JP2001249485A - Toner and method of fixing by heating - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide toner having good transparency for OHP, excellent low temperature fixing property and offset resistance at high temperature, and excellent blocking resistance when it is left in a high temperature environment. SOLUTION: The toner contains (i) a polyester resin, (ii) a hydrocarbon wax, (iii) a wax dispersant containing a polyolefin and a copolymer synthesized from styrene monomers, and (iv) a coloring agent. The endothermic curve of the polyolefin measured by DSC during the temperature elevation shows the maximum in the largest endothermic peak at 90 to 130 deg.C. The endothermic curve of the hydrocarbon wax measured by DSC during the temperature elevation satisfies the maximum of the largest endothermic peak at 55 to 80 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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 a heat fixing 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 usually used, when the toner is melted in the heating and pressurizing fixing step, the self-cohesive force of the binder resin is low, so that a problem tends to occur in the high-temperature offset resistance.

In general black toners for black-and-white copying machines, relatively high-crystalline waxes such as polyethylene waxes and polypropylene waxes are used as a release agent to improve the high-temperature offset resistance during fixing. For example, it is proposed in JP-B-52-3304, JP-B-52-3305, and JP-A-57-52574. However, 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 refractive index from the material of the OHP sheet, and the projected image has a high saturation. And the brightness becomes lower.

[0006] In order to solve this problem, a method of lowering the crystallinity of wax by using a nucleating material in combination with wax is disclosed in JP-A-4-149559 and JP-A-4-107.
No. 467.

Further, a method using a wax having a low crystallinity is disclosed in JP-A-4-301853 and JP-A-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.

Therefore, Japanese Patent Application Laid-Open No. 8-314300 discloses
Japanese Patent Application Laid-Open No. 8-50368 proposes a toner and an image forming method which do not use a fixing oil by encapsulating a wax by a polymerization suspension method.

However, in these toners, although oil streaks on a fixed image are suppressed, a large amount of wax must be included in the toner, and styrene-
Since a binder containing acrylic as a main component is used, unevenness on the surface of a fixed image is inevitable, and as a result, it is hard to say that the OHP permeability is satisfactory.

At the same time, the image recorded matter using these toners necessarily has a low gloss. Therefore, in a graphic image in which a graph and a character portion are mixed, there is an advantage that a good image without a sense of incongruity can be obtained. In a real image, since the toner after fixing is not sufficiently melted, there is a disadvantage that the color mixing property of the secondary colors is low and the color reproduction range is narrow.

Therefore, in the heat and pressure fixing means which does not use oil or uses less oil,
A high gloss is achieved by using a polyester having a high sharp melt property as a main binder, a toner having excellent secondary color mixing properties, a wide color reproduction range, and an excellent OHP transparency has been desired.

[0016]

SUMMARY OF THE INVENTION An object of the present invention is to provide a toner and a heat fixing method which solve the above-mentioned problems.

An object of the present invention is to provide a toner and a heat fixing method 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 and a heat-fixing method because of its good transparency in OHP and good color mixing of secondary colors.

An object of the present invention is to provide a toner excellent in low-temperature fixing property and high-temperature offset resistance and a heat fixing method.

An object of the present invention is to provide a toner having excellent blocking resistance when left in a high-temperature environment and a heat fixing method.

[0021]

Specifically, the present invention provides:
(I) a polyester resin, (ii) a hydrocarbon wax, (iii) a styrene monomer and an N-containing vinyl monomer, a carboxyl group-containing monomer, a hydroxyl group-containing monomer, an acrylate monomer and a methacrylate monomer. Or a toner containing a wax dispersant having at least a polyolefin and a copolymer synthesized using two or more types of monomers, and (iv) a colorant. In the endothermic curve, the maximum value of the maximum endothermic peak is 90 to 130 ° C., and the maximum value of the maximum endothermic peak is 55 to 80 ° C. in the endothermic curve of the hydrocarbon wax measured by DSC. The total polyester resin content (W
1), the content of the hydrocarbon wax (W2), the content of the copolymer (W3), and the content of the polyethylene (W
The mass ratio of 4) has the following relationship: W1: W2: W3: W4 = 100: (0.1 to 6):
(0.1 to 20): (0.1 to 2) A toner which satisfies W3: W4 = 100: (1 to 400).

Further, according to the present invention, a fixing member is brought into contact with the surface of a toner image formed on a recording material, and the toner image is applied to the recording material by applying heat and pressure to the toner image. In the heat fixing method for fixing, when the toner image is fixed on the recording material, the amount of silicone oil supplied from the fixing member to the fixing surface of the toner image of the recording material per unit area of the recording material is 0 to 0. 1 × 10 ^-7 g
/ Cm ² , wherein the toner comprises (i) a polyester resin, (ii) a hydrocarbon-based wax, (iii) a styrene-based monomer and an N-containing vinyl monomer, a carboxyl-containing monomer, a hydroxyl-containing monomer, an acrylate monomer, A wax dispersant having at least a polyolefin and a copolymer synthesized by using one or more monomers selected from methacrylate monomers, and (iv) a colorant, wherein the polyolefin In the endothermic curve at the time of temperature rise measured by DSC, the maximum value of the maximum heat peak is 90 to 130 ° C.
In the endothermic curve at the time of temperature rise measured by DSC of the hydrocarbon wax, the maximum value of the maximum thermal peak is at 55 to 80 ° C., and the content (W1) of the total polyester resin in the toner (W1); The mass ratio of the hydrocarbon wax content (W2), the copolymer content (W3), and the polyethylene content (W4) has the following relationship: W1: W2: W3: W4 = 100: (0. 1-6):
(0.1 to 20): (0.1 to 2) A heat fixing method characterized by satisfying W3: W4 = 100: (1 to 400).

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION We have (i) a polyester resin, (ii) a hydrocarbon wax, (iii) a styrene monomer and an N-containing vinyl monomer, a carboxyl group-containing monomer, a hydroxyl group-containing monomer, and acrylic acid. A toner containing a wax dispersant having at least a polyolefin and a copolymer synthesized using one or two or more monomers selected from an ester monomer and a methacrylate monomer, and (iv) a colorant. In the endothermic curve at the time of temperature rise measured by DSC of the polyolefin, the maximum value of the maximum endothermic peak is 90%.
To 130 ° C., and the maximum value of the maximum endothermic peak is 55 to 80 ° C. in the endothermic curve at the time of temperature rise measured by DSC of the hydrocarbon wax, and the content of all polyester resins (W1 ), Content of the hydrocarbon wax (W2), content of the copolymer (W3)
And the mass ratio of the polyolefin content (W4) is as follows: W1: W2: W3: W4 = 100: (0.1-6):
(0.1 to 20): (0.1 to 2) W3: W4 = 100: (1 to 400) In the case of a toner that satisfies: In the heat and pressure fixing unit using a small amount, it is known that a toner and an image forming method that satisfy high gloss, have excellent secondary color mixing properties, have a wide color reproduction range, and have excellent OHP transparency can be provided. Thus, the present invention has been achieved. Hereinafter, the present invention will be described in detail.

In the present invention, the binder resin of the toner particles is a polyester resin having a carboxyl group,
A polyester resin having a carboxyl group and having a molecular skeleton represented by the following formula (A) is preferable.

[0025]

Embedded image [In the formula, x and y are integers of 1 or more, and the average value of x + y is 2 to 4. R is an alkyl or alkenyl group of H or C ₁ -C _20. ]

The polyester resin having a molecular skeleton represented by the formula (A) is liable to form a metal ion cross-linking structure when melt-kneaded with a metal salicylate compound which will be described in detail later. And a toner having a clear minimum value (G′min) can be satisfactorily generated.

For example, in the dynamic elastic modulus curve of the toner similar to the below-described embodiment shown in FIG. 1, the dynamic elastic modulus (G ′ ₁₇₀ ) in the region of 170 ° C. is different from that in the region of 140 ° C. Since the toner has high viscoelasticity at a temperature higher than the elastic modulus (G ' ₁₄₀ ), the toner has extremely high hot offset resistance.

On the other hand, a toner having a similar formulation to the below-described comparative toner exhibiting viscoelasticity as shown in FIG.
It does not have a definite minimum in the region of 0 ° C.
The storage elastic modulus of the toner decreases as the temperature increases even on the side higher than ℃. Such a toner is inferior in high-temperature offset resistance and has a narrower fixing temperature range than the toner of the present invention.

