JP2002372804A - Image forming method, fixing method and toner - Google Patents

Abstract

(57) [Summary] (with correction) [PROBLEMS] To provide an image forming method having a wide color reproduction range because of good transparency in OHP and good color mixing of secondary colors. An image forming method in which an image is heated and pressurized and fixed by a fixing roller having a surface layer made of a fluorine-based resin and a pressing roller in pressure contact with the fixing roller, the DSC heat absorption of wax added in the toner. In the curve, the maximum endothermic peak in the temperature range of 30 to 160 ° C. is at 55 to 80 ° C., the half width of the maximum endothermic peak is 2 to 7 ° C., and the binder resin component has a polyester resin as a main component, The toner has a dynamic elastic modulus (G ′ ₁₄₀ ) at a temperature of 140 ° C. of 5 × 10 ^{2 to} 1 × 10 ⁵ d.
N / m ² , and the ratio (G ′ ₁₄₀ / G ′ ₁₇₀ ) to the dynamic elastic modulus (G ′ ₁₇₀ ) at a temperature of 170 ° C. is 0.05.
To 50.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a toner and an image forming method for developing an electrostatic image formed in an image forming method such as an electrophotographic method, an electrostatic recording method, an electrostatic printing method, and a toner jet method. Things.

[0002]

2. Description of the Related Art Conventionally, electrophotography has been disclosed in U.S. Pat. No. 2,297,691, Japanese Patent Publication No. 42-23910.
Many methods are known as described in Japanese Patent Publication No. JP-A-Heisei, 43-24878 and Japanese Patent Publication No. 43-24748. Generally, a photoconductive substance is used to form an electric latent image on a photoreceptor by various means. Forming and then developing the latent image with toner,
The toner image is transferred to a transfer material such as paper using direct or indirect means as necessary, and is then fixed by heating, pressure, heat and pressure, or solvent vapor to obtain a copy. The toner remaining on the body without being transferred is cleaned by various methods, and the above steps are repeated.

Various methods and apparatuses have been developed for fixing the toner image onto a sheet such as paper, which is the above-mentioned final step. However, a general method is a pressure roller heating method using a heat roller method or a film heating method. It is.

FIG. 1 shows a heat roller fixing device conventionally used as a toner image fixing device in a color image forming apparatus such as an electrophotographic apparatus. In the following description with reference to the drawings, a pressure roller 32 is pressed against the fixing roller 31 to perform a driven rotation while forming a nip portion between the pressure roller 32 and the fixing roller 31. The fixing roller 31 has a silicone rubber layer on a metal core in the form of a hollow cylinder, and a halogen heater 33 is built in a hollow space of the metal core to supply heat necessary for fixing. The pressure roller 32 has a silicone rubber layer on a metal core in the form of a hollow cylinder like the fixing roller 31,
It is heated by the halogen heater 33 'in the hollow space of the cored bar. The temperature control of the roller is performed by disposing a thermistor 34 as a temperature detecting element on the fixing roller 31 or a thermistor 34 ′ on the pressing roller 32, and detecting the surface temperature of the roller based on a change in resistance according to the detected temperature. On / off control of the halogen heaters 33 and 33 'is performed by a device (not shown) so that the roller surface temperature becomes a predetermined value.

[0005] An oil application roller 42 is provided in contact with the surface of the fixing roller 31, and the oil application roller 42 is rotated in contact with the surface to apply oil (silicone oil or the like). At the time of fixing, contact is made to perform coating. In the above-described apparatus, the unfixed recording material is guided by the guide 38, enters the nip portion from the left, and forms the fixing roller 31 on which the uniform oil layer is formed. Guide 38 'after being pressed and heated by the surface and fixed.
And is discharged. Fixing roller 31 that has performed fixing
Is again rubbed with the cleaning web 37 during the rotation, so that the offset toner is removed and oil is applied at the same time, while excess oil is stripped off. 39 denotes a fixed recording material and a pressure roller 32
And separation claw. Here, for example, the fixing temperature is 110
The roller peripheral speed is in the range of 10 to 200 mm / sec.

The oil supply section is connected to an oil tank 48, which is a replaceable oil container, or to an oil pump 46 via a joint 47 by a tube of silicone resin or the like. The configuration of the oil tank 48 has oil contained in an aluminum pack in a rigid case. The structure of the joint 47 is formed by a combination of a rubber seal, a spring, and the like. The oil pump 46 serves to send oil to the oil supply nozzle 43 of the application section. on the other hand,
The surplus oil in the application section is once collected in the oil tank 48 from the oil case 45 and reused.

As for the oil application section, the oil sent from the oil supply nozzle 43 is used for holding a very small amount of replenished oil closely or extremely close to the oil application roller 42 having silicone rubber as a surface layer. 4
After the oil is supplied by the oil application roller 42, the oil is held between the oil application roller 42 and the oil application roller 42 for a short period of time. A homogeneous thin layer application is made on top. The surplus oil falls from the plate 44 for oil and travels along the bottom surface of the oil case 45 and is collected again by the oil pump 46.

The fixing roller 3 is fixed by the oil application roller 42.
The oil applied on the sheet 1 is absorbed or adhered to the sheet as the sheet passes, and goes out of the machine. However, the oil applied during the non-sheet passing portion of the fixing roller 31 or at the time of front / rear rotation is
The toner adheres to and transfers to the pressure roller 32, and the pressure roller 32 is moved by the cleaning blade 35 together with paper powder and toner.
It is scraped off from above, falls below the cleaning blade 35, and is immediately absorbed by an oil absorption band 40 in an oil pan 36, which is a waste oil recovery container.

[0009] Compared with black toner for general black-and-white copiers and printers, full-color toners are sufficiently mixed with multicolor toners in the fixing process, and provide color reproducibility and transparency of overhead projector film (OHP) images. It is essential to obtain a color toner. Generally, a sharper melt resin is required for a color toner.

However, when a sharp-melting binder resin is used, the self-cohesive force of the binder resin is low when the toner is melted in the heating and pressurizing fixing step.

In general, black toner for black-and-white copying machines and printers uses a relatively high crystalline wax represented by polyethylene wax or polypropylene wax as a release agent in order to improve high-temperature offset resistance during fixing. ing. For example, Japanese Patent Publication No. 52-3304, Japanese Patent Publication No. 5
It has been proposed in JP-A-2-3305 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.

In order to solve this problem, a method of reducing the crystallinity of the wax by using a nucleating material together with the 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 a silicone oil or a 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 its 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.

Further, the fixed image obtained in this way is not preferable because extra silicone oil or the like adheres to the surface thereof, which causes discomfort when used by a user. In order not to generate oil streaks on the fixed image, it is necessary to supply oil uniformly and quantitatively onto the surface of the fixing roller, and the size of the fixing device tends to increase.

[0017] Therefore, the toner which does not use oil for preventing high-temperature offset, or in which the occurrence of offset is suppressed in the heating and pressurizing fixing means in which the amount of oil used is reduced, is further improved. There is a long-awaited demand for toners having excellent transparency.

Therefore, Japanese Patent Application Laid-Open No. 8-314300 discloses
JP-A-8-50368, JP-A-10-28282
No. 2 proposes a toner and an image forming method that does not use a fixing oil by encapsulating a wax by a polymerization suspension method.

However, in these toners, although oil streaks on the fixed image are suppressed, a large amount of wax must be included in the toner, 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, since a fixed image with these toners inevitably has a low gloss, a so-called graphic fixed image in which a graph and a character portion are output mainly for a full-color printer is good without causing a sense of incongruity. Although there is an advantage that an image can be obtained, in a pictorially fixed image output mainly for a full-color copying machine, since the toner after fixing is not sufficiently melted, the color mixing property of the secondary color is low, and as a result, However, since the color reproduction range becomes narrower, there is a disadvantage that only a fixed image having a poor three-dimensional effect can be obtained.

Therefore, in the heat and pressure fixing means in which no oil is used or the amount of oil used is reduced,
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.

[0022]

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

An object of the present invention is to provide an image forming method, a fixing method and a toner which can be fixed without applying a large amount of oil or without applying any oil.

An object of the present invention is to use an image forming apparatus having a double-sided recording function as an image heating and fixing apparatus.
It is an object of the present invention to provide an image forming method and a fixing method capable of achieving uniform glossiness (gloss) at a front end and a rear end of an image on a material to be heated, and also at a front surface and a back surface.

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

An object of the present invention is to provide an image forming method, a fixing method, and a toner which are excellent in low-temperature fixing property and high-temperature offset resistance.

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

[0028]

Specifically, the present invention provides:
An image is formed with a toner on a recording material, and a heat-press fixing unit having a fixing roller having a base layer of a heat-resistant rubber and a surface layer of a fluororesin on the surface of the base layer and a pressing roller pressed against the fixing roller is used. An image forming method of heating and pressurizing and fixing the toner image formed on the recording material to form a fixed image on the recording material, wherein the toner comprises a binder resin;
A toner particle having at least a colorant and a wax; and a toner having an external additive. In a DSC endothermic curve of the wax, a maximum endothermic peak in a temperature range of 30 to 160 ° C is 55 to 80 ° C, and a half of the maximum endothermic peak. The value range is 2 to 7 ° C., the binder resin component is mainly composed of a polyester resin, and the toner has a temperature of 140 ° C.
Has a dynamic elastic modulus (G ′ ₁₄₀ ) of 5 × 10 ^{2 to} 1 ×
10 ⁵ dN / m ² , and the ratio (G ′ ₁₄₀ / G ′ ₁₇₀ ) to the dynamic elastic modulus (G ′ ₁₇₀ ) at a temperature of 170 ° C. is 0.0
In the Soxhlet extraction of a toner using tetrahydrofuran (THF) as a solvent, the THF-insoluble content A of the binder resin component at 8 hours after the start of the extraction.
Is 10 to 20% by mass, and the THF-insoluble content B of the binder resin component at 24 hours from the start of the extraction is 1 to 1
0% by mass and a toner satisfying that the ratio (B / A) of THF-insoluble component A to THF-insoluble component B is 0.1 to 0.8. The product hardness of the fixing roller and the pressure roller is set to 50 to 75 degrees by Asker C, and the surface temperature of the fixing roller is set to 160 degrees.
° C and the pressing force between the fixing roller and the pressure roller is 39
2 to 588 N (40 to 60 kgf), a recording material having a basis weight of 75 to 130 g / m ² was used as the recording material, and a toner carrying amount formed on the recording paper was 0.7 to 1.3 mg. / Cm ^{2 on} the recording material under heat and pressure, and the peripheral speed of the fixing roller is 100 to 130 mm / s.
In the case of ec, the glossiness (60 degree gloss) is 15 to 3
The present invention relates to an image forming method characterized in that a fixed image of 0 is formed.

Further, the present invention provides a heat and pressure fixing means having a fixing roller having a base layer of a heat-resistant rubber, a surface layer of a fluororesin on the surface of the base layer, and a pressing roller pressed against the fixing roller. In a fixing method of fixing a formed image on a recording material under heat and pressure to form a fixed image on the recording material, the toner includes a binder resin, a toner, a toner having at least a colorant and a wax, and an external additive. In the DSC endothermic curve of the wax, the maximum endothermic peak in the temperature range of 30 to 160 ° C. is 55 to 80 ° C., the half width of the maximum endothermic peak is 2 to 7 ° C., and the binder resin component is The toner has a dynamic elastic modulus (G ′ ₁₄₀ ) at a temperature of 140 ° C. of 5 × 10 ^{2 to} 1 × 10 ⁵ d.
N / m ² , and the ratio (G ′ ₁₄₀ / G ′ ₁₇₀ ) to the dynamic elastic modulus (G ′ ₁₇₀ ) at a temperature of 170 ° C. is 0.05.
In Soxhlet extraction of a toner using tetrahydrofuran (THF) as a solvent, the THF-insoluble content A of the binder resin component at 8 hours after the start of the extraction is:
10 to 20% by mass, the THF-insoluble content B of the binder resin component at 24 hours from the start of the extraction is 1 to 10% by mass, and the ratio of the THF-insoluble content A to the THF-insoluble content B (B / A ) Is 0.1 to 0.8, and the product hardness of the fixing roller and the pressing roller is set to 50 to 75 degrees by Asker C as the heating and pressing fixing means. The surface temperature of the fixing roller is set to 160 ° C., and the pressing force between the fixing roller and the pressure roller is set to 392 to 392.
588 N (40 to 60 kgf), and a recording paper having a basis weight of 75 to 130 g / m ² was used as the recording material.
The amount of toner carried on the recording paper is 0.7 to 1.
A toner image of 3 mg / cm ² is heated and pressed and fixed on the recording material, and the peripheral speed of the fixing roller is 100 to 130 mm / sec.
In the case of (1), the present invention relates to a fixing method characterized by forming a fixed image having a glossiness (60-degree gloss) of 15 to 30.

