferred are polyethylene and polypropylene.

The softening point of the polyolefin resin (1) is usually 80 to 170 ° C, preferably 90 to 160 ° C, more preferably 100 to 155 ° C. If the softening point exceeds 80 ° C., the fluidity of the toner will be good, and 1
A sufficient releasing effect is exhibited at a temperature of less than 70 ° C.

The melt viscosity of (1) is usually 2 to 10,000 (mPa · s) at 160 ° C., preferably 3 to
7,000 (mPa · s), more preferably 5 to 450
It is 0 (mPa · s).

The number average molecular weight of (1) is usually 500 to 20 from the viewpoint of filming to a carrier and releasability.
000, the weight average molecular weight is 800 to 100,000, preferably the number average molecular weight is 1,000 to 15,000,
The weight average molecular weight is 1500 to 60,000, and more preferably, the number average molecular weight is 1500 to 10,000 and the weight average molecular weight is 2000 to 30,000.

The needle penetration degree of (1) is usually 5.0 or less, preferably 3.5 or less, and more preferably
It is 1.0 or less.

The SP value (solvability parameter) of the vinyl resin (2) is usually 10.6-12.6.
(Cal / cm ³ ) _1/2 , preferably 10.6-1
2.0 (cal / cm ³ ) _1/2 , more preferably 1
0.7 to 11.8 (cal / cm ³ ) _1/2 , and particularly preferably 10.8 to 11.5 (cal / cm ³ ) _{1
/ 2} . If the SP value exceeds 12.6 or is less than 10.6, the difference in SP value with the binder resin becomes too large, resulting in poor dispersion of the release agent. The SP value is a known Fed
It can be calculated by the ors method.

As the vinyl resin (2), the SP value of the homopolymer (a) is 10.6 to 12.6 (cal / c).
Although it may be a homopolymer of a monomer having m ³ ) _1/2 ,
(B) The SP value of the homopolymer is 11.0 to 18.0, particularly preferably 11.0 to 16.0 (cal / cm ³ ).
The SP value of the vinyl-based monomer (A) which is _1/2 and the homopolymer is 8.0 to 11.0, particularly preferably 9.0 to 1.
0.8 (cal ^/ cm ₃₎ monomers that are _1/2 (B)
And a copolymer thereof with is more preferable.

Examples of (A) include unsaturated nitrile monomers (A1) and α, β-unsaturated carboxylic acids (A2).

Examples of (A1) include (meth) acrylonitrile and cyanostyrene. Of these, (meth) acrylonitrile is preferable. (A
As 2), unsaturated carboxylic acids and their anhydrides [(meth) acrylic acid, maleic acid, fumaric acid, itaconic acid and their anhydrides], unsaturated dicarboxylic acid monoesters [monomethyl maleate, monobutyl maleate] , Monomethyl itaconate, etc.] and the like.
Of these, (meth) acrylic acid and unsaturated dicarboxylic acid monoesters are preferable, and (meth) acrylic acid and maleic acid monoester [monomethyl maleate, monobutyl maleate] are particularly preferable.

Examples of (B) include styrene-based monomers [styrene, α-methylstyrene, p-methylstyrene, m
-Methylstyrene, p-methoxystyrene, p-hydroxystyrene, p-acetoxystyrene, vinyltoluene, ethylstyrene, phenylstyrene, benzylstyrene, etc.], alkyl of unsaturated carboxylic acid (having 1 to 1 carbon atoms).
18) Ester [methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate,
2-Ethylhexyl (meth) acrylate, etc.], vinyl ester monomers [vinyl acetate, etc.], vinyl ether monomers [vinyl methyl ether, etc.], halogen element-containing vinyl monomers [vinyl chloride, etc.], diene monomers (butadiene, isobutylene, etc.) ) And combinations thereof. Of these, preferred are styrene monomers, unsaturated carboxylic acid alkyl esters and their combined use, and particularly preferred are styrene and styrene and (meth) acrylic acid alkyl esters combined.

The vinyl resin (2) has a number average molecular weight of 1500 to 100,000 and a weight average molecular weight of 5
2,000 to 200,000, preferably 2,500 to 50,000 in number average molecular weight and 6,000 in weight average molecular weight.
Up to 100,000, particularly preferably a number average molecular weight of 28
00 to 20,000, weight average molecular weight of 7,000 to 500
00.

The Tg (glass transition point) of (2) is usually 40.
To 90 ° C, preferably 45 to 80 ° C, and particularly preferably 50 to 70 ° C. When Tg is 40 ° C. or higher, the storage stability is good, and when Tg is 90 ° C. or lower, the low temperature fixability is good.

(1) and (2) constituting the graft polymer (3) having a structure in which the vinyl monomer constituting (2) is grafted to (1) are the same as the above (1) and (2). And preferred ones are also the same.
Regarding the amount of each component constituting (3), the amount of (1) is usually 1 to 90% by weight, preferably 5 based on the weight of the produced (3).
-80% by weight, (2) is usually 10-99% by weight, preferably 20-95%.

The above (1) which constitutes the resin composition of the present invention
The amounts of (1) to (3) are usually 0.5 to 70% by weight, and (2) is usually 2 based on the weight of the resin composition produced.
9 to 98.5% by weight, and (3) is usually 1 to 70% by weight.

Specific examples of the resin composition of the present invention include the following (1), (2), and a graft polymer (3 having a structure in which the vinyl monomer constituting (2) is grafted to (1). ) And so on. (1): Oxidized polypropylene (2): Styrene / acrylonitrile copolymer (1): Polyethylene / polypropylene mixture (2): Styrene / acrylonitrile copolymer (1): Ethylene / propylene copolymer (2): Styrene / Acrylic acid / butyl acrylate copolymer (1): polypropylene (2): styrene / acrylonitrile / butyl acrylate / monobutyl maleate copolymer (1): maleic acid modified polypropylene (2): styrene / acrylonitrile / acrylic Acid / butyl acrylate copolymer (1): Maleic acid modified polypropylene (2): Styrene / acrylonitrile / acrylic acid / 2-ethylhexyl acrylate copolymer (1): Polyethylene / maleic acid modified polypropylene mixture (2): Acrylonitrile / acrylic acid Butyl / styrene / monobutyl maleate copolymer

Exemplifying the method for producing the resin composition of the present invention,
For example, first, the polyolefin resin (1) is dissolved or dispersed in a solvent such as toluene or xylene to obtain a temperature of 100 ° C to 20 ° C.
After heating to 0 ° C., (A) or a mixture of (A) and (B) is added dropwise with a peroxide-based initiator (benzoyl peroxide, ditertiary butyl peroxide, tert-butyl peroxide benzoate, etc.), The resin composition of the present invention is obtained by distilling off the solvent.

The amount of peroxide-based initiator used to synthesize the solution of the above polymer mixture is usually 0.2 to 10% by weight, preferably 0.5 to 5% by weight, based on the weight of the polymer mixture formed. %.

What is important in the present invention is the type and acid value of the wax used. In the case of paraffin wax represented by polypropylene, the toner spent by the wax on the carrier due to long-term copying is extremely unsuitable for a long-life developer. In the present invention, the main object is to improve the wax dispersibility in the toner, but generally, there are the following two points in improving the wax dispersibility. Improving wax dispersibility during toner kneading Relieving wax re-aggregation during cooling of the kneaded material immediately after toner kneading

The free fatty acid type carnauba wax, oxidized rice wax, and montan wax used in the present invention have the acid value described in the present invention to improve the wax dispersibility in the toner. This is because the terminal group in the wax affects the affinity with the graft polymer composed of the vinyl monomer. On the other hand, if the solubility parameter (SP value) is in the range of 10.6 to 12.6, reaggregation of the wax that occurs during cooling immediately after kneading the toner is alleviated. This is because the wax is embedded inside the graft polymer by adjusting the content within this range.

When the acid value of the released free fatty acid type carnauba wax is 6 KOHmg / g or more and the acid value of the oxidized rice wax or montan wax is 31 KOHmg / g or more, the wax dispersibility is poor and the desired releasability is obtained. It also impairs low temperature fixability. However, since the dipentaerythritol fatty acid ester wax is superior in wax dispersibility to these waxes, it is not within this range. When the solubility parameter (SP value) is 10.5 or less, or 12.7 or more, it is difficult to embed the wax in the graft polymer even if the wax is finely dispersed in the wax. Occurs, and the desired dispersion cannot be obtained.

The free fatty acid-type carnauba wax is obtained by removing free fatty acids from carnauba wax as a raw material, and is more easily crystallized than conventional carnauba wax to improve dispersibility. Montan wax is refined from minerals and, like carnauba wax, tends to form fine crystals. Oxidized rice wax is air-oxidized from rice bran wax. These waxes may be used alone or in combination, and may be 1 to 1 of the total toner.
Good results are obtained by containing 5% by weight, preferably 2 to 10% by weight.

The release agent dispersion diameter in the toner can be measured by any method, but it is preferable to obtain the particle diameter from the average value of the long axis type and the short axis type from the photograph of the toner cross section by TEM. At this time, in order to improve the measurement accuracy, it is more preferable to obtain the measurement sample from the average value of 30 or more data.

Next, the dipentaerythritol fatty acid ester wax will be explained, but in the present invention, pentaerythritol is more preferable because it can obtain the same or more effective effect. The dipentaerythritol fatty acid ester wax is (A) 100 parts by weight of dipentaerythritol fatty acid ester having 12 to 22 carbon atoms in the fatty acid portion and having 60 mol% or more of hydroxyl groups in the dipentaerythritol portion having an ester bond. , (B) 1 to 50 parts by weight of a phenolic antioxidant and (C) a sulfuric antioxidant 1
-50 parts by weight.

As the component (A), dipentaerythritol fatty acid ester is used. The fatty acid which constitutes this dipentaerythritol fatty acid ester has 12 to 2 carbon atoms.
2, such as lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, oleic acid, linoleic acid,
Examples thereof include linolenic acid and erucic acid, and these may be used alone or in combination of two or more. Of these, palmitic acid and stearic acid are particularly preferable. Carbon number 1
When a fatty acid of 1 or less is used, the kneading torque value is large and the processing stability is insufficient, and when a fatty acid having 23 or more carbon atoms is used, the Vicat softening point is greatly lowered and the heat distortion temperature of the resin is lowered. Bring Further, in dipentaerythritol constituting the dipentaerythritol fatty acid ester, 60 mol% or more of the hydroxyl groups must have an ester bond. In the composition of the present invention, the dipentaerythritol fatty acid ester as the component (A) may be used alone or in combination of two or more. Examples of the phenolic antioxidant used as the component (B) in the composition of the present invention include 2,6
-Di-t-butyl-p-cresol, 2,4,6-tri-t-butylphenol, n-octadecyl-3-
(4'-Hydroxy-3 ', 5'-di-t-butylphenol) propionate, tetrakis [methylene-3-
(3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, triethylene glycol bis [3- (3'-t-butyl-5'-methyl-4'
-Hydroxyphenyl) propionate] and the like. Among these, tetrakis [methylene-3-
(3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane and triethylene glycol bis [3- (3'-t-butyl-5'-methyl-
4'-Hydroxyphenyl) propionate] is preferred. In the composition of the present invention, the phenolic antioxidant as the component (B) may be used alone or in combination of two or more. The production examples of dipentaerythritol fatty acid ester wax are shown below, but the production method is not limited thereto.

[0035]

[Table 1]

Next, the polyester used in the present invention will be described. As a polyester toner binder,
Examples thereof include polycondensates of polyols and polycarboxylic acids. As the polyol, a diol (a) and a polyol having a valence of 3 or more (c) are used, and as the polycarboxylic acid,
Examples thereof include dicarboxylic acid (b) and trivalent or higher polycarboxylic acid (d).

The diol (a) has a hydroxyl value of 180.
~ 1900 mg KOH / g diols, specifically,
Alkylene glycol (ethylene glycol, 1,2-
Propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycols (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether) Alicyclic diol (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.); C2-C4 alkylene oxide of the above alicyclic diol ( Ethylene oxide, propylene oxide, butylene oxide, etc.) adduct; C2-C4 alkylene oxide (ethylene oxide, propylene oxide Pyrene oxide, and the like butylene oxide, etc.) adducts. Among these, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols, and alkylene oxide adducts thereof and 2 to 12 carbon atoms.
In combination with alkylene glycol. The trivalent or higher polyol (c) has a hydroxyl value of 150 to 1900 m.
gKOH / g polyols, specifically, trivalent to octahydric or higher aliphatic polyhydric alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); C2-C4 alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct; trisphenols (trisphenol PA, etc.); novolak resin (phenol novolac, cresol novolac, etc.); C2-C4 alkylene of the above trisphenols Oxide adducts: C2-C4 alkylene oxide adducts of the above novolak resins and the like can be mentioned. Of these, the preferred one is
An alkylene oxide adduct of a trihydric or higher valent aliphatic polyhydric alcohol and a novolak resin,
Particularly preferred are alkylene oxide adducts of novolak resins.

The dicarboxylic acid (b) has an acid value of 180.
˜1250 mg KOH / g dicarboxylic acid, specifically alkylenedicarboxylic acid (succinic acid, adipic acid,
Sebacic acid, dodecenyl succinic acid, etc.); alkenylene dicarboxylic acid (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acid (phthalic acid, isophthalic acid, terephthalic acid,
Naphthalene dicarboxylic acid, etc.) and the like. Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. The trivalent to hexavalent or higher polycarboxylic acid (d) has an acid value of 150 to 1250 mgKOH /
g of polycarboxylic acid, specifically, aromatic polycarboxylic acid having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, etc.), vinyl polymer of unsaturated carboxylic acid (styrene /
Maleic acid copolymer, styrene / acrylic acid copolymer,
α-olefin / maleic acid copolymer, styrene / fumaric acid copolymer, etc.) and the like. Of these, preferred are aromatic polycarboxylic acids having 9 to 20 carbon atoms, and particularly preferred are trimellitic acid and pyromellitic acid. As the dicarboxylic acid (b) or the tricarboxylic or higher polycarboxylic acid (d), an acid anhydride or a lower alkyl ester (methyl ester, ethyl ester, isopropyl ester, etc.) of the above may be used.

The ratio of the polyol to the polycarboxylic acid is usually 2/1 to 1/2 as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH],
It is preferably 1.8 / 1 to 1 / 1.8, and more preferably 1.5 / 1 to 1 / 1.5.

The toner binders are required to have different physical properties for monochrome and full color, respectively, and the design of the polyester toner binder is also different. That is, since a high-gloss image is required for full-color use, it is necessary to use a low-viscosity binder, but for monochrome use, gloss is not particularly necessary and hot offset properties are important, so it is necessary to use a high-elasticity binder. .

To obtain a low-gloss image useful for a monochrome copying machine, etc., a diol (a), a dicarboxylic acid (b), a polyol (c) having a valence of 3 or more and / or a polycarboxylic acid having a valence of 3 (d) or ) Is preferable, and the non-linear polyester is preferably 4) of (a), (b), (c) and (d).
A polyester consisting of the components is particularly preferred. By using both (c) and (d), the hot offset resistance is further improved. The ratio of the trivalent or more polyol (c) and the trivalent or more polycarboxylic acid (d) is such that the sum of the mole numbers of (c) and (d) is the total of the mole numbers of (a) to (d). hand,
It is usually 0.1 to 40 mol%, preferably 0.5 to 25 mol%, and more preferably 1 to 20 mol%. The molar ratio of (b) and (d) is usually 0/100 to 100/0, preferably 90/10 to 20/80, and more preferably 8.
It is 5/15 to 30/70.

The molecular weight of the monochrome polyester toner binder is 1000 to 100 by GPC.
The maximum value is preferably 00, more preferably the maximum value is 2000 to 8500, and particularly preferably the maximum value is 2500 to 8000. When it is 1,000 or more, heat-resistant storage stability and powder fluidity are good, and when it is less than 10,000, toner pulverizability is improved and productivity is good. Further, it preferably contains 5 to 70% by weight of tetrahydrofuran (THF) insoluble matter, and more preferably,
It is 15 to 60%, particularly preferably 20 to 50%. T
If the HF insoluble content exceeds 5%, the hot offset resistance becomes good, and if it is less than 70%, good low temperature fixability is obtained.

For obtaining a high gloss image useful for a full-color copying machine or the like, a diol (a) and a dicarboxylic acid (b) are used.
Even in the case of a linear polyester using, a diol (a), a dicarboxylic acid (b), and a polyol (c) having a valence of 3 or more are further added.
And / or a non-linear polyester in which a polycarboxylic acid (d) having a valence of 3 or more is used in combination may be used. In the case of a non-linear polyester, the ratio of the trivalent or higher valent polyol (c) and / or the trivalent or higher valent polycarboxylic acid (d) is such that the sum of the mole numbers of (c) and (d) is (a) to (( It is usually 20 mol% or less, preferably 15 mol% or less, and more preferably 10 mol% or less, based on the total number of moles of d).

Regarding the molecular weight of the full-color polyester toner binder, the number average molecular weight in GPC is usually 1,000 to 10,000, preferably 1,500 to 850.
0, more preferably 1800 to 6500. When the number average molecular weight is 1,000 or more, heat-resistant storage stability and powder fluidity are good, and when it is less than 10,000, pulverizability of the toner is improved and productivity is good. Further, the tetrahydrofuran (THF) insoluble content is usually less than 10% by weight, preferably less than 5% by weight from the viewpoint of glossiness.

A method for producing the polyester-based toner binder of the present invention will be exemplified. Polyester is a polyol and polycarboxylic acid, in the presence of a known esterification catalyst such as tetrabutoxy titanate, dibutyltin oxide,
It is obtained by heating to 150 to 280 ° C. and dehydration condensation. It is also effective to reduce the pressure in order to improve the reaction rate in the final stage of the reaction.

In the toner binder composition of the present invention, other resin can be contained together with the polyester toner binder. Other resins include styrene resins (copolymers of styrene and alkyl (meth) acrylates, copolymers of styrene and diene monomers, etc.), epoxy resins (addition condensates of bisphenol A and epichlorohydrin, etc.), urethanes. Examples thereof include resins (polyaddition products of diol and diisocyanate, etc.).

Specific examples of the polyester-based toner binder include the following. : Bisphenol A ethylene oxide 2 mol adduct /
Bisphenol A Propylene oxide 2 mol adduct /
Ethylene oxide adduct of phenol novolac / terephthalic acid / trimellitic anhydride polycondensate. : Bisphenol A propylene oxide 3 mol adduct / phenol novolac ethylene oxide adduct /
Maleic anhydride / terephthalic acid / dimethyl terephthalate / trimellitic anhydride polycondensate. : Bisphenol A ethylene oxide 2 mol adduct /
Bisphenol A Propylene oxide 3 mol adduct /
Propylene oxide adduct of phenol novolac /
Terephthalic acid / dimethyl terephthalate / trimellitic anhydride polycondensate. : Bisphenol A propylene oxide 2 mol adduct / bisphenol A propylene oxide 3 mol adduct / phenol novolac propylene oxide adduct / terephthalic acid polycondensate. : Bisphenol A propylene oxide 2 mol adduct / Bisphenol A propylene oxide 3 mol adduct / Propylene oxide adduct of phenol novolac / isophthalic acid / dimethyl isophthalate / trimellitic anhydride polycondensate.

The toner binder composition of the present invention comprises the toner resin composition (I) of the present invention and a polyester toner binder (II). The amount of the resin composition for a toner (I) of the present invention in the present toner binder composition is usually 0.1 to 3 based on the amount of the toner binder.
0% by weight, preferably 0.3 to 20% by weight, the amount of polyester-based toner binder (II) is usually 65 to 99.9% by weight, based on the amount of toner binder.
It is preferably 75 to 99.7% by weight.

In order to obtain the toner binder composition of the present invention, (I) and (II) and, if necessary, other members may be powder-mixed, a twin-screw extruder, or a mixing pot capable of heating and stirring. It may be melt-mixed in the presence of (I) in the presence of (I
I) may be polymerized.

In the present invention, the solubility parameter is Hi.
Considering the attractive force between molecules in the ldebrand-Scachard solution theory, it is defined by the following formula.

[0051]

## EQU1 ## SP≡ (ΔEv / V) _1/2 where ΔEv is the evaporation energy and V is the molecular volume. There are various methods for obtaining the SP value of each compound.
In the structural formula of the compound to be obtained, it can be calculated by the following formula from the data of the evaporation energy and the molar volume of the atom or atomic group.

SP = (ΣΔEi / ΣΔVi) _1/2 Here, ΔEi and ΔVi represent the evaporation energy and the molar volume of the atom or atomic group, respectively. )

(Colorant) As the colorant, carbon black, nigrosine dye, aniline blue, calcoil blue, chrome yellow, ultramarine blue, DuPont oil red, quinoline yellow, methylene blue chloride, phthalocyanine blue, malachite green oxalate. , Lamp black, rose bengal,
C. I. Pigment Red 48: 1, C.I. I. Pigment Red 57: 1, C.I. I. Pigment Red 122,
C. I. Pigment Yellow 12, C.I. I. Pigment Yellow 97, C.I. I. Pigment Blue 15: 1,
C. I. Pigment Blue 15: 3 and the like can be illustrated as a typical example.

The content of the coloring agent is the same as that of the binder resin 10 described above.
0.5 to 20 parts by weight is preferable with respect to 0 parts by weight, and 1 to 1
0 weight part is more preferable. When the content is less than 0.5 part by weight, the coloring power may be weakened. On the other hand, if the content is more than 20 parts by weight, the transparency may deteriorate.

The toner of the present invention can be made into a magnetic one-component developer by using a magnetic powder for a part or all of the colorant. As the magnetic powder dispersed in the binder resin, known magnetic materials such as iron and cobalt,
Metals such as nickel and their alloys, Fe ₃ O ₄ , γ-
Fe ₂ O ₃ , metal oxides such as cobalt-added iron oxide, Mn
Various ferrites such as Zn ferrite and NiZn ferrite, magnetite, hematite and the like can be used, and those whose surface is treated with a surface treatment agent such as a silane coupling agent or a titanate coupling agent, or those coated with a polymer may be used. .

(Other Components) In order to control the charge amount of the toner of the present invention, if necessary, for example, a fluorine-based surfactant, a chromium-based dye such as a chromium salicylate complex, and maleic acid are used as monomers. A polymeric acid such as a copolymer contained as a component, a quaternary ammonium salt, an azine dye such as nigrosine, carbon black or the like can be added. Further, for the purpose of improving the fluidity and charging property of the toner, inorganic fine powder such as silica, metal oxide such as titanium oxide, fatty acid or its derivative, organic fine powder such as metal salt, fluorine resin fine powder, etc. Can also be added.

The volume average particle diameter D50 of the toner of the present invention is about 4 to 15 μm, preferably 5 to 9 μm. When the volume average particle diameter D50 is smaller than 3 μm, the developing density may be lowered, and when the volume average particle diameter D50 is larger than 10 μm, the graininess may be deteriorated.

[0058]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples. In the following description, all "parts" mean "parts by weight". The particle size of the toner was measured with a particle size analyzer TA-II manufactured by Coulter Counter, Inc., with an aperture diameter of 100 μm.

The method of toner performance test in the present invention is shown below. (1) Minimum fixing temperature, hot offset generation temperature, gloss generation temperature Monochrome toner using carbon black, and full-color toner uniformly mix 30 parts of toner and 800 parts of ferrite carrier (F-150 manufactured by Powder Tech Co., Ltd.). And tested as a two-component developer. (I) In the case of monochrome toner using carbon black (low gloss image) Minimum fixing temperature (MFT) Unfixed image developed using a commercially available monochrome copying machine (Ricoh imagio450 modified machine) is used for the above copying machine. Fixing was performed at a process speed of 250 mm / sec by a fixing machine in which the fixing unit was modified to change the heat roller temperature. 80% residual image density after rubbing a fixed image with a cloth pad
The above heat roller temperature was made into the minimum fixing temperature. Hot Offset Occurrence Temperature The toner was fixed in the same manner as in the above copying machine, and the presence or absence of hot offset on the fixed image was visually determined. The temperature at which hot offset began to occur was defined as the hot offset occurrence temperature. (Ii) Monochrome toner using magnetic powder (low gloss image) Obtain an unfixed image using a commercially available monochrome printer (Remodeled Ipsio NX720, manufactured by Ricoh Co., Ltd.), and set the process speed of the fixing unit to 80 mm / sec. Other than the above, the same test as above is performed. (Iii) Full color toner (high gloss image) Commercial full color copying machine (ipsio color800 manufactured by Ricoh Co., Ltd.)
Unfixed image developed using a 0 remodeling machine), using the fixing unit of the above full-color copying machine, process speed 1
It was fixed at 80 mm / sec. Commercial gloss meter (MURAK
AMI COLOR RESEARCH LABORA
GMX-202-60 type manufactured by TORY) was used, and the hot roller temperature at which the reflectance of the fixed image at 60 ° exceeds 10% was defined as the gloss development temperature. Further, the temperature at which hot offset began to occur by visual determination was defined as the hot offset occurrence temperature.

Method for Measuring Toner Spent on Developer Surface: The developer is put in a container surrounded by 500 mesh, and the toner frictionally charged on the developer surface is blown off with compressed air. 5g of the remaining agent was immersed in 100 ml of toluene, and the turbidity of the toluene solution was evaluated as ◯. ◯: Turbidity due to toner cannot be recognized X: Turbidity due to toner can be recognized.

1. Acid value The method specified in JIS K0070. 2. Glass transition point (Tg) Method specified in ASTM D3418-82 (DSC
Law). Equipment: Seiko Electronics Co., Ltd. DSC20, SSC
/ 580

Polyester Resin Production Example 1 4533 parts of bisphenol A propylene oxide 2 mol adduct, 4460 parts of bisphenol A ethylene oxide 2 mol adduct, phenol novolac resin were placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introducing pipe. Ethylene oxide 5 mol adduct 6 (nucleus number about 5) 6
18 parts, terephthalic acid 2789 parts, maleic anhydride 41
4 parts and 24 parts of dibutyltin oxide were added, and dehydration reaction was carried out at 230 ° C. under a nitrogen stream until the acid value became 1.5. Then, 1720 parts of dimethyl terephthalate and 400 parts of xylene were added thereto, and the mixture was heated at 220 ° C. under normal pressure for 3
The reaction was continued for 2 hours, and further under a reduced pressure of 10 to 15 mmHg for 2 hours. Then, 439 parts of trimellitic anhydride was added and reacted at a reduced pressure of 10 to 15 mmHg, and when the melt index (150 ° C., 5000 g) reached 2.1 g / 10 minutes, it was taken out of the reaction tank and the polyester (F
-1) was obtained. The THF insoluble content of (F-1) is 32.4.
%, The peak molecular weight is 3600, and the acid value is 8.1 mgK.
The OH / g and the hydroxyl value were 15.6 mgKOH / g.
The glass transition point is 59.7 ° C, TG1 is 165 ° C,
TE1 was 120 ° C.

Polyester Resin Production Example 2 Bisphenol A propylene oxide 2 mol adduct 37 was placed in a reaction vessel equipped with a cooling tube, a stirrer and a raw material introduction tube.
73 parts, 3546 parts of bisphenol A ethylene oxide 2 mol adduct, 968 parts of ethylene oxide 5 mol adduct of phenol novolac resin (about 5 nuclides), 3406 parts of terephthalic acid, and 22 parts of dibutyltin oxide were added under normal pressure. Dehydration reaction at 230 ℃, then 10-1
The reaction was continued under a reduced pressure of 5 mmHg, and when the melt index (150 ° C., 5000 g) reached 2.3 g / 10 min, the reaction product was taken out of the reaction tank and the polyester (F-2) was used.
Got The THF insoluble content of (F-2) was 36%, the peak molecular weight was 3940, the acid value was 1.8 mgKOH / g, and the hydroxyl value was 47.1 mgKOH / g. The glass transition point is 59.8 ° C, TG1 is 161 ° C, and TE2 is 11 ° C.
It was 7 ° C.

Polyester Resin Production Example 3 Bisphenol A propylene oxide 2 mol adduct 23 was placed in a reaction vessel equipped with a cooling tube, a stirrer and a raw material introduction tube.
10 parts, 2172 parts of bisphenol A ethylene oxide 2 mol adduct, 1892 parts of terephthalic acid and 18 parts of dibutyltin oxide were added, and the mixture was added at 10 ° C under normal pressure at 10 ° C.
After reacting for a time, further under reduced pressure of 10 to 15 mmHg,
The reaction was carried out until the acid value reached 1.3 mgKOH / g to obtain polyester (F-3). (F-3) had no THF insoluble content, and had a number average molecular weight of 3020, a weight average molecular weight of 8040, and a hydroxyl value of 35 mgKOH / g. The glass transition point was 63.7 ° C and TE2 was 132 ° C.

Polyester Resin Production Example 4 Bisphenol A ethylene oxide 2 mol adduct 745 was placed in a reaction vessel equipped with a cooling pipe, a stirrer and a raw material introduction pipe.
6 parts, 529 parts of ethylene oxide 5 mol adduct of phenol novolac resin (about 5 nuclides), 3320 parts of terephthalic acid, and 20 parts of dibutyltin oxide were added, and the reaction was carried out at 225 ° C for 10 hours under atmospheric pressure, and then 10 ~ 15
The reaction was performed under reduced pressure of mmHg until the acid value reached 1.3 mgKOH / g. To this, trimellitic anhydride 151
Parts were added and reacted until the acid value became 7.0 mg KOH / g to obtain polyester (F-4). TH for (F-4)
There was no F insoluble matter, the number average molecular weight was 3340, the weight average molecular weight was 19,800, and the hydroxyl value was 42 mgKOH / g. Also, the glass transition point is 59.7 ° C., TE2 is 131
It was ℃.

The graft polymer comprising the vinyl monomer of the present invention will be further described below, but the present invention is not limited thereto. Hereinafter, parts are parts by weight.

Graft Polymer Resin Production Example 1 In an autoclave reaction vessel equipped with a thermometer and a stirrer, 650 parts of xylene, 410 parts of low molecular weight polypropylene (Viscole 330P manufactured by Sanyo Chemical Industry Co., Ltd.), low molecular weight polyethylene (Sanyo Chemical Co., Ltd.) Sangwax LEL-400 manufactured by Kogyo Co., Ltd .: softening point 128 ° C.) 120 parts was sufficiently dissolved and, after nitrogen substitution, 2010 parts styrene, 155 parts acrylonitrile, 210 parts monobutyl maleate,
A mixed solution of 71 parts of di-t-butylperoxyhexahydroterephthalate and 465 parts of xylene was added dropwise at 175 ° C. for 4 hours for polymerization, and the mixture was kept at this temperature for 50 minutes. Then, the solvent was removed to obtain a graft polymer resin composition (E-1). The SP value of the graft chain of (E-1) is 11.2 (cal / cm ³ ) _1/2 , the number average molecular weight is 2900, the weight average molecular weight is 10800, the glass transition point is 83.4 ° C., and the acid Value is 21.9mgKOH
/ G.

Graft Polymerized Resin Production Example 2 In an autoclave reaction vessel equipped with a thermometer and a stirrer, 1010 parts of xylene and low molecular weight polypropylene (Viscole 660P manufactured by Sanyo Chemical Industry Co., Ltd .: softening point 1
(45 ° C.) 740 parts were sufficiently dissolved and, after nitrogen substitution, 2385 parts of styrene, 264 parts of acrylonitrile, 340 parts of butyl acrylate, 25 parts of acrylic acid, 34.5 parts of di-t-butylperoxyhexahydroterephthalate and xylene. 550 parts of the mixed solution was added dropwise at 175 ° C. over 5 hours, and further maintained at this temperature for 50 minutes. Then, the solvent is removed, and the graft polymer resin composition (E-
2) was obtained. The SP value of the graft chain of (E-2) is 11.
4 (cal / cm ³ ) _1/2 , number average molecular weight is 305
0, weight average molecular weight 8100, glass transition point 56.
The acid value was 4 mg and 2.4 mgKOH / g.

Graft Polymer Resin Production Example 3 In an autoclave reaction vessel equipped with a thermometer and a stirrer, 350 parts of xylene and low molecular weight polypropylene (Viscole 440P manufactured by Sanyo Chemical Industry Co., Ltd .: softening point 153) were prepared.
220 parts, low molecular weight polyethylene (manufactured by Sanyo Kasei Co., Ltd. Sunwax LEL-400: softening point 12
(8 ° C.) 40 parts was sufficiently dissolved and after nitrogen substitution, 869 parts styrene, 41 parts acrylonitrile, 120 parts butyl acrylate, 4 parts acrylic acid, 35.5 parts di-t-butylperoxyhexahydroterephthalate and xylene. 141 parts of the mixed solution was added dropwise at 175 ° C. over 5 hours, and the temperature was maintained at this temperature for 50 minutes. Then, the solvent was removed to obtain the graft polymer resin composition (E-3) of the present invention. The SP value of the graft chain of (E-3) is 10.24 (c
al / cm ³ ) _1/2 , the number average molecular weight was 2900, the weight average molecular weight was 7900, the glass transition point was 56.4 ° C., and the acid value was 7.6 mgKOH / g.

Comparative Example 1 for Preparation of Graft Polymer Resin In an autoclave reaction vessel equipped with a thermometer and a stirrer, 400 parts of xylene, low molecular weight polypropylene (manufactured by Sanyo Chemical Industry Co., Ltd., Viscole 440P: softening point 153).
(° C) 50 parts was sufficiently dissolved and, after nitrogen substitution, styrene 7 was added.
A mixed solution of 82 parts, 218 parts of butyl acrylate, and 8.5 parts of di-t-butylperoxyhexahydroterephthalate was added dropwise at 160 ° C. over 2 hours, and the mixture was kept for 1 hour. Then, the solvent was removed to obtain a resin composition (E-4). The SP value of the graft chain of (E-4) is 10.41 (c
al / cm ³ ) _1/2 , the number average molecular weight was 8310, the weight average molecular weight was 22,900, and the glass transition point was 60.5 ° C.

Preparation of Graft Polymer Resin Comparative Example 2 1500 parts of xylene was placed in an autoclave reaction vessel equipped with a thermometer and a stirrer, and after purging with nitrogen, styrene 1 was added.
A mixed solution of 992 parts, acrylonitrile 118 parts, monobutyl maleate 240 parts, di-t-butylperoxyhexahydroterephthalate 38 parts and xylene 455 parts was added dropwise at 175 ° C. over 3 hours for polymerization, and further at this temperature for 30 minutes. Held Then, the solvent was removed to obtain a resin composition (E-5). The SP value of (E-5) is 13.1.
3 (cal / cm ³ ) _1/2 , number average molecular weight is 295
0, weight average molecular weight 9800, glass transition point 80.
It was 6 ° C. and the acid value was 25.8 mgKOH / g.

Toner Binder Production Example 1 10 parts of the graft polymer resin composition (E-1) and 2900 parts of the polyester type toner binder (F-1) were used in a Henschel mixer (FM10B manufactured by Mitsui Miike Kakoki Co., Ltd.). After pre-mixing, twin-screw kneader (made by Ikegai Co., Ltd. PCM
-30) and kneaded to obtain the toner binder of the present invention (G-
1) was obtained.

Toner Binder Production Example 2 After adding 444 parts of trimellitic anhydride in Polyester Production Example 1, the reaction temperature was lowered to 170 ° C. and 450 parts of the graft polymer resin composition (E-2) was further added. Has a melt index (150 ° C, 5000g) of 3.0g
The reaction was continued for 10 minutes to obtain a binder (G-2) for the toner of the present invention.

Toner Binder Production Example 3 When the acid value reached 1.3 in Polyester Production Example 3, the temperature was lowered to 160 ° C. and the graft polymer resin composition (E-
60 parts of 3) was added, and the mixture was stirred and mixed for 1 hour to obtain a binder for toner (G-4).

In the following, "part" means "part by weight". In each case, the developer was mixed with 97 parts of iron oxide powder carrier of 150 to 250 mesh (TEFV manufactured by Nippon Iron Powder Co., Ltd.) with 3 parts of toner by a ball mill to obtain a two-component developer.

(Toner Example 1) Polyester resin (F-1) 100 parts Graft polymer resin composition (E-1) 3 parts Carbon black (MA100 manufactured by Mitsubishi Chemical Corporation) 8 parts Charge control agent (Hodogaya Chemical Co., Ltd.) Spirone Black TRH manufactured by Co., Ltd. 1 part Degreased fatty acid type carnauba wax (acid value 4.2 KOHmg / g) 3 parts The above materials are Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.)
FM10B) was premixed and then melt-kneaded with a twin-screw kneader (PCM-30 manufactured by Ikegai Co., Ltd.) whose temperature was set to 130 ° C. After cooling the kneaded material, it is roughly crushed and then supersonic jet crusher Lab Jet (Nippon Pneumatic Mfg. Co., Ltd.)
Finely pulverized by using an air stream classifier (MDS-I manufactured by Nippon Pneumatic Mfg. Co., Ltd.) to obtain a particle size D50.
To give toner particles having a particle size of 9.0 μm. Then, 100 parts of the toner particles and 1.5 parts of colloidal silica (Aerosil R972 manufactured by Nippon Aerosil) were mixed (externally added) to obtain a toner (T-1). When (T-1) was observed with an electron microscope, the average dispersed particle diameter of the release agent was about 0.2 μm,
The release agent dispersion ratio (a) of this toner was 2.2, which was a uniform and good dispersion state. The minimum fixing temperature of (T-1) was 145 ° C, and hot offset was not observed at 230 ° C or lower. When Ricoh's modified imagio 450 was used to output 300,000 images, clear and high-quality images were obtained until the end. At this time, the toner spent on the surface of the developer was measured according to the measuring method, and it was confirmed that the toner spent was small (evaluation: ◯) and excellent.

(Toner Example 2) Polyester resin (F-2) 100 parts Graft polymer resin composition (E-2) 6 parts Carbon black (MA100 manufactured by Mitsubishi Chemical Corporation) 11 parts Charge control agent (Hodogaya Chemical Co., Ltd.) Spirone Black TRH manufactured by Co., Ltd. 2 parts Acid value rice wax (acid value 25.3 KOHmg / g) 10 parts Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.)
FM10B) was premixed and then melt-kneaded with a twin-screw kneader (PCM-30 manufactured by Ikegai Co., Ltd.) whose temperature was set to 130 ° C. After cooling the kneaded material, it is roughly crushed and then supersonic jet crusher Lab Jet (Nippon Pneumatic Mfg. Co., Ltd.)
Finely pulverized by using an air stream classifier (MDS-I manufactured by Nippon Pneumatic Mfg. Co., Ltd.) to obtain a particle size D50.
To give toner particles having a particle size of 7.0 μm. Then, 100 parts of the toner particles and 2.5 parts of colloidal silica (Aerosil R972 manufactured by Nippon Aerosil) were mixed (externally added) to obtain a toner (T-2). When (T-2) was observed with an electron microscope, the average dispersed particle diameter of the release agent was about 0.2 μm,
The release agent dispersion ratio (a) was 2.9, which was a uniform and good dispersion state. The minimum fixing temperature of (T-2) was 140 ° C, and hot offset was not observed at 230 ° C or less.
When Ricoh's modified imagio 450 was used to output 300,000 images, clear and high-quality images were obtained until the end. At this time, the toner spent on the surface of the developer was measured, and it was confirmed that the toner spent was small (evaluation: ◯) and excellent.

(Toner Example 3) Polyester resin (F-3) 100 parts Graft polymer resin composition (E-3) 8 parts Carbon black (MA100 manufactured by Mitsubishi Chemical Corporation) 11 parts Charge control agent (Hodogaya Chemical Co., Ltd.) Spiron Black TRH manufactured by Co., Ltd. 1.5 parts Montan wax (acid value 21.2KOHmg / g) 13 parts Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.)
FM10B) was premixed and then melt-kneaded with a twin-screw kneader (PCM-30 manufactured by Ikegai Co., Ltd.) whose temperature was set to 130 ° C. After cooling the kneaded material, it is roughly crushed and then supersonic jet crusher Lab Jet (Nippon Pneumatic Mfg. Co., Ltd.)
Finely pulverized by using an air stream classifier (MDS-I manufactured by Nippon Pneumatic Mfg. Co., Ltd.) to obtain a particle size D50.
To obtain toner particles of 8.5 μm. Then, 100 parts of the toner particles and 1.8 parts of colloidal silica (Aerosil R972 manufactured by Nippon Aerosil) were mixed (externally added) to obtain a toner (T-3). When (T-3) was observed with an electron microscope, the average dispersed particle diameter of the release agent was about 0.3 μm,
The release agent dispersion ratio (a) was 3.5, which was a uniform and good dispersion state. The minimum fixing temperature of (T-3) was 148 ° C., and hot offset was not observed at 230 ° C. or less. When Ricoh's modified imagio 450 was used to output 300,000 images, clear and high-quality images were obtained until the end.
At this time, the toner spent on the surface of the developer was measured, and it was confirmed that the toner spent was small (evaluation: ◯) and excellent.

(Toner Example 4) Polyester resin (F-1) 100 parts Graft polymer resin composition (E-3) 8 parts Carbon black (MA100 manufactured by Mitsubishi Chemical Corporation) 11 parts Charge control agent (Hodogaya Chemical Co., Ltd.) Spirone Black TRH manufactured by Mfg. Co., Ltd. 1.0 part Production Example A of dipentaerythritol fatty acid ester wax A 5 parts The above materials were made by Henschel mixer (Mitsui Miike Kakoki Co., Ltd.).
FM10B) was premixed and then melt-kneaded with a twin-screw kneader (PCM-30 manufactured by Ikegai Co., Ltd.) whose temperature was set to 130 ° C. After cooling the kneaded material, it is roughly crushed and then supersonic jet crusher Lab Jet (Nippon Pneumatic Mfg. Co., Ltd.)
Finely pulverized by using an air stream classifier (MDS-I manufactured by Nippon Pneumatic Mfg. Co., Ltd.) to obtain a particle size D50.
To give toner particles having a particle size of 8.0 μm. Then, 100 parts of the toner particles and 1.3 parts of colloidal silica (Aerosil R972 manufactured by Nippon Aerosil) were mixed (externally added) to obtain a toner (T-4). When (T-4) was observed with an electron microscope, the average dispersed particle diameter of the release agent was about 0.1 micron,
The release agent dispersion ratio (a) was 1.3, indicating a uniform and good dispersion state. The minimum fixing temperature of (T-4) is 140 ° C,
No hot offset was observed below 230 ° C. When Ricoh's modified imagio 450 was used to output 300,000 images, clear and high-quality images were obtained until the end. At this time, the toner spent on the surface of the developer was measured, and it was confirmed that the toner spent was small (evaluation: ◯) and excellent.

(Toner Comparative Example 1) Polyester resin (F-1) 100 parts Graft polymer resin composition (E-1) 3 parts Carbon black (MA100 manufactured by Mitsubishi Chemical Corporation) 8 parts Charge control agent (Hodogaya Chemical Co., Ltd.) Spirone Black TRH manufactured by Co., Ltd. 1 part Carnauba wax (acid value 29.6 KOHmg / g) 3 parts Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.)
FM10B) was premixed and then melt-kneaded with a twin-screw kneader (PCM-30 manufactured by Ikegai Co., Ltd.) whose temperature was set to 130 ° C. After cooling the kneaded material, it is roughly crushed and then supersonic jet crusher Lab Jet (Nippon Pneumatic Mfg. Co., Ltd.)
Finely pulverized by using an air stream classifier (MDS-I manufactured by Nippon Pneumatic Mfg. Co., Ltd.) to obtain a particle size D50.
To give toner particles having a particle size of 9.0 μm. Then, 100 parts of the toner particles and 1.5 parts of colloidal silica (Aerosil R972 manufactured by Nippon Aerosil) were mixed (externally added) to obtain a toner (TR-1). When (TR-1) was observed with an electron microscope, the average dispersed particle diameter of the release agent was about 0.9 micron or more, and the release agent dispersion ratio (a) was 10 or more, showing a non-uniform dispersion state. (TR-1) has a minimum fixing temperature of 175
It was inferior to ℃. When Ricoh's modified imagio 450 was used to output 300,000 images, clear and high-quality images were obtained until the end. At this time, when the toner spent on the surface of the developer was measured, a large amount of toner spent (evaluation:
X), it was confirmed to be inferior.

(Toner Comparative Example 2) Polyester resin (F-1) 100 parts Graft polymer resin production comparative example 1 (E-4) 7 parts Carbon black (MA100 manufactured by Mitsubishi Chemical Corporation) 8 parts Charge control agent ( Hodogaya Chemical Co., Ltd. Spyron Black TRH 1 part Defreeized fatty acid type carnauba wax (acid value 4.2) 3 parts Henschel mixer (Mitsui Miike Kako Co., Ltd.)
FM10B) was premixed and then melt-kneaded with a twin-screw kneader (PCM-30 manufactured by Ikegai Co., Ltd.) whose temperature was set to 130 ° C. After cooling the kneaded material, it is roughly crushed and then supersonic jet crusher Lab Jet (Nippon Pneumatic Mfg. Co., Ltd.)
Finely pulverized by using an air stream classifier (MDS-I manufactured by Nippon Pneumatic Mfg. Co., Ltd.) to obtain a particle size D50.
To give toner particles having a particle size of 9.0 μm. Then, 100 parts of the toner particles and 1.5 parts of colloidal silica (Aerosil R972 manufactured by Nippon Aerosil) were mixed (externally added) to obtain a toner (TR-2). When (TR-2) is observed with an electron microscope, the average dispersed particle diameter of the release agent is about 0.5 to 8.
It was a very nonuniform dispersion state of 0 micron or more, and reaggregation after kneading was clearly observed. Also, (TR-
The minimum fixing temperature of 2) was inferior at 175 ° C. Made by Ricoh
When 300,000 images were output with the modified imagio450, clear and high-quality images were obtained to the end. At this time, when the toner spent on the surface of the developer was measured, it was confirmed that the toner spent was large (evaluation: ×) and inferior.

(Toner Comparative Example 3) Polyester resin (F-2) 100 parts Graft polymer resin Production Comparative Example 1 (E-5) 11 parts Carbon black (MA100 manufactured by Mitsubishi Chemical Corporation) 8 parts Charge control agent ( Hodogaya Chemical Co., Ltd. Spiron Black TRH 2 parts Acid value rice wax (acid value 25.3) 5 parts Henschel mixer (Mitsui Miike Kakoki Co., Ltd.)
FM10B) was premixed and then melt-kneaded with a twin-screw kneader (PCM-30 manufactured by Ikegai Co., Ltd.) whose temperature was set to 130 ° C. After cooling the kneaded material, it is roughly crushed and then supersonic jet crusher Lab Jet (Nippon Pneumatic Mfg. Co., Ltd.)
Finely pulverized by using an air stream classifier (MDS-I manufactured by Nippon Pneumatic Mfg. Co., Ltd.) to obtain a particle size D50.
To give toner particles having a particle size of 9.0 μm. Then, 100 parts of the toner particles and 1.4 parts of colloidal silica (Aerosil R972 manufactured by Nippon Aerosil) were mixed (externally added) to obtain a toner (TR-3). When (TR-3) was observed with an electron microscope, the average dispersed particle diameter of the release agent was about 0.5 to 9.
The release agent dispersion ratio (a) was 0 micron or more, and the release agent dispersion ratio (a) was around 100, which was a very nonuniform dispersion state, and reaggregation was clearly observed after kneading. Further, the minimum fixing temperature of (TR-3) was inferior at 170 ° C. When Ricoh's modified imagio 450 was used to output 300,000 images, clear and high-quality images were obtained until the end. At this time, when the toner spent on the surface of the developer was measured, it was confirmed that the toner spent was large (evaluation: ×) and inferior.

(Toner Example 5) C.I. I. Pigment Red 48:15 parts were used to obtain a toner (T-5) in the same manner as in Example 1. As a result of observing (T-5) with an electron microscope, the average dispersed particle diameter of the release agent was about 0.2 μm, and the release agent dispersion ratio (a) was 2.2, which was uniform and in a good dispersion state. . (T
The minimum fixing temperature of -5) was 145 ° C, and hot offset was not observed at 230 ° C or lower. Ricoh ipsio co
When the gloss development temperature was measured using a modified lor8000, it was 155 ° C, which was superior to the targeted 160 ° C or lower.
Further, the hot offset generation temperature was excellent at 230 ° C. as compared to the target 220 ° C. or higher. Ricoh ipsio color800
0 When 300,000 images were output with a modified machine, clear and high-quality images were obtained to the end. At this time, the toner spent on the surface of the developer was measured according to the following measuring method, and it was confirmed that the toner spent was small (evaluation: ◯) and excellent.

[0084]

As is clear from the above detailed and specific description, according to the present invention, even when the polyester resin is used as the binder resin, the wax is uniformly dispersed in the binder resin to stabilize the stability. It is possible to provide a highly durable developer with less toner spent due to wax while obtaining the image density
In addition, even when the toner is left under high temperature and high humidity, the image density unevenness does not occur, a stable image is formed for a long time, and the fixing temperature range is not narrowed. Further, it is possible to provide an extremely excellent effect that an image forming method using the electrophotographic toner can be provided.

Continued front page    (72) Inventor Hiroto Higuchi             1-3-3 Nakamagome, Ota-ku, Tokyo Stocks             Company Ricoh (72) Inventor Zhu Jing             1-3-3 Nakamagome, Ota-ku, Tokyo Stocks             Company Ricoh (72) Inventor Maiko Kondo             1-3-3 Nakamagome, Ota-ku, Tokyo Stocks             Company Ricoh (72) Inventor Takayuki Koike             1-3-3 Nakamagome, Ota-ku, Tokyo Stocks             Company Ricoh F-term (reference) 2H005 AA01 AA06 AA15 CA05 CA08                       CA13 CA14 CA18 EA05

Claims (6)

[Claims] 1. A binder resin containing at least a polyester resin, a colorant, a free fatty acid type carnauba wax having an acid value of 5 KOHmg / g or less, and a polyolefin resin having a solubility parameter (SP value) of 10.6 to 12. An electrophotographic toner containing a graft polymer composed of a vinyl monomer in the range of 6. 2. A binder resin containing at least a polyester resin, a colorant, an oxidized rice wax having an acid value of 30 KOHmg / g or less, and a polyolefin resin having a solubility parameter (SP value) in the range of 10.6 to 12.6. An electrophotographic toner comprising a graft polymer composed of a vinyl monomer. 3. A binder resin containing at least a polyester resin, a colorant, a dipentaerythritol fatty acid ester wax, and a vinyl resin having a solubility parameter (SP value) in the range of 10.6 to 12.6 with a polyolefin resin. An electrophotographic toner comprising a graft polymer composed of 4. A binder resin which is at least a polyester resin, a colorant, a montan wax having an acid value of 30 KOHmg / g or less, and a polyolefin resin and a solubility parameter (SP value) within a range of 10.6 to 12.6. An electrophotographic toner containing a graft polymer composed of a vinyl monomer. 5. The toner for electrophotography according to claim 1, wherein the wax contained in the toner has an average dispersed particle diameter in the range of 0.05 to 0.8 μm. 6. The toner particle diameter D50 is A, the average dispersed particle diameter of the wax contained in the toner is B, and the wax dispersion ratio (a) expressed by B / A × 100 is 0.7 to 7.5. The toner for electrophotography according to any one of claims 1 to 5, wherein the toner is within the range.