The reason why the molecular skeleton represented by the formula (A) is specifically selected from an aromatic oxycarboxylic acid and an aromatic alkoxycarboxylic acid or an aromatic carboxylic acid derivative or a metal compound of the aromatic carboxylic acid derivative Although it is not fully known whether or not the phenyl group having an electron-donating phenyl group at the p-position is likely to form a conformation that easily interacts with the flexibility characteristic of this molecular chain (molecular arrangement interaction). It is thought that the electron donating property and the π electron donating interaction of —CH ＝ CH— are closely related.

The dihydric alcohol component for producing the polyester resin which is the main binder resin in the present invention includes, for example, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, , 3-butanediol, diethylene glycol,
Triethylene glycol, 1,5-pentanediol,
1,6-hexanediol, neopentyl glycol,
2-ethyl-1,3-hexanediol, hydroxylated bisphenol A, and a bisphenol derivative represented by the formula (B)

[0031]

Embedded image [Wherein, R is an ethylene or propylene group, x and y are each an integer of 1 or more, and the average value of x + y is 2
10 to 10. ].

The trivalent or higher alcohol component for forming the non-linear polyester resin includes, for example,
Sorbitol, 1,2,3,6-hexanetetrol,
1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,2
4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2
-Methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxybenzene. The amount of the trihydric or higher polyhydric alcohol used is 0.1 to 1.9 based on all monomers.
mol% is preferred.

As the divalent acid component for producing the polyester resin, for example, fumaric acid, maleic acid, maleic anhydride, succinic acid, adipic acid, sebacic acid, malonic acid and those having 8 to 14 carbon atoms are used. An aliphatic acid component monomer substituted with 22 saturated or unsaturated hydrocarbon groups; and phthalic acid,
Isophthalic acid, phthalic anhydride, terephthalic acid and ester derivatives thereof.

Examples of the trivalent or higher polycarboxylic acid component for forming the non-linear polyester resin include 1,2,4-benzenetricarboxylic acid, 1,2,5
-Benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, and anhydrides and ester compounds thereof. The amount of the trivalent or higher polyvalent carboxylic acid component used is preferably 0.1 to 1.9 mol% based on all monomers.

In the present invention, the polyester resin TH
In GPC measurement of F-soluble component, number average molecular weight (Mn)
Is from 1300 to 9500, and the weight average molecular weight (Mw)
And the ratio (Mw / Mn) between the mass average molecular weight (Mw) and Mn of the THF-soluble component of the polyester resin is preferably 2 to 20.

The acid value of the polyether resin is preferably 1 to 60 mgKOH / g, more preferably 5 to 60 mKOH / g.
gKOH / g, more preferably 5 to 50 gKOH / g.
mgKOH / g, particularly preferably 7 to 50 mgKOH / g.
g is preferable.

Number average molecular weight (Mn) of polyester resin
Is less than 1300 or the weight average molecular weight (Mw) is 2
In the case of less than 600, the fixed image surface has high smoothness and vivid appearance, but tends to cause high-temperature offset in durability, furthermore, the long-term storage stability is reduced, and the In addition, there is a concern about a new problem such as fusion of the toner and occurrence of carrier spent due to adhesion of the toner component to the carrier surface. Further, it is difficult to apply a shear during the melt-kneading of the toner raw material during the production of the color toner particles, the dispersibility of the colorant is easily reduced, and therefore, the coloring power of the toner is reduced and the charge amount of the toner is easily changed.

Number average molecular weight (Mn) of polyester resin
Is more than 9500 or when the weight average molecular weight (Mw) is more than 190000, all have excellent offset resistance, but the fixing temperature must be increased, and the degree of dispersion of the pigment is temporarily controlled. Even if it is possible, the surface smoothness in the image area is reduced, and the color reproducibility is likely to be reduced.

When the Mw / Mn of the polyester resin is less than 2, the generally obtained polyester resin has a small molecular weight itself. Therefore, similarly to the case where the molecular weight is small, a high-temperature offset phenomenon due to durability and long-term storage stability are obtained. In addition, toner fusing and carrier spent in the developing device are likely to occur, and furthermore, the charge amount of the toner tends to vary.

When the Mw / Mn of the polyester resin is more than 20, although the high temperature offset resistance is excellent, the fixing temperature must be increased, and even if the degree of dispersion of the pigment can be controlled, Since the surface smoothness in the image portion is reduced, and the color mixing of the secondary colors is reduced, the color reproducibility is likely to be reduced.

The acid value of the polyester resin is 1 mg KOH
If it is less than / g, an increase in the amount of charge during durability, that is, a so-called charge-up tends to occur, and it becomes difficult to maintain the image density for a long period of time.

The acid value of the polyester resin is 60 mg KO
If it exceeds H / g, the charge-up tendency disappears, but "charge fogging" due to the charge-down tendency, particularly in a high-temperature and high-humidity environment, occurs,
This leads to a decrease in image quality.

The following are examples of the release agent (wax) used in the present invention. Low molecular weight polyethylene,
Aliphatic hydrocarbon waxes such as low molecular weight polypropylene, microcrystalline wax and paraffin wax; aliphatic hydrocarbon wax oxides such as oxidized polyethylene wax; aliphatic hydrocarbon wax block copolymers; carnauba wax; Waxes mainly containing fatty acid esters such as sol wax and montanic acid ester wax; and those obtained by partially or entirely deoxidizing fatty acid esters such as deoxidized carnauba wax. Further, as a releasing agent, saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brandic acid, eleostearic acid, and vinaric acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, and carnaubyl alcohol Polyhydric alcohols such as sorbitol; fatty acid amides such as linoleic acid amide, oleic acid amide, and lauric acid amide; methylenebisstearic acid amide, ethylenebiscapric acid amide, ethylenebislaurin Acid amides, saturated fatty acid bisamides such as hexamethylene bisstearic acid amide; ethylene bisoleic acid amide, hexamethylene bis oleic acid amide, N, N'-dioleyl adipamide, N, N - dioleylsebacic acid amide such unsaturated fatty acid amides; m-xylene bis-stearic acid amide, N, N'-distearyl such aromatic bisamides of isophthalic acid amide; calcium stearate, calcium laurate, zinc stearate,
Metal salts of fatty acids such as magnesium stearate (commonly referred to as metallic soaps); graft waxes obtained by grafting vinyl monomers such as styrene and acrylic acid onto aliphatic hydrocarbon waxes; fatty acids such as behenic acid monoglyceride; Partial esterified products of polyhydric alcohols; and methyl ester compounds having a hydroxyl group obtained by hydrogenating vegetable oils and fats.

Particularly preferred waxes are aliphatic hydrocarbon waxes such as paraffin wax.

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

The method of adding the wax in the present invention is not a simultaneous addition with a binder or other materials during the production of the toner, but a "wax dispersant" in which a release agent such as paraffin is finely dispersed in the resin composition in advance. It is good to add in the form. Hereinafter, the wax dispersant will be described.

Examples of the wax dispersant include (i) a polyester resin, (ii) a hydrocarbon wax, (iii) a styrene monomer and an N-containing vinyl monomer, a carboxyl group-containing monomer, a hydroxyl group-containing monomer, an acrylate monomer and What has at least a polyolefin and a copolymer synthesized using one or two or more monomers selected from acrylic acid ester monomers is preferable.

The hydrocarbon wax used in the present invention is finely dispersed in the wax dispersant in advance.

In the endothermic curve at the time of temperature rise measured by DSC of the hydrocarbon wax, the maximum value of the maximum endothermic peak is 55 to 80 ° C., and 0.1 to 6% by mass based on the mass of the toner. %.

When the amount of the wax is less than 0.1% by mass, the releasing effect cannot be obtained particularly when the amount of the fixing oil applied is reduced or not used at all, and when the amount is more than 6% by mass, Dispersion of the pigment becomes worse, and as a result, the chroma of the toner is impaired.

Further, when a wax having a maximum endothermic peak of less than 55 ° C. is used, it becomes lower than the glass transition temperature of the resin used in the present invention. Blocking resistance is greatly deteriorated. On the other hand, if the maximum endothermic peak is higher than 80 ° C., the wax cannot be quickly transferred to the surface of the molten toner at the time of fixing and melting the toner, and the releasability is deteriorated.

In the molecular weight distribution of the hydrocarbon wax by GPC, the weight average molecular weight (Mw) is 400 to 80.
0, the number average molecular weight (Mn) is 400 to 600, and the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 1.0 to 2.0. preferable.

The number average molecular weight (M
When n) is less than 400 or when the weight average molecular weight (Mw) is less than 400, the toner melts on the toner surface when left in a high temperature environment, so that the blocking resistance is significantly deteriorated.

