JP2002091087A - Toner and method for forming full-color image - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner which can be fixed without applying much oil, which shows good transparency for an OHP, excellent low temperature fixing property and high temperature offset resistance. SOLUTION: The toner contains at least a binder resin, coloring agent and wax. The binder resin contains (a) polyester resin, (b) hybrid resin having a polyester unit and a vinyl copolymer unit or (c) mixture of these. The wax contains wax having specified polar groups.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner used for developing an electrostatic image formed in an image forming method such as an electrophotographic method, an electrostatic recording method, and an electrostatic printing method, and to form a full-color image using the toner. It is about the method.

[0002]

2. Description of the Related Art Recently, in a full-color copying machine proposed, four photosensitive members and a belt-shaped transfer member are used, and an electrostatic charge image formed on each photosensitive member is cyan toner, magenta toner, and yellow toner. After the development using black toner, the transfer material is transported between the photoreceptor and the belt transfer member and transferred between straight passes, and then a full-color image is formed. Alternatively, the electrostatic force or gripper is applied to the surface of the transfer member facing the photoreceptor. A method of obtaining a full-color image by winding a transfer material by a mechanical action as described above and performing a development-transfer step four times is generally used.

[0003] Toners loaded on these full-color copiers need to be sufficiently mixed in the heat and pressure fixing step without increasing color reproducibility and without impairing the transparency of overhead projector (OHP) images. It is.

[0004] Compared with general black toners for black-and-white copying machines, toners for full-color images are preferably low-molecular-weight binder resins having sharp melt properties. However, when a sharp-melting binder resin is used, the self-cohesive force of the binder resin is low when the toner is melted in the heat-press fixing step, and thus a problem tends to occur in the high-temperature offset resistance.

In a general black toner for a black-and-white copying machine, a relatively high crystalline wax typified by a polyethylene wax or a polypropylene wax is used as a releasing agent in order to improve the high-temperature offset resistance during fixing. For example, Japanese Patent Publication No. 52-3304, Japanese Patent Publication No. 52-3305
And Japanese Patent Publication No. 57-52574. In the case of full-color image toner, transparency is hindered when projected through OHP due to the high crystallinity of the release agent itself and the difference in the refractive index from the material of the OHP sheet, and the projected image becomes saturated or light. Becomes lower.

In order to solve this problem, a method of lowering the crystallinity of the wax by using a nucleating agent in combination with the wax is disclosed in Japanese Patent Application Laid-Open Nos. 4-149559 and 4-10.
No. 7467 has proposed this.

Further, a method of using a wax having a low crystallinity is disclosed in Japanese Patent Application Laid-Open Nos. Hei 4-301853 and Hei 5-6123.
No. 8 has been proposed. As a wax having a relatively high transparency and a low melting point, there is a montan-based wax. The use of a montan-based wax is described in JP-A-1-185660, JP-A-1-185661, and JP-A-1-185.
No. 662, Japanese Patent Application Laid-Open No. 1-185663, and Japanese Patent Application Laid-Open No. 1-238672.

However, these waxes are OH
All of the transparency in P, the low-temperature fixability at the time of heat and pressure fixing, and the high-temperature offset resistance are not sufficiently satisfied. For this reason, in a normal color toner, an oil such as silicone oil or fluorine oil is applied to a heat fixing roller without adding a release agent as much as possible, thereby improving high-temperature offset resistance and transparency in OHP.

However, the fixed image thus obtained has extra oil adhered to the surface. Oil may adhere to the photoconductor and contaminate it, or the oil may swell the fixing roller, shortening the life of the fixing roller.

In order not to generate oil streaks on the fixed image, it is necessary to supply oil uniformly and quantitatively on the surface of the fixing roller, and the size of the fixing device tends to increase.

[0011] Therefore, the toner for which the occurrence of offset is suppressed in the heating and pressurizing fixing means using no oil for preventing high-temperature offset or using a small amount of oil is used. There is a long-awaited demand for toners having excellent transparency.

JP-A-8-314300 and JP-A-8-314300
Japanese Patent Publication No. -50368 proposes a toner and an image forming method which do not use a fixing oil by encapsulating wax in toner particles by a polymerization suspension method.

However, in these toners, although oil streaks on the fixed image are suppressed, a large amount of wax must be included in the toner particles inside the toner, and a binder containing styrene-acryl resin as a main component is required. Is used, unevenness is likely to occur on the surface of the fixed image, and as a result, the transparency of OHP is reduced.

At the same time, an image recorded matter using these toners tends to have a low gloss, and although a graphic image in which a graph and a character portion are mixed has an advantage that a good image without a sense of incongruity can be obtained, a pictorial image has an advantage. However, since the toner after fixing is not sufficiently melted, the color mixing of secondary colors is low, and the color reproduction range tends to be narrow.

Therefore, in the heat and pressure fixing means which does not use oil or uses less oil,
There has been a long-awaited demand for toners having excellent secondary color mixing and OHP transparency, a wide color reproduction range, and a wide non-offset temperature range.

[0016]

SUMMARY OF THE INVENTION An object of the present invention is to provide a toner which solves the above-mentioned problems.

An object of the present invention is to provide a toner which can be fixed without applying a large amount of oil or without applying any oil.

An object of the present invention is to provide a toner having a wide color reproduction range because of good transparency in OHP and good color mixing of secondary colors.

An object of the present invention is to provide a toner having good fluidity and developability.

An object of the present invention is to provide a toner having a wide non-offset temperature range, which is excellent in low-temperature fixability and high-temperature offset resistance.

An object of the present invention is to provide a toner having excellent storage stability when left in a high-temperature environment.

An object of the present invention is to provide an image forming method for forming a full color image using the toner.

[0023]

Specifically, the present invention provides:
A toner containing at least a binder resin, a colorant and a wax, wherein the binder resin comprises: (a) a polyester resin;
(B) at least a hybrid resin having a polyester unit and a vinyl copolymer unit, or (c) a mixture thereof, wherein the wax contains a wax having a polar group, The wax having a polar group has a structural unit of any of the following formulas (I) to (IV), or has a structural formula of the following formula (V)

[0024]

Embedded image The present invention relates to a toner having at least one kind of wax.

Further, the present invention provides (i) a first image bearing member.
Forming an electrostatic charge image of cyan toner, magenta toner,
An electrostatic charge image is developed with a first toner selected from the group consisting of a yellow toner and a black toner to form a first toner image on an image carrier, and the first toner image is transferred via an intermediate transfer member. Or (ii) a second electrostatic image is formed on the image carrier, and a second electrostatic image is formed on the image carrier, and a second electrostatic image is formed from a group consisting of a cyan toner, a magenta toner, a yellow toner, and a black toner. Developing an electrostatic image with toner to form a second toner image on the image carrier, and transferring the second toner image to a transfer material with or without an intermediate transfer member; (iii) A third electrostatic image is formed on the image carrier, and the electrostatic image is developed with a third toner selected from the group consisting of cyan toner, magenta toner, yellow toner, and black toner to form a third toner image. Image bearer (Iii) forming a fourth electrostatic image on the image carrier by transferring the third toner image to a transfer material with or without an intermediate transfer member; The electrostatic image is developed with a fourth toner selected from the group consisting of magenta toner, yellow toner and black toner to form a fourth toner image on the image carrier, and the fourth toner image is transferred to the intermediate transfer member. And (v) fixing a cyan toner image, a magenta toner image, a yellow toner image, and a black toner image on the transfer material by heating and pressurizing, so that a full-color image is transferred onto the transfer material. This is a full-color image forming method for forming an image, wherein (a) the cyan toner contains at least a binder resin, a cyan colorant and a wax, and the binder resin comprises (a) a polyester resin, b) a hybrid resin having a polyester unit and a vinyl-based copolymer unit, or (c) at least a mixture thereof, wherein the wax contains a wax having a polar group; Wax having a polar group,
It has any of the structural units of the following formulas (I) to (IV), or has the structural formula of the following formula (V)

[0026]

Embedded image Having at least one kind of wax,

(B) The magenta toner contains at least a binder resin, a magenta colorant and a wax, and the binder resin comprises (a) a polyester resin, (b) a polyester unit and a vinyl copolymer unit. And (c) at least a mixture thereof, the wax contains a polar group-containing wax, and the polar group-containing wax is
It has any of the structural units of the following formulas (I) to (IV), or has the structural formula of the following formula (V)

[0028]

Embedded image Having at least one kind of wax,

(C) The yellow toner contains at least a binder resin, a yellow colorant and a wax, and the binder resin comprises (a) a polyester resin, (b) a polyester unit and a vinyl copolymer unit. And (c) at least a mixture thereof, the wax contains a polar group-containing wax, and the polar group-containing wax is
It has any of the structural units of the following formulas (I) to (IV), or has the structural formula of the following formula (V)

[0030]

Embedded image Having at least one kind of wax,

(D) The black toner contains at least a binder resin, a black colorant and a wax, and the binder resin comprises (a) a polyester resin, (b) a polyester unit and a vinyl copolymer unit. And (c) at least a mixture thereof, the wax contains a polar group-containing wax, and the polar group-containing wax is
It has any of the structural units of the following formulas (I) to (IV), or has the structural formula of the following formula (V)

[0032]

Embedded image The present invention relates to a full-color image forming method comprising at least one kind of wax.

[0033]

BEST MODE FOR CARRYING OUT THE INVENTION The toner of the present invention does not use oil, or the heat and pressure fixing means using a small amount of oil has high color reproduction and excellent color mixing of secondary colors. The reproduction range is wide, and the non-offset temperature region is widened by combining the optimum resin composition and wax. Further, the toner particles used in the toner of the present invention have excellent developability due to excellent fluidity,
Further, a toner having good heat resistance and excellent OHP permeability can be obtained.

Hereinafter, the present invention will be described in more detail.

When a polyester resin is used as the binder resin, an alcohol and a carboxylic acid, or a carboxylic acid anhydride, a carboxylic acid ester, or the like can be used as a raw material monomer. Specifically, as the dihydric alcohol component,
Polyoxypropylene (2.2) -2,2-bis (4-
(Hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2-bis (4-hydroxyphenyl)
Propane, polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0)-
Alkylene oxide adducts of bisphenol A such as 2,2-bis (4-hydroxyphenyl) propane and polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane; ethylene glycol, diethylene glycol, triethylene glycol , 1,2-propylene glycol, 1,3-propylene glycol,
1,4-butanediol, neopentyl glycol,
1,4-butenediol, 1,5-pentanediol,
Examples thereof include 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A, and hydrogenated bisphenol A.

The trihydric or higher alcohol component includes sorbitol, 1,2,3,6-hexanetetrol,
4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-
Butanetriol, 1,2,5-pentanetriol,
Examples include glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, and 1,3,5-trihydroxymethylbenzene.

As the acid component, aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or anhydrides thereof; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or anhydrides thereof;
Succinic acid or an anhydride thereof substituted with an alkyl group having 6 to 12 carbon atoms; and unsaturated dicarboxylic acids such as fumaric acid, maleic acid and citraconic acid, or anhydrides thereof.

Among them, a bisphenol derivative represented by the following formula (1) is used as a diol component.
A carboxylic acid component comprising a carboxylic acid having a valency or higher or an acid anhydride thereof or a lower alkyl ester thereof (for example, fumaric acid, maleic acid, maleic anhydride, phthalic acid, terephthalic acid, trimellitic acid, and pyromellitic acid). As an acid component, a polyester resin obtained by polycondensation of these is preferable because it has good charging characteristics as a color toner.

[0039]

Embedded image

In the binder resin contained in the toner of the present invention, “hybrid resin” means a resin in which a vinyl polymer unit and a polyester unit are chemically bonded. Specifically, a vinyl-based polymer unit obtained by polymerizing a monomer having a carboxylic acid ester group such as a polyester unit and a (meth) acrylic acid ester, or a monomer obtained by polymerizing a monomer having a carboxylic acid group such as (meth) acrylic acid is used. It is formed by a transesterification reaction or a condensation polymerization reaction with a vinyl polymer unit. Preferably, a graft copolymer (or block copolymer) having a polyester unit as a trunk polymer and a vinyl polymer as a branch polymer is preferred.