Further, the present invention provides a fixing roller which forms an image on a recording material with a toner, has a base layer of a heat-resistant rubber, and a surface layer of a fluororesin on the surface of the base layer, and a pressure roller which presses against the fixing roller. The product hardness of the fixing roller and the pressing roller is set to 50 to 75 degrees by Asker C, the surface temperature of the fixing roller is set to 160 ° C. The pressure contact force with the pressure roller is set to 392 to 588 N (40 to 60 kgf), a recording paper having a basis weight of 75 to 130 g / m ² is used as the recording material, and the toner carrying amount formed on the recording paper is A toner image of 0.7 to 1.3 mg / cm ² is heat-pressed and fixed on the recording material, and the peripheral speed of the fixing roller is 100 to 13
In the case of 0 mm / sec, the toner used in an image forming method for forming a fixed image having a glossiness (60-degree gloss) of 15 to 30 is a toner having at least a binder resin, a colorant, and a wax. A toner having particles and an external additive, wherein in a DSC endothermic curve of the wax, the maximum endothermic peak in the temperature range of 30 to 160 ° C. is 55 to 80 ° C., and the half-value width of the maximum endothermic peak is 2 to 7 ° C. The binder resin component is mainly composed of a polyester resin, and the toner has a dynamic elastic modulus (G ′ ₁₄₀ ) at a temperature of 140 ° C. of 5 × 10 ^{2 to} 1 × 10 ^5.
dN / m ² and the ratio (G ′ ₁₄₀ / G ′ ₁₇₀ ) to the dynamic elastic modulus (G ′ ₁₇₀ ) at a temperature of 170 ° C. is 0.05.
In Soxhlet extraction of a toner using tetrahydrofuran (THF) as a solvent, the THF-insoluble content A of the binder resin component at 8 hours after the start of the extraction is:
10 to 20% by mass, the THF-insoluble content B of the binder resin component at 24 hours from the start of the extraction is 1 to 10% by mass, and the ratio of the THF-insoluble content A to the THF-insoluble content B (B / A ) Is 0.1 to 0.8.

[0031]

BEST MODE FOR CARRYING OUT THE INVENTION As the toner used in the image forming apparatus and the fixing method of the present invention, a toner having at least a binder resin, a colorant and a wax, and a toner having an external additive are used. In the DSC endothermic curve of the wax, the temperature is 30 to 1
The maximum endothermic peak in the range of 60 ° C. is 55 to 80 ° C.
The half width of the maximum endothermic peak is 2 to 7 ° C., the binder resin component is mainly composed of a polyester resin, and the toner has a dynamic elastic modulus (G ′) at a temperature of 140 ° C.
₁₄₀ ) is 5 × 10 ^{2 to} 1 × 10 ⁵ dN / m ² , and the ratio (G ′) to the dynamic elastic modulus (G ′ ₁₇₀ ) at a temperature of 170 ° C.
₁₄₀ / G ′ ₁₇₀ ) is 0.05 to 50, and in Soxhlet extraction of toner using tetrahydrofuran (THF) as a solvent, the THF-insoluble content A of the binder resin component at 8 hours from the start of extraction is 10 to 20 mass %, The THF-insoluble content B of the binder resin component at 24 hours from the start of extraction is 1 to 10% by mass, and THF is
The ratio (B / A) of the insoluble matter A to the THF insoluble matter B is 0.1
In the case of satisfying 0.8 to 0.8, the oil is not used, or the heat and pressure fixing means using a small amount of oil satisfies high gloss, is excellent in the color mixing of secondary colors, The present invention has reached the present invention because it has been found that an image forming method and a fixing method having a wide reproduction range and excellent OHP transparency can be provided. 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.

[0033]

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. ]

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 an organic metal 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 toner production example described later shown in FIG.
Since the dynamic elastic modulus (G ′ ₁₇₀ ) in the region of ° C. is higher than the dynamic elastic modulus (G ′ ₁₄₀ ) in the region of 140 ° C., the toner has high viscoelasticity. Excellent in high temperature offset resistance.

On the other hand, a toner having a 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 present inventors have determined the ratio (G ′ ₁₄₀ / G ′ ₁₇₀ ) of the dynamic elastic modulus (G ′ ₁₄₀ ) at a temperature of ₁₄₀ ° C. to the dynamic elastic modulus (G ′ ₁₇₀ ) at a temperature of 170 ° C. However, those having a strong correlation with high-temperature offset resistance and having G ′ ₁₄₀ / G ′ _{170 in} the range of 0.05 to 50 have good transparency in OHP and good color mixing of secondary colors. Therefore, it has been found that a toner and an image forming method having a wide color reproduction range can be provided, and a toner and an image forming method having excellent low-temperature fixability and excellent high-temperature offset resistance can be provided.

When the value of G ′ ₁₄₀ / G ′ ₁₇₀ is less than 0.05, the transparency in OHP is insufficient, and the color mixing range of secondary colors is insufficient, so that the color reproduction range is narrow.

On the other hand, when the value of G ′ ₁₄₀ / G ′ ₁₇₀ exceeds 50, the storage elastic modulus of the toner is remarkably reduced as the temperature increases even on the side higher than 140 ° C.

Such a toner is inferior in high-temperature offset resistance and has a narrower fixing temperature range than the toner of the present invention.

G ′ ₁₄₀ is 5 × 10 ^{2 to} 1 × 10 ⁵
dN / m ^{2, and if} it is less than 5 × 10 ² dN / m ² , it is inferior in high-temperature offset resistance and 1 × 10 ⁵ dN / m ^2.
If the ratio exceeds the above range, a problem occurs in the low-temperature fixability.

Although the reason why the molecular skeleton represented by the formula (A) specifically interacts with an organometallic compound is not fully understood, the flexibility inherent in this molecular chain forms a conformation that is likely to interact. (Molecular arrangement interaction), the electron donating property of a phenyl group having an electron donating property at the p-position, and -CH
Π-electron donating interaction of = CR- seems to be closely related.

The metal ion cross-linking structure of the toner of the present invention appears in the Soxhlet extraction of the tetrahydrofuran (THF) -insoluble portion with the extraction time.

The THF-insoluble content A of the binder resin component at 8 hours after the start of the extraction is 10 to 20% by mass, and the THF-insoluble content B of the binder resin component at 24 hours after the start of the extraction is 1 to 10%. %, And the ratio (B / A) of the THF-insoluble component A to the THF-insoluble component B is 0.1 to 0.8.
It is important that a soft crosslinked structure is formed such that the crosslinked structure is loosened by the solvation energy of THF.

The present inventors have found that the correlation between the THF-insoluble component B of the binder resin component at 24 hours from the start of the extraction and the THF-insoluble component A at 8 hours is related to the fixing performance. When the ratio (B / A) of the THF-insoluble component A to the THF-insoluble component B is in the range of 0.1 to 0.8, the high-temperature offset resistance, the glossiness of the fixing surface, the low-temperature fixing property, etc. are satisfied. it can. When (B / A) is less than 0.1, the crosslinked structure is too weak and the hot offset resistance is insufficient,
When it exceeds 0.8, the glossiness of the fixing surface tends to be low due to the strong and hard crosslinked structure, and the translucency of the OHP tends to deteriorate.

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)

[0047]

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. ].

Examples of the trihydric or higher alcohol component for forming the non-linear polyester resin include sorbitol, 1,2,3,6-hexane tetrol,
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.

The divalent acid component for producing the polyester resin includes, for example, fumaric acid, maleic acid, maleic anhydride, succinic acid, adipic acid, sebacic acid, malonic acid and those having 8 to 14 carbon atoms. 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 use amount of the trivalent or higher polycarboxylic acid component is preferably 0.1 to 1.9 mol% based on all monomers.

In the present invention, the glass transition temperature of the polyester resin is preferably from 52 to 69 ° C., more preferably from 54 to 69 ° C.
The temperature is preferably 67 ° C. The glass transition temperature of the toner is 55 to 72 ° C., preferably 57 to 70 ° C.
It is good to be ° C.

The glass transition temperature of the polyester resin is 52
° C or the glass transition temperature of the toner is 55
When the temperature is lower than 0 ° C., although the fixing property is excellent, the offset resistance is deteriorated, and contamination of the fixing roller and winding around the fixing roller occur. Further, the gloss of the image surface after fixing becomes too high, and the image quality deteriorates, which is not preferable.

When the glass transition temperature of the polyester resin is higher than 69 ° C., or when the glass transition temperature of the toner is higher than 72 ° C., the fixability deteriorates, and the set fixing temperature of the copying machine body cannot be increased. The resulting image generally has low gloss and low color mixing for full-color toner.

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 weight average molecular weight (Mw) and Mn of the THF-soluble component of the polyester resin is preferably 2 to 20.

Further, the G content of the THF-soluble matter
In the PC measurement, the number average molecular weight (Mn) was 1500 to
10,000 and a weight average molecular weight (Mw) of 3000
And the ratio (Mw / Mn) of the weight-average molecular weight (Mw) to Mn of the THF-soluble component of the toner is preferably 2 to 20, which is the same as that of the polyester resin.

Number average molecular weight (Mn) of polyester resin
Is less than 1300 or the weight average molecular weight (Mw) is 2
When the number average molecular weight (Mn) of the toner is less than 1500, or when the weight average molecular weight (Mw) is 3
When the molecular weight is less than 000, the smoothness of the fixed image surface is high and the appearance of the image is vivid, but high-temperature offset is liable to occur in the durability, and the long-term storage stability is reduced. 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
Exceeds 9500, the weight average molecular weight (Mw) exceeds 19,000, the number average molecular weight (Mn) of the toner exceeds 10,000, or the weight average molecular weight (Mw) exceeds 200,000. Although it has excellent properties, it is necessary to set the fixing temperature high, and even if the degree of dispersion of the pigment can be controlled, the surface smoothness in the image area is reduced and color reproducibility is likely to be reduced. turn into.

Mw / polyester resin or toner
When Mn is less than 2, generally the obtained polyester resin has a small molecular weight itself. Therefore, similarly to the case where the molecular weight is small, high-temperature offset development due to durability, deterioration of long-term storage stability, , The toner is easily fused and the carrier spent is easily generated, and the charge amount of the toner is apt to vary.

Mw / polyester resin or toner
When Mn is more than 20, although the high-temperature offset resistance is excellent, the fixing set temperature must be increased, and even if the degree of dispersion of the pigment can be controlled, the surface smoothness in the image area is not improved. Is reduced, and the color mixing of the secondary colors is reduced, so that the color reproducibility tends to be reduced.

In the toner of the present invention, the charge control agent
Organometallic compounds are used.
Is an aromatic oxycarboxylic acid and an aromatic alkoxycar
Aromatic carboxylic acid derivatives selected from boric acid, said aromatic
Metal compounds of aromatic carboxylic acid derivatives,
It is preferable that the metal compound is a metal citrate compound.
In addition, a divalent or higher valent metal atom is preferable. Divalent metal
Mg²⁺, Ca²⁺, Sr ²⁺, Pb²⁺, Fe²⁺, Co²⁺,
Ni²⁺, Zn²⁺, Cu²⁺Is mentioned. Divalent metal
The Zn²⁺, Ca²⁺, Mg²⁺, Sr²⁺Is preferred. 3
Al or higher metal³⁺, Cr³⁺, Fe³⁺, Ni³⁺
Is raised. Preferred among these metals is A
l³⁺, Cr³⁺And particularly preferred is Al³⁺It is.

In the present invention, as the organometallic compound, an aluminum compound of di-tert-butylsalicylic acid is particularly preferred. Salicylic acid metal compound, for example, dissolving salicylic acid in aqueous sodium hydroxide,
An aqueous solution in which divalent or higher-valent metal atoms are melted is dropped into an aqueous sodium hydroxide solution, and the mixture is heated and stirred.
After cooling to room temperature, a metal compound of aromatic salicylic acid can be synthesized by washing with filtered water. However, the present invention is not limited to the above synthesis method.

When the organometallic compound is used in an amount of 0.1 to 10% by mass (more preferably 0.5 to 9% by mass) based on the mass of the toner, the initial fluctuation of the charge amount of the toner is small,
It is preferable that the absolute amount of charge required during development is easily obtained, and as a result, there is no decrease in image quality such as "fog" or a decrease in image density.

As the coloring agent, 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. Modant Red 30, C.I. I. Direct Blue 1, C.I. 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 1,3,8,2
3,24,25,27,30,49,81,82,8
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 the coloring pigment for cyan include C.I. I. Pigment Blue 2, 3, 15, 16, 17; I. Acid Blue 6; C.I. I. Acid Blue 45 or a copper phthalocyanine pigment obtained by substituting 1 to 5 phthalimidomethyl groups in a phthalocyanine skeleton.

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

The colorant is used in an amount of 1 to 15 parts by weight, preferably 3 to 12 parts by weight, more preferably 4 to 10 parts by weight, based on 100 parts by weight of the binder resin.

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

When the content of the coloring agent is less than 1 part by mass, it is difficult to obtain a desired coloring power, and it is difficult to obtain a high quality image having a high 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, iron trioxide
(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), Neodymium iron oxide (NdFe
_TwoO_Three), Barium iron oxide (BaFe) ₁₂O₁₉), Iron oxide
Gnesium (MgFe_TwoO_Four), Iron manganese oxide (MnF)
e_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 795.8 kA / m
(10k Oersted) Improves magnetic properties with coercive force of 1.6
１２12 kA / m (20-150 Oe), saturation magnetization 50-200 Am ² / kg (preferably 50-100
Am ² / kg), it is preferable for the residual magnetization 2~20Am ² / kg.

The magnetic substance 1 was added to 100 parts by mass of the binder resin.
It is preferable to use 0 to 200 parts by mass, preferably 20 to 150 parts by mass.

In the present invention, if necessary, one or more release agents may be contained in the toner particles.

The following are examples of the release agent. Aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax and paraffin wax; aliphatic hydrocarbon wax oxides such as oxidized polyethylene wax; block copolymers of aliphatic hydrocarbon waxes; Carnauba wax,
And waxes mainly containing fatty acid esters such as sasol 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 brassic 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,
Unsaturated fatty acid amides such as N'-dioleyl sebacamide; m-xylenebisstearic acid amide;
Aromatic bisamides such as N'-distearyl isophthalic acid amide; fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate and magnesium stearate (commonly referred to as metallic soaps); aliphatic hydrocarbon waxes Graft wax obtained by grafting a vinyl monomer such as styrene or acrylic acid on the surface; partially esterified product of fatty acid such as behenic acid monoglyceride and polyhydric alcohol; methyl ester compound having hydroxyl group obtained by hydrogenating vegetable oil or fat And the like.

Particularly preferred waxes include aliphatic hydrocarbon waxes such as paraffin wax, waxes mainly containing fatty acid esters such as ester waxes, and saturated fatty acid bisamides.

The amount of the wax is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 8 parts by mass per 100 parts by mass of the binder resin.

When the amount of the wax is less than 0.1 part by mass, the releasing effect cannot be obtained particularly when the amount of the fixing oil applied is reduced or when the amount is not used at all, and when the amount is more than 10 parts by mass, Dispersion of the pigment becomes worse, and as a result, the chroma of the toner is impaired.

In the DSC endothermic curve of the wax, the maximum endothermic peak in the temperature range of 30 to 160 ° C. is 55
To 80 ° C. is preferred. Maximum endothermic peak is 5
When a wax having a temperature of less than 5 ° C. is used, since the resin has a lower glass transition temperature than the resin used in the present invention, it melts out on the surface of the toner when left in a high-temperature environment. On the other hand, the maximum endothermic peak was 8
If the temperature is higher than 0 ° C., the wax cannot be quickly transferred to the surface of the molten toner at the time of melting and fixing the toner, and the releasability is deteriorated.

The wax used in the present invention preferably has a half-value width of an endothermic peak of 7 ° C. or less. When the half-width of the endothermic peak exceeds 7 ° C., the toner cannot be transferred to the surface of the molten toner at the time of fixing and melting, and particularly in a resin having a structure crosslinked with a metal compound, the transfer speed of the wax is reduced. A sufficient release effect and high-temperature offset resistance cannot be satisfied, and the above-mentioned soft metal ion crosslinking is not achieved.

The amount of the wax is preferably from 0.1 to 10 parts by mass, more preferably from 0.5 to 8 parts by mass, per 100 parts by mass of the binder resin. If the amount exceeds 10 parts by mass, the dispersibility of the colorant in the toner is impaired, and sufficient color reproducibility cannot be obtained. On the other hand, if the amount is less than 0.1 part by mass, it is insufficient to prevent a high-temperature offset that cannot be visually judged.

The wax is contained in the binder resin by dissolving the resin in a solvent, increasing the temperature of the resin solution, and adding and mixing while stirring, by adding internally before synthesizing the resin, or by mixing during kneading. .

It is preferable that a fluidity improver is externally added to the toner particles in order to improve the image quality. As a fluidity improver, by externally adding to a toner particle, fluidity can be increased before and after addition.

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

The fluidity improver has a specific surface area of 30 m ² / g or more, preferably 5 m ² / g or more by nitrogen adsorption measured by the BET method.
Those of 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.
It is preferably from 0 to 12.0 μm.

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

[0093] Furthermore, the toner of the present invention, the volume average particle diameter (D _v) is 2.5μm to 6.0μm are preferred more for the formation of high quality images.

[0094] 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.

In the present invention, a fixing roller containing a heat source, a pressure roller disposed to press against the fixing roller, and a surface of the fixing roller or a surface of the pressure roller are disposed. A temperature control element for maintaining the surface temperature of the fixing roller or the pressure roller at a predetermined temperature based on the temperature detected by the temperature detection element; In a fixing device for fixing a non-fixed developer image on a recording material by nipping and conveying a recording material carrying a multi-layer or single-color unfixed toner image, the fixing roller or the pressure roller has a surface layer made of a fluororesin. The base layer is made of heat-resistant rubber, and the hardness of the product rubber is 50 to 75 degrees by Asker C.

According to the present invention, the fixing roller and the pressing roller preferably have a product hardness of 50 to 75 degrees in Asker C. Within this range, the lower layer of the toner melts and is fixed to the recording material, and the upper layer maintains the shape of the toner particles without smoothing the surface, thereby improving the fixing property. A pictorially fixed image can be realized without any loss.

The rubber hardness of the base layer of the fixing and pressing roller in the present invention is preferably 5 to 50 degrees in Asker C. If the rubber hardness of the base layer is less than 5 degrees, the durability of the roller will be poor. If the rubber hardness of the base layer exceeds 50 degrees, the glossiness of the fixed image becomes too high.

Further, according to the present invention, by using as an image fixing device in an image forming apparatus having a double-sided recording function and adjusting the heating from the pressing member side on the second side, uniformity can be obtained on the front side and the back side. The image gloss (gloss) can be controlled.

According to the combination of the toner and the fixing device of the present invention, the surface temperature of the fixing roller is set at 160 ° C., and the pressure contact force between the fixing roller and the pressure roller is 392 to
588 N (40 to 60 kgf), and a recording paper having a basis weight of 75 to 130 g / m ² was used as the recording material.
The amount of toner carried on the recording paper is 0.7 to 1.
A toner image of 3 mg / cm ² is heated and pressed and fixed on the recording material, and the peripheral speed of the fixing roller is 100 to 130 mm / sec.
In the case of (1), it is possible to form a fixed image having a glossiness (60-degree gloss) of 15 to 30 and capable of oilless fixing.

Next, a specific example of a multi-color or full-color image forming apparatus applicable when the toner is a cyan toner, a magenta toner, a yellow toner and / or a black toner will be described with reference to FIG.

FIG. 4 shows an image forming apparatus (copier or laser printer) capable of forming a mono-color image, a multi-color image and a full-color image using an electrophotographic process.
FIG. A medium-resistance elastic roller 5 is used as an intermediate transfer member, and a transfer belt 10 is used as secondary contact transfer means. Reference numeral 1 denotes a rotating drum type electrophotographic photosensitive member (hereinafter, referred to as a photosensitive member) that is repeatedly used as an image carrier, and is rotated at a predetermined peripheral speed (process speed) in a clockwise direction indicated by an arrow. Photoreceptor 1 is a-Se, C
It may be a photosensitive drum or a photosensitive belt having a photoconductive insulating material such as dS, ZnO ₂ , OPC, and a-Si.

As the photosensitive member 1, a photosensitive member having an amorphous silicon photosensitive layer or an organic photosensitive layer is preferably used.

As the organic photosensitive layer, the photosensitive layer contains a charge generating substance and a substance having charge transporting ability in the same layer.
It may be a single layer type, or may be a function-separated type photosensitive layer having a charge transport layer and a charge generation layer as components. A laminated photosensitive layer having a structure in which a charge generation layer and then a charge transport layer are laminated on a conductive substrate in this order is one of preferred examples.

The binder resin for the organic photosensitive layer is preferably a polycarbonate resin, a polyester resin, or an acrylic resin, particularly having good transferability and cleaning properties, poor cleaning, fusion of toner to the photoreceptor, and filming of external additives. Less likely.

In the charging step, there are a method of non-contact with the photoreceptor 1 using a corona charger and a method of contact type using a roller or the like, and any of them is used. For efficient uniform charging, simplification, and low ozone generation, a contact type as shown in FIG. 4 is preferably used.

The charging roller 2 basically has a core 2b at the center and a conductive elastic layer 2a forming the outer periphery thereof. The charging roller 2 is pressed against the surface of the photoconductor 1 with a pressing force, and is rotated by the rotation of the photoconductor 1.

As a preferable process condition when the charging roller is used, the contact pressure of the roller is 4.9 to 490 N / m.
(5 to 500 g / cm), when an AC voltage superimposed on a DC voltage is used, AC voltage = 0.5 to 5 kVp
p, AC frequency = 50 Hz to 5 kHz, DC voltage = ±
0.2 to ± 1.5 kV, and when a DC voltage is used, the DC voltage is ± 0.2 to ± 5 kV.

As other charging means, there are a method using a charging blade and a method using a conductive brush. These contact charging means are effective in that high voltage is not required and generation of ozone is reduced.

The material of the charging roller and the charging blade as the contact charging means is preferably conductive rubber, and a release film may be provided on the surface thereof. As the release coating, a nylon resin, PVDF (polyvinylidene fluoride), PVDC (polyvinylidene chloride) or the like can be applied.

The photosensitive drum 1 is uniformly charged to a predetermined polarity and potential by the primary charging roller 2 during the rotation process.
Then, image exposure means (not shown) (for example, a color separation / imaging exposure optical system for a color original image, a scanning exposure system using a laser scanner for outputting a laser beam modulated corresponding to a time-series electric digital pixel signal of image information) 1) of the target color image.
(For example, a cyan component image) is formed.

Next, the electrostatic image is transferred to the first developing device 4-1.
(Cyan developing device) is developed with cyan toner as the first color. The developing device 4-1 is an apparatus unit, which is detachable from the image forming apparatus main body. FIG. 5 is an enlarged view of the developing device 4-1.

In FIG. 5, reference numeral 22 denotes an outer wall containing a one-component non-magnetic cyan toner. Inside the outer wall 22, a developing sleeve 16 is provided as a toner carrier, which is opposed to the photosensitive member 1 rotating in the direction of arrow a in FIG. The toner image is formed on the photoconductor 1 by developing the electrostatic charge image on the photoconductor 1 with toner. The developing sleeve 16 protrudes into the outer wall 22 at a substantially right half circumferential surface as viewed in the figure, and exposes a substantially left half circumferential surface outside the outer wall 22.
, And are rotatably provided sideways so as to face. A minute interval is provided between the developing sleeve 16 and the photoconductor 1. The developing sleeve 16 is driven to rotate in the direction of arrow b with respect to the rotation direction a of the photoconductor 1.

The developing sleeve 16 is not limited to a cylindrical shape, but may be a rotating endless belt.
A conductive rubber roller may be used.

Further, inside the outer wall 22, an elastic blade 19 is provided as an elastic regulating member at a position above the developing sleeve 16, and a toner coating roller 18 is located at a position upstream of the elastic blade 19 in the rotation direction of the developing sleeve 16. Is provided. An elastic roller may be used as the elastic regulating member.

The elastic blade 19 is provided so as to be inclined downward toward the upstream side in the rotation direction of the developing sleeve 16, and abuts against the upper outer peripheral surface of the developing sleeve 16 in the rotation direction.

The toner application roller 18 is used for the developing sleeve 1.
6 is abutted on the opposite side of the photoconductor 1 and is rotatably supported.

In the developing device 4-1, the toner application roller 18 rotates in the direction of the arrow in the above-described configuration.
8, the cyan toner is carried by the rotation of
The cyan toner on the toner applying roller 18 is supplied to the developing sleeve 16 at a contact portion (nip portion) where the developing sleeve 16 and the toner applying roller 18 are in contact with each other.
And adheres onto the developing sleeve 16.

With the rotation of the developing sleeve 16, the cyan toner adhering to the developing sleeve 16
At the abutting portion between the developing sleeve 9 and the developing sleeve 16, it penetrates between them, and when passing therethrough, is rubbed by both the surface of the developing sleeve 16 and the elastic blade 19, and a sufficient frictional band charge is applied. .

The toner triboelectrically charged as described above passes through the contact portion between the elastic blade 19 and the developing sleeve 16, and a thin layer of cyan toner is formed on the developing sleeve 16. Is transported to the developing section. By applying an alternating voltage in which DC and AC are superimposed as a developing bias to the developing sleeve 16 by the bias applying means 17, the cyan toner on the developing sleeve 16 is transferred according to the electrostatic charge image of the photoconductor 1, Attaches to the charge image to form a toner image.

In the developing section, the cyan toner remaining on the developing sleeve 16 without transferring to the photoreceptor 1 is transferred from the lower portion of the developing sleeve 16 to the outer wall 2 with the rotation of the developing sleeve 16.
Collected in 2.

The collected cyan toner is peeled off from the developing sleeve 16 by the toner application roller 18 at a contact portion with the developing sleeve 16. At the same time, new cyan toner is supplied onto the developing sleeve 16 by the rotation of the toner application roller 18, and the new cyan toner is transported again to the contact portion between the developing sleeve 16 and the elastic blade 19.

On the other hand, most of the stripped cyan toner is mixed with other toner in the outer wall 22 with the rotation of the toner applying roller 18, and the triboelectric charge of the stripped toner is dispersed. The toner at a position distant from the toner application roller 18 is sequentially supplied to the toner application roller 18 by the stirring means 21.

The developing sleeve 16 is preferably a conductive cylinder formed of a metal or alloy such as aluminum or stainless steel. The conductive cylinder may be formed of a resin composition having sufficient mechanical strength and conductivity. Further, the developing sleeve 16 may have a coating layer formed of a resin composition in which conductive fine particles are dispersed on a metal or alloy cylindrical surface.

As the coating layer, a resin material containing conductive fine particles is used. The conductive fine particles are 1176
It is preferable that the resistance value after pressing at 0 kPa (120 kg / cm ² ) is 0.5 Ω · cm or less.

As the conductive fine particles, carbon fine particles,
A mixture of carbon fine particles and crystalline graphite, or crystalline graphite is preferred. The conductive fine particles preferably have a particle size of 0.005 to 10 μm.

Examples of the resin material include thermoplastic resins such as styrene resins, vinyl resins, polyether sulfone resins, polycarbonate resins, polyphenylene oxide resins, polyamide resins, fluorine resins, cellulose resins, and acrylic resins; A thermosetting resin such as a resin, a polyester resin, an alkyd resin, a phenol resin, a melamine resin, a polyurethane resin, a urea resin, a silicone resin, and a polyimide resin or a photocurable resin can be used.

Among them, those having a releasable property such as silicone resin and fluorine resin, or polyether sulfone,
Polycarbonate, polyphenylene oxide, polyamide, phenolic resin, polyester, polyurethane,
Those having excellent mechanical properties such as styrene resins are more preferable. Particularly, an acrylic resin or a phenol resin is preferable.

The conductive fine particles are preferably used in an amount of 3 to 20 parts by mass per 100 parts by mass of the resin component.

When carbon fine particles and graphite particles are used in combination, it is preferable to use 1 to 50 parts by mass of carbon fine particles per 100 parts by mass of graphite. The volume resistance value of the resin coat layer of the sleeve in which the conductive fine particles are dispersed is preferably 10 ⁻⁶ to 10 ⁶ Ω · cm.

Magenta developing device 4-2, yellow developing device 4
-3 and the black developing device 4-4 are non-magnetic one-component developing devices having the same structure as the cyan developing device 4-1.

The black developing device alone may be a magnetic one-component developing type developing device using an insulating magnetic toner in some cases.

The intermediate transfer member 5 is driven to rotate at the same peripheral speed as the photosensitive drum 1 in the direction of the arrow. Photosensitive drum 1
The first color cyan toner image formed and carried thereon passes through a nip portion between the photosensitive drum 1 and the intermediate transfer member 5, and an electric field formed by a primary transfer bias 6 applied to the intermediate transfer member 5. With the pressure, the intermediate transfer is performed on the outer peripheral surface of the intermediate transfer body 5. Hereinafter, this step is referred to as primary transfer. The intermediate transfer member may have a drum shape or an endless belt shape.

Similarly, the magenta toner image of the second color, the yellow toner image of the third color, and the black toner image of the fourth color are successively superimposed and transferred onto the intermediate transfer member 5 in the same manner, and are synthesized corresponding to the target color image. A color toner image is formed.

The transfer belt 10 is disposed in contact with the lower surface of the intermediate transfer member 5 so as to bear in parallel with the rotation axis of the intermediate transfer member 5. The transfer belt 10 is supported by a bias roller 11 and a tension roller 12.
, A desired secondary transfer bias is applied by a secondary transfer bias source 23, and the tension roller 12 is grounded.

First to first transfer from the photosensitive drum 1 to the intermediate transfer member 5
A primary transfer bias for sequentially superimposing transfer of the fourth color toner image is applied from a bias power supply 6 with a polarity (+) opposite to that of the toner.

First to first transfer from the photosensitive drum 1 to the intermediate transfer member 5
In the sequential transfer execution step of the fourth color toner image, the transfer belt 10 and the intermediate transfer body cleaning roller 7 can be brought into contact with and separated from the intermediate transfer body 5.

The transfer of the composite color toner image superimposedly transferred onto the intermediate transfer member 5 onto the transfer material P is carried out while the transfer belt 10 is in contact with the intermediate transfer member 5 and the registration roller 13. The transfer material P is fed at a predetermined timing to the contact nip between the intermediate transfer body 5 and the transfer belt 10 through the pre-transfer guide 24, and at the same time, the secondary transfer bias is applied from the bias power source 23 to the bias roller 11. Applied. The composite color toner image is transferred from the intermediate transfer body 5 to the transfer material P by the secondary transfer bias. Hereinafter, this step is referred to as secondary transfer. The secondary transfer may be performed by a transfer roller to which a bias is applied.

The transfer material P to which the toner image has been transferred is introduced into a heat-pressure fixing device 25 having a heating roller 14 and a pressure roller 15, and is heat-fixed.

The intermediate transfer member 5 is a pipe-shaped conductive core 5
b and a medium resistance elastic layer 5a formed on the outer peripheral surface thereof. The metal core 5b may be formed by applying a conductive plating to a plastic pipe.

The medium resistance elastic layer 5a is made of silicone rubber, fluorine rubber, chloroprene rubber, urethane rubber,
EPDM (terpolymer of ethylene propylene diene)
A conductive material such as carbon black, zinc oxide, tin oxide, or silicon carbide is mixed and dispersed in an elastic material such as the above, so that the electric resistance value (volume resistivity) becomes a medium resistance of 10 ⁵ to 10 ¹¹ Ω · cm. A conditioned, solid or foamy layer.

After the transfer of the toner image to the transfer material, the intermediate transfer member 5
Is cleaned. When there is a toner image on the intermediate transfer member, the cleaning unit is separated from the surface of the intermediate transfer member so as not to disturb the toner image.

For example, the cleaning of the intermediate transfer member 5
At the same time as the primary transfer from the photosensitive drum 1 to the intermediate transfer member 5, the secondary transfer residual toner on the intermediate transfer member 5 is reversely transferred back to the photosensitive drum 1 and collected by the cleaner 9 of the photosensitive drum 1. It is done by.

The mechanism will be described. Intermediate transfer member 5
The toner image formed on the transfer belt 10 by a strong electric field formed by applying a secondary transfer bias having a polarity opposite to the charging polarity (non-polarity) of the toner image to the bias roller 11. The image is transferred to the transferred transfer material P.

At this time, the secondary transfer residual toner remaining on the intermediate transfer member 5 without being transferred to the transfer material P is charged to a polarity (positive polarity) opposite to a normal charging polarity (negative polarity). There are many.

However, not all the secondary transfer residual toner is inverted to the positive polarity, and some toners are neutralized and have no charge, and some toners maintain the negative polarity.

A charging means 7 for inverting the toner, which is partially neutralized and has no charge, or maintains the negative polarity, to the opposite polarity is provided after the secondary transfer position and before the primary transfer position. .

As a result, almost all of the secondary transfer residual toner can be returned to the photosensitive member 1.

The secondary transfer residual toner is reverse-transferred to the photosensitive member 1, and the toner image formed on the photosensitive member 1 is transferred to the intermediate transfer member 5.
When the primary transfer is performed simultaneously, the intermediate transfer member 5
The reversely-charged secondary transfer residual toner and the primary-transferred normal toner are reversely charged in the nip portion between the photosensitive drum 1 and the intermediate transfer member 5 without being electrically substantially neutralized. The toner is transferred to the photosensitive drum 1, and the normally charged toner is transferred to the intermediate transfer member 5.

This is because, by lowering the primary transfer bias, the electric field applied between the photosensitive drum 1 and the intermediate transfer member 5 at the primary transfer nip is weakened, thereby suppressing the discharge at the nip. This is because the polarity of the toner is prevented from changing.

Further, since the triboelectrification toner has an electrical insulation property, the charges of the opposite polarities cancel each other out in a short time and the polarity is not reversed or neutralized.

Therefore, the secondary transfer residual toner charged to the positive polarity on the intermediate transfer member 5 is transferred to the photosensitive drum 1, and the negatively charged toner image on the photosensitive drum 1 is transferred to the intermediate transfer member 5. Each of them behaves independently, such as being transferred to

When an image is formed on one transfer material P by one image formation start signal, the toner image is not transferred from the photosensitive drum 1 to the intermediate transfer member 5 after the secondary transfer.
The secondary transfer residual toner remaining on the intermediate transfer member is reversely transferred to the photosensitive drum 1.

In this embodiment, as the charging means for charging the secondary transfer residual toner on the intermediate transfer member 5, a contact type charging means, specifically, an elastic roller having a plurality of layers is used as the intermediate transfer member cleaning roller 7. Used.

The mechanical structure of the fixing device 25 is as follows. The roller 14 on the side of the image carrier which is in direct contact with the toner layer (hereinafter referred to as a fixing roller, which corresponds to a heat roller 53 in FIG. 6 described later).
It is preferable to use an elastic roller. That is, when the fixing roller has elasticity, the surface of the fixing roller itself deforms and presses against the unevenness of the surface of the unfixed toner image. It is effective for uniformity of

FIG. 6 is a diagram showing a configuration example of the fixing device of the present invention. Reference numeral 53 denotes a fixing roller, and a pressure roller 54 is pressed against the fixing roller 53 to perform a driven rotation while forming a nip portion with the fixing roller 53. The fixing roller 53 is in the form of a hollow cylinder, and a halogen heater 55 is built in the hollow space to supply heat necessary for fixing. The pressure roller 54 is heated by a halogen heater 55. To control the temperature of the roller, a thermistor 58 as a temperature detecting element or a thermistor 58 is disposed in contact with the pressure roller 54 in a non-sheet passing area of the fixing roller 53, and the surface temperature of the roller is changed by a resistance value change according to the detected temperature. Upon detection, the current of the halogen heater 55 is controlled by a control device (not shown) so that the roller surface temperature becomes a predetermined value.

In the above-described apparatus, the unfixed transfer material is guided by the guide 62, enters the nip from the right side, and is pressed and heated by the surface of the fixing roller 53.
The sheet is discharged after being fixed. Reference numeral 59 denotes a separation claw between the fixed transfer material and the fixing roller 53 or the pressure roller 54.

The fixing roller 53 has an elastic layer of several tens of μm on a core shaft of aluminum or the like in order to follow the thickness (several to several tens of μm) of the multicolor toner 61 of one to four colors of a color image.
m or more. If the elasticity is low, the resolution is lowered due to the unfixed toner concave portion and the collapse of the toner. The material of the elastic layer is preferably a methyl-based or methyl vinyl-based liquid silicone rubber RTV or LTV type, because it has elasticity. RTV, L on the surface
Using a TV, a heat-resistant HTV layer is provided below the TV,
It is also possible to adopt a multi-layer configuration in which thermal deterioration and peeling of the back surface of the surface layer are prevented. In Example 1 described later, an LTV type elastic layer 52 of dimethyl silicone rubber having a rubber hardness (Asker C) of 15 degrees was provided on an aluminum core metal 51 by 2.5 mm, and a PFA tube layer 63 was provided thereon by 50 μm. Is φ46
mm. At this time, the product hardness is Asker C
At 60 degrees. In addition, a methylphenyl silicone rubber can also be used.

The structure of the pressure roller 54 is the same as that of the fixing roller 53.
Since the elasticity may be smaller than that of the above, simplification is possible and only the layer of HTV, fluoro rubber or the like may be provided on the aluminum core shaft. Of course, a roller having substantially the same configuration as the fixing roller may be used. In Example 1 to be described later, an LTV-type elastic layer 52 of dimethyl silicone rubber having a rubber hardness (Asker C) of 15 degrees was provided on an aluminum core metal 51 as a pressure roller by 1.5 mm, and a PFA tube layer 63 was formed thereon. 50
The one provided with μm was formed into φ46 mm and used. At this time, the product hardness of