When the number average molecular weight (Mn) of the hydrocarbon wax exceeds 600 or when the weight average molecular weight (M
w) exceeds 800, or the ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn)
Exceeds 2.0, the wax cannot quickly move to the surface of the molten toner at the time of melting and fixing of the toner, and the releasability is deteriorated.

Since the compatibility between the polyester resin, which is the main binder in the present invention, and the hydrocarbon wax is originally poor, when added as it is to form a toner, the wax segregates in the toner. As a result, free wax and the like are also generated, and as a result, problems such as white spots and poor charging occur.

Therefore, (iii) a styrene monomer, an N-containing vinyl monomer, a carboxyl group-containing monomer,
In a copolymer obtained by grafting a polyolefin and a copolymer synthesized using one or two or more monomers selected from a hydroxyl group-containing monomer, an acrylate monomer and a methacrylate monomer, (i)
i) A resin composition in which a hydrocarbon wax is finely dispersed in advance is used as a wax dispersant, and the wax dispersant is melt-mixed as a masterbatch in (i) a polyester resin to form a "wax dispersant masterbatch". Was used during the production of the toner.

A copolymer synthesized using a styrene monomer and one or more monomers selected from N-containing vinyl monomers, carboxyl group-containing monomers, hydroxyl group-containing monomers, acrylate monomers and methacrylate monomers. Examples of monomers that can be used for synthesizing the union include the following.

Examples of the styrene monomer include styrene, o-methylstyrene, m-methylstyrene, p-
Methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-n-butylstyrene, p-tert-butyl Styrene such as styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene and pn-dodecyl styrene, and derivatives thereof.

Examples of the N-containing vinyl monomer include amino group-containing α-methylene aliphatic monocarboxylic acid esters such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; acrylic acid or methacrylic acid such as acrylonitrile, methacrylonitrile and acrylamide; Acid derivatives.

Examples of the carboxyl group-containing monomer 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 And unsaturated dibasic acid anhydrides such as alkenyl succinic anhydride; methyl maleate half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester Half esters of unsaturated dibasic acids such as esters, methyl itaconic acid half ester, methyl alkenyl succinate half ester, methyl fumarate half ester and methyl mesaconic acid half ester; dimethyl maleic acid, dimethyl fumaric acid Saturated 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, Alkenyl adipic acids, their anhydrides and their monoesters are mentioned.

Examples of the hydroxyl group-containing monomer include acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate;
(Hydroxy-1-methylbutyl) styrene, 4- (1-
(Hydroxy-1-methylhexyl) styrene.

Examples of the acrylate monomer include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate,
Examples include acrylates such as 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, and phenyl acrylate.

The methacrylic acid ester monomers include:
For example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, phenyl methacrylate Α-methylene aliphatic monocarboxylic acid esters such as dimethylaminoethyl and diethylaminoethyl methacrylate.

Among them, a terpolymer of styrene-acrylonitrile-butyl acrylate is particularly preferable.

A copolymer synthesized using a styrene monomer and one or more monomers selected from N-containing vinyl monomers, carboxyl group-containing monomers, hydroxyl group-containing monomers, acrylate monomers and methacrylate monomers. In the molecular weight distribution of the polymer by GPC, the weight average molecular weight (Mw) is 5,000 to 5,000.
100000 and a number average molecular weight (Mn) of 1500
It is preferable that the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 2 to 40.

A copolymer synthesized using a styrene monomer and one or more monomers selected from N-containing vinyl monomers, carboxyl group-containing monomers, hydroxyl group-containing monomers, acrylate monomers and methacrylate monomers. Weight average molecular weight of polymer (M
w) is less than 5000 or the number average molecular weight (M
n) is less than 1500, or the weight average molecular weight (M
w) and the ratio (Mw / Mn) of the number average molecular weight (Mn) is 2
If it is less than 1, the blocking resistance of the toner is significantly impaired.

A copolymer synthesized using a styrene monomer and one or more monomers selected from N-containing vinyl monomers, carboxyl group-containing monomers, hydroxyl group-containing monomers, acrylate monomers and methacrylate monomers. Weight average molecular weight of polymer (M
w) exceeds 100,000, or the number average molecular weight (Mn) exceeds 15,000, or the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw / M
When n) is more than 40, the hydrocarbon wax finely dispersed in the wax dispersant cannot be transferred to the surface of the molten toner quickly at the time of fixing and melting, and the releasability is deteriorated. Become.

Further, it is synthesized using a styrene monomer and one or more monomers selected from N-containing vinyl monomers, carboxyl group-containing monomers, hydroxyl group-containing monomers, acrylate monomers and methacrylate monomers. The copolymer is preferably contained in the toner in an amount of 0.1 to 20% by mass based on the mass of the toner.

A copolymer synthesized using a styrene monomer and one or two or more monomers selected from N-containing vinyl monomers, carboxyl group-containing monomers, hydroxyl group-containing monomers, acrylate monomers and methacrylate monomers. When the content based on the mass of the toner in the polymer exceeds 20% by mass, the low-temperature fixing (sharp melt property) of the polyester resin as the main binder is impaired, so that a problem that the non-offset temperature region is narrowed is caused. .

A copolymer synthesized using a styrene monomer and one or more monomers selected from the group consisting of an N-containing vinyl monomer, a carboxyl group-containing monomer, a hydroxyl group-containing monomer, an acrylate monomer and a methacrylate monomer. The polyolefin used for the graft polymerization with the polymer preferably has a maximum endothermic peak at a maximum of 90 to 130 ° C. in an endothermic curve at the time of temperature rise measured by DSC.

When the maximum value of the maximum endothermic peak of the polyolefin is less than 90 ° C. or exceeds 130 ° C., any of the styrene monomer and the N-containing vinyl monomer, the carboxyl group-containing monomer, the hydroxyl group-containing monomer, the acrylate monomer and the Since the branched structure in a graft copolymer with a copolymer synthesized using one or more monomers selected from acrylate monomers is impaired, fine dispersion of a hydrocarbon wax is performed. Therefore, when the toner is converted into toner, segregation of the hydrocarbon wax occurs, and image defects such as white spots occur.

In the present invention, the weight average molecular weight (Mw) of the polyolefin contained in the wax dispersant in the molecular weight distribution by GPC is from 500 to 30,000, the number average molecular weight (Mn) is from 500 to 3,000,
The ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) is 1.0 to 20, and the density is 0.9 to
Preferably, it has a low density of 0.95.

The polyolefin has a weight average molecular weight (M
w) is less than 500, or number average molecular weight (Mn)
Is less than 500, or the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is less than 1.0, or the weight average molecular weight (Mw) is 300
00 or when the number average molecular weight (Mn) is 30
When the ratio is more than 00, or when the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) exceeds 20, the hydrocarbon wax finely dispersed in the wax dispersant is used as a toner at the time of fixing. The high-temperature offset resistance deteriorates because the surface does not effectively seep out.

The polyolefin has a density of 0.95
Exceeds (not low density), one or more monomers selected from styrene monomers and N-containing vinyl monomers, carboxyl group-containing monomers, hydroxyl group-containing monomers, acrylate monomers and methacrylate monomers, Since the effective branching structure in the graft copolymer with the copolymer synthesized by using the toner is impaired, segregation of the hydrocarbon-based wax occurs when the toner is converted into toner, and image defects such as white spots occur. .

Further, the polyolefin is preferably contained in the toner in an amount of 0.1 to 2% by mass based on the mass of the toner.

When the content of the polyolefin based on the mass of the toner exceeds 2% by mass, the styrene monomer and the N-containing vinyl monomer, the carboxyl group-containing monomer, the hydroxyl group-containing monomer and the acrylic A hydrocarbon-based compound because an effective branched structure in a graft copolymer with a copolymer synthesized using one or more monomers selected from acid ester monomers and methacrylate monomers is impaired; Fine dispersion of the wax is not performed, and segregation of the hydrocarbon-based wax occurs when the toner is converted into a toner, resulting in image defects such as white spots.

In the present invention, the content (W1) of the total polyester resin in the toner, the content of the hydrocarbon wax (W2), a styrene monomer and an N-containing vinyl monomer, a carboxyl group-containing monomer, a hydroxyl group-containing monomer, and acrylic acid The mass ratio of the content (W3) of the copolymer synthesized using one or two or more monomers selected from ester monomers and methacrylate monomers and the content of the polyolefin (W4) is as follows. W1: W2: W3: W4 = 100: (0.1 to 6):
(0.1 to 20): (0.1 to 2) is preferably satisfied.

Only W2 has W1: W2: W3: W4 = 1
00: (0.1 to 6): (0.1 to 20): (0.1 to
When the amount is less than the range of 2), the releasing effect cannot be obtained when the coating amount of the fixing oil is reduced or when the fixing oil is not used at all.

In addition, only W2 has W1: W2: W3: W
4 = 100: (0.1-6): (0.1-20):
If the ratio exceeds the range (0.1 to 2), the dispersion of the pigment becomes poor, and as a result, the saturation of the toner is impaired.

Only W3 has W1: W2: W3: W4 = 1
00: (0.1 to 6): (0.1 to 20): (0.1 to
If it is less than the range of 2), the effect of the wax dispersant itself will not be exhibited, so that the fine dispersion of the hydrocarbon wax will not be performed, and the hydrocarbon wax will be segregated when the toner is formed, resulting in white spots and the like. Image defects occur.

Further, only W3 has W1: W2: W3: W
4 = 100: (0.1-6): (0.1-20):
If it exceeds (0.1 to 2), the low-temperature fixing (sharp melt property) of the polyester resin as the main binder is impaired, so that the non-offset temperature region becomes narrower.

Only W4 has W1: W2: W3: W4 = 1.
00: (0.1 to 6): (0.1 to 20): (0.1 to
If it is less than the range of 2), the effect of the wax dispersant itself will not be exhibited, so that the fine dispersion of the hydrocarbon wax will not be performed, and the hydrocarbon wax will be segregated when the toner is formed, resulting in white spots and the like. Image defects occur.

Also, only W4 is W1: W2: W3: W
4 = 100: (0.1-6): (0.1-20):
If it exceeds the range of (0.1 to 2), as in the case of the above result, the effective branched structure in the graft copolymer with the styrene-acrylonitrile- (meth) acrylic acid-based copolymer is impaired. As a result, the hydrocarbon wax is not finely dispersed, segregation of the hydrocarbon wax occurs when toner is formed, and image defects such as white spots occur.

Further, it is synthesized by using a styrene monomer and one or more monomers selected from N-containing vinyl monomers, carboxyl group-containing monomers, hydroxyl group-containing monomers, acrylate monomers and methacrylate monomers. Copolymer content (W
3) and the mass ratio of the polyolefin content (W4) preferably satisfies the following formula: W3: W4 = 100: (1 to 400).

If the ratio is out of this range, the effective branching structure of the graft copolymer of the copolymer and polyethylene is impaired, so that the fine dispersion of the hydrocarbon wax is not carried out, and the hydrocarbon wax when toner is formed is not obtained. Segregation of the wax occurs, and image defects such as white spots occur.

The organic metal compound used in the present invention is preferably 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. The metal is preferably a divalent or higher valent metal atom. Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , P
b ²⁺ , Fe ²⁺ , Co ²⁺ , Ni ²⁺ , Zn ²⁺ , and Cu ²⁺ . As divalent metals, Zn ²⁺ , Ca ²⁺ , M
g ²⁺ and Sr ²⁺ are preferred. Al is a trivalent or higher metal
³⁺ , Cr ³⁺ , Fe ³⁺ , Ni ³⁺ . Preferred among these metals are Al ³⁺ and Cr ³⁺ , and particularly preferred is Al ³⁺ .

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

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 include, for example, oxycarboxylic acid and alkoxycarboxylic acid in an aqueous sodium hydroxide solution. An aqueous solution in which a metal atom having a valence of 2 or more is melted is dropped into an aqueous sodium hydroxide solution, heated and stirred, then the pH of the aqueous solution is adjusted, cooled to room temperature, and then filtered and washed with water to obtain a fragrance. Metal compounds of aromatic oxycarboxylic acids and aromatic alkoxycarboxylic acids can be synthesized. 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 a decrease in image density.

When the content of the organometallic compound is less than 0.1% by mass (not added at all) on the basis of the mass of the toner, the charge amount at the time of durability becomes unstable, and as a result, the maintenance of the image density becomes poor. It will be inferior. If the content of the organometallic compound exceeds 10% by mass on the basis of the mass of the toner, on the contrary, charge-up occurs at the time of endurance, resulting in a decrease in image density.

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. Examples of the magnetic material include iron oxides such as magnetite, maghemite, and ferrite, and iron oxides containing other metal oxides; Fe, Co, N
i, 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 and V, and mixtures thereof.

For example, as a magnetic material, triiron tetroxide
(Fe_ThreeO_Four), Iron sesquioxide (γ-Fe _TwoO_Three), Iron oxide
Lead (ZnFe_TwoO_Four), Yttrium iron oxide (Y_ThreeFe_FiveO
₁₂), Cadmium iron oxide (CdFe_TwoO_Four), Iron oxide gado
Linium (Gd_ThreeFe_FiveO₁₂), Copper iron oxide (CuFe
_TwoO_Four), Lead iron oxide (PbFe₁₂O₁₉), Nickel iron oxide
(NiFe_TwoO_Four), Iron neodymium oxide (NdFe_TwoO_Three),
Barium oxide (BaFe)₁₂O₁₉), Iron oxide magnesium
(MgFe_TwoO_Four), Iron manganese oxide (MnFe)
_TwoO_Four), Iron oxide lanthanum (LaFeO)_Three), Iron powder (F
e), cobalt powder (Co), nickel powder (Ni), etc.
I can do it. Preferred magnetic materials are ferric oxide, magnetic ferrite
Or fine powder of γ-iron sesquioxide.

The magnetic material has an average particle size of 0.1 to 2 μm (preferably 0.1 to 0.5 μm) and 796 kA / m (10
k Oersted) and the coercive force is 1.6 to 12
kA / m (20-150 Oe), saturation magnetization 50
~200Am ² / kg (preferably 50~100Am ² /
kg), and those having a residual magnetization of ^{2 to 20} Am ² / kg are preferable.

When the magnetic material is used as a magnetic one-component developer supported with a magnetic binding force on a developer carrying member containing a magnet, the magnetic material is 5 parts by mass based on the toner mass.
Preferably, it is contained in an amount of about 120% by mass.

When used as a system non-magnetic one-component developer which is carried on a developer carrying member having no magnet without a magnetic restraining force, the magnetic material is used in an amount of 0.1% based on the mass of the toner. It is preferable to contain 1 to 5% 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 is 5 based on the mass of the toner,
If the amount is more than 5% by mass, the surface of the regulating blade or the roller carrying the toner will be significantly damaged (cut), causing poor charging.

When used as a two-component developer by being mixed with magnetic carrier particles, the magnetic material preferably contains 0.1 to 5% by mass based on the mass of the toner.

When the content is within this range, the magnetic binding force with the roller carrying the developer is increased, so that the toner scattering phenomenon (dirt in the machine) at the time of durability can be suppressed.

When the content of the magnetic material is 5 based on the mass of the toner,
If the amount is more than 10% by mass, the magnetic binding force with the roller carrying the developer is excessively increased, which causes a decrease in image density.

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 and the like.

Examples of 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, final yellow green G and the like.

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, 35 and the like.

Although such a pigment may be used alone,
It is more preferable to improve the sharpness by using a dye and a pigment in combination from the viewpoint of the image quality of a full-color image. Magenta dyes include C.I. I. Solvent red 1,3,8,
23, 24, 25, 27, 30, 49, 81, 82, 8
3,84,100,109,121, C.I. I. Disperse Red 9, C.I. I. Solvent Violet 8,1
3, 14, 21, 27, C.I. I. Oil-soluble dyes such as Disperse Violet 1; I. Basic Red 1,
2, 9, 12, 13, 14, 15, 17, 18, 22,
23, 24, 27, 29, 32, 34, 35, 36, 3
7, 38, 39, 40, C.I. I. Basic violet 1,3,7,10,14,15,21,25,26,
And basic dyes such as 27 and 28.

Examples of cyan color pigments include C.I. I. Pigment Blue 2, 3, 15, 16, 17, C.I. 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.

As the yellow color pigment, 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 and the like.

The colorant is used in an amount of 1 to 15 parts by mass, preferably 3 to 12 parts by mass, more preferably 4 to 10 parts by mass based on 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 reduced, and the reproducibility of an intermediate color typified by human skin color is also easily reduced. 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, it is difficult to obtain a desired coloring power, 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 it to toner particles, the fluidity can be increased before and after the addition. For example, fluorine resin powders such as vinylidene fluoride fine powder and polytetrafluoroethylene fine powder; silica fine powder such as silica fine powder by a wet method, silica fine powder such as a silica fine powder by a dry method, and a silane coupling agent; Fine powder of treated silica which has been surface-treated with a treating agent such as a titanium coupling agent or 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 by nitrogen adsorption measured by the BET method.
Those with 0 m ² / g or more give good results. It is preferable to use 0.01 to 8 parts by mass, preferably 0.1 to 4 parts by mass of the fluidity improver 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 by a mixer such as a Henschel mixer or a ball mill, and then heated 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 fluidity 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.
0 to 12.0 μm is good.

The toner has a weight average particle size (D ₄ ) of 3.0 μm.
If it is less than m, it becomes difficult to stabilize charging, and fog and toner scattering tend to occur in durability.

The weight average particle diameter (D ₄ ) of the toner is 15.0.
When the thickness exceeds μm, the reproducibility of the halftone portion is greatly reduced, and the obtained image becomes a rough image.

Further, the toner of the present invention preferably has a volume average particle diameter (D _v ) of 2.5 μm to 6.0 μm for forming a higher quality image.

[0120] The volume average particle diameter of the toner (D _v) is 2.5μ
If it is less than m, the charging stability of the toner decreases, and
If it exceeds 0 μm, the image quality tends to be coarse.

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. 3 is a schematic diagram showing an example of an image forming apparatus for forming a full-color image by electrophotography. The image forming apparatus shown in FIG. 3 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. 3, 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 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-separated image signal is processed by a video processing unit (not shown) through an amplifier circuit (not shown) and 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 rotatably carried 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.

At the time of image formation, 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 of the separated colors, and the electrostatic charge is charged on the photosensitive drum 1. Form an image.

Next, a predetermined developing unit 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 according to 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 5d. 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 transported from the cassette 7a, 7b or 7c to the transfer drum 5a through a transfer sheet transport 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 directly transferred from the photoreceptor to the transfer material. Alternatively, the toner image on the photoreceptor 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.

[0131] The above image forming step is performed by using 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 onto which the four color toner images 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.

At this time, the fixing operation speed of the heating / pressing fixing unit 9 is set to 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. 4, 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. 4, the outer diameter of both the fixing roller and the pressure roller is 60 mmφ. However, the hardness of the pressure roller is higher than that of the pressure roller. , The paper discharge direction is on the pressure roller side. 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 discharging direction to the pressure roller side, a method of making the hardness difference described above, or a method of making the diameter of the pressure roller smaller than that of the fixing roller,
There is a method in which the set temperature of the pressure roller side is set higher than that of the fixing roller, and a small amount of paper dust is used by evaporating more water on the back side of the fixing paper, that is, the paper surface of the pressure roller side. .

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 based on the detected temperatures, the control devices 49a and 49b
Controls the halogen heaters 46 and 47, respectively, so that both the temperature of the fixing roller 39 and the temperature of the pressure roller 40 are controlled to be kept at a constant temperature (for example, 160 ° C. ± 10 ° C.). Roller 4
0 is a total pressure of about 390N (4
0 kgf).

In FIG. 4, C is a fixing roller cleaning device using an oil-impregnated paper web, and C1 is a cleaning blade for removing oil and dirt attached to the pressure roller. Oil for paper web impregnation is 5
The use of a silicone oil of 0 to 3000 cs (silicone oils such as dimethyl silicone oil and diphenyl silicone oil) makes it easy to supply a small amount of the applied oil and keeps the quality of the fixed image (particularly uniform). Glossiness, 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 performs cleaning by pressing a nonwoven fabric web 56 made of Nomex (trade name) against the fixing roller 39 with a pressing roller 55.
The web 56 is appropriately wound by a winding device (not shown) so that toner and the like do not accumulate in the contact portion with the fixing roller 39.

Since the toner of the present invention is excellent in low-temperature fixability and high-temperature offset resistance, 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 fixing roller surface temperature of 150 ° C. ± 30 ° C. When the toner image is fixed on the recording material,
The amount of silicone oil supplied from the fixing member 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 amount of coating exceeds 1 × 10 ⁻⁷ g / cm ² , the recording material has a large glare, and particularly impairs the visibility of a character image.

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

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

(1) Measurement of Acid Value (JIS Acid Value) 2 to 10 g of a sample are weighed in a 200 to 300 ml Erlenmeyer flask, and about 50 ml of a mixed solvent of methanol: toluene = 30: 70 is added to dissolve the resin. If the solubility is poor, a small amount of acetone may be added. 0.1%
Of bromthymol blue and phenol red, and titration with a pre-standardized N / 10 potassium hydroxide-alcohol solution, and the acid value is calculated by the following calculation from the consumption of the alcoholic potassium solution.

Acid value = KOH (ml) × f × 56.1 / sample weight (where f is a factor of N / 10 KOH)

(2) Measurement of molecular weight by GPC (Polyester
Ester resin, the molecular weight of the chromatogram obtained by copolymers) 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 as a solvent at a flow rate of 1 ml per minute.
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 molecular weight by GPC (polio
(Refin, hydrocarbon waxes) (GPC measurement conditions)-Apparatus: GPC-150 (Waters)-Column: GMH-HT 30 cm double (manufactured by Tosoh Corporation)-Temperature: 135 ° C-Solvent: o-dichlorobenzene (0.・ Flow rate: 1.0 ml / min ・ Sample: Inject 0.4 ml of 0.15% sample Under the above conditions, the molecular weight of the sample was calculated using a monodisperse polystyrene standard sample. Use curves. Further, it is calculated by polystyrene conversion using a conversion formula derived from the Mark-Houwink viscosity formula.

(4) Maximum heat absorption peak of wax and toner
Click measurement differential thermal analysis measuring apparatus (DSC measuring device), DSC-7
(Perkin Elmer). The measurement sample is precisely weighed in an amount of 5 to 20 mg, preferably 10 mg.
This is put in an aluminum pan, and an empty aluminum pan is used as a reference.
The measurement is performed at a temperature rising rate of 10 ° C./min under normal temperature and normal humidity. In this heating process, an endothermic peak of a main peak in a temperature range of 30 to 160 ° C. is obtained. The endothermic peak is, of course, the temperature at which the maximum value is exhibited.

(5) Toner particle or toner particle size distribution
As a measuring device, Coulter Counter TA-II or Coulter Multisizer II (manufactured by Coulter Inc.)
Is used. As an electrolytic solution, about 1% NcCl 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 mass average particle diameter (D ₄ ) and the volume average particle diameter (D _v ) of the toner particles or the toner on a mass basis 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.

[0154]

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

Example 1 The following constituent materials for toner were prepared. Binder resin: polyester resin No. 1 100 parts by mass Wax: Wax dispersant master batch Equivalent to 3 parts by mass of paraffin wax Charge control agent: 6 parts by mass of aromatic oxycarboxylic acid Al compound (I) 6 parts by mass Pigment: 5 parts by mass of copper phthalocyanine

Among them, polyester resin No. as a binder resin was used. The monomer composition ratio used in No. 1 is shown below. -(Formula (B); x + y = 3.0) Diol component 59 mol%-Fumaric acid 21 mol%-Terephthalic acid 11 mol%-Trimellitic acid 9 mol%

The obtained non-linear polyester resin no. 1
Was found to have a Tg of 60 ° C., a GPC of a THF-soluble component, Mn of 3,300, Mw of 33,000, and Mw / Mn of 10.0.

Next, the procedure for producing the wax dispersant will be described below. -Copolymer resin (I) 90 mass%-Polyethylene (I) 10 mass% The copolymer resin (I) is a terpolymer of styrene-acrylonitrile-butyl acrylate. In a wax dispersion medium (I) obtained by grafting the copolymer resin (I) to the polyethylene (I) at the above mixing ratio, a hydrocarbon wax was dispersed at the following mixing ratio to obtain a wax dispersant. -Wax dispersion medium (I) 50% by mass-Paraffin wax (A) 50% by mass

The wax dispersant obtained as described above is melted in advance with a polyester resin at an appropriate blending ratio, and is added in the form of a wax dispersant master batch when forming a toner.

The polyester resin No. 1. Wax dispersant master batch, aromatic oxycarboxylic acid Al compound (I) and copper phthalocyanine are sufficiently premixed by a Henschel mixer, melt-kneaded at an arbitrary barrel temperature using a twin-screw extruder, and cooled. Thereafter, roughly pulverizing about 1 to 2 mm using a hammer mill, and then pulverizing with a pulverizer using an air jet method. The obtained finely pulverized material was strictly removed at the same time by a multi-segmentation classifier to obtain a cyan color toner having a weight average particle size of 7.8 μm.

To the toner particles, 1.5% by mass of titanium oxide fine particles having a primary particle diameter of 50 nm and surface-treated with isobutyltrimethoxysilane were externally added and mixed to produce a cyan toner 1.

The characteristic values of the main binder, the hydrocarbon wax, the styrene-acrylonitrile- (meth) acrylic acid copolymer and the polyolefin used in the cyan toner 1 are shown in Tables 1 to 4, respectively.

The toner-based content of the wax dispersant of the cyan toner 1, the type and number of charge control agents, and the results of measuring the molecular weight distribution of the obtained toner by GPC,
And the content of all polyester resins (W1), the content of hydrocarbon wax (W2), the styrene monomer and N
One or two selected from vinyl-containing monomers, carboxyl-containing monomers, hydroxyl-containing monomers, acrylate monomers and methacrylate monomers
W1: W2: W3: W, which are the respective relational expressions when the content (W3) of the copolymer synthesized using at least one kind of monomer and the content (W4) of the polyolefin are used.
Table 5 shows a list of the contents of W4 and W3: W4.

Cyan toner 1 and magnetic ferrite carrier particles (surface having an average particle diameter of 50 μm) coated with a silicone resin
m) was mixed so that the toner concentration became 6% by mass, to obtain a two-component cyan developer 1.

Regarding the evaluation of the fixable temperature range and the color reproduction range caused by the color mixing of the secondary colors, the above two-component cyan developer was supplied to a commercially available plain paper full-color copier (a color laser copier) from which the fixing unit was removed. CLC700, manufactured by Canon Inc.) and outputs an unfixed image in a single color mode under normal temperature and normal humidity environment (23 ° C., 60%), and fixes while changing the set temperature with a fixing tester having the configuration shown in FIG. Images were output and evaluated by measuring gloss (gloss).

Regarding the gloss (gloss) measurement, VG-
Using a 10-type gloss meter (manufactured by Nippon Denshoku), measurement is performed using each solid image used for chromaticity measurement as a sample.

[0167] As a measurement, first, 6 V
Set to. Next, the light projection angle and the light reception angle are each set to 6
Adjust to 0 °. Using the zero point adjustment and the standard plate, after setting the standard, place the sample image on the sample table, further superimpose the white paper on three sheets and perform measurement.
Read in units. At this time, the S, S / 10 switch SW is set to S, and the angle and sensitivity switch SW is set to 45-60. A sample having an image density of 1.5 ± 0.1 is used.

The OHP transmittance was measured using a Shimadzu self-recording spectrophotometer UV2200 (manufactured by Shimadzu Corporation) with the transmittance of the OHP film alone as 100%. For magenta toner: 650 nm For cyan toner: 500 nm yellow For toner: Measure the transmittance at the maximum absorption wavelength at 600 nm.

The blocking resistance of the sample toner was evaluated by 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 fluidity is very good. B: Aggregates are not seen at all. C: Some aggregates are seen but loosened immediately. D: Aggregates are loosened by the developer stirring device (normal E: Aggregates are not sufficiently loosened in the developer stirring device (somewhat bad)

Table 8 shows a list of the results of the fixing test and the results of the OHP permeability and anti-blocking tests.

In Table 8, as a criterion for determining the color mixing of the secondary colors, the temperature range where the reflectance at an incident angle of 60 degrees obtained by the gloss measurement method exceeded "7%" was used.

The image quality of the sample toner was evaluated based on the level of white spots visually observed in the solid portion of the image after fixing. As the evaluation, the level of cohesiveness was visually determined.

The evaluation criteria for image white spots are shown below. A: No white spots are seen B: Some white spots are seen C: White spots are clearly seen

<Examples 2 to 9> Content of all polyester resins (W1), content of hydrocarbon wax (W2),
Of a copolymer synthesized using a styrene monomer and one or two or more monomers selected from N-containing vinyl monomers, carboxyl group-containing monomers, hydroxyl group-containing monomers, acrylate monomers and methacrylate monomers The cyan toner shown in Table 5 in the same manner as in Example 1 except for the content ratio (W3) and the content ratio of W1: W2: W3: W4, which is a relational expression when the content of the polyolefin is (W4). 2 to 9 and developer 2
To 9 were prepared and evaluated in the same manner as in Example 1. Table 8 shows the evaluation results.

<Examples 10 to 13> Polyester resin N
o. In place of polyester resin No. 1 shown in Table 1, 2 polyester resin No. In the same manner as in Example 1 except that No. 5 was used, cyan toners 10 to 10 shown in Table 5 were used.
13 and Developers 10 to 13 were prepared and evaluated in the same manner as in Example 1. Table 8 shows the evaluation results.

<Examples 14 to 17> [0177] The same procedures as in Example 1 were carried out except that paraffin wax (B) to paraffin wax (E) shown in Table 2 were used instead of paraffin wax (A) contained in the dispersant. Similarly, cyan toners 14 to 17 and developers 14 to 17 shown in Table 5 were prepared and evaluated in the same manner as in Example 1. Table 8 shows the evaluation results.
Shown in

<Examples 18 and 19> The procedure was carried out except that the copolymer resin (II) and the copolymer resin (III) shown in Table 3 were used instead of the copolymer (I) contained in the dispersant. In the same manner as in Example 1, the cyan toners 18 and
19 and developers 18, 19 were prepared and evaluated in the same manner as in Example 1. Table 8 shows the evaluation results.

Examples 20 to 23 In place of polyethylene (I) contained in the dispersant, polypropylene and polyethylene (II), (III) and (I) shown in Table 4 were respectively used.
Cyan toners 20 to 23 and developers 20 to 23 shown in Table 5 were prepared in the same manner as in Example 1 except that V) was used, and evaluated in the same manner as in Example 1. Table 8 shows the evaluation results.

<Examples 24 to 25> The cyan toners 24 and 25 shown in Table 5 were prepared in the same manner as in Example 1 except that the addition amount of the aromatic metal oxycarboxylate Al compound (I) was changed. Example 1 was prepared by preparing developers 24 and 25.
The evaluation was performed in the same manner as described above. Table 8 shows the evaluation results.

Example 26 Table 5 was repeated in the same manner as in Example 1 except that the aromatic oxycarboxylic acid Cr compound (I) was used instead of the aromatic oxycarboxylic acid Al compound (I) as the organometallic compound. Were prepared and evaluated in the same manner as in Example 1. Table 8 shows the evaluation results.

<Example 27> The pigment was copper phthalocyanine;
Magenta toner 1 and developer 27 obtained in the same manner as in Example 1 except that 5 parts by mass of quinacridone was used in place of 5 parts by mass, and copper phthalocyanine; PY. 17: Yellow toner 1 and developer 28 obtained in the same manner as in Example 1 except that 5 parts by mass were used, and copper phthalocyanine; carbon black instead of 5 parts by mass; A black toner 1 and a developer 29 obtained in the same manner as in Example 1 were prepared.

Therefore, the cyan developer 1, the magenta developer 27, the yellow developer 28, and the black developer 29 obtained in Example 1 were respectively used as the developing units 4C and 4M shown in FIG.
4Y and 4K, and the heating and fixing unit 9 shown in FIG.
A full-color image fixed at 150 ° C. was obtained.

Since the image has a high gloss and a sufficiently wide color reproduction range, it is suitable especially when pictorial expression is required. Also, the non-offset area is sufficiently large, and the toner after fixing is sufficiently melted.
Also excellent in OHP permeability.

<Comparative Examples 1 to 8> Content of all polyester resins (W1), content of hydrocarbon wax (W2),
Of a copolymer synthesized using a styrene monomer and one or two or more monomers selected from N-containing vinyl monomers, carboxyl group-containing monomers, hydroxyl group-containing monomers, acrylate monomers and methacrylate monomers The cyan toner shown in Table 6 in the same manner as in Example 24 except for the content ratio (W3) and the content ratio of W1: W2: W3: W4, which is the relational expression when the content of the polyolefin is (W4). 27 to 34 and developers 30 to 37 were prepared and evaluated in the same manner as in Example 24. Table 9 shows the evaluation results.

<Comparative Examples 9 to 12> Polyester resin N
o. In place of polyester resin No. 1 shown in Table 1, 6 to polyester resin no. 9 in the same manner as in Comparative Example 1 except that No. 9 was used.
38 and developers 38 to 41 were prepared and evaluated in the same manner as in Example 24. Table 9 shows the evaluation results.

<Comparative Examples 13 to 17> Comparative Examples 13 to 17 were conducted except that the ester wax and the paraffin wax (F) to the paraffin wax (I) shown in Table 2 were used instead of the paraffin wax (A) contained in the dispersant. Cyan toners 39 to 43 and developers 42 to 46 shown in Table 6 were prepared in the same manner as in Example 2, and evaluated in the same manner as in Example 24. Table 9 shows the evaluation results.

<Comparative Examples 18 to 20>
As shown in Table 3, the copolymer resin (I) contained in the dispersant
Resin (IV), which is a formulation obtained by removing acrylonitrile from, and copolymer resin (V) to copolymer resin (VI)
The cyan toners 44 to 46 and the developers 47 to 49 shown in Table 6 were prepared in the same manner as in Comparative Example 4 except that
Evaluation was performed in the same manner as in Example 24. Table 9 shows the evaluation results.

<Comparative Examples 21 to 25> Instead of polyethylene (I) contained in the dispersant, behenyl behenate and polyethylene (V), which are esters shown in Table 4, respectively, were used.
Except for using (VIII), in the same manner as in Comparative Example 5,
Cyan toners 47 to 51 and developers 50 to 5 shown in Table 7
4 was prepared and evaluated in the same manner as in Example 24. Table 9 shows the evaluation results.

Comparative Example 26 A cyan toner 52 shown in Table 7 was prepared in the same manner as in Comparative Example 6 except that no Al compound (I) of an aromatic metal oxycarboxylate as an organometallic compound was added.
And a developer 55 were prepared and evaluated in the same manner as in Example 24. Table 9 shows the evaluation results.

If the charge control agent is not used, ionic crosslinking is not formed during kneading, so that a high-temperature offset occurs, and the blocking resistance of the toner decreases.

<Comparative Examples 27 and 28> Instead of the aromatic oxycarboxylic acid Al compound (I) as the organometallic compound,
Cyan toners 53 and 54 and developers 56 and 57 shown in Table 7 were prepared in the same manner as in Comparative Example 6 except that Zn compound (I) and Fe compound (I) having the following structures were used. It evaluated similarly. Table 9 shows the evaluation results.

[0193]

Embedded image

When these charge control agents are used, ionic cross-linking is not formed during kneading of the cyan toners 53 and 54, so that high-temperature offset occurs and the blocking resistance of the toner decreases.

[0195]

[Table 1]

[0196]

[Table 2]

[0197]

[Table 3]

[0198]

[Table 4]

[0199]

[Table 5]

[0200]

[Table 6]

[0201]

[Table 7]

[0202]

[Table 8]

[0203]

[Table 9]

[0204]

According to the present invention, it is possible to obtain a color toner having good transparency in OHP, excellent anti-offset properties and fixing properties, and having the same developing property even after long-term storage as before. it can.

[Brief description of the drawings]

FIG. 1 is a diagram showing an example of a dynamic elastic modulus curve of the toner of the present invention.

FIG. 2 is a diagram illustrating an example of a dynamic elastic modulus curve of a conventional toner.

FIG. 3 is a schematic sectional view showing an example of an image forming apparatus using the toner of the present invention.

FIG. 4 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 heating / pressing fixing device

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] June 20, 2000 (2006.2.
0)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claim 1

[Correction method] Change

[Correction contents]

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] Claim 19

[Correction method] Change

[Correction contents]

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0021

[Correction method] Change

[Correction contents]

[0021]

Specifically, the present invention provides:
(I) a polyester resin, (ii) a hydrocarbon wax, (iii) a styrene monomer and an N-containing vinyl monomer, a carboxyl group-containing monomer, a hydroxyl group-containing monomer, an acrylate monomer and a methacrylate monomer. Or a toner containing a wax dispersant having at least a polyolefin and a copolymer synthesized using two or more types of monomers, and (iv) a colorant. In the endothermic curve, the maximum value of the maximum endothermic peak is 90 to 130 ° C., and the maximum value of the maximum endothermic peak is 55 to 80 ° C. in the endothermic curve of the hydrocarbon wax measured by DSC. The total polyester resin content (W
1) The mass ratio of the hydrocarbon wax content (W2), the copolymer content (W3), and the polyolefin content (W4) has the following relationship: W1: W2: W3: W4 = 100: (0.1-6):
(0.1 to 20): (0.1 to 2) A toner which satisfies W3: W4 = 100: (1 to 400).

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0022

[Correction method] Change

[Correction contents]

Further, according to the present invention, a fixing member is brought into contact with the surface of a toner image formed on a recording material, and the toner image is applied to the recording material by applying heat and pressure to the toner image. In the heat fixing method for fixing, when the toner image is fixed on the recording material, the amount of silicone oil supplied from the fixing member to the fixing surface of the toner image of the recording material per unit area of the recording material is 0 to 0. 1 × 10 ^-7 g
/ Cm ² , wherein the toner comprises (i) a polyester resin, (ii) a hydrocarbon-based wax, (iii) a styrene-based monomer and an N-containing vinyl monomer, a carboxyl-containing monomer, a hydroxyl-containing monomer, an acrylate monomer, A wax dispersant having at least a polyolefin and a copolymer synthesized by using one or more monomers selected from methacrylate monomers, and (iv) a colorant, wherein the polyolefin In the endothermic curve at the time of temperature rise measured by DSC, the maximum value of the maximum heat peak is 90 to 130 ° C.
In the endothermic curve at the time of temperature rise measured by DSC of the hydrocarbon wax, the maximum value of the maximum thermal peak is at 55 to 80 ° C., and the content (W1) of the total polyester resin in the toner (W1); The mass ratio of the content of the hydrocarbon wax (W2), the content of the copolymer (W3), and the content of the polyolefin (W4) is as follows: W1: W2: W3: W4 = 100: (0. 1-6):
(0.1 to 20): (0.1 to 2) A heat fixing method characterized by satisfying W3: W4 = 100: (1 to 400).

[Procedure amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0026

[Correction method] Change

[Correction contents]

The polyester resin having a molecular skeleton represented by the formula (A) is an aromatic carboxylic acid derivative selected from aromatic oxycarboxylic acids and aromatic alkoxycarboxylic acids, which will be described in detail later, or the aromatic carboxylic acid derivative When the metal compound is melt-kneaded at the same time as the metal compound, a metal ion crosslinked structure is easily formed, and a toner having a clear minimum value (G′min) in a dynamic elastic modulus curve of the toner can be satisfactorily generated.

[Procedure amendment 6]

[Document name to be amended] Statement

[Correction target item name] 0029

[Correction method] Change

[Correction contents]

The reason why the molecular skeleton represented by the formula (A) is specifically selected from an aromatic oxycarboxylic acid and an aromatic alkoxycarboxylic acid or an aromatic carboxylic acid derivative or a metal compound of the aromatic carboxylic acid derivative Although it is not fully known whether or not the phenyl group having an electron-donating phenyl group at the p-position is likely to form a conformation that easily interacts with the flexibility characteristic of this molecular chain (molecular arrangement interaction). It seems that the electron donating property and the π electron donating interaction of —CH ＝ CR— are closely related.

[Procedure amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0063

[Correction method] Change

[Correction contents]

The methacrylic acid ester monomers include:
For example, methacryl such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate Acid esters.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03G 15/20 104 G03G 9/08 346 (72) Inventor Yojiro Hotta 3- 30-2 Shimomaruko, Ota-ku, Tokyo No. Canon Inc. (72) Inventor Masaaki Taya 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Takaaki Uetaki 3-30-2 Shimomaruko, Ota-ku, Tokyo Non-corporation F term (reference) 2H005 AA01 AA02 AA06 AA21 CA04 CA06 CA08 CA13 CA14 CA21 CA25 CA28 DA02 DA04 DA06 DA10 EA03 EA06 EA07 EA10 FA01 FA06 FA07 FB01 2H033 AA09 AA47 BA42 BA46 BA58 BB01 BB28

Claims (37)

[Claims] 1. (i) a polyester resin, (ii) a hydrocarbon-based wax, (iii) a styrene-based monomer and an N-containing vinyl monomer, a carboxyl-containing monomer, a hydroxyl-containing monomer, an acrylate monomer and a methacrylate monomer. A wax dispersant having at least a polyolefin and a copolymer synthesized using one or more monomers selected from the group consisting of: and (iv) a colorant, which is measured by DSC of the polyolefin. In the endothermic curve at the time of temperature increase, the maximum value of the maximum endothermic peak is 90 to 1
30 ° C., and the maximum value of the maximum endothermic peak is 55 in the endothermic curve at the time of temperature rise measured by DSC of the hydrocarbon wax.
To 80 ° C., and the content (W
1), the content of the hydrocarbon wax (W2), the content of the copolymer (W3), and the content of the polyethylene (W
The mass ratio of 4) has the following relationship: W1: W2: W3: W4 = 100: (0.1 to 6):
(0.1 to 20): (0.1 to 2) A toner characterized by satisfying W3: W4 = 100: (1 to 400). 2. In the molecular weight distribution of the hydrocarbon wax by GPC, the weight average molecular weight (Mw) is 400-400.
800 and a number average molecular weight (Mn) of 400 to 600.
And the weight average molecular weight (Mw) and the number average molecular weight (M
2. The toner according to claim 1, wherein the ratio (Mw / Mn) to n) is 1.0 to 2.0. 3. The toner according to claim 1, wherein the hydrocarbon wax is contained in the toner in an amount of 0.1 to 6% by mass based on the mass of the toner. 4. The copolymer comprises a styrene monomer, N
The toner according to any one of claims 1 to 3, wherein the toner is a ternary copolymer comprising a vinyl monomer and a (meth) acrylic acid-based monomer. 5. The molecular weight distribution of the copolymer by GPC, wherein the weight average molecular weight (Mw) is 5,000 to 1,000.
00 and a number average molecular weight (Mn) of 1500 to 150
5. The toner according to claim 1, wherein the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 2 to 40. 6. 6. The toner according to claim 1, wherein the copolymer contains 0.1 to 20% by mass of the toner based on the mass of the toner. 7. The polyolefin has a weight average molecular weight (Mw) of 500 to 3 in a molecular weight distribution by GPC.
0000 and a number average molecular weight (Mn) of 500 to 30.
00, the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 1.0 to 20,
7. The toner according to claim 1, wherein the toner has a low density of 0.9 to 0.95. 8. The toner according to claim 1, wherein the polyolefin is contained in the toner in an amount of 0.1 to 2% by mass based on the mass of the toner. 9. The toner according to claim 1, wherein the toner contains an organometallic compound. 10. The organic metal compound is an aromatic carboxylic acid derivative selected from an aromatic oxycarboxylic acid and an aromatic alkoxycarboxylic acid, or a metal compound of the aromatic carboxylic acid derivative. The toner according to claim 9. 11. The toner according to claim 9, 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. 12. The polyester resin has a weight average molecular weight (Mw) of 2600 in a molecular weight distribution by GPC.
１９０190000, and a number average molecular weight (Mn) of 130
The toner according to any one of claims 1 to 11, wherein the toner has a weight average molecular weight (Mw) and a number average molecular weight (Mn) of 2 to 20 (Mw / Mn). . 13. The polyester resin has an acid value of 1 to 6.
The toner according to claim 1, wherein the toner content is 0 mgKOH / g. 14. The polyether resin has an acid value of 5-6.
The toner according to claim 1, wherein the toner content is 0 mgKOH / g. 15. The polyether resin has an acid value of 5 to 5.
The toner according to claim 1, wherein the toner content is 0 mgKOH / g. 16. The toner contains a magnetic material in an amount of 5 to 120% by mass based on the mass of the toner, and the toner is carried on a developer carrying member containing a magnet with a magnetic binding force. 16. The toner according to claim 1, wherein the toner is used as a magnetic one-component developer. 17. The toner contains a magnetic substance in an amount of 0.1 to 5% by mass based on the mass of the toner, and the toner exerts a magnetic binding force on a developer carrying member having no magnet. The toner according to any one of claims 1 to 15, wherein the toner is used as a system non-magnetic one-component developer carried without accompanying. 18. The toner contains a magnetic substance in an amount of 0.1 to 5% by weight based on the mass of the toner, and the toner is mixed with magnetic carrier particles to be used as a two-component developer. The toner according to any one of claims 1 to 15, wherein: 19. A heat fixing device for fixing a toner image to a recording material by bringing a fixing member into contact with the surface of the toner image formed on the recording material and applying heat and pressure to the toner image. In the method, when the toner image is fixed to the recording material, the coating amount per unit area of the recording material of silicone oil supplied from the fixing member to the fixing surface of the toner image of the recording material is 0 to 1 × 10 ^{−. 7} g / cm ² , wherein the toner comprises (i) a polyester resin, (ii) a hydrocarbon wax, (iii) a styrene monomer and an N-containing vinyl monomer, a carboxyl group-containing monomer, a hydroxyl group-containing monomer, and an acrylic ester. Reduce the amount of a copolymer and a polyolefin synthesized using one or more monomers selected from monomers and methacrylate monomers. A wax dispersant having
v) It contains a colorant, and the endothermic curve of the polyolefin at the time of temperature rise measured by DSC has a maximum value of a maximum heat peak of 90 to 1
30 ° C., and the maximum value of the maximum heat peak is 55 in the endothermic curve at the time of temperature rise measured by DSC of the hydrocarbon wax.
To 80 ° C., and the content (W
1), the content of the hydrocarbon wax (W2), the content of the copolymer (W3), and the content of the polyethylene (W
The mass ratio of 4) has the following relationship: W1: W2: W3: W4 = 100: (0.1 to 6):
(0.1 to 20): (0.1 to 2) W3: W4 = 100: (1 to 400) 20. In the molecular weight distribution of the hydrocarbon wax by GPC, the weight average molecular weight (Mw) is 400.
And a number average molecular weight (Mn) of 400 to 60.
0, the weight average molecular weight (Mw) and the number average molecular weight (M
20. The heat fixing method according to claim 19, wherein the ratio (Mw / Mn) to n) is 1.0 to 2.0. 21. The heat fixing method according to claim 19, wherein the hydrocarbon wax is contained in the toner in an amount of 0.1 to 6% by mass based on the mass of the toner. 22. The copolymer comprises a styrene monomer,
22. The heat fixing method according to claim 19, wherein the ternary copolymer comprises an N-containing vinyl monomer and a (meth) acrylic acid-based monomer. 23. In the molecular weight distribution of the copolymer by GPC, the weight average molecular weight (Mw) is 5,000 to 100.
000 and a number average molecular weight (Mn) of 1500 to 15
23. The heat fixing method according to claim 19, wherein the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 2 to 40. . 24. The heat fixing method according to claim 19, wherein the copolymer is contained in the toner in an amount of 0.1 to 20% by mass based on the mass of the toner. 25. The polyolefin has a weight average molecular weight (Mw) of from 500 to 500 in a molecular weight distribution by GPC.
30,000 and a number average molecular weight (Mn) of 500 to 3
000, and the ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) is 1.0 to 20,
25. The heat fixing method according to claim 19, wherein the density is as low as 0.9 to 0.95. 26. The heat fixing method according to claim 19, wherein the polyolefin is contained in the toner in an amount of 0.1 to 2% by mass based on the mass of the toner. 27. The heat fixing method according to claim 19, wherein the toner contains an organometallic compound. 28. The organic metal compound is an aromatic carboxylic acid derivative selected from an aromatic oxycarboxylic acid and an aromatic alkoxycarboxylic acid, or a metal compound of the aromatic carboxylic acid derivative. Claim 27
3. The heat fixing method according to 1. 29. The heat fixing method according to claim 27, 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. 30. The polyester resin has a weight average molecular weight (Mw) of 2600 in GPC molecular weight distribution.
１９０190000, and a number average molecular weight (Mn) of 130
30. The heating according to any one of claims 19 to 29, wherein the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 2 to 20. Fixing method. 31. The polyester resin has an acid value of 1 to 6.
31. The heat fixing method according to claim 19, wherein the amount is 0 mgKOH / g. 32. The polyether resin has an acid value of 5-6.
31. The heat fixing method according to claim 19, wherein the amount is 0 mgKOH / g. 33. The polyether resin has an acid value of 5 to 5.
31. The heat fixing method according to claim 19, wherein the amount is 0 mgKOH / g. 34. The fixing device according to claim 19, wherein when the toner image is fixed on the recording material, fixing is performed without supplying silicone oil from the fixing member to the recording material.
The heat fixing method according to any one of the above. 35. The toner contains a magnetic material in an amount of 5 to 120% by mass based on the mass of the toner, and the toner is carried on a developer carrying body containing a magnet with a magnetic binding force. 35. The heat fixing method according to claim 19, wherein the heat fixing method is used as a magnetic one-component developer. 36. The toner contains a magnetic substance in an amount of 0.1 to 5% by mass based on the mass of the toner, and the toner exerts a magnetic binding force on a developer carrying member having no magnet. 35. The heat fixing method according to claim 19, wherein the heat fixing method is used as a system non-magnetic one-component developer carried without accompanying. 37. The toner contains a magnetic substance in an amount of 0.1 to 5% by weight based on the mass of the toner, and the toner is mixed with magnetic carrier particles to be used as a two-component developer. The heat fixing method according to any one of claims 19 to 34, characterized in that: