JPH09269608A - Electrophotographic toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a toner having excellent low fixing property and offset resistance which can be fixed at a low fixing temp. and has high fixing strength to a transfer paper by incorporating a specified vicinal dicarboxylate as a binder resin. SOLUTION: As for the binder resin, a vicinal dicarboxylate expressed by formula I is included. In the formula I, R<1> and R<2> may be the same as or different from each other and are hydrogen atoms, 1 to 5C alkyl groups, 6 to 11C aryl groups or aralkyl groups. R<3> is a 1 to 35C alkyl group or 7 to 40C aralkyl group. EX is a polyol residue having a polyether skeleton of divalent phenols expressed by formulae II-IV, WX is a polyolefin residue by grafting with maleic acid anhydride. In formulae II-IV, R<4> may have alcohol type hydroxyl groups, R<5> and R<6> may be the same as or different from each other, R<7> is a 2 to 4C alkylene group, (m) is 0 or an integer 1 to 10, and (x) and (y) are integers >1.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic toner, and more particularly to an electrophotographic toner that is excellent in low-temperature fixability and offset resistance and is suitable as a toner for a copying machine or printer that employs a heat roll fixing method. Regarding

[0002]

2. Description of the Related Art In copiers, printers and the like, there are a wet developing system and a dry developing system as a system for converting a latent image formed on a photosensitive material by exposure into a visible image. In the dry development method, the toner is usually charged by friction with the carrier, adheres to the electrostatic latent image on the photosensitive drum by an electric attraction, is then transferred onto the paper, and then fixed by a heat roll or the like. Converted into a permanently visible image.
As a fixing method, a heating roller method is often used in which a toner image on a sheet to be fixed is caused to pass while being brought into contact with the surface of a heating roller coated with a material having releasability for toner. Has been done.

By the way, in recent years, with the spread of electrophotographic copying machines and printers in general households and the like, lower energy consumption (reduction of power consumption) when copying machines or printers is operated, and copying speed is increased. For the purpose of speeding up or lowering the machine cost, it is desired to lower the roll pressure to simplify the heat fixing roll. In addition, as copiers equipped with a double-sided copy function and an automatic document feeder are becoming more widespread as the copiers become more sophisticated, the electrophotographic toner used in copiers and printers has a low fixing temperature and is durable. It is required to have excellent offset property and fixing strength on transfer paper.

As a method for improving the low-temperature fixability of the toner, a method of lowering the molecular weight of the toner resin has been proposed. However, according to these methods, although the fixing property of the toner is certainly improved, a part of the toner forming an image at the time of fixing is transferred to the surface of the heat roller and is re-applied to the paper fed next. There is a problem that a phenomenon (offset phenomenon) in which toner migrates and stains an image is likely to occur.

On the other hand, various methods have heretofore been studied in order to prevent the toner from adhering to the surface of the heat roller used in the copying machine of the pressure heating type. For example, the surface of the heat roller is coated with a material having excellent releasability for toner (for example, fluorocarbon resin), and in order to prevent further offset and reduce fatigue of the heat roller surface, a liquid release agent such as silicone oil is used. The surface of the roller is coated with a moldable material. However, this method is extremely effective in preventing the offset phenomenon, but it requires a separate device for supplying the liquid for offset prevention, which complicates the fixing device or causes oil to adhere to the copy. It may interfere with handling. Especially OH
There is a problem that the phenomenon becomes remarkable when the image is copied to P or the like.

Therefore, it is desired to develop a toner having a wide fixing temperature range and excellent offset resistance without using these releasing liquid materials. So now,
In most copying machines, the occurrence of the offset phenomenon is prevented by adding a small amount of wax such as low molecular weight polyethylene (PE) or propylene (PP), which can be sufficiently melted during heating under pressure, to the toner.

However, although the method using wax has some effect in preventing offset, when the binder is a polyester resin, the compatibility with the PP wax is poor, and the hue of the toner image is particularly great for full-color use. There are problems such as deterioration, increased cohesiveness of toner, and destabilization of charging characteristics.

As another method for preventing the offset phenomenon, various methods for improving the binder resin constituting the toner have been tried. For example, a method is known in which the melt viscoelasticity of the toner is improved by increasing the glass transition temperature (Tg) or the molecular weight of the binder resin.

[0009]

However, when the offset resistance is imparted by such a method, there arises a new problem that the fixability at low temperature (that is, the low temperature fixability) is deteriorated. On the other hand, in order to improve the low temperature fixability of the toner, it is necessary to reduce the viscosity of the toner when melted,
It is required to lower the Tg and molecular weight of the binder resin. As described above, the properties of low-temperature fixing property and anti-offset property generally exhibit contradictory aspects, which makes it extremely difficult to develop a toner that simultaneously satisfies the two properties.

Under such a background, a binder excellent in offset resistance in a wide fixing temperature range and excellent in fixability at low temperature without applying a liquid release agent such as silicone oil to the fixing roller. The advent of resins is strongly desired.

Therefore, an object of the present invention is that it is excellent in low-temperature fixing property and offset resistance and can be fixed at a low fixing temperature, and it does not cause any practical problem in offset resistance, and it is fixed to a transfer paper. An object is to provide an electrophotographic toner having excellent strength.

[0012]

In order to solve the above problems, the present invention provides a binder resin represented by the following general formula (a):

[0013]

Embedded image

[0014] (wherein, R ¹ and R ² may be the same or different, represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group or an aralkyl group having 6 to 11 carbon atoms .R ³ Is an alkyl group having 1 to 35 carbon atoms or an aralkyl group having 7 to 40 carbon atoms, and may have an alcoholic hydroxyl group, a double bond or an ether group.
EX is a polyol residue having a polyether skeleton of a dihydric phenol represented by the following formula (b1), (b2) or (b3), and WX is a maleic anhydride grafted polyolefin residue. )

[0015]

Embedded image

(Equations (b1), (b2) or (b3)
In the above, two R ^{4 s} may be the same or different, are an alkylene group having 1 to 30 carbon atoms, R ⁴ may have an alcoholic hydroxyl group, and R ⁵ and R ⁶ are
They may be the same or different and are a hydrogen atom, a methyl group, an ethyl group or a phenyl group. n is an integer of 1 or more. R ⁷ is an alkylene group having 2 to 4 carbon atoms, and m is 0.
Alternatively, it is an integer of 1 to 10. x and y are integers of 1 or more, and the average value of the sum is 2 to 16. The present invention provides an electrophotographic toner containing a vicinal dicarboxylic acid diester represented by the formula (1).

Hereinafter, the electrophotographic toner of the present invention will be described in detail.

The electrophotographic toner of the present invention contains the vicinal dicarboxylic acid diester represented by the general formula (a) as a binder resin. In the general formula (a) that represents a vicinal dicarboxylic acid diester, R ¹ and R ² may be the same or different and each is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a carbon atom having 6 to 6 carbon atoms.
11 is an aryl group or an aralkyl group. Carbon number 1
Examples of the alkyl group of 5 to 5 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group,
Examples thereof include an isobutyl group, a tert-butyl group and a neopentyl group. Examples of the aryl group having 6 to 11 carbon atoms include a phenyl group, a tolyl group, a cumyl group and a naphthyl group. Examples of the aralkyl group having 6 to 11 carbon atoms include benzyl group, α-phenethyl group and β-
And a phenethyl group.

In the general formula (a), R ³ is an alkyl group having 1 to 35 carbon atoms or an aralkyl group having 7 to 40 carbon atoms, and has an alcoholic hydroxyl group, a double bond or an ether group. May be. As the alkyl group having 1 to 35 carbon atoms, for example, methyl group, ethyl group, 2
-Hydroxyethyl group, 2-acetoxyethyl group, 2-
Butoxyethyl group, 2-hydroxy-n-propyl group,
2,3-dihydroxy-n-propyl group, n-propyl group, allyl group, isopropyl group, n-butyl group, 2-butyl group, isobutyl group, tert-butyl group, 4-hydroxybutyl group, n-amyl group , A tert-amyl group,
Neopentyl group, cyclohexyl group, 6-hydroxy-
n-hexyl group, 2-ethylhexyl group, 2-hydroxy-3-butoxy-n-propyl group, 2-hydroxy-
3-phenoxy-n-propyl group, capryl group, cetyl group, lauryl group, myristyl group, eicosyl group, tetracosyl group, octacosyl group, arachidyl group, myricyl group, linoleyl group, palmityl group, stearyl group, oleyl group, ricinoleyl group Etc. 7 to 4 carbon atoms
Examples of the aralkyl group of 0 include a benzyl group and α-
Examples thereof include a phenethyl group, a β-phenethyl group, and a group represented by the following structural formula.

[0020]

Embedded image (K represents 0 or an integer of 1 or more)

R ⁷ is an alkylene group having 2 to 4 carbon atoms such as ethylene group, propylene group and butylene group. n is an integer of 1 or more. x and y are integers of 1 or more, and the average value of the sum is 2 to 16.

EX is a polyol residue having a polyether skeleton of a dihydric phenol represented by the above general formula (b1), (b2) or (b3). The general formula (b
In 1) or (b2), two R ^{4 s} may be the same or different and each is an alkylene group having 1 to 30 carbon atoms, and R ⁴ may have an alcoholic hydroxyl group, R ⁵ And R ⁶ may be the same or different,
It is a hydrogen atom, a methyl group, an ethyl group, or a phenyl group. As the alkylene group having 1 to 30 carbon atoms, for example,
Examples include those having a structure represented by the following formula.

[0023]

Embedded image

Further, WX represents a maleic anhydride grafted polyolefin residue, and as will be described later, a polyolefin such as a homopolymer of ethylene or propylene, or a copolymer of ethylene or propylene with another α-olefin is used as an anhydride. It is a polyolefin residue grafted with maleic anhydride obtained by reacting with maleic acid or a derivative thereof. Examples of other α-olefins include 1-butene, 1-hexene, 4-
An α-olefin having 4 to 12 carbon atoms such as methyl-1-pentene is preferable.

The vicinal type dicarboxylic acid diester represented by the general formula (a) may be produced by any method and is not particularly limited. For example, it can be carried out according to the following two types of production method (1) or production method (2).

Production method (1): primary alcohol having 1 to 35 carbon atoms and the following general formula (c):

Embedded image The method carried out by dehydration condensation reaction with the carboxyl group in the vicinal dicarboxylic acid monoester represented by. In the general formula (c), R ¹ , R ² , EX and WX
Is the same as the above general formula (a). Further, the primary alcohol having 1 to 35 carbon atoms may have other secondary alcoholic hydroxyl group, double bond and ether group in the molecule, such as methanol, ethanol, n-propyl alcohol, and 2 -Methoxyethanol, 2-butoxyethanol, n-butyl alcohol, isobutyl alcohol, n-amyl alcohol, furfuryl alcohol, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol vinyl ether, n-hexanol, 2-ethylhexanol, n-octanol, n-nonyl alcohol, n-decyl alcohol, lauryl alcohol, tetradecyl alcohol, cetyl alcohol, octadecyl alcohol, benzyl alcohol, α-phenethyl alcohol,
β-phenethyl alcohol and the like can be exemplified.

Since the esterification reaction by dehydration condensation is an equilibrium reaction, a reaction accelerating method such as proceeding the reaction while performing dehydration operation can be adopted, and a catalyst can be used. Examples of preferable catalysts include mineral acids such as sulfuric acid and hydrochloric acid, organic acids such as p-toluenesulfonic acid, boron fluoride etherate, and Lewis acids such as aluminum chloride.

In the esterification reaction, the reaction temperature is usually 70 to 170 ° C. in the coexistence of the catalyst and the continuous removal of the produced water outside the system by using Stark Deinto Trap. Complete within 5 hours.

Process (2): A process carried out by an addition reaction between an epoxy group-containing compound having 2 to 40 carbon atoms and a carboxyl group in the vicinal dicarboxylic acid monoester represented by the general formula (c). Examples of the epoxy group-containing compound having 2 to 40 carbon atoms include ethylene oxide, propylene oxide, epichlorohydrin, allyl glycidyl ether, butyl glycidyl ether, amyl glycidyl ether, hexyl glycidyl ether, phenyl glycidyl ether, and tert-butylphenyl. A compound having one epoxy group such as glycidyl ether in the molecule; a so-called bisphenol type epoxy resin obtained by reacting a dihydric phenol such as bisphenol A with epichlorohydrin and then treating with an aqueous solution of caustic soda; o- After reacting polychlorophenol such as cresol novolac resin with epichlorohydrin,
Examples thereof include so-called polyfunctional epoxy resins obtained by treating with an aqueous solution of caustic soda.

In this addition reaction, a catalyst can be used to accelerate the reaction. Examples of the catalyst used include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, lithium halides such as lithium chloride and lithium bromide, tetramethylammonium chloride and benzyltriethylammonium chloride. An ammonium salt etc. can be illustrated.

This addition reaction is normally completed within 3 hours at a reaction temperature of 70 to 160 ° C. when the above catalyst is present.

The vicinal dicarboxylic acid monoester represented by the general formula (c) is produced by grafting a maleic anhydride grafted polyolefin with the following general formulas (d1) and (d).
2) or (d3):

Embedded image It can be carried out by an addition reaction with a polyol represented by

General formula (d1), (d2) or (d3)
In, R ⁴ , R ⁵ , R ⁶ , R ⁷ , n and m are the same as those in the general formulas (b1), (b2) and (b3).

The maleic anhydride-grafted polyolefin is obtained by grafting a polyolefin with maleic anhydride represented by the following general formula (e) or a derivative thereof in the presence of a peroxide.

Embedded image (In the general formula (e), R ¹ and R ^2, the general formula (the same as the definitive R ¹ and R ² Contact in a).) In this the maleic anhydride grafted polyolefin, containing the maleic anhydride The amount is an amount of 0.1 to 20% by weight with respect to the base polyolefin.

The maleic anhydride grafted polyolefin has a number average molecular weight (Mn) of 200 to 10,000, or from the viewpoint of compatibility with polyolefin waxes added as a release agent to electrophotographic toners. The one having a weight average molecular weight (Mw) of 300 to 50,000 is used, and the weight average molecular weight (Mw) is 50.
Those of 0 to 30,000 are preferably used.

As a specific example of the maleic anhydride grafted polyolefin, modified polyethylenes marketed by Mitsui Petrochemical Co., Ltd .: # 2203A, # 220M.
P, # 4202E, 2203A, maleated polypropylene # NP0555A, # EP014 and the like.

The polyol represented by the general formula (d1), (d2) or (d3) is not particularly limited and is usually produced by the following production method (A), (B) or (C). Is something that can be done.

Production method (A): The following formula (f) obtained from dihydric phenols and epichlorohydrin:

Embedded image By the addition reaction of the bisphenol type epoxy resin represented by and the polyalcohol having at least two primary alcoholic hydroxyl groups in the molecule, general formulas (d1) and (d
The polyol represented by 2) or (d3) can be produced.

In the formula (f) representing the bisphenol type epoxy resin, R ⁵ and R ⁶ are represented by the general formula (b).
1), (b2), or (b3), p
Is 0 or an integer of 1 or more. The bisphenol type epoxy resin represented by the formula (f) is excellent in blocking resistance, has a viscosity in a proper range at the time of melting, and obtains an electrophotographic toner having excellent low-temperature fixability. Those having a molecular weight (Mn) of 800 to 8000 are preferable, and those having a molecular weight (Mn) of 1500 to 6000 are particularly preferable.

Further, as the polyalcohol, for example,
Examples thereof include ethylene glycol, propylene glycol, glycerol, trimethylolpropane, pentaerythritol, sorbitol, and alkylene oxide adducts of bisphenol A.

In this addition reaction, a catalyst can be usually used in order to allow the reaction to proceed efficiently. Examples of the catalyst used include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, lithium halides such as lithium chloride and lithium bromide, and ammonium salts such as tetramethylammonium chloride and benzyltriethylammonium chloride. Examples thereof include boron trifluoride / ether complex, tin tetrachloride, tin acetate, titanium tetrabutoxide, Lewis acids such as zirconium acetate, and fluoroboric acid.

A solvent may be used in the above addition reaction. Preferred solvents include aromatic hydrocarbons such as toluene, xylene and ethylbenzene, 2
Examples thereof include glycol-based compounds such as -hydroxy-3-methoxypropane, 2-hydroxy-3-ethoxypropane, 2-hydroxy-3-butoxypropane, ethylene glycol dimethyl ether, propylene glycol dimethyl ether and diethylene glycol dimethyl ether.

This addition reaction is usually completed in the presence of the above catalyst at a reaction temperature of 70 to 170 ° C. for 1 to 15 hours.

Process (B): The following general formula (g) obtained from dihydric phenol and epichlorohydrin:

Embedded image (R ⁵ and R ⁶ are the same as those in the general formula (c), and q is an integer of 0 or 1 or more), and a hydroxyl group-terminated phenol resin having phenolic hydroxyl groups at both ends, and the following formula: (H):

Embedded image (In the formula (h), r is 0 or an integer of 1 to 20), by the addition reaction with the glycidol or the self-polymerized product thereof, the compound represented by the general formula (d1), (d2) or (d3) The represented polyols can be produced.

The hydroxyl group-terminated phenol resin represented by the general formula (g) is excellent in blocking resistance, has a viscosity in the proper range when melted, and provides an electrophotographic toner having excellent low-temperature fixability. It is preferable that the number average molecular weight (Mn) is 800 to 8000, and especially 1500
What is -6000 is preferable.

In this addition reaction, glycerol-α-monochlorohydrin is used in the presence of an equimolar amount of an aqueous sodium hydroxide solution instead of glycidol or its self-polymerized product, and glycidol or its self-polymerization is carried out in the reaction system. It is also possible to generate a polymer to proceed the addition reaction.

In this production method (B), a catalyst can be usually used in order to promote the addition reaction efficiently. Examples of the catalyst include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, lithium halides such as lithium chloride and lithium bromide, and ammonium salts such as tetramethylammonium chloride and benzyltriethylammonium chloride. It can be illustrated.

In addition reaction, it is also possible to use the solvents exemplified in the production method (A). Furthermore, this addition reaction is usually carried out at a reaction temperature of 70 to 1 in the presence of the above-mentioned catalyst.
It is completed in 1 to 12 hours at 60 ° C.

Production method (C): The above reaction is carried out by addition reaction of a hydroxyl group-terminated phenol resin represented by the above formula (g) and having phenolic hydroxyl groups at both ends, and an alkylene oxide represented by the following formula (i). The polyol represented by the general formula (d1), (d2) or (d3) can be produced.

Embedded image (In the formula, R ⁸ is hydrogen or an alkyl group having 1 to 3 carbon atoms)

This addition reaction is usually carried out in a pressure resistant vessel, and it is possible to use a solvent together. Suitable solvents include xylene, aromatic compounds such as toluene, 2-butanone, methyl isobutyl ketone, ketones such as cyclohexanone, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dioxane, ethers such as anisole, N, N. −
Dimethylformamide, dimethyl sulfoxide, 1-
An aprotic polar solvent such as methyl-2-pyrrolidinone can be exemplified. These solvents may be used alone or 2
A mixture of more than one species can be used. The amount of the solvent used is usually 1 to 100% by weight, preferably 5 to 50% by weight based on the weight of the reaction product.

This addition reaction is usually carried out at a reaction temperature of 180 ° C. or lower. Although depending on the coexisting solvent species, it is usually possible to complete the reaction by stirring and mixing at a temperature of 50 to 150 ° C. for 2 to 8 hours. Reaction temperature 50
If the temperature is lower than ℃, the viscosity of the contents is generally high, so a high-torque stirrer is required for mixing, and the time required to complete the reaction is 8 hours or more, which is not economical. . On the other hand, if the reaction temperature exceeds 150 ° C., the reaction may occur rapidly, which is not preferable in terms of safety.

The progress of the reaction generally depends on the amount of phenolic hydroxyl group, the amount of change with time of the pressure in the pressure vessel, the softening point, the GP.
It can be traced by measuring the number average molecular weight by C, but in the present invention, the method of estimating the complete consumption of the charged alkylene oxide from the pressure in the pressure vessel is simple.

The ratio of the charged amounts of the phenolic hydroxyl group-terminated resin represented by the general formula (g) having a regular secondary hydroxyl group in the main chain and the alkylene oxide represented by the general formula (i) is Can be appropriately selected according to the chain length of the polyalkylene oxide groups at both ends in the polyol structure having a polyalkylene oxide group at the terminal represented by the general formula (b3), that is, the sum of the polymerization degrees x and y. . For example, x + y
However, when preparing a polyol represented by the formula (b3) having a minimum value of 2, the alkylene is twice equivalent to the total amount of the phenolic hydroxyl group in the phenolic hydroxyl group-terminated resin represented by the general formula (g). Oxide should be charged, while x + y
However, when preparing a polyol represented by the formula (b3) having a maximum value of 16, it is sufficient to charge 16 times the equivalent amount of alkylene oxide.

In the production method (C), a catalyst is usually used in order to promote the addition reaction efficiently. Examples of the catalyst used include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, alkali metal alcoholates such as sodium methylate and potassium t-butoxide, sodium phenoxide and potassium.
Alkali metal salts of phenols such as t-butylphenoxide, tertiary amines such as N, N-dimethylbenzylamine, triethylamine and pyridine, quaternary ammonium salts such as tetramethylammonium chloride and benzyltriethylammonium chloride, triphenyl Examples thereof include organic phosphorus compounds such as phosphine and triethylphosphine, alkali metal salts such as lithium chloride and lithium bromide, and Lewis acids such as boron trifluoride, aluminum chloride and tin tetrachloride. The amount of the catalyst used is usually 5 to 10000 wtppm, preferably 10 to 5000 wtppm, based on the amount of the product.

The electrophotographic toner of the present invention requires, as a binder resin, a vicinal type dicarboxylic acid diester represented by the general formula (a), a charge control agent, a colorant, a release agent, and magnetic powder. The particles are composed of a composition obtained by appropriately dispersing and mixing the components to be blended accordingly, and the average particle diameter is in the range of 5 to 20 μm.

The charge control agent to be used can be appropriately selected depending on whether the toner for electrophotography of the present invention is used as a positively charged toner or a negatively charged toner, or its application.

When the electrophotographic toner of the present invention is used as a positively charged toner, a conventionally known positively chargeable charge control agent is used. For example, electron donating dyes represented by nigrosine dyes, imidazole derivatives, alkoxylated amines, triphenylmethane derivatives, quaternary ammonium salts, alkylamides, phosphorus and tungsten simple substances and their compounds, molybdic acid chelate pigments, etc. Can be mentioned.

When the electrophotographic toner of the present invention is used as a negatively charged toner, a conventionally known negatively chargeable charge control agent is used. Examples thereof include electron accepting dyes such as metal complex salts of monoazo dyes, chlorinated polyolefins, sulfonylamines of copper phthalocyanine, oil black, metal salts of naphthenic acid, metal salts of fatty acids, and the like.

The colorant used in the present invention is not particularly limited, and a commonly used colorant is used. For example, when a black electrophotographic toner is prepared, a conventionally known black colorant can be used without particular limitation.
Specific examples thereof include pigments such as carbon black and grafted carbon black whose surface is chemically treated.

When preparing an electrophotographic toner other than black, for example, an electrophotographic toner of the three primary colors of yellow, magenta or cyan, conventionally known colorants can be used, respectively, without any particular limitation. Examples of the colorant used when preparing a yellow electrophotographic toner include chrome yellow and quinoline yellow.

Examples of the colorant used when preparing a magenta electrophotographic toner include DuPont Oil Red and Rose Bengal.

Examples of the colorant used when preparing a cyan electrophotographic toner include aniline blue, methylene blue chloride and phthalocyanine blue.

When these colorants are blended in the electrophotographic toner of the present invention, the blending amount is 0.01 to 20% by weight, preferably 1 to 10% by weight based on the total amount of the toner.

Further, as the releasing agent to be added for the purpose of improving the releasing property of the electrophotographic toner of the present invention, for example,
Examples thereof include low molecular weight polypropylene, low molecular weight polyethylene, fatty acids, fatty acid metal salts, fatty acid esters, partially saponified fatty acid esters, higher alcohols, paraffin wax, amide wax, and silicone oil.
They may be used alone or in combination of two or more.
When a release agent is blended with the electrophotographic toner of the present invention, the blending amount is 0.5 to 10 with respect to the total amount of the binder resin.
It is the amount that becomes the weight%.

When the electrophotographic toner of the present invention is a magnetic toner which is a one-component developer, magnetic powder is mixed. Examples of the magnetic powder used include those made of iron oxides such as ferrite and magnetite, and metals such as iron, cobalt, and nickel. These may be used alone or in combination of two or more. The magnetic powder is preferably a fine powder having a particle size of 1 μm or less.

When the magnetic powder is blended in the electrophotographic toner of the present invention, the blending amount is 30 to 300% by weight based on the weight of the binder resin.

Further, the electrophotographic toner of the present invention comprises
A fluidity improver can be added as needed. Examples of the fluidity improver used include hydrophobic silica fine powder, alumina, titanium oxide, silica sand, mica, etc. These may be used alone or in combination of two or more. Among these, hydrophobic silica fine powder is particularly preferable. When the fluidity improver is blended with the electrophotographic toner of the present invention, the blending amount is 0.01 to 1.0% by weight based on the total amount of the binder resin.

[0068]

In the present invention, the vicinal dicarboxylic acid diester represented by the general formula (a) is used as a phase with a wax such as low molecular weight polyethylene (PE) or propylene (PP) which is a general-purpose releasing agent. Since it has excellent solubility and lowers the melting start temperature, it improves low-temperature fixability, and at the same time, many alcoholic hydroxyl groups present in the binder resin skeleton strongly interact with the cellulose that constitutes the paper. It is considered that the fixing strength is improved.

Since the binder resin skeleton does not have a strongly polar functional group such as carboxyl, a toner for electrophotography which does not cause blocking even when stored for a long time under high humidity can be obtained.

[0070]

EXAMPLES The present invention will be specifically described below with reference to examples of the present invention and comparative examples, but the present invention is not limited to these examples. In addition, measurement of properties (epoxy equivalent, number average molecular weight, weight average molecular weight, Tg, Tm (flow softening temperature), softening point, hydroxyl value, phenolic hydroxyl group amount and acid value) in Synthesis Examples, Examples and Comparative Examples and The performance (blocking resistance) was evaluated according to the following method.

(1) Epoxy equivalent (g / eq) 0.2 to 5 g of a resin sample is precisely weighed and put in a 200 ml Erlenmeyer flask, and then 25 ml of dioxane is added and dissolved. 25 ml of 1/5 normal hydrochloric acid solution (dioxane solvent)
Is added, and the mixture is tightly closed, mixed thoroughly, and allowed to stand for 30 minutes. Next, a toluene-ethanol mixed solution (1: 1 volume ratio) 5
After adding 0 ml, use cresol red as an indicator 1
Titrate with / 10 normal sodium hydroxide solution. Epoxy equivalent (g / eq) according to the following formula based on the titration result
Is calculated. Epoxy equivalent (g / eq) = 1000 × W / [(B-
S) × N × F] W: Sampling amount (g) B: 1/10 N aqueous sodium hydroxide solution (ml) required for blank test S: 1/10 N aqueous sodium hydroxide solution required for sample test ( ml) N: normality of aqueous sodium hydroxide solution F: titer of 1/10 normal aqueous sodium hydroxide solution

(2) Number average molecular weight (Mn) by GPC
And weight average molecular weight (Mw) measurement resin sample 80 mg
Was dissolved in 10 ml of THF to prepare a sample solution, 100 μl of this sample solution was injected into the column below, the elution amount at the peak of the chromatogram was measured, and the molecular weight was calculated based on the calibration curve prepared in advance. Was calculated. The calibration curve was prepared using polystyrene with a known average molecular weight as a standard substance. In addition, the columns and configuration used are as follows.・ Column configuration: (Guard column) + GLR400M
+ GLR400M + GLR400 (all manufactured by Hitachi) ・ Column temperature: 40 ° C ・ Mobile phase (flow rate): THF (1 ml / min) ・ Peak detection method: UV (254 nm)

(3) Tg (glass transition temperature) Tg was measured under the following conditions using the following differential scanning calorimeter. -Differential scanning calorimeter: SEIKO1DSC100 SEIKO1SSC5040 (Disk Station) -Measurement conditions: Temperature range: 25-150 ° C Temperature rising rate: 10 ° C / min Sampling time: 0.5sec Sample amount: 10mg

(4) Tm (flow softening temperature) (° C.) Using a flow tester (CFT500A, manufactured by Shimadzu Corporation), nozzle diameter 1.0 mm × length 1.0 mm, measuring load = 20 Kg, heating rate = The temperature when half the amount of the sample flows out under the condition of 6 ° C./min (starting at 60 ° C.) and the sample amount = 1.0 g was defined as Tm.

(5) Softening point (SP) The softening point of the sample was measured at a temperature rising rate of 1 ° C./min using a softening point measuring device (FP90 manufactured by METTLER CORPORATION).

(6) Hydroxyl value 1.5-2.0 g of a sample is precisely weighed and a 25 ml volumetric flask is prepared.
, Filter with Molecular Sieve 4A and ethanol
And about 15 ml of purified chloroform with water removed are added.
Dissolve completely. Furthermore, add purified chloroform,
The liquid volume was adjusted to the 25 ml marked line to prepare a sample liquid. next,
Take the sample solution in a cell for KBr liquid (thickness 0.2 mm),
Using purified chloroform as a control solution, wavelengths of 3000-40
00 cm ^-1Measure the absorbance at. Shown in the absorbance curve
Absorbance T of two absorption peaks ₁And T_TwoThe contrast
The absorbance of the liquid was determined with the zero standard. Then follow the procedure below
Therefore, based on the calibration curve created in advance,
T required by law₁+ T_TwoFrom the value of hydroxyl group concentration (eq /
l) was determined, and the hydroxyl value was determined according to the following formula. Hydroxyl value (mg / g) = [(hydroxyl group concentration / 4) x 56.1 x F]
/ Sample resin weight × 100 where F: cell thickness correction factor (L₁+ L_Two) L₁: Cell thickness (mm) L when creating the calibration curve_Two: Thickness of cell used for measuring absorbance (mm)

(7) Amount of Phenolic Hydroxyl Group 10 g of resin is precisely weighed and put in a 100 ml measuring flask,
Dioxane 50 is added and dissolved. After complete dissolution, dioxane was further added to adjust the liquid volume to the 100 ml marked line to prepare a sample liquid. Next, add 5 ml of the sample solution to 5
Add to a 0 ml beaker and add 5 ml of dioxane to bring the total volume to 10 ml. 2 ml of a methanol solution of 0.5 wt% 3-methyl-2-benzothiazolinonehydrazine, 0.4 ml of 25 wt% aqueous ammonia, and 2
2 ml of a wt% potassium ferricyanide aqueous solution is sequentially added and left for 30 minutes. After the insoluble matter is filtered off with 5C filter paper, the absorbance is measured with a spectrophotometric system (wavelength 510 nm, cell capacity 10 ml). In addition, a blank test is performed on the blank liquid obtained after the same operation without adding the sample. The absorbance calibration curve prepared in advance using bisphenol A as a standard substance is read, and the amount of phenolic hydroxyl group in the resin is quantified as bisphenol A.

(8) Acid value 10 to 20 g of the resin is precisely weighed, put in a 200 ml Erlenmeyer flask, and 40 ml of 99.5 wt% ethanol is added and dissolved. Using a 1 wt% phenolphthalein aqueous solution as an indicator, titration is performed with a 1/10 N sodium hydroxide solution. The acid value is calculated according to the following formula based on the titration result. Acid value (mgKOH / g) = [5.610 × V × N × F]
/ WW W: sampled amount (g) S: 1/10 normal sodium hydroxide aqueous solution (ml) required for sample test N: normality of sodium hydroxide aqueous solution F: titer of 1/10 normal sodium hydroxide aqueous solution

(9) Blocking resistance Toner powder 5 is placed in a glass container having a diameter of 5 cm and a height of 15 cm.
0 cm ³ is charged, and a weight of 500 g is applied on the SUS weight having a diameter of 5 cm. Humidity 60% RH, Temperature 50 ° C
After being left for 5 days in the atmosphere described in 1), it is left for 3 hours at room temperature. After the weight is removed, the flowability of the powder when the glass container containing the powder is horizontally inverted is visually observed and evaluated according to the following criteria. ◎; All the toner flows out just by turning the glass container upside down. ○; 9 by turning the glass container upside down and shaking it lightly
More than one percent of toner flows out. △; About 70% of the toner remains in the container even when the glass container is turned upside down and shaken lightly. ×; Even if the glass container is turned upside down and shaken lightly, more than half of the toner remains in the container.

(Synthesis Example 1) Production Example of Polyol Represented by General Formula (d) (Production Method A) A 500 ml separable flask equipped with a stirrer, a thermometer, a nitrogen inlet, and a condenser was placed in a bisphenol flask. A type epoxy resin [manufactured by Mitsui Petrochemical Co., Ltd., Epomic R304, epoxy equivalent: 906 (g / eq), softening point: 92 ° C] 302 g, glycerol 32 g, and propylene glycol monomethyl ether 30 ml were charged, and under a nitrogen atmosphere. Then, the temperature rise was started and the internal temperature was 80 ° C., and uniform dissolution was performed. Next, 0.2 ml of fluoroboric acid (purity 49%) as a reaction catalyst was added, and the temperature was further raised, and stirring was continued while maintaining the internal temperature at 150 ° C. During the reaction, when the residual amount of the epoxy group was measured at regular intervals, the epoxy equivalent was 20,000 (g / eq) or more in 5 hours, and when the epoxy group was confirmed to have substantially disappeared, the reaction The pressure in the system was immediately reduced to remove the reaction solvent propylene glycol monomethyl ether. Then, after maintaining the state of 10 mmHg at 150 ° C. for 30 minutes, the obtained molten polyol was extracted from the flask.

With respect to the obtained polyol, softening point: 9
8 (° C.), epoxy equivalent: 20000 (g / eq), number average molecular weight (Mn): 2100, weight average molecular weight (Mw): 5
It was 100 and Mw / Mn 2.43. Hereinafter, this polyol is referred to as (P-1).

(Synthesis Example 2) Production Example of Polyol Represented by General Formula (d) (Production Method B) Bisphenol was placed in a separable flask having a capacity of 1 liter equipped with a stirrer, a thermometer, a nitrogen inlet, and a cooling tube. A type liquid epoxy resin [Mitsui Petrochemical Industry Co., Ltd., Epomic R140P, epoxy equivalent: 188 (g / eq), viscosity: 13500 mPa.s] 188 g, bisphenol A1
73 g and 70 ml of xylene were charged, and heating was started in a nitrogen atmosphere. When the internal temperature reached 80 ° C., 2.82 ml of 0.5% tetramethylammonium chloride aqueous solution was added. The temperature is further raised to an internal temperature of 130
When the temperature reached ℃, the pressure inside the reaction system was reduced and xylene and water were extracted out of the system. The reaction was performed while maintaining the reaction temperature at 130 ° C., and 1 hour later, nitrogen was introduced to return the pressure in the reaction system to normal pressure. When the mixture was stirred for 5 hours after reaching 130 ° C, the epoxy equivalent was 20000 (g /
eq) and above, so the reaction was terminated. The softening point of the obtained hydroxyl group-terminated phenol resin is 106 ° C., the hydroxyl value is 280 KOHmg / g, Mn by GPC is 2270, M
It was w: 4670 and Mw / Mn: 2.06.

The obtained hydroxyl group-terminated phenolic resin was added to 80
After cooling to 0 ° C, 400 g of 2-butanone was added to make a uniform solution. Next, 190.8 g of glycidol was added to the solution having an internal temperature of 70 ° C., and the reaction was continued at the same temperature. During the reaction, the amount of phenolic hydroxyl groups remaining in the contents was traced at regular intervals. As a result, it was confirmed that the amount of the phenolic hydroxyl group in the system was 100 wtppm or less (converted value when bisphenol A was used) in 4 hours. Therefore, 300 ml of water was added to the system and washed with water at 70 ° C. for 30 hours. It was done for a minute and then stopped. After withdrawing the lower aqueous layer, the same operation was repeated for the oil layer.

2-Butanone was distilled off by gradually raising the temperature of the oil layer portion under a reduced pressure atmosphere. After maintaining the state of 10 mmHg at the system internal temperature of 150 ° C. for 1 hour, the molten polyol was taken out of the system. Regarding the obtained polyol, softening point: 113 ° C., Tg (DSC): 57
° C, epoxy equivalent: 20000 (g / eq) or more, M
It was n: 2410, Mw: 5980, Mw / Mn: 2.5. Hereinafter, this polyol is referred to as (P-2).

(Synthesis Example 3) Production Example of Polyol Represented by General Formula (d) (Production Method C) Volume 5 equipped with vertical stirring device, thermometer and nitrogen inlet
Into a 00 ml autoclave, 200 g of a solution containing 500 g of the hydroxyl-terminated phenolic resin obtained in Synthesis Example 2 and 100 g of xylene, which had been prepared in advance, and 3.0 ml of 1.0 N KOH aqueous solution as a catalyst were charged. After substituting the system with nitrogen, 14.7 g of propylene oxide cooled to about 10 ° C. was rapidly charged. After the container was sealed, the temperature was slowly raised with stirring. The temperature of the contents is 100 ° C
Then, the reaction was carried out for 5 hours while maintaining this temperature. After cooling to about 50 ° C., the content solution was transferred to a 1-liter flask, 200 ml of xylene and 20 g of a 5 wt% sodium dihydrogen phosphate aqueous solution were added, and the mixture was stirred at 80 ° C. for about 30 minutes. Next, the liquid was transferred to a separating funnel, the separated aqueous layer was removed, and then the xylene layer was azeotropically dehydrated. After filtering with a 5G glass filter, immerse the filtrate in a 150 ° C oil bath,
Xylene was distilled off under reduced pressure to obtain a polyol. The property values of the obtained polyol were as follows. Softening point: 110.9 ° C. Glass transition temperature: 65 ° C. Hydroxyl value: 210 (mgKOH / g) Mn: 2970 Mw: 6920 Mw / Mn: 2.33 Hereinafter, this polyol is referred to as (P-3).

(Synthesis Example 4) Synthesis of vicinal type dicarboxylic acid monoester (E-1) from (P-1) and a maleic anhydride grafted polyolefin. A stirrer, a thermometer, a nitrogen inlet, and a cooling pipe were provided. In a 500 ml separable flask, 200 g of the polyol (P-1) obtained in Synthesis Example 1, maleinized polyolefin wax (Mitsui Petrochemical Co., Ltd., Chemipearl PS2000, viscosity average molecular weight: 2300, maleic acid group content) : 17% by weight) 6 g, and toluene 200
A uniform solution was prepared by charging ml and slowly stirring at about 50 ° C. After adding 0.7 ml of a solution of tin octate in toluene (tin content: 2.8 wt%) at the same temperature, the temperature was gradually raised to 120 ° C. further,
While continuing stirring at the same temperature, a part of the solution was sampled at regular intervals, and the infrared absorption spectrum was measured to determine 1670 cm ^-1 , 171 based on the maleic anhydride group.
The degree of decrease of the absorption peak at 0 cm ^-1 was traced. As a result, after 4 hours, the two peaks almost disappeared, and an absorption peak based on an ester bond was newly observed at 1730 cm ^-1 . At this time, the concentration of maleic anhydride and the above-mentioned 2
From the calibration curve created in advance for the absorption peak intensity of the book,
It was found that 79% of the maleic anhydride group was ring-opened to form a vicinal type half ester. Then, xylene as a reaction solvent was distilled off under reduced pressure in the system.
After maintaining a state of 10 mmHg at a system temperature of 130 ° C. for 30 minutes, the molten vicinal type monoester was taken out of the system. The properties of the obtained vicinal type monoester were as follows. Softening point: 102 ° C. Number average molecular weight (Mn): 2300 Weight average molecular weight (Mw): 5900 Mw / Mn: 2.56 Acid value: 18 (mgKOH / g) Hydroxyl value: 260 (mgKOH / g) Below, this vicinal Let the type monoester be (E-1).

(Synthesis Example 5) Synthesis of vicinal type dicarboxylic acid monoester (E-2) from (P-2) and maleic anhydride grafted polyolefin-In Synthesis Example 4, instead of (P-1) as the polyol. (P-2) 200 g, as a maleinized wax, instead of Chemipearl PS2000, Chemipearl SEP
The reaction was performed in the same manner as in Synthesis Example 4 except that 5 g of S2300 (viscosity average molecular weight: 2800, maleic group content: 8% by weight) was used. As a result, it was found that 86% of the maleic anhydride group was ring-opened to form a vicinal type monoester after a reaction time of 6 hours. After removing the reaction solvent,
The properties of the obtained vicinal type monoester were as follows. Softening point: 105 (° C.) Number average molecular weight (Mn): 2095 Weight average molecular weight (Mw): 7400 Mw / Mn: 3.53 Acid value: 17 (mgKOH / g) Hydroxyl value: 310 (mgKOH / g) or less, This vicinal type monoester is designated as (E-2).

(Synthesis Example 6) Synthesis of vicinal dicarboxylic acid monoester (E-3) from (P-3) and maleic anhydride grafted polyolefin In Synthesis Example 4, (P-1) was used as a polyol instead of (P-1). P-3), 200 g, as a maleinized wax, instead of Chemipal PS2000, a pyrolytic wax (NP5555A manufactured by Mitsui Petrochemical Co., Ltd., viscosity average molecular weight: 17,000, maleic group content: 5% by weight).
The reaction was performed in the same manner as in Synthesis Example 4 except that 5 g was used. As a result, the reaction time was 4 hours and the amount of the maleic anhydride group was 8
It was found that 8% of the ring was opened to form a vicinal type monoester. The properties of the obtained vicinal type monoester after the removal of the reaction solvent were as follows. Softening point: 112 (° C.) Number average molecular weight (Mn): 3030 Weight average molecular weight (Mw): 7290 Mw / Mn: 2.41 Acid value: 16 (mgKOH / g) Hydroxyl value: 205 (mgKOH / g) or less, Let this vicinal type monoester be (E-3).

(Synthesis Example 7) Synthesis of vicinal type dicarboxylic acid diester (Z-1) from (E-1) and methanol The vicinal type monoester (E-1) obtained in Synthesis Example 4
After dispersing 100 g in 80 g toluene at 70 ° C.,
While maintaining the temperature, 10 g of methanol was added and mixed with stirring for 2 hours. Then, toluene and unreacted methanol were distilled off under reduced pressure, and the vacuum condition was maintained at a temperature of the reaction mixture of 130 to 135 ° C. for 1 hour to obtain a vicinal dicarboxylic acid diester. The properties of the obtained vicinal dicarboxylic acid diester were as follows. Softening point: 103 (° C) Tg: 62 ° C Number average molecular weight (Mn): 2200 Weight average molecular weight (Mw): 5900 Mw / Mn: 2.68 Acid value: 1 (mgKOH / g) or less This vicinal dicarboxylic acid Acid diester (Z-
1).

(Synthesis Example 8) Synthesis of vicinal dicarboxylic acid diester (Z-2) from (E-2) and phenylglycidyl ether The vicinal monoester (E-2) obtained in Synthesis Example 5
After 100 g was dispersed in 80 g of toluene at 100 ° C., the temperature was maintained and phenyl glycidyl ether 6.8 was added.
g and mixed with stirring for 3 hours. Then, toluene and unreacted phenyl glycidyl ether were distilled off under reduced pressure, and the reaction mixture was kept at 140 ° C. for 1 hour under vacuum to obtain a vicinal dicarboxylic acid diester. The properties of the obtained vicinal dicarboxylic acid diester were as follows. Softening point: 105 (° C.) Tg: 59 ° C. Number average molecular weight (Mn): 2100 Weight average molecular weight (Mw): 7500 Mw / Mn: 3.57 Acid value: 1 (mgKOH / g) or less This vicinal dicarboxylic acid Acid diester (Z-
2).

(Synthesis Example 9) Synthesis of vicinal dicarboxylic acid diester (Z-3) from (E-3) and bisphenol A type epoxy resin The vicinal monoester (E-3) obtained in Synthesis Example 6
After 100 g was dispersed in 100 g of xylene at 120 ° C., the temperature was maintained and a bisphenol A type epoxy resin (Mitsui Petrochemical Industry Co., Ltd., R309SS, softening point:
132 ° C, epoxy equivalent: 2300 (g / eq)) 70
g was added, the temperature was raised to 140 ° C., and the temperature was maintained while stirring and mixing for 4 hours. Then, xylene was distilled off under reduced pressure,
The vacuum condition was maintained for 1 hour to obtain a vicinal dicarboxylic acid diester. The properties of the obtained vicinal dicarboxylic acid diester were as follows. Softening point: 118 (° C) Tg: 64 ° C Number average molecular weight (Mn): 3140 Weight average molecular weight (Mw): 8580 Mw / Mn: 2.73 Acid value: 1 (mgKOH / g) or less This vicinal dicarboxylic acid Acid diester (Z-
3).

(Examples 1 to 3) In each example, the vicinal dicarboxylic acid diester (Z-1), (Z-2) or (Z-3) 180 obtained in Synthesis Example 7, 8 or 9 was used.
g and Nigrosine dye (Orient Chemical N-04) 4
g, carbon black (Mitsubishi Chemical's MA-100) 12
g and polypropylene wax (manufactured by Sanyo Kasei Co., Viscole 660P) 6 g were mixed with a super mixer,
It was melt-kneaded with a two-roll mill. After cooling, pulverize with a jet mill and classify with a dry airflow classifier to obtain an average particle size of 10 μm.
Particles were obtained. Then, 0.3 g of hydrophobic silica (R972 manufactured by Nippon Aerosil Co., Ltd.) was mixed per 100 g of particles, and the mixture was stirred for 30 seconds in a Henschel mixer to produce an electrophotographic toner. 5 g of this electrophotographic toner and 95 g of an iron powder carrier having an average particle size of 60 to 100 μm were uniformly mixed to prepare a developer, and the fixing strength and the offset generation temperature were measured by the following methods.

The surface temperature of the fixing heat roller was set to 100 to 200 ° C. by using a copying tester modified so that the surface temperature of the fixing heat roller of the electrophotographic copying machine (Fuji Xerox 3500) manufactured by Fuji Xerox Co., Ltd. could be changed. In the range of
A copy was made with the above developer. The surface temperature of the heat roller for fixing is set to 150 ° C., a fixed image obtained by copying is rubbed with a cotton pad, and the image density before and after the rubbing is measured with a reflection densitometer (Macbeth, RD-91
4) and the fixing strength was calculated according to the following formula. Fixing strength (%) = [(fixed image density after rubbing) / (fixed image density before rubbing)] × 100 Further, the offset generation temperature is 10 ° C. from the surface temperature of the fixing heat roller at 10 ° C. The fixing rate is 85%
The temperature at which the temperature exceeded the value was defined as the minimum fixing temperature. When the temperature was further raised, the temperature at which the molten toner began to adhere to the heat roller was defined as the high temperature offset start temperature. The region between the minimum fixing temperature and the high temperature offset start temperature was defined as the non-offset fixing temperature region. The results are shown in Table 1.

(Comparative Examples 1 to 3) In each of Examples 1, 2 and 3, (Z-
1), (Z-2) or (Z-3) instead of (P-1), (P-2) or (P-3), respectively, in the same manner as in Example 1 A photographic toner was manufactured, and the fixing strength and the offset generation temperature were measured. The results are shown in Table 1.

(Comparative Example 4) In the same manner as in Example 1 except that a commercially available polyester resin (NCP-001, manufactured by Nippon Carbide Industry Co., Ltd.) was used in place of (E-1) as the binder. An electrophotographic toner was manufactured, and fixing strength and offset generation temperature were measured. The results are shown in Table 1.

[0096]

[0097]

[0098]

INDUSTRIAL APPLICABILITY The electrophotographic toner of the present invention is excellent in low-temperature fixing property and offset resistance, can be fixed at a low fixing temperature, and does not cause any problem in offset resistance in practical use. It has excellent fixing strength to.

Claims (5)

[Claims] 1. A binder resin represented by the following general formula (a): (In the formula, R ¹ and R ² may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a carbon atom having 6 to 6 carbon atoms.
11 represents an aryl group or an aralkyl group. R ³ is
It is an alkyl group having 1 to 35 carbon atoms or an aralkyl group having 7 to 40 carbon atoms, and may have an alcoholic hydroxyl group, a double bond or an ether group. EX is a polyol residue having a polyether skeleton of a dihydric phenol represented by the following formula (b1), (b2) or (b3), and WX is a maleic anhydride grafted polyolefin residue. ) (In the formula (b1), (b2) or (b3), two R ^{4
May be} the same or different, are alkylene groups having 1 to 30 carbon atoms, R ⁴ may have an alcoholic hydroxyl group, and R ⁵ and R ⁶ may be the same or different. Often, a hydrogen atom, a methyl group, an ethyl group or a phenyl group. n is an integer of 1 or more. R ⁷ is an alkylene group having 2 to 4 carbon atoms, m is 0 or 1 to 10
Is an integer. x and y are integers of 1 or more, and the average value of the sum is 2 to 16. ) An electrophotographic toner containing a vicinal dicarboxylic acid diester represented by 2. The toner for electrophotography according to claim 1, wherein the binder resin contains 0.5 to 15% by weight of the vicinal dicarboxylic acid diester. 3. A vicinal dicarboxylic acid diester represented by the general formula (a) is a vicinal dicarboxylic acid monoester represented by the following general formula (c), and a carbon number of 1 to 3
The toner for electrophotography according to claim 1, which is an ester of 5 with a primary alcohol. Embedded image (In the formula, R ¹ and R ² may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a carbon atom having 6 to 6 carbon atoms.
11 represents an aryl or aralkyl group. EX is a polyol residue having a polyether skeleton of a dihydric phenol represented by the following formula (b1), (b2) or (b3), and WX is a maleic anhydride grafted polyolefin residue. ) [Chemical 4] (In the formula (b1), (b2) or (b3), two R ^{4
May be} the same or different, are alkylene groups having 1 to 30 carbon atoms, R ⁴ may have an alcoholic hydroxyl group, and R ⁵ and R ⁶ may be the same or different. Often, a hydrogen atom, a methyl group, an ethyl group or a phenyl group. n is an integer of 1 or more. R ⁷ is an alkylene group having 2 to 4 carbon atoms, m is 0 or 1 to 10
Is an integer. x and y are integers of 1 or more, and the average value of the sum is 2 to 16. ) 4. The vicinal dicarboxylic acid diester represented by the general formula (a) is a vicinal dicarboxylic acid monoester represented by the general formula (c), and an epoxy group-containing compound having 2 to 40 carbon atoms. The toner for electrophotography according to claim 1, which is an adduct of Embedded image (In the formula, R ¹ and R ² may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a carbon atom having 6 to 6 carbon atoms.
11 represents an aryl or aralkyl group. EX is a polyol residue having a polyether skeleton of a dihydric phenol represented by the following formula (b1), (b2) or (b3), and WX is a maleic anhydride grafted polyolefin residue. ) (In the formula (b1), (b2) or (b3), two R ^{4
May be} the same or different, are alkylene groups having 1 to 30 carbon atoms, R ⁴ may have an alcoholic hydroxyl group, and R ⁵ and R ⁶ may be the same or different. Often, a hydrogen atom, a methyl group, an ethyl group or a phenyl group. n is an integer of 1 or more. R ⁷ is an alkylene group having 2 to 4 carbon atoms, m is 0 or 1 to 10
Is an integer. x and y are integers of 1 or more, and the average value of the sum is 2 to 16. ) 5. The vicinal dicarboxylic acid monoester represented by the general formula (c) has a weight average molecular weight of 500 to 500.
The toner for electrophotography according to claim 3, which is an addition reaction product of the partially maleated polyolefin of 30,000 and a polyol represented by the following formula (d1), (d2) or (d3). Embedded image (In formula (d1), (d2) or (d3), two R ^{4
May be} the same or different, may be an alkylidene group having 1 to 30 carbon atoms, and may have an alcoholic hydroxyl group, R ⁵ and R ⁶ may be the same or different, and may be a hydrogen atom or methyl. A group, an ethyl group or a phenyl group. R ⁷ is an alkylene group having 2 to 4 carbon atoms, and n is an integer of 1 or more. m is an integer of 1-10. x and y are integers of 1 or more, and the average value of the sum is 2 to 1.
6. )