As the vinyl monomer for producing the vinyl resin, styrene; o-methylstyrene, m-
Methylstyrene, p-methylstyrene, α-methylstyrene, p-phenylstyrene, p-ethylstyrene,
2,4-dimethylstyrene, pn-butylstyrene,
p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p-chloro styrene,
3,4-dichlorostyrene, m-nitrostyrene, o-
Styrene and derivatives thereof such as nitrostyrene and p-nitrostyrene; styrene unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; unsaturated polyenes such as butadiene and isoprene; vinyl chloride, vinyl chloride, vinyl bromide, Vinyl halides such as vinyl fluoride; vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, methacrylic acid α-methylene fats such as n-octyl, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate Monocarboxylic acid esters: methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, acrylic acid Acrylic esters such as 2-chloroethyl and phenyl acrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl Pyrrole, N-vinylcarbazole, N
N- such as vinylindole and N-vinylpyrrolidone
Vinyl compounds; vinyl naphthalenes; and acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide.

Further, the vinyl monomers include unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid and mesaconic acid; maleic anhydride, citraconic anhydride, itaconic anhydride Products, unsaturated dibasic acid anhydrides such as alkenyl succinic anhydrides; methyl maleate half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, butyl citraconic acid Half esters of unsaturated dibasic acids such as half ester, methyl itaconic acid half ester, methyl alkenyl succinate half ester, methyl fumarate half ester and methyl mesaconic acid half ester; non-ester such as dimethyl maleic acid and dimethyl fumaric acid Kazuji dibasic acid esters, acrylic acid, methacrylic acid, crotonic acid, such as cinnamic acid alpha, beta
Unsaturated acids; α, β-unsaturated acid anhydrides such as crotonic anhydride and cinnamic anhydride; anhydrides of the α, β-unsaturated acids with lower fatty acids; alkenylmalonic acid, alkenylglutaric acid, Monomers having a carboxyl group such as alkenyl adipic acid, acid anhydrides and monoesters thereof are mentioned.

Further, as the vinyl monomer, 2-
Acrylic acid or methacrylic acid esters such as hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate; 4
-(1-hydroxy-1-methylbutyl) styrene, 4
And monomers having a hydroxy group such as-(1-hydroxy-1-methylhexyl) styrene.

In the toner of the present invention, the vinyl polymer unit of the binder resin may have a cross-linked structure cross-linked with a cross-linking agent having two or more vinyl groups. Crosslinking agents used include, for example, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; as diacrylate compounds linked by an alkyl chain,
Ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6 hexanediol diacrylate, neopentyl glycol diacrylate and the above compounds Examples of the acrylate include methacrylates; diacrylate compounds linked by an alkyl chain containing an ether bond include, for example, diethylene glycol diacrylate, triethylene glycol diacrylate,
Tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate and the above compounds in which the acrylate is replaced with methacrylate; including an aromatic group and an ether bond Examples of chain-linked diacrylate compounds include polyoxyethylene (2) -2,2
-Bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,2-bis (4-
(Hydroxyphenyl) propane diacrylate and those obtained by replacing the acrylate of the above compound with methacrylate.

Examples of the polyfunctional crosslinking agent include pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethanetetraacrylate, oligoester acrylate and those obtained by replacing acrylate of the above compounds with methacrylate; Triallyl cyanurate and triallyl trimellitate;

In the present invention, it is preferable that the components constituting the vinyl copolymer component and / or the polyester resin contain a monomer component capable of mutually reacting with the components of both resins. Among the monomers constituting the polyester resin component, those that can react with the vinyl copolymer include phthalic acid,
Unsaturated dicarboxylic acids such as maleic acid, citraconic acid and itaconic acid or anhydrides thereof are exemplified. Among the monomers constituting the vinyl copolymer component, those which can react with the polyester resin component include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.

In the present invention, it is preferable to use a molecular weight modifier in order to adjust the molecular weight distribution of the vinyl copolymer component. As the molecular weight modifier, generally, RSH (R:
Mercaptans represented by the formula:
Dodecyl mercaptan and the like, or α-methylstyrene, α-methylstyrene dimer, and α-methylstyrene oligomers are exemplified.

As a method for obtaining a reaction product of a vinyl resin and a polyester resin, either a polymer containing a monomer component capable of reacting with each of the above-mentioned vinyl resins and polyester resins is used. Alternatively, a method obtained by polymerizing both resins is preferable.

The polymerization initiator used for producing the vinyl copolymer of the present invention includes 2,2'-azobisisobutyronitrile and 2,2'-azobis (4-methoxy-2,4 -Dimethylvaleronitrile), 2,2'-azobis (-2,4-dimethylvaleronitrile), 2,
2'-azobis (-2methylbutyronitrile), dimethyl-2,2'-azobisisobutyrate, 1,1'-azobis (1-cyclohexanecarbonitrile), 2-
(Carbamoylazo) -isobutyronitrile, 2,2 ′
-Azobis (2,4,4-trimethylpentane), 2-
Ketone peroxides such as phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2,2′-azobis (2-methyl-propane), methyl ethyl ketone peroxide, acetylacetone peroxide and cyclohexanone peroxide; Screw (t-
Butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide, 1,1,
3,3-tetramethylbutyl hydroperoxide,
Di-t-butyl peroxide, t-butyl cumyl peroxide, di-cumyl peroxide, α, α′-bis (t-butylperoxyisopropyl) benzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide , Lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-trioil peroxide, di-isopropylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, di-n- Propyl peroxydicarbonate, di-
2-ethoxyethyl peroxycarbonate, di-methoxyisopropylperoxydicarbonate, di (3-
Methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide, t-butylperoxyacetate, t-butylperoxyisobutyrate, t-butylperoxyneodecanoate, t-butylperoxy2- Ethyl hexanoate, t-butyl peroxy laurate, t-butyl peroxy benzoate, t-butyl peroxy isopropyl carbonate, di-t-butyl peroxy isophthalate, t-butyl peroxy allyl carbonate, t
-Amyl peroxy 2-ethylhexanoate, di-t
-Butylperoxyhexahydroterephthalate and di-t-butylperoxyazelate.

The production method for preparing the hybrid resin used in the toner of the present invention includes the following (1) to
The manufacturing method shown in (6) can be mentioned.

(1) This is a method in which a vinyl resin, a polyester resin and a hybrid resin are blended after each production. The blend is produced by dissolving and swelling in an organic solvent (for example, xylene) and then distilling off the organic solvent. The hybrid resin is synthesized by separately producing a vinyl polymer and a polyester resin, dissolving and swelling in a small amount of an organic solvent, adding an esterification catalyst and an alcohol, and heating to carry out a transesterification reaction.

(2) After the production of the vinyl polymer unit,
This is a method for producing a polyester unit and a hybrid resin in the presence of this. The hybrid resin is produced by reacting a vinyl-based polymer unit (a vinyl-based monomer can be added if necessary) with a polyester monomer (alcohol, carboxylic acid) and / or polyester. Also in this case, an organic solvent can be appropriately used.

(3) A method of producing a vinyl-based polymer unit and a hybrid resin in the presence of a polyester unit after the production. The hybrid resin is produced by reacting a polyester unit (a polyester monomer can be added, if necessary) with a vinyl monomer and / or a vinyl polymer unit.

(4) After the production of the vinyl polymer unit and the polyester unit, a hybrid resin is produced by adding a vinyl monomer and / or a polyester monomer (alcohol, carboxylic acid) in the presence of these polymer units. . Also in this case, an organic solvent can be appropriately used.

(5) After the production of the hybrid resin, vinyl polymer and / or polyester monomer (alcohol, carboxylic acid) is added and addition polymerization and / or polycondensation reaction is carried out to produce vinyl polymer and / or polyester. Is manufactured. In this case, as the hybrid resin, a resin produced by the production method of the above (2) to (4) can be used, and if necessary, a resin produced by a known production method can be used. further,
An organic solvent can be used as appropriate.

(6) A vinyl polymer unit, a polyester unit and a hybrid resin are produced by mixing a vinyl monomer and a polyester monomer (alcohol, carboxylic acid, etc.) and continuously performing addition polymerization and polycondensation reaction. You. Further, an organic solvent can be appropriately used.

In the above-mentioned production methods (1) to (5), a plurality of polymer units having different molecular weights and different degrees of crosslinking can be used as the vinyl polymer unit and / or the polyester unit.

In the present invention, the ratio of the vinyl polymer unit to the polyester unit (vinyl polymer unit / polyester unit) in the hybrid resin is preferably 1.0 or less in terms of mass. More preferably, the ratio of the vinyl polymer unit to the polyester unit in the hybrid resin (vinyl polymer unit /
(Polyester unit) is preferably 0.5 or less in terms of mass.

Further, the ratio between the vinyl polymer unit and the polyester unit in the hybrid resin component in the present invention is from 0.5: 99.5 to 50: 5 in terms of mass.
It is preferably 0.

This is because when the mass ratio of the vinyl polymer unit in the hybrid resin component exceeds 50% by mass, the glass transition temperature (Tg) of the main chain decreases due to the influence of the vinyl polymer as a side chain. As a result, the storage stability of the toner decreases.

When the mass ratio of the vinyl polymer unit portion in the hybrid resin is less than 0.5% by mass, the vinyl polymer or wax is added to the polyester resin as the main binder resin in a powdery state. This is because if they are mixed with each other, they become slightly difficult to mix, and in order to obtain a uniform dispersion system, a method such as melt blending in advance or blending by applying a temperature while being dissolved in a solvent is required.

The binder resin contained in the toner of the present invention is:
A mixture of a polyester resin and a hybrid resin may be used.

The binder resin contained in the toner of the present invention is:
A mixture of a polyester resin and a vinyl copolymer may be used.

The binder resin contained in the toner of the present invention is:
A mixture of a hybrid resin and a vinyl copolymer may be used.

Next, the content of intensive studies on the wax used in the present invention will be described.

The wax having the structural unit (I) can be obtained by imparting a hydroxyl group (alcohol modification) to an aliphatic hydrocarbon wax such as paraffin wax.

The wax having the structural unit (I) is obtained by converting an aliphatic hydrocarbon wax having an average carbon number in the range of 20 to 60 (paraffin wax) in the presence of a catalyst such as boric acid, boric anhydride or metaboric acid. It can be produced by being able to be converted to alcohol by liquid phase oxidation with a molecular oxygen-containing gas. After the completion of the liquid phase oxidation reaction, there is no solid component of the catalyst such as boric acid, boric anhydride or metaboric acid in the reaction system, and the alcohol forms a borate ester and dissolves in the liquid phase. The amount of the catalyst used is preferably 0.01 to 1 mol, particularly preferably 0.3 to 0.5 mol, per 1 mol of the raw aliphatic hydrocarbon wax.

As the molecular oxygen-containing gas blown into the reaction system, oxygen, air, or a wide range of those diluted with an inert gas can be used. An oxygen concentration of 3 to 20% is preferred, and a wax having an excellent whiteness and having a hydroxyl group is obtained when the oxygen concentration is 5 to 10%. Further, the reaction temperature is 150 to 250 ° C, preferably 170 to 200 ° C.
It is. The aliphatic hydrocarbon is preferably paraffin wax.

The wax having the structure (I) in the present invention preferably has a hydroxyl value in the range of 5 to 80 mgKOH / g, and more preferably has a hydroxyl value in the range of:
10-70 mgKOH / g.

When the hydroxyl value is less than 5 mg KOH / g, the wax functions as a non-polar wax close to paraffin as a property of the wax, so that the wax has compatibility or dispersibility in a polyester resin occupying a part of the main binder of the present invention. , Image defects due to wax release tend to occur.

On the other hand, when the hydroxyl value exceeds 80 mgKOH / g, the polarity becomes too strong, and consequently, the compatibility or dispersibility in the binder resin decreases. Defects tend to occur.

In the alcohol denaturation process, the generated alcohol component undergoes sequential oxidation, and a polymethylene molecule (fatty acid) having a carboxyl group is partially generated.

The wax more preferably has a constituent unit represented by the formula (I) and a constituent unit represented by the formula (II). And in that case, the wax has a hydroxyl value of 5 to 80 mgKOH / g (more preferably,
The acid value of the wax is preferably 1 to 20 mgKOH / g, and more preferably the acid value is in the range of 2 to 15 mgKOH / g.

The acid value is a numerical value indicating the effect on heat resistance. When the acid value is less than 1 mgKOH / g,
As in the case where the hydroxyl value is less than 5 mgKOH / g, the compatibility or dispersibility in the polyester resin occupying a part of the main binder is reduced, so that image defects tend to occur due to release of the wax.

On the other hand, when the acid value exceeds 20 mgKOH / g, the wax is softened, and the heat blocking performance of the toner is reduced.

The wax preferably satisfies that the maximum endothermic peak in the temperature range of 30 to 200 ° C. is in the range of 55 to 90 ° C. in the endothermic curve in the differential thermal analysis (DSC) measurement. Further, the peak temperature of the maximum endothermic peak is preferably in the range of 60 to 85 ° C, and most preferably in the range of 65 to 80 ° C.

When a wax having a maximum endothermic peak of less than 55 ° C. is used, the glass transition temperature of the toner is significantly lowered. In particular, when the wax is left in a high-temperature environment, it melts out on the surface of the toner particles. descend.

On the other hand, when the maximum endothermic peak is higher than 90 ° C., the wax cannot be transferred to the surface of the molten toner quickly at the time of melting and fixing the toner, and the releasability is deteriorated.

The wax preferably satisfies that the peak temperature of the maximum exothermic peak in a temperature range of 30 to 200 ° C. is in a range of 45 to 90 ° C. in an exothermic curve measured by differential thermal analysis (DSC). Further, the peak temperature of the maximum exothermic peak is preferably in the range of 50 to 85 ° C.

When a wax having a maximum exothermic peak of less than 45 ° C. is used, the glass transition temperature of the toner is remarkably lowered. In particular, when the wax is left in a high-temperature environment, the wax is dissolved on the surface of the toner particles. Performance decreases.

On the other hand, when the maximum heat generation peak is higher than 90 ° C., the wax cannot be transferred to the surface of the fixed image quickly at the time of fixing the toner, and the releasability is lowered, so that a high-temperature offset easily occurs.

At the time of temperature rise, a change when heat is applied to the wax can be seen, and an endothermic peak accompanying the transition and melting of the wax is observed. At a temperature decrease, the change at the time of cooling of the wax and the state at normal temperature are observed. And an exothermic peak accompanying the coagulation / crystallization / transition of the wax is observed. The largest exothermic peak among the exothermic peaks at the time of cooling is the exothermic peak accompanying the coagulation and crystallization of the wax. The existence of an endothermic peak accompanying melting at the time of heating to a temperature close to this exothermic peak temperature,
This indicates that the wax is more homogeneous, such as the structure and molecular weight distribution of the wax, and the difference is preferably within 6 ° C. That is, by reducing this difference, the wax is made into a sharp melt (that is, hard at low temperatures, melts quickly when melted, and the melt viscosity is greatly reduced), so that developability, blocking resistance, fixability, The anti-offset property can be made to stand in a well-balanced manner.

The wax having the structural unit (II) is subjected to alcohol oxidation after the aliphatic hydrocarbon wax such as paraffin wax is denatured in the same manner as in the above-mentioned method for producing the wax having the structure (II). It is obtained by doing.

The wax having the structural unit (II) thus obtained has an acid value of 1 to 60 mgKOH /
g is preferable, and a more preferable acid value is in the range of 2-45 mgKOH / g.

The acid value is a numerical value indicating the effect on the heat resistance. When the acid value is less than 1 mgKOH / g,
The compatibility or dispersibility in the polyester resin occupying a part of the main binder is reduced, and image defects tend to occur due to release of the wax. Acid value is 60mg
If it exceeds KOH / g, when the toner is used, the wax is softened, and the heat blocking performance of the toner is reduced.

The wax having the structural unit (III) is synthesized by further converting the wax having the structural unit (II) into an ammonium salt and then dehydrating or ammonolytic.

The wax having the structural unit (IV) can be obtained by bonding the OH group to the wax having the structural unit (I) described above with diisocyanate.

Examples of the diisocyanate include aliphatic diisocyanates such as hexamethylene diisocyanate; 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,5-naphthalenediisocyanate, and the following (a) or (b): Diisocyanate

[0089]

Embedded image Aromatic diisocyanates such as: diisocyanates represented by the following formula (c)

[0090]

Embedded image And alicyclic diisocyanates.

The wax having the structural unit (V) is obtained by subjecting trimellitic acid or trimellitic anhydride or a lower alkyl ester thereof to a condensation reaction with an aliphatic alcohol having 8 or more carbon atoms, or an esterification reaction. Obtained by an exchange reaction.

In the present invention, a combination of a wax having a polar group having a specific structure and a hydrocarbon wax having no polar group can be used as the wax at low temperature fixability.
It is preferable to further improve the high-temperature offset resistance and the blocking resistance.

When a polyester-based resin is used as the main binder resin, when a hydrocarbon-based wax having no polar group is added, a moderate fixing performance can be obtained, but the compatibility with the main binder resin is poor. The dispersion of the wax becomes poor, and the developability as a toner decreases. When a wax having a polar group is used, it is dispersed uniformly, but the toner fixing performance is not sufficiently satisfactory. The inventors of the present invention have made intensive studies and arrived at the present invention. By using a polar group wax having a specific structure, the dispersibility of a hydrocarbon-based wax having no polar group, which has poor dispersibility in a polyester resin, but has good fixability, is improved, and as a color toner, , Developability and fixability could be satisfied.

The wax having a polar group was found to have an effect of improving not only the dispersibility of the colorant but also the dispersibility of the charge control agent. Particularly, in the polar group wax having a specific structure in the present invention (wax having a polar group located in a side chain), this effect was remarkably obtained.
This is probably because the wax having a polar group has good dispersibility in the polyester resin and the polar group is affected by the colorant.However, the polar group at the end of the main chain has an effect of the main chain. Therefore, the influence on the dispersion of the colorant, the charge control agent, and the like is considered to be less effective than the polar group located in the side chain.

Considering only the fixability of the full-color toner described above, it is sufficient that a certain amount of wax exists on the toner surface. Considering developability, wax having a polar group is more advantageous because it is dispersed more uniformly. In a combination system of these waxes, a wax having a polar group at a side chain is more advantageous in terms of toner performance than a wax having a polar group at a main chain terminal. This is because the entire main chain is uniformly dispersed in the polyester resin by the polar groups present as side chains in the main chain, and the polar groups having the main chains of the waxes located in the side chains do not have a polar group. This is because it is considered that the hydrogen-based wax can be uniformly dispersed in the toner particles in a form in which a part of the hydrogen-based wax is incorporated. As described above, the hydrocarbon-based wax having no polar group incorporated into the wax having the polar group has specific thermal characteristics, and thus can be exuded on the toner particle surface by the amount of heat given at the time of fixing. This satisfies the above-described fixability and developability as a full-color image forming toner at the same time.

As the hydrocarbon wax having no polar group used in the present invention, low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax,
An aliphatic hydrocarbon-based wax such as paraffin wax is exemplified. Particularly preferred waxes are aliphatic hydrocarbon waxes such as paraffin wax.

The hydrocarbon-based wax having no polar group used in the present invention has an endothermic curve in differential thermal analysis (DSC) measurement having a maximum endothermic peak temperature in the range of 30 to 200 ° C. of 55 to 90 ° C. It is preferable that it exists in the range of 60 degreeC, and it is more preferable that it exists in the range of 60-85 degreeC in order to achieve the objective of this invention.

The hydrocarbon wax was subjected to differential thermal analysis (D
SC) In the endothermic curve in the measurement, the temperature was 30 to 20.
The peak temperature of the maximum endothermic peak in the range of 0 ° C. is 55
It is preferable to satisfy that it is in the range of ~ 90 ° C,
Further, the peak temperature of the maximum endothermic peak is preferably in the range of 60 to 85 ° C, and most preferably in the range of 65 to 80 ° C.

When a wax having a maximum endothermic peak of less than 55 ° C. is used, the glass transition temperature of the toner is significantly lowered. In particular, when the wax is left in a high temperature environment, it melts out on the surface of the toner particles. descend.

On the other hand, if the maximum endothermic peak is higher than 90 ° C., the wax cannot be transferred to the surface of the fixed image quickly at the time of fixing the toner, and the releasability is lowered, so that a high-temperature offset easily occurs.

The hydrocarbon wax was subjected to differential thermal analysis (D
SC) In the exothermic curve in the measurement, the temperature was 30 to 20.
The peak temperature of the maximum exothermic peak in the range of 0 ° C. is 45
It is preferable to satisfy that it is in the range of ~ 90 ° C,
Further, the peak temperature of the maximum exothermic peak is preferably in the range of 50 to 85 ° C.

When a wax having a maximum exothermic peak of less than 45 ° C. is used, the glass transition temperature of the toner is remarkably lowered. In particular, when the wax is left in a high-temperature environment, it melts out on the surface of the toner particles. descend.

On the other hand, when the maximum heat generation peak is larger than 90 ° C., the wax cannot be transferred to the surface of the fixed image quickly when fixing the toner, and the releasability is lowered, so that a high-temperature offset easily occurs.

The wax having a polar group and the hydrocarbon wax having no polar group used in the present invention are preferably used in an amount of 0.1 to 10% by mass based on the mass of the toner. More preferably, each is preferably used in an amount of 0.2 to 7% by mass based on the mass of the toner. More preferably, the wax is contained in the toner particles in a total amount of 0.4 to 14% by mass based on the mass of the toner.

As the organometallic compound used in the present invention,
Is an aromatic oxycarboxylic acid and an aromatic alkoxycar
Aromatic carboxylic acid derivatives selected from boric acid, said aromatic
Preferably a metal compound of an aromatic carboxylic acid derivative
No. The metal is preferably a divalent or higher valent metal atom.
No. Mg as divalent metal²⁺, Ca²⁺, Sr²⁺, P
b²⁺, Fe²⁺, Co²⁺, Ni²⁺, Zn²⁺, Cu²⁺Is raised
Can be Above all, as the divalent metal, Zn²⁺, Ca²⁺,
Mg²⁺, Sr²⁺Is preferred. A as a trivalent or higher metal
l ³⁺, Cr³⁺, Fe³⁺, Ni³⁺Is raised. Especially good
Al is better³⁺, Cr³⁺And particularly preferred is A
l³⁺It is.

In the present invention, as the organometallic compound, an aluminum compound of di-tert-butylsalicylic acid is particularly preferred.

The metal compound of an aromatic carboxylic acid derivative selected from an aromatic oxycarboxylic acid and an aromatic alkoxycarboxylic acid can be obtained, for example, by dissolving oxycarboxylic acid and alkoxycarboxylic acid in an aqueous sodium hydroxide solution,
An aqueous solution in which divalent or higher-valent metal atoms are dissolved is added dropwise to the aqueous sodium hydroxide solution, and the mixture is heated and stirred.
After cooling to room temperature, a metal compound of an aromatic carboxylic acid can be synthesized by washing with filtered water. However, the present invention is not limited to the above synthesis method.

When the organometallic compound is used in an amount of 0.1 to 10% by mass based on the mass of the toner, the initial variation of the charge amount of the toner is small, and the absolute charge amount required during development is easily obtained. This is preferable because there is no decrease in image quality such as "" or a decrease in image density.

When the content of the organometallic compound is less than 0.1% or not added at all based on the mass of the toner, the amount of charge during durability tends to decrease, and the image density tends to decrease.

When the content of the organometallic compound exceeds 10% based on the mass of the toner, charge-up tends to occur at the time of running many sheets, and the image density tends to decrease.

In the molecular weight distribution of the soluble portion of tetrahydrofuran (THF) of the toner by GPC, the main peak molecular weight (Mp) is 6,000 to 8,000, and the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is determined. (M
(w / Mn) is preferably 300 or more, more preferably 500 or more.

The main peak molecular weight (Mp) of the toner is 6
If it is less than 000, the fixability at a low temperature is good, but the hot offset temperature decreases, and as a result, the non-offset temperature region becomes narrow. Further, the peak molecular weight (Mp) is 80
If it exceeds 00, the hot offset temperature will be high,
As a result, the non-offset temperature region is widened, but the gloss of the image is low and the OHP transparency is low.

When the ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the toner is less than 300, a soft gel produced by a crosslinking reaction during the heat kneading of the organometallic compound and the resin. The high-temperature offset is likely to occur because the amount of the polymer-side component, which is considered to be caused by the above, is reduced.

When the toner of the present invention is used as a magnetic toner, the magnetic toner particles include a magnetic substance. In that case, the magnetic material also has a function as a colorant. Magnetic materials include iron oxides such as magnetite, maghemite, and ferrite, and iron oxides containing other metal oxides; Fe, Co,
Metals such as Ni, or these metals and Al, C
o, Cu, Pb, Mg, Ni, Sn, Zn, Sb, B
Alloys with metals such as e, Bi, Cd, Ca, Mn, Se, Ti, W, V, and mixtures thereof.

As the magnetic material, triiron tetroxide (Fe
₃ O ₄ ), iron sesquioxide (γ-Fe ₂ O ₃ ), zinc iron oxide (Z
nFe ₂ O ₄ ), yttrium iron oxide (Y ₃ Fe ₅ O ₁₂ ),
Cadmium iron oxide (CdFe ₂ O ₄ ), gadolinium iron oxide (Gd ₃ Fe ₅ O ₁₂ ), copper iron oxide (CuFe ₂ O ₄ ), lead iron oxide (PbFe ₁₂ O ₁₉ ), nickel iron oxide (NiFe
₂ O ₄ ), iron neodymium oxide (NdFe ₂ O ₃ ), barium oxide (BaFe ₁₂ O ₁₉ ), magnesium iron oxide (MgF
e ₂ O ₄ ), iron manganese oxide (MnFe ₂ O ₄ ), lanthanum iron oxide (LaFeO ₃ ), iron powder (Fe), cobalt powder (Co), and nickel powder (Ni). Preferred magnetic materials are fine powders of ferric oxide, magnetic ferrite or gamma-iron sesquioxide.

The magnetic material has an average particle diameter of 0.1 to 2 μm (more preferably, 0.1 to 0.5 μm) and 795.8 kA.
/ M (10 k Oersted), the magnetic properties are 1.6 to 12.0 kA / m in coercive force and 50 to 200 Am in saturation magnetization.
² / kg (preferably 50 to 100 Am ² / kg) and a remanent magnetization of ^{2 to 20} Am ² / kg are preferable.

When the magnetic material is used as a magnetic one-component developer that is carried with a magnetic binding force on a developer carrying body containing a magnet, the toner binder resin 10
It is preferably contained in an amount of 5 to 120 parts by mass with respect to 0 parts by mass.

When used as a one-component developer which is carried on a developer carrying member having no magnet without a magnetic restraining force, the magnetic material is used as a binder resin for toner.
The content is preferably 0.1 to 4 parts by mass with respect to 00 parts by mass.

When the content is within this range, the toner scattering phenomenon (dirt in the machine) at the time of durability can be suppressed.

When the content of the magnetic substance exceeds 5 parts by mass,
The surface of the regulating blade or the roller carrying the toner is significantly damaged (cut), which causes charging failure.

When used as a two-component developer by being mixed with magnetic carrier particles, the magnetic material is added to the binder resin 1
It is preferably contained in an amount of 0.1 to 4 parts by mass with respect to 00 parts by mass.

When the content is within this range, the magnetic binding force with the roller carrying the developer is increased.
It is possible to suppress the toner scattering phenomenon (dirt in the machine) at the time of durability.

When the content of the magnetic substance exceeds 5 parts by mass,
Since the magnetic binding force with the roller carrying the developer is excessively increased, the image density is reduced.

As the colorant used in the present invention, pigments and / or dyes can be used.

For example, dyes include C.I. I. Direct Red 1, C.I. I. Direct Red 4, C.I. I. Acid Red 1, C.I. I. Basic Red 1, C.I. I.
Modant Red 30, C.I. I. Direct Blue 1,
C. I. Direct Blue 2, C.I. I. Acid Blue 9, C.I. I. Acid Blue 15, C.I. I. Basic Blue 3, C.I. I. Basic Blue 5, C.I. I. Modant Blue 7, C.I. I. Direct Green 6, C.I.
I. Basic Green 4, C.I. I. Basic Green 6.

The pigments include mineral fast yellow, navel yellow, naphthol yellow S, Hansa yellow G, permanent yellow NCG, tartrazine lake, molybdenum orange, permanent orange GTR, pyrazolone orange, benzidine orange G,
Permanent Red 4R, Watching Red Calcium Salt, Eosin Lake, Brilliant Carmine 3B, Manganese Purple, Fast Violet B, Methyl Violet Lake, Cobalt Blue, Alkaline Blue Lake, Victoria Blue Lake, Phthalocyanine Blue, First Sky Blue, Indanthrene Blue BC, chrome green, pigment green B, malachite green lake, and final yellow green G.

When used as a toner for forming a full-color image, the color pigment for magenta may be C.I.
I. Pigment Red 1, 2, 3, 4, 5, 6, 7,
8, 9, 10, 11, 12, 13, 14, 15, 16,
17, 18, 19, 21, 22, 23, 30, 31, 3
2,37,38,39,40,41,48,49,5
0, 51, 52, 53, 54, 55, 57, 58, 6
0, 63, 64, 68, 81, 83, 87, 88, 8
9, 90, 112, 114, 122, 123, 163,
202, 206, 207, 209, 238, C.I. I. Pigment Violet 19, C.I. I. Bat Red 1,
2, 10, 13, 15, 23, 29, and 35.

Although the pigment may be used alone, it is more preferable to use the dye and the pigment together to improve the sharpness from the viewpoint of the image quality of a full-color image.

Examples of magenta dyes include C.I. I. Solvent Red 1,3,8,23,24,25,27,3
0, 49, 81, 82, 83, 84, 100, 109,
121, C.I. I. Disperse Red 9, C.I. I. Solvent Violet 8, 13, 14, 21, 27, C.I.
I. Oil-soluble dyes such as Disperse Violet 1,
C. I. Basic Red 1,2,9,12,13,1
4,15,17,18,22,23,24,27,2
9, 32, 34, 35, 36, 37, 38, 39, 4
0, C.I. I. Basic violet 1,3,7,1
And basic dyes such as 0, 14, 15, 21, 25, 26, 27, 28.

Examples of the coloring pigment for cyan include C.I. I. Pigment Blue 2, 3, 15, 16, 17; I. Acid Blue 6; C.I. I. Acid Blue 45 or a copper phthalocyanine pigment obtained by substituting 1 to 5 phthalimidomethyl groups in a phthalocyanine skeleton.

Examples of the coloring pigment for yellow include C.I. I. Pigment Yellow 1,2,3,4,5,6,7,10,
11, 12, 13, 14, 15, 16, 17, 23, 6
5,73,83,93,97,180, C.I. I. Bat Yellow 1, 3, 20.

The amount of the colorant used is 1 to 15 parts by mass, preferably 3 to 12 parts by mass, more preferably 4 to 10 parts by mass with respect to 100 parts by mass of the binder resin.

When the content of the coloring agent is more than 15 parts by mass, the transparency is lowered, and the reproducibility of an intermediate color typified by human skin color is also easily lowered. The stability of the properties is reduced, and it becomes difficult to obtain a desired charge amount.

When the content of the coloring agent is less than 1 part by mass, the coloring power is reduced, and it is difficult to obtain a high quality image having a high image density.

It is preferable that a fluidity improver is externally added to the toner particles in order to improve the image quality.

As a fluidity improver, by externally adding to a toner particle, fluidity can be increased before and after addition.

For example, fluororesin powders such as vinylidene fluoride fine powder and polytetrafluoroethylene fine powder;
Silica fine powder such as silica fine powder by a wet method and silica fine powder by a dry method, and treated silica fine powder obtained by subjecting the silica fine powder to a surface treatment with a treating agent such as a silane coupling agent, a titanium coupling agent, and silicone oil. Fine powder of titanium oxide; fine powder of alumina, fine powder of treated titanium oxide, and fine powder of treated alumina oxide.

The fluidity improver has a specific surface area of 30 m ² / g or more, preferably 5 m ² / g or more, as measured by nitrogen adsorption according to the BET method.
Those with 0 m ² / g or more give good results. The fluidity improver is used in an amount of 0.01 to 8 parts by mass, preferably 0.1 to 4 parts by mass, based on 100 parts by mass of the toner particles.

The toner particles are sufficiently mixed with a binder resin, a colorant, an organometallic compound and other optional additives using a mixer such as a Henschel mixer or a ball mill, and then using a heat kneader such as a kneader or an extruder. Melting,
After kneading and kneading, cooling and solidifying the melt-kneaded product, pulverizing the solidified product, and classifying the pulverized product, toner particles having a predetermined average particle size can be produced.

Further, the fluidity improver and the toner particles are sufficiently mixed by a mixer such as a Henschel mixer to obtain a toner having the flowability improver on the surface of the toner particles.

In the present invention, the weight average particle diameter (D ₄ ) of the toner is 3.0 to 15.0 μm, preferably 4.
It is preferably from 0 to 12.0 μm.

The weight average particle diameter (D ₄ ) of the toner is 3.0 μm.
If it is less than m, the charge stabilization is reduced, and fog and toner scattering are liable to occur in multi-sheet durability.

The weight average particle diameter (D ₄ ) of the toner is 15.0.
If it exceeds μm, the reproducibility of the halftone portion is reduced, and the obtained image tends to be rough.

Further, the toner of the present invention preferably has a weight average particle size (D ₄ ) of 4.5 μm to 9.0 μm for forming a higher quality image.

Next, a method of forming a full-color image by electrophotography using the toner of the present invention will be described with reference to FIG.

FIG. 1 is a schematic diagram showing an example of an image forming apparatus for forming a full-color image by electrophotography. 1 is used as a full-color copying machine or a full-color printer. In the case of a full-color copying machine, as shown in FIG. 1, a digital color image reader section is provided at an upper portion, and a digital color image printer section is provided at a lower portion.

In the image reader section, the original 30 is placed on an original platen glass 31, and is exposed and scanned by an exposure lamp 32, so that a reflected light image from the original 30 is condensed on a full color sensor 34 by a lens 33, and a color image is formed. Obtain a decomposed image signal. The color separation image signal is processed by a video processing unit (not shown) through an amplification circuit (not shown), and is sent to a digital image printer unit.

In the image printer section, the photosensitive drum 1, which is an image carrier, has a photosensitive layer having, for example, an organic photoconductor, and is carried rotatably in the direction of the arrow. Around the photosensitive drum 1, a pre-exposure lamp 11, a corona charger 2, a laser exposure optical system 3, a potential sensor 12, four developing devices 4Y, 4C, 4M, 4B of different colors, and a light amount detecting means 13 on the drum , A transfer device 5 and a cleaning device 6 are arranged.

In the laser exposure optical system, an image signal from the reader section is converted into an optical signal for image scan exposure by a laser output section (not shown), and the converted laser light is reflected by the polygon mirror 3a. The light is projected onto the surface of the photosensitive drum 1 via the lens 3b and the mirror 3c.

When an image is to be formed, the printer unit
Is rotated in the direction of the arrow, and after the charge is removed by the pre-exposure lamp 11, the photosensitive drum 1 is uniformly negatively charged by the charger 2 to irradiate a light image E for each separation color, and the electrostatic charge Form an image.

Next, a predetermined developing device is operated to develop the electrostatic charge image on the photosensitive drum 1 to form a toner image on the photosensitive drum 1 with toner. Developing units 4Y, 4C, 4M,
4B are eccentric cams 24Y, 24C, 24M,
By the operation of 24B, development is performed by selectively approaching the photosensitive drum 1 in accordance with each separation color.

The transfer device includes a transfer drum 5a, a transfer charger 5b, an attraction charger 5c for electrostatically attracting a transfer material as a recording material and an attraction roller 5g opposed thereto, an inner charger 5d, and an outer charger. It has a charger 5e and a separation charger 5h. The transfer drum 5a is rotatably supported so as to be rotatable, and a transfer sheet 5f, which is a transfer material carrier that supports a transfer material in an opening area of a peripheral surface thereof, is integrally adjusted on a cylinder. A resin film such as a polycarbonate film is used for the transfer sheet 5f.

The transfer material is conveyed from the cassette 7a, 7b or 7c to the transfer drum 5a through a transfer sheet conveying system, and is carried on the transfer drum 5a. The transfer material carried on the transfer drum 5a is repeatedly conveyed to the transfer position facing the photosensitive drum 1 as the transfer drum 5a rotates, and is transferred onto the transfer material by the action of the transfer charger 5b in the process of passing through the transfer position. Is transferred onto the photosensitive drum 1.

The toner image may be transferred directly from the photoconductor to the transfer material. Alternatively, the toner image on the photoconductor may be transferred to the intermediate transfer member, and the toner image may be transferred from the intermediate transfer member to the transfer material. good.

In the above image forming step, yellow (Y),
By repeating the process for magenta (M), cyan (C), and black (B), a color image in which four color toner images are superimposed on the transfer material on the transfer drum 5 is obtained.

The transfer material on which the toner images of four colors have been transferred in this manner is separated from the transfer drum 5a by the action of the separation claw 8a, the separation push-up roller 8b and the separation charger 5h, and is heated and pressed by the fixing device. 9, where the toner is heated and pressurized and fixed, so that the toner is mixed, colored and fixed on the transfer material, and is fixed to a full-color image. Then, the image is discharged to the tray 10 and the formation of the full-color image is completed. I do.

With reference to FIG. 1, an image forming method in which four color developing units are installed on one photosensitive member has been described.
A tandem type image forming method in which four color developing units are installed on different photoconductors, and toner images formed on the photoconductors are sequentially transferred to a transfer material via an intermediate or without an intermediate. There may be.

At this time, the fixing operation speed of the heating / pressing fixing unit 9 is controlled by the process speed of the main body (for example, 160 mm /
sec) later (for example, 90 mm / sec). This is because a sufficient amount of heating must be given to the toner when the unfixed image in which two to four layers of toner are stacked is melted and mixed. The amount is large.

In FIG. 2, a fixing roller 39 serving as a fixing means is, for example, a 2 mm thick RTV (room temperature vulcanization type, JIS-A hardness 2) on a 5 mm thick aluminum core bar 41.
0) A silicone rubber layer 42 and a 50 μm-thick polytetrafluoroethylene (PTFE) layer 43 on the outside thereof.

On the other hand, a pressing roller 40 as a pressing means
Is placed on an aluminum cored bar 44 having a thickness of, for example, 5 mm.
mm RTV silicone rubber layer 45 (rubber hardness JIS-
A hardness 40), 150 μm thick PTFE on the outside
Layers.

In FIG. 2, the outer diameter of both the fixing roller and the pressure roller is 60 mm, but the hardness of the pressure roller is higher than that of the pressure roller.
The paper discharge direction is closer to the pressure roller than the perpendicular to the line connecting the center lines of both rollers. It is extremely important that the paper ejection direction be on the pressure roller side to prevent the fixing roller from winding around the fixing support when fixing a copy image having a large image area. As a means for setting the paper discharge direction to the pressure roller side, the above-described method of providing a hardness difference, or
By making the diameter of the pressure roller smaller than the fixing roller, setting the temperature of the pressure roller side higher than that of the fixing roller, and evaporating more water on the back of the fixing paper, that is, the paper surface of the pressure roller side, There is a method using a very small amount of paper.

The fixing roller 39 is provided with a halogen heater 46 as a heat generating means.
At 0, a halogen heater 47 is disposed in the metal core to heat from both sides. Thermistors 48a and 48 in contact with the fixing roller 39 and the pressure roller 40
b, the temperatures of the fixing roller 39 and the pressure roller are detected, and the control devices 49a and 49
b controls the halogen heaters 46 and 47, respectively, so that the temperature of the fixing roller 39 and the temperature of the pressure roller 40 are both controlled to be constant (for example, 160 ° C. ± 10 ° C.). Pressure roller 4
0 is a total pressure of 390N (40) by a pressurizing mechanism (not shown).
kgf).

In FIG. 2, a fixing roller cleaning device using a C oil impregnated paper web, and C1 is a cleaning blade for removing oil and dirt adhering to the pressure roller. Oil for paper web impregnation is 50
The use of silicone oils of up to 3000 cSt (silicone oils such as dimethyl silicone oil and diphenyl silicone oil) makes it easy to supply a small amount of applied oil and keeps the quality of fixed images (particularly uniform gloss). Nature, oil marks). When the oil is not applied, it is preferable to remove the cleaning device of C, use paper or a cloth web not impregnated with oil, or use a cleaning blade, a cleaning pad, or a cleaning roller.

The cleaning device C includes a nonwoven fabric web 46.
Is pressed against the fixing roller 29 by the pressing roller 45 for cleaning. The web 46 is appropriately wound by a winding device (not shown) so that toner and the like do not accumulate on the contact portion with the fixing roller 29.

The toner of the present invention is excellent in low-temperature fixability and high-temperature offset resistance, so that the amount of the release agent applied can be reduced, and the amount of dirt in the cleaning device is also small.

The toner image of the toner of the present invention is preferably fixed by heating and pressing at a temperature condition of a surface temperature of a fixing roller of 150 ° C. ± 30 ° C. When the toner image is fixed on the recording material, the fixing member is fixed. Therefore, the amount of silicone oil supplied to the fixing surface of the toner image of the recording material per unit area of the recording material is preferably 0 to 1 × 10 ⁻⁷ g / cm ² .

When the coating amount exceeds 1 × 10 ⁻⁷ g / cm ² , glare of the recording material is large, and particularly the visibility of a character image is reduced.

The color image formed on the recording sheet is obtained by fixing the color toner image having at least the toner of the present invention on the recording material sheet by the above-described image forming process.

The methods for measuring the physical properties of the binder resin and the toner particles will be described below.

(1) Measurement of hydroxyl value and acid value According to the method specified in JIS K0070. However, when the sample does not dissolve, a solvent such as dioxane or tetrahydrofuran is used as the solvent.

Preparation of sample for measuring molecular weight distribution : To measure the molecular weight of the THF-soluble component of the toner, the toner is dissolved in THF, extracted by Soxhlet reflux for 6 hours, and the dissolved sample is measured.

(2) Measurement of molecular weight by GPC The molecular weight of a chromatogram by gel permeation chromatography (GPC) is measured under the following conditions.

The column was stabilized in a heat chamber at 40 ° C., and tetrahydrofuran (THF) was passed through the column at this temperature at a flow rate of 1 ml per minute as a solvent.
The measurement is performed by injecting 50 to 200 μl of a THF sample solution of a resin adjusted to a sample concentration of 0.05 to 0.6% by mass. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the count number. As standard polystyrene samples for creating calibration curves,
For example, Pressure Chemical Co.
Or Toyo Soda Kogyo Co., Ltd. has a molecular weight of 6 × 1
0 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ ,
5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8.
It is suitable to use 6 × 10 ⁵ , 2 × 10 ⁶ , and 4.48 × 10 ⁶ , and to use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector.

In order to accurately measure the molecular weight region of 10 ³ to 2 × 10 ^6, a plurality of commercially available polystyrene gel columns may be used in combination.
μ-styragel 500, 10 ³ , 1
0 ⁴ 10 ⁵ of combinations and, shodex of Showa Denko Co., Ltd.
KA-801, 802, 803, 804, 805, 80
6,807 combinations are preferred.

(3) Measurement of maximum endothermic and exothermic peaks of wax Differential thermal analysis measuring device (DSC measuring device), DSC-7
(Perkin Elmer).

The measurement sample is 5 to 20 mg, preferably 10
Weigh the mg precisely. This was put in an aluminum pan, and an empty aluminum pan was used as a reference. The temperature was raised and lowered at a rate of 10 ° C./min between 30 and 200 ° C.
At normal temperature and normal humidity.

In the process of raising the temperature, endothermic and exothermic peaks of the main peak in the temperature range of 30 to 160 ° C. are obtained. The maximum endothermic peak is, of course, the temperature at which the maximum value is shown.

(4) Measurement of Particle Size Distribution of Toner Particles or Toner As a measuring device, Coulter Counter TA-II or Coulter Multisizer II (manufactured by Coulter Inc.)
Is used. As the electrolyte, about 1% NaCl aqueous solution is prepared using primary sodium chloride. For example, ISOTON
(Registered trademark) -II (manufactured by Coulter Scientific Japan) can be used. As a measuring method, a surfactant (preferably alkyl benzene sulfone hydrochloride) is used as a dispersant in 100 to 150 ml of the electrolytic aqueous solution.
And 0.1 to 5 ml, and the measurement sample is further added to 2 to 20 ml.
Add mg. The electrolytic solution in which the sample was suspended was subjected to a dispersion treatment for about 1 to 3 minutes with an ultrasonic disperser, and the volume and the number of toner particles were measured for each channel by the measuring device using an aperture of 100 μm as an aperture. Then, the volume distribution and the number distribution of the toner are calculated. Then, the weight average particle diameter (D ₄ ) and volume average particle diameter (D _v ) of the mass-based toner particles or toner determined from the volume distribution of the toner particles (the median value of each channel is a representative value for each channel) Ask for.

The channels are 2.00 to 2.52
μm; 2.52 to 3.17 μm; 3.17 to 4.00 μm
m; 4.00 to 5.04 μm; 5.04 to 6.35 μm
m; 6.35 to 8.00 μm; 8.00 to 10.08 μm
m; 10.08 to 12.70 μm; 12.70 to 16.
00 μm; 16.00-20.20 μm; 20.20
25.40 μm; 25.40 to 32.00 μm;
13 channels of 40.30 μm are used.

(5) Measurement of the degree of aggregation The degree of aggregation is used as one means for measuring the flow characteristics of a sample (toner having an external additive, a classified product). Judge that sex is bad.

As a measuring device, a powder tester (manufactured by Hosokawa Micron Corporation) having a digital vibrometer (Digi Vibro Model 1332) is used. As a measuring method, a 200-mesh, 100-mesh, and 60-mesh sieve are placed on a shaking table in the order of narrow opening, that is, a 200-mesh, 100-mesh, and 60-mesh sieve are stacked so as to be at the highest position. I do. 5 g of a sample accurately weighed on the set 60 mesh sieve
To adjust the input voltage to the shaking table to 21.7 V, the displacement value of the digital vibrometer to 0.130, and the amplitude of the shaking table at that time to fall within the range of 60 to 90 μm. (Rheostat scale about 2.5), and vibrate for about 15 seconds. Thereafter, the mass of the sample remaining on each sieve is measured to obtain the degree of agglomeration based on the following equation.

[0182]

(Equation 1)

The sample was heated for about 1 hour at 23 ° C. and 60% RH.
The measurement environment is 23 ℃, 60%
RH.

[0184]

EXAMPLES Examples of the toner of the present invention will be described below, but the present invention is not limited to these examples.

Production Examples of Hybrid Resins (1) to (4) As a vinyl copolymer, styrene (2.0 mol)
0.21 mol of ethylhexyl acrylate, 0.16 mol of fumaric acid, 0.03 dimer of α-methylstyrene
mol and 0.06 mol of dicumyl peroxide were placed in the dropping funnel. In addition, polyoxypropylene (2.
2) 7.0 mol of -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.2) -2,
2-bis (4-hydroxyphenyl) propane 3.0 m
ol, 3.5 mol of terephthalic acid, 1.5 mol of trimellitic anhydride, 5.0 mol of succinic acid and 0.2 g of dibutyltin oxide in a 4 liter glass four-necked flask, a thermometer, a stirring rod, a condenser and nitrogen. An inlet tube was attached and placed in the mantle heater. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually increased while stirring.
While stirring at a temperature of 40 ° C., the vinyl copolymer monomer and the polymerization initiator were added dropwise from the previous dropping funnel over 4 hours. Next, the temperature was raised to 200 ° C., and the mixture was reacted for 4 hours to obtain a hybrid resin (1). Table 1 shows the results of the molecular weight measurement by GPC.

In the hybrid resin (2), the composition of the vinyl copolymer was 8.0 mol of styrene, 0.84 mol of 2-ethylhexyl acrylate, 0.64 mol of fumaric acid, and 0.12 mol of α-methylstyrene dimer.
mol, and in the hybrid resin (3), the composition of the vinyl copolymer was changed to 16.3 mol of styrene,
Ethylhexyl acrylate 1.50 mol, fumaric acid 1.20 mol, dimer of α-methylstyrene 0.20
mol, and in the hybrid resin (4), 18.0 mol of styrene, 2.0 mol of 2-ethylhexyl acrylate, 1.2 mol of fumaric acid, 0.8 mol of α-methylstyrene dimer, and change the amount with respect to the polyester. Except for the above, hybrid resins (2) to (4) shown in Table 1 were obtained in the same manner as above.

Production Examples of Polyester Resins (1) to (3) Polyoxypropylene (2.2) -2,2-bis (4-
(Hydroxyphenyl) propane 3.7 mol, polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane 1.6 mol, terephthalic acid 1.5
mol, 1.2 mol of trimellitic anhydride, 2.5 mol of fumaric acid and 0.1 g of dibutyltin oxide made of glass 4
The mixture was placed in a 4-liter four-necked flask, fitted with a thermometer, a stirring rod, a condenser and a nitrogen inlet tube, and placed in a heating mantle. The mixture was reacted at 220 ° C. for 5 hours under a nitrogen atmosphere to obtain a polyester resin (1). Table 1 shows the results of the molecular weight measurement by GPC.

Next, the polyester resins (2) to (3) shown in Table 1 were obtained by changing the composition ratio and the molecular weight without changing the type of the acid component and the type of the alcohol component.

Production Example of Vinyl Copolymer (1) 1000 ml of toluene solvent and vinyl copolymer were used.
Styrene 2.4 mol, n-butyl acrylate 0.2
6 mol, monobutyl malate 0.09 mol, di-t
0.11 mol of -butyl peroxide is placed in a 3 liter 4-neck flask equipped with a thermometer, a stainless steel stirring rod, a flow-down condenser and a nitrogen inlet tube, and stirred at a temperature of 120 ° C. in a nitrogen atmosphere in a mantle heater. The reaction was carried out while refluxing toluene while heating to obtain a vinyl copolymer (1). Table 1 shows the results of the molecular weight measurement by GPC.

[0190]

[Table 1]

Of the waxes (A) to (G) having polar groups
Production Example Production Example (A) The maximum endothermic peak temperature (melting point) was 69 with an average carbon number of 35.
1200 g of paraffin wax at 5 ° C. was placed in a glass cylindrical reaction vessel, and the molar ratio of boric acid to boric anhydride was 1.5.
Was added at a temperature of 140 ° C., and immediately an oxygen concentration of about 10 vol.
vol. of a mixed gas at a rate of 20 liters per minute was blown in at a rate of 20 liters per minute, and the reaction was carried out at 180 ° C. for 2.5 hours. Was collected.

The obtained wax had a hydroxyl value of 35 mg.
KOH / g, the acid value is 5 mg KOH / g,
The endothermic main peak temperature in the SC curve was 67 ° C, and the exothermic main peak temperature was 63 ° C. The obtained wax is referred to as a wax (A) having a polar group.

[0193]

Embedded image

Production Example (B) After completion of the reaction in Production Example (A), a polar group was prepared in the same manner as in Production Example (A) except that 40 g of a mixed catalyst was further added and the reaction was carried out at 180 ° C. for 6 hours. A wax (B) having the following formula was prepared. The obtained wax (B) has an acid value of 3
It was 0 mgKOH / g, the endothermic main peak temperature in the DSC curve was 66 ° C, and the exothermic peak main temperature was 62 ° C.

Production Example (C) A wax (C) having a structural unit of the formula (IV) was prepared by ammonolysis of a wax (B) having a polar group. Wax (C) had an endothermic main peak temperature of 70 ° C. and an exothermic main peak temperature of 69 ° C. in the DSC curve.

Production Example (D) Wax (A) having a polar group and diisocyanate of the following formula [a]

[0197]

Embedded image Was reacted to prepare a wax (D) having a structural unit of the formula (V). The obtained wax (D) had an endothermic main peak temperature of 75 ° C and an exothermic main peak temperature of 70 ° C.

Production Example (E) Trimellitic anhydride and ceryl alcohol [CH ₃ (C
H ₂ ) ₂₃ CH ₂ OH] to give a wax (E) having a structural unit of the formula (V). Wax (E) had an acid value of 10 mgKOH / g, an endothermic main peak temperature in the DSC curve of 68 ° C, and an exothermic peak temperature of 63 ° C.

Production Example (F) Instead of paraffin wax having an average carbon number of 35, the average carbon number was 130, and the endothermic main peak temperature (melting point)
A wax (F) having a structural unit of the formula (I) was prepared in the same manner as in Production Example (A) except that a polyethylene wax having a temperature of 141 ° C. was used. Wax (F)
Has a hydroxyl value of 12 mgKOH / g and an acid value of 1 m
gKOH / g, the endothermic main peak temperature in the DSC curve is 143 ° C., and the exothermic main peak temperature is 1
35 ° C.

Production Example (G) Instead of paraffin wax having an average carbon number of 35, the average carbon number was 25, and the endothermic main peak temperature was 50.5.
A wax (G) having a structural unit of the formula (I) was prepared in the same manner as in Production Example (A) except that a paraffin wax at a temperature of ° C was used. The wax (G) has a hydroxyl value of 65 mgKOH / g, an acid value of 1 mgKOH / g and an endothermic main peak temperature of 48 in the DSC curve.
° C and the exothermic main peak temperature was 44 ° C.

Example 1 Binder resin: hybrid resin (1) 100 parts by mass Wax having polar group: wax having polar group (A) 3 parts by mass Wax not having polar group: paraffin wax (1) (Endothermic main peak temperature 72 ° C, average carbon number 37) 3 parts by mass ・ Negative charge control agent: 6 parts by mass of aluminum compound of 3,5-di-tert-butylsalicylic acid ・ Pigment: 4 parts by mass of copper phthalocyanine Henschel mixer After sufficiently performing preliminary mixing, the mixture was melt-kneaded with a twin-screw extruder, cooled, and coarsely ground to a particle size of about 1 to 2 mm using a hammer mill. Next, it was pulverized by a pulverizer using an air jet method. Further, the obtained finely pulverized product was classified by a multi-segment classifier (elbow jet classifier) to obtain cyan resin particles (cyan toner particles) having a weight average particle size of 7.0 μm.

The obtained cyan-based resin particles (classified middle powder: M powder) and the classified fine powder (F) were weighed, and the wax content was quantified by DSC measurement. Table 2 shows the ratio (the amount of wax in powder F / the amount of wax in powder M). F /
As the value of M is closer to 1.0, the wax is more uniformly dispersed, and as the value of M is larger, the dispersion becomes uneven and the toner has poorer chargeability. In particular, the value of F / M is
If it is 1.35 or more, fog and scattering become worse.

To 100 parts by mass of the cyan resin particles, 1.0 part by mass of hydrophobic titanium oxide (BET110 m ^{2 /} g) treated with nC ₄ H ₉ Si (OCH ₃ ) ₃ was externally added, and cyan was added. A toner (1) was obtained. Furthermore, cyan toner (1)
And magnetic ferrite carrier particles (average particle size: 50 μm) surface-coated with a silicone resin so that the toner concentration becomes 7% by mass, and a two-component cyan developer (1)
I got Table 2 shows the physical properties of Cyan Toner (1).

Using this cyan developer (1), an unfixed image was formed in a single color mode using a color copying machine CLC-800 (manufactured by Canon Inc.). The obtained unfixed image is shown in FIG.
The fixing test was performed by changing the fixing temperature and changing the fixing speed to 100 mm / sec and 250 mm / sec using the fixing device in which the roller cleaning device C was removed from the fixing device shown in FIG. The image area ratio at this time is 25%
And the amount of applied toner per unit area is 0.7 m
g / cm ² . Table 5 shows the evaluation results.

Pressure roller stain (fixed paper back stain) The pressure roller stain level is set at a fixing temperature of 200 ° C., and 100 sheets of images are continuously printed in an environment of normal temperature and normal humidity (23.5 ° C./50%). The paper was passed through and the fixing paper was ranked as follows according to the number of stains on the back of the fixing paper. A: 0 to 3 B: 4 to 6 C: 7 to 9 D: 10 to 20 E: 21 or more

Curl level of the fixed paper after fixing The curl level of the copy image is 84 g /
used as a m ^2, and out the same image as the above, 200
After fixing at ° C., the fixed image was placed on a flat plate, and the curling height was measured and ranked. A: less than 0.5 cm B: 0.5 to less than 1.0 cm C: 1.0 to less than 1.5 cm D: 1.5 to less than 3.0 cm E: more than 3.0 cm

OHP Transmittance The OHP transparency was measured by setting the fixing speed to 30 mm / sec, fixing at a fixing temperature of 10 ° C. lower than the high-temperature offset start temperature, and using a Shimadzu self-recording spectrophotometer UV2200 (manufactured by Shimadzu Corporation). Is used, the transmittance of the OHP film alone is set to 100%, and for the magenta toner: 650 nm,
The transmittance at the maximum absorption wavelength at 500 nm for the cyan toner and 600 nm for the yellow toner is measured. A: 85% or more B: 75 to 84% C: 65 to 74% D: 50 to 64% E: Less than 50%

Heat Resistance Test (Blocking Resistance Test) The blocking resistance of the toner was evaluated by placing 100 g of the toner in a 500 ml polyethylene cup and leaving it in an oven at 50 ° C. for one week. As the evaluation, the level of cohesiveness was visually determined.

The evaluation criteria for toner cohesion are shown below. A: No aggregates are seen at all, and the flowability is very good. B: Aggregates are not seen at all. C: Some aggregates are seen, but are loosened immediately. E: Aggregates are not sufficiently loosened with the developer stirring device (somewhat bad)

Aggregation (Fluidity) The fluidity of the toner was measured using an externally added product. For the fluidity, based on the results of the measurement of the degree of agglomeration described above, the numerical range for the criterion for evaluating the properties was determined as follows. A: very good fluidity: a sample with a measured cohesion of 40% or less B: good fluidity: a measured cohesion of 41% to 50%
Sample C: Normal flowability: Measurement result of cohesion degree is 51% to 60%
Of sample D: Poor fluidity: Measurement result of cohesion degree is 61% to 70%
Of sample E: very poor fluidity: sample whose measurement result of agglomeration degree is 71% or more

Examples 2, 3, 4 In place of the copper phthalocyanine pigment, C.I. I. Pig. Red 1
22 as 4 parts by mass yellow toner. I. Pig. Yellow
180 as 7 mass parts black toner, carbon black (particle diameter 20
m) was used in the same manner as in Example 1 to prepare a magenta developer, a yellow developer, and a black developer, respectively. Table 2 shows the physical properties of the obtained toners.

Table 5 shows the evaluation results of each color.

The blocking resistance of each color toner was good. Evaluation was made in the single-color mode in the same manner as in Example 1 using the developers of the respective colors. Table 5 shows the results.

Further, using the four-color developers of Examples 1 to 4, using a remodeling machine of Canon CLC800 (remodeling the fixing machine configuration to an oilless configuration similar to CP660), endurance in full-color mode image output. Tested. The endurance of 10,000 sheets was performed, but no offset occurred, and a copy image with excellent color mixing properties and a wide color reproduction area was obtained.

The obtained full-color image has good gloss,
Even if an OHT sheet is produced, it has good translucency, plain paper and O
The non-offset fixing temperature range was wide in both HP sheets.

Examples 5 to 9 Cyan toners (2) to (E) were prepared in the same manner as in Example 1 except that waxes (B) to (E) having polar groups were used instead of waxes (A) having polar groups. 6) was produced.

Each toner was evaluated in the same manner as in Example 1. Table 5 shows the evaluation results.

Examples 10 to 19 In the formulations shown in Table 3, the hybrid resin (1) was replaced with a different kind of resin, or the hybrid resin (1) was left as it was and the kind of wax was changed. The toners (7) to (16) were produced in the same manner as in Example 1 except that both were changed. Table 3 shows the physical properties of the obtained toner.

Next, a two-component developer was prepared and evaluated in the same manner as in Example 1. Table 5 shows the evaluation results.

Comparative Example 1 The procedure of Example 1 was repeated except that 100 parts by mass of the polyester resin (1), 6 parts by mass of the paraffin wax (1), and 6 parts by mass of the chromium compound of di-tert-butylsalicylic acid were used. A comparative cyan toner (A) was prepared.
Table 4 shows the physical properties of Comparative Cyan Toner (A). Table 6 shows the evaluation results.

The non-offset temperature region also becomes narrow, and the OHP
The permeability also deteriorated. Also, the level of dirt on the back of the pressure roller was poor, and the curl of the copy paper was also poor. Furthermore, the uniformity of wax dispersibility was low.

Comparative Examples 2, 3, and 4 Instead of the copper phthalocyanine pigment, C.I. I. Pig. Red 1
22 as 4 parts by mass yellow toner. I. Pig. Yellow
180 as 7 mass parts black toner, carbon black (particle diameter 20
magenta developer, yellow developer, and black developer were prepared in the same manner as in Comparative Example 1 by using 4 parts by mass of each of the dyes of the present invention. Table 4 shows the physical properties of the obtained toners.

Example 1 using the obtained developers of each color
The evaluation was performed in the same manner as described above. Table 6 shows the evaluation results.

Next, using the four color developers of Comparative Examples 1 to 4, a full color mode image endurance test was carried out with a modified machine of Canon CLC800 (fixed machine configuration was changed to oilless configuration). .

In comparison with the toners of Examples 1 to 4,
Offset was liable to occur, the obtained full-color image on plain paper had low gloss, the full-color image on the OHP sheet had low translucency, and the non-offset fixing temperature region was narrow.

[0226]

[Table 2]

[0227]

[Table 3]

[0228]

[Table 4]

[0229]

[Table 5]

[0230]

[Table 6]

Production Example of Hybrid Resin (5) As a vinyl copolymer, 2.0 mol of styrene and 2-mol
0.21 mol of ethylhexyl acrylate, 0.16 mol of fumaric acid, 0.03 dimer of α-methylstyrene
mol and 0.05 mol of dicumyl peroxide were placed in the dropping funnel. In addition, polyoxypropylene (2.
2) 7.0 mol of -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.2) -2,
2-bis (4-hydroxyphenyl) propane 3.0 m
ol, 3.0 mol of terephthalic acid, 2.0 mol of trimellitic anhydride, 5.0 mol of succinic acid and 0.2 g of dibutyltin oxide were placed in a 4-liter glass four-necked flask, and a thermometer, a stirring rod, a condenser and nitrogen were added. An inlet tube was attached and placed in the mantle heater. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually increased while stirring.
While stirring at a temperature of 40 ° C., the vinyl copolymer monomer and the polymerization initiator were added dropwise from the previous dropping funnel over 4 hours. Next, the temperature was raised to 200 ° C., and the mixture was reacted for 4 hours to obtain a hybrid resin (5). Table 7 shows the results of the molecular weight measurement by GPC.

Production Example of Polyester Resin (4) Polyoxypropylene (2.2) -2,2-bis (4-
(Hydroxyphenyl) propane 3.5 mol, polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane 1.5 mol, terephthalic acid 1.5
mol, 1.0 mol of trimellitic anhydride, 2.5 mol of fumaric acid and 0.1 g of dibutyltin oxide made of glass 4
The mixture was placed in a 4-liter four-necked flask, fitted with a thermometer, a stirring rod, a condenser and a nitrogen inlet tube, and placed in a heating mantle. The mixture was reacted at 220 ° C. for 5 hours under a nitrogen atmosphere to obtain a polyester resin (4). Table 7 shows the results of the molecular weight measurement by GPC.

Production Example of Vinyl Copolymer (2) As a vinyl copolymer, 1000 ml of a toluene solvent and
Styrene 2.4 mol, n-butyl acrylate 0.2
6 mol, 0.09 mol of monobutyl maleate, 0.0001 mol of divinylbenzene, and 0.11 mol of di-t-butyl peroxide were added to a 3 liter solution equipped with a thermometer, a stainless steel stirrer, a falling condenser, and a nitrogen inlet tube. The mixture was placed in a one-necked flask and reacted in a mantle heater while refluxing toluene with stirring at a temperature of 120 ° C. in a nitrogen atmosphere to obtain a vinyl copolymer (2). Table 7 shows the results of the molecular weight measurement by GPC.

[0234]

[Table 7]

Example 20 Binder resin: Hybrid resin (5) 100 parts by mass Polar group-containing wax (A) (alcohol-modified paraffin wax) 3 parts by mass Charge control agent: Aluminum compound of di-tert-butylsalicylic acid 6 parts by mass Part Pigment: copper phthalocyanine 5 parts by mass After sufficiently premixing the above materials with a Henschel mixer, melt kneading with a twin screw extruder, and after cooling, coarsely pulverizing to a particle size of about 1 to 2 mm using a hammer mill. . Next, it was pulverized by a pulverizer using an air jet method. Further, the obtained finely pulverized product was classified by a multi-segment classifier to obtain cyan resin particles having a weight average particle size of 7.0 μm.

To 100 parts by mass of the cyan resin particles, 1.0 part by mass of hydrophobic titanium oxide (BET110 m ^{2 /} g) treated with nC ₄ H ₉ Si (OCH ₃ ) ₃ was externally added, and cyan was added. The toner (17) was obtained. In addition, cyan toner (1
7) and magnetic ferrite carrier particles (average particle size: 50 μm) surface-coated with a silicone resin were mixed so that the toner concentration became 7% by mass to obtain a two-component cyan developer (17).

Using this cyan developer (17), an unfixed image was formed on a color copying machine CLC-800 (manufactured by Canon Inc.). The obtained unfixed image was subjected to a fixing test using a fixing device in which the roller cleaning device C was removed from the fixing device shown in FIG. 2 while changing the fixing temperature and speed. At this time, the image area ratio was 25%, and the amount of applied toner per unit area was set to 0.7 mg / cm ² .

The image obtained in Example 20 was glossy, OH
T: good light transmission, wide non-offset fixing temperature range, and good blocking resistance. Table 8 shows the GPC measurement result of the toner, and Table 10 shows the evaluation result.

Example 21 A cyan toner (18) and a cyan developer (18) were obtained in the same manner as in Example 20, except that the polyester resin (4) was used instead of the hybrid resin (5).

Further, the toner was evaluated in the same manner as in Example 20. Table 8 shows the GPC measurement result of the toner, and Table 10 shows the evaluation result.

Example 22 55 parts of the hybrid resin (5) was replaced with 100 parts by mass.
Example 2 except that a mixture of parts by weight of the polyester resin (4) and 45 parts by weight of the hybrid resin (5) was used.
0, a cyan toner (19) and a cyan developer (19) were obtained. Further, the toner was evaluated in the same manner as in Example 20. Table 8 shows the GPC measurement result of the toner, and Table 10 shows the evaluation result.

Example 23 85 parts of the hybrid resin (5) was replaced with 100 parts by mass.
Example 2 except that a mixture of parts by weight of the polyester resin (4) and 15 parts by weight of the vinyl copolymer (2) was used.
0, a cyan toner (20) and a cyan developer (20) were obtained. Further, the toner was evaluated in the same manner as in Example 20. Table 8 shows the GPC measurement results of the toner, and Table 10 shows a list of the evaluation results.

Example 24 95 parts of the hybrid resin (5) were replaced with 100 parts by mass.
Example 20 except that a mixture of 5 parts by mass of the hybrid resin (5) and 5 parts by mass of the vinyl copolymer (2) was used.
In the same manner as in the above, a cyan toner (21) and a cyan developer (21) were obtained. Further, the toner was evaluated in the same manner as in Example 20. Table 8 shows the GPC measurement results of the toner, and Table 10 shows a list of the evaluation results.

Example 25 Instead of 100 parts by mass of the hybrid resin (5), 60 parts by mass of the polyester resin (4), 30 parts by mass of the hybrid resin (5) and 10 parts by mass of the vinyl copolymer (2) A cyan toner (22) and a cyan developer (22) were obtained in the same manner as in Example 20, except for using the mixture of Further, the toner was evaluated in the same manner as in Example 20. Table 8 shows the GPC measurement results of the toner, and Table 10 shows a list of the evaluation results.

Examples 26 to 29 Example 20 was repeated except that the alcohol-modified paraffin wax (I) to (L) shown in Table 8 was used instead of the polar group-containing wax (A) having a polar group. Similarly, cyan toners (23) to (26)
And cyan developers (23) to (26). further,
The toner was evaluated in the same manner as in Example 20. G of toner
Table 8 shows the PC measurement results, and Table 10 shows a list of the evaluation results.

Examples 30 to 32 In the same manner as in Example 20, except that the addition amount was changed to 2 parts by mass and 8 parts by mass instead of 6 parts by mass of the aluminum compound of di-tert-butylsalicylic acid. Toner (27), (28) and cyan developer (27),
(28) was obtained. Also, a cyan toner (29) and a cyan developer (29) were obtained in the same manner as in Example 20, except that a chromium compound of di-tert-butylsalicylic acid was used instead of the aluminum compound of di-tert-butylsalicylic acid. Was. Further, the toner was evaluated in the same manner as in Example 20. Table 8 shows the GPC measurement results of the toner.
Table 10 shows a list of the evaluation results.

Example 33 C.I. was replaced with 6 parts by mass of copper phthalocyanine. I. Pigment Red 202, 6 parts by mass of C.I. I. Pigment Yellow 17 and 3 parts by mass of carbon black, except that magenta toner (2) and magenta developer (2), yellow toner (2) and yellow developer (2) were used in the same manner as in Example 20. ), Black toner (2) and black developer 2. Example 2
The toner was evaluated in the same manner as 0.

Further, the cyan developer (1
7), a color copier CLC-800 using a magenta developer (2), a yellow developer (2) and a black developer (2).
A fixing test was performed in a full-color mode under normal temperature and normal humidity (23 ° C., 60%) using an original manuscript using a modified machine in which an oil application mechanism of a fixing unit (manufactured by Canon) was removed. Wide non-offset temperature range, glossiness,
A high-definition full-color image with good transparency of the OHT was obtained.

Comparative Example 5 A vinyl copolymer (2) was used in place of the hybrid resin (5), and the alcohol-modified paraffin wax (A) having a polar group was used. Comparative cyan toner (B) in the same manner as in Example 20 except that paraffin wax (F) was used.
And cyan developer (B). Further, the toner was evaluated in the same manner as in Example 20. Table 9 shows the GPC measurement results of the toner, and Table 11 shows the evaluation results.

When the vinyl copolymer was used, the non-offset temperature range was narrowed, and the OHP permeability was also deteriorated. In addition, when a wax having a high alcohol modification rate (having a large hydroxyl value) is used, an acid as a by-product is also formed at the same time, so that the endothermic peak of DSC is lowered and the blocking resistance is deteriorated.

Comparative Example 6 A comparative cyan toner (C) and a cyan developer were prepared in the same manner as in Comparative Example 5 except that the alcohol-modified paraffin wax (F) shown in Table 9 was used instead of the alcohol-modified paraffin wax (F). (C) was obtained. Further, the toner was evaluated in the same manner as in Example 20. Table 9 shows the GPC measurement results of the toner, and Table 11 shows a list of the evaluation results.

When a wax having a small alcohol modification ratio (having a small hydroxyl value) was used, its properties were very close to those of the base paraffin wax, so that the fluidity of the toner was lowered and the quality of the image was lowered.

Comparative Example 7 Comparative cyan toner (D) and cyan developer were prepared in the same manner as in Comparative Example 6 except that alcohol-modified paraffin wax (H) shown in Table 9 was used instead of alcohol-modified paraffin wax (F). (D) was obtained. Further, the toner was evaluated in the same manner as in Example 20. Table 9 shows the GPC measurement results of the toner, and Table 11 shows the evaluation results.

When a wax having an extremely high alcohol modification rate (an extremely large hydroxyl value) was used, the endothermic peak of DSC was low as in Comparative Example 5, and the blocking resistance was reduced.

Comparative Example 8 A comparative cyan toner (E) and a cyan developer (E) were obtained in the same manner as in Comparative Example 7, except that the polypropylene wax shown in Table 9 was used instead of the alcohol-modified paraffin wax (H). Was. Further, the toner was evaluated in the same manner as in Example 20. Table 9 shows the GPC measurement results of the toner, and Table 11 shows the evaluation results.

When a wax such as polypropylene having both high endothermic and exothermic peaks was used, the hot hot offset temperature was lowered because the wax could not efficiently transfer to the surface when the toner was melted during fixing. Further, the transfer paper was easily wound around the fixing roller (heating roller).

Comparative Example 9 Comparative cyan toner (F) was prepared in the same manner as in Comparative Example 5 except that no organometallic compound was used in place of 6 parts by mass of the aluminum compound of di-tert-butylsalicylic acid.
And a cyan developer (F). Further, the toner was evaluated in the same manner as in Example 20. Table 9 shows the GPC measurement results of the toner, and Table 11 shows the evaluation results.

When an organometallic compound capable of generating a crosslinking reaction is not used, ionic crosslinking is not formed at the time of melt-kneading, so that high-temperature offset is likely to occur, and the blocking resistance of the toner is also reduced.

Comparative Example 10 Comparative cyan toner (G) was prepared in the same manner as in Comparative Example 5 except that the addition amount was changed to 11.5 parts by mass instead of 6 parts by mass of the aluminum compound of di-tert-butylsalicylic acid.
And a cyan developer (G). Further, the toner was evaluated in the same manner as in Example 20. Table 9 shows the GPC measurement results of the toner, and Table 11 shows the evaluation results.

The surface of the toner-fixed image had large irregularities, and the OHP transmittance was reduced due to the irregular reflection of incident light.

Comparative Examples 11 and 12 The organometallic compound was changed to an aluminum compound of di-tert-butylsalicylic acid, and a Zn compound of di-tert-butylsalicylic acid and 2-hydroxy-6-
Comparative Cyan Toners (H) and (I) and Developers (H) and (I) were prepared in the same manner as in Comparative Example 10 except that an Fe compound of tertiary butyl-naphthoic acid was used. Evaluation was performed in the same manner as in Example 20. GPC of toner
Table 9 shows the measurement results, and Table 11 shows a list of the evaluation results.

When these charge control agents are used, both the comparative cyan toners (H) and (I) do not substantially form ionic crosslinks during kneading, so that high-temperature offset is likely to occur, and the toner has anti-blocking performance. Also fell.

[0263]

[Table 8]

[0264]

[Table 9]

[0265]

[Table 10]

[0266]

[Table 11]

[0267]

According to the present invention, it is possible to obtain a toner which can be fixed satisfactorily without applying oil, has good transparency with OHP, and has excellent hot offset resistance and low temperature fixability.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing an example of an image forming apparatus using a toner of the present invention.

FIG. 2 is a schematic explanatory view showing an example of a heating and pressing fixing unit.

[Explanation of symbols]

 Reference Signs List 1 photosensitive drum (image carrier) 4 developing device 9 heat-press fixing device

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03G 15/20 104 G03G 9/08 331 325 346 (72) Inventor Yasuyoshi Sugawara 3-chome Shimomaruko, Ota-ku, Tokyo 30-2 Canon Inc. (72) Takayuki Itakura, the inventor 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Yojiro Hotta 3-30-2, Shimomaruko, Ota-ku, Tokyo F term in Canon Inc. (reference) 2H005 AA01 AA06 AA21 CA04 CA08 CA14 CA21 CA25 DA02 DA04 DA06 EA03 EA06 EA07 EA10 2H030 AA06 AD01 AD04 BB63 2H033 AA02 BA42 BA46 BA58 BB01

Claims (31)

[Claims] 1. A toner containing at least a binder resin, a colorant and a wax, wherein the binder resin comprises (a) a polyester resin, (b) a polyester unit and a vinyl copolymer unit. The wax contains a polar group-containing wax, and the polar group-containing wax has the following formula (I) to (I)
V) has any of the structural units, or
Having the structural formula of the following formula (V): A toner comprising at least one wax. 2. The toner according to claim 1, wherein the binder resin further contains a vinyl copolymer. 3. The toner according to claim 1, wherein the binder resin contains at least a polyester resin and a hybrid resin. 4. The toner according to claim 2, wherein the binder resin contains at least a mixture of a hybrid resin and a vinyl copolymer. 5. The toner according to claim 1, wherein the wax further contains a hydrocarbon wax having no polar group. 6. The hydrocarbon wax having no polar group has a maximum endothermic peak in a temperature range of 30 to 200 ° C. in a temperature range of 55 to 90 ° C. in an endothermic curve measured by differential thermal analysis (DSC). The toner according to any one of claims 1 to 5, wherein 7. The hydrocarbon wax having no polar group has a maximum endothermic peak in a temperature range of 30 to 200 ° C. in a range of 60 to 85 ° C. in an endothermic curve measured by differential thermal analysis (DSC). The toner according to any one of claims 1 to 5, wherein 8. The hydrocarbon wax having no polar group has a maximum exothermic peak in a temperature range of 30 to 200 ° C. in a temperature range of 45 to 90 ° C. in an exothermic curve measured by differential thermal analysis (DSC). The toner according to any one of claims 1 to 7, wherein 9. The hydrocarbon wax having no polar group has a maximum exothermic peak temperature in the range of 30 to 200 ° C. in the range of 50 to 85 ° C. in the exothermic curve measured by differential thermal analysis (DSC). The toner according to any one of claims 1 to 7, wherein 10. The resin component soluble in tetrahydrofuran of the toner has a molecular weight of 60 as determined by molecular weight distribution by gel permeation chromatography (GPC).
A main peak is present in the range of 00 to 8000, and the ratio (Mw) between the weight average molecular weight (Mw) and the number average molecular weight (Mn)
/ Mn) is 300 or more.
10. The toner according to any one of claims 1 to 9. 11. The resin component soluble in tetrahydrofuran of the toner has a molecular weight of 60 as determined by molecular weight distribution by gel permeation chromatography (GPC).
A main peak is present in the range of 00 to 8000, and the ratio (Mw) between the weight average molecular weight (Mw) and the number average molecular weight (Mn)
/ Mn) is 500 or more.
10. The toner according to any one of claims 1 to 9. 12. The wax containing a polar group having a structural unit of the formula (I) has a hydroxyl value of 10 to 70 mg KOH.
The toner according to any one of claims 1 to 11, wherein the ratio is in the range of / g. 13. The toner according to claim 1, wherein the polar group-containing wax having the structural unit of the formula (I) has an acid value in the range of 1 to 20 mgKOH / g. . 14. The wax containing a polar group having a structural unit of the formula (II) has an acid value of 1 to 60 mgKOH / g.
The toner according to any one of claims 1 to 13, wherein: 15. A wax having a polar group has a temperature of 30 in an endothermic curve measured by differential thermal analysis (DSC).
The toner according to any one of claims 1 to 14, wherein the peak temperature of the maximum endothermic peak in the range of -200C is in the range of 60-140C. 16. A wax having a polar group has a temperature of 30 in an endothermic curve measured by differential thermal analysis (DSC).
The toner according to any one of claims 1 to 14, wherein the peak temperature of the maximum endothermic peak in the range of -200C is in the range of 65-120C. 17. The wax having a polar group has a temperature of 30 in an exothermic curve measured by differential thermal analysis (DSC).
The toner according to any one of claims 1 to 16, wherein the peak temperature of the maximum exothermic peak in the range of -200 ° C is in the range of 45-140 ° C. 18. The wax having a polar group has a temperature of 30 in an exothermic curve measured by differential thermal analysis (DSC).
17. The toner according to claim 1, wherein a peak temperature of a maximum heat generation peak in a range of from 200 to 200 [deg.] C. is in a range of from 50 to 120 [deg.] C. 19. The toner according to claim 1, wherein the toner further contains an organometallic compound. 20. The organic metal compound is an aromatic carboxylic acid derivative selected from an aromatic oxycarboxylic acid and an aromatic alkoxycarboxylic acid, and a metal compound of the aromatic carboxylic acid derivative. 20. The toner according to 19 above. 21. The toner according to claim 19, wherein the organometallic compound is contained in the toner in an amount of 0.1 to 10% by mass based on the mass of the toner. 22. The wax having a polar group is represented by the formula (I):
The toner according to any one of claims 1 to 21, comprising a structural unit represented by formula (II) and a structural unit represented by formula (II). 23. The toner according to claim 1, wherein the wax having a polar group is contained in the toner in an amount of 0.1 to 10% by mass based on the mass of the toner. 24. The toner according to claim 1, wherein the wax having no polar group is contained in the toner in an amount of 0.1 to 10% by mass based on the mass of the toner. . 25. The wax may be used in an amount of 0.1% based on the mass of the toner.
25. The toner according to claim 1, wherein the toner is contained in 4 to 14% by mass of the toner. 26. The toner according to claim 1, wherein the toner is a color toner. 27. The toner according to claim 1, wherein the toner is a color toner selected from the group consisting of a cyan toner, a magenta toner, and a yellow toner.
6. The toner according to any one of the above items 6. 28. (i) forming a first electrostatic image on an image carrier, and developing the electrostatic image with a first toner selected from the group consisting of cyan toner, magenta toner, yellow toner and black toner; To form a first toner image on the image carrier, and transfer the first toner image to a transfer material with or without the intermediate transfer member, and (ii) a second static image on the image carrier. Forming a charge image, developing an electrostatic charge image with a second toner selected from the group consisting of cyan toner, magenta toner, yellow toner, and black toner to form a second toner image on the image carrier; Transferring the second toner image to a transfer material with or without an intermediate transfer member, and (iii) forming a third electrostatic image on the image carrier, a cyan toner, a magenta toner, a yellow toner and Black tona Developing an electrostatic charge image with a third toner selected from the group consisting of: forming a third toner image on the image carrier, and applying the third toner image via an intermediate transfer member or not; (Iv) forming a fourth electrostatic image on the image carrier, and forming an electrostatic image with the fourth toner selected from the group consisting of cyan toner, magenta toner, yellow toner, and black toner To form a fourth toner image on the image carrier, and transfer the fourth toner image to a transfer material with or without an intermediate transfer member. (V) cyan on the transfer material A full-color image forming method for forming a full-color image on a transfer material by heating and pressing and fixing a toner image, a magenta toner image, a yellow toner image, and a black toner image. The binder resin contains at least a cyan colorant and a wax, and the binder resin is (a) a polyester resin, (b) a hybrid resin having a polyester unit and a vinyl copolymer unit, or (c) The wax contains a polar group-containing wax, and the polar group-containing wax has the following formula (I) to (I)
V) has any of the structural units, or
Having the structural formula of the following formula (V): (B) the magenta toner contains at least a binder resin, a magenta colorant and a wax, and the binder resin comprises (a) a polyester resin, and (b) a polyester resin. A hybrid resin having a unit and a vinyl copolymer unit, or (c) a mixture thereof, and the wax contains a wax having a polar group. The wax has the following formulas (I) to (I)
V) has any of the structural units, or
Having the structural formula of the following formula (V): (C) the yellow toner contains at least a binder resin, a yellow colorant and a wax, and the binder resin comprises (a) a polyester resin, and (b) a polyester A hybrid resin having a unit and a vinyl copolymer unit, or (c) a mixture thereof, and the wax contains a wax having a polar group. The wax has the following formulas (I) to (I)
V) has any of the structural units, or
Having the structural formula of the following formula (V): (D) the black toner contains at least a binder resin, a black colorant and a wax, and the binder resin comprises (a) a polyester resin, and (b) a polyester. A hybrid resin having a unit and a vinyl copolymer unit, or (c) a mixture thereof, and the wax contains a wax having a polar group. The wax has the following formulas (I) to (I)
V) has any of the structural units, or
Having the structural formula of the following formula (V): A full-color image forming method comprising at least one kind of wax. 29. The toner image, wherein the coating amount of silicone oil supplied from the fixing member to the fixing surface is 0 to 1 × 10 ^−7.
29. The full-color image forming method according to claim 28, wherein the transfer material is heat-pressed and fixed under a condition of g / cm < ² >. 30. The full-color image forming method according to claim 28, wherein the toner image is heat-pressed and fixed to the transfer material under the condition of oilless fixing in which no silicone oil is supplied from the fixing member to the fixing surface. Method. 31. The toner according to claim 2, wherein the cyan toner, the magenta toner, the yellow toner, and the black toner are the toner according to claim 2.
31. The full-color image forming method according to any one of 8 to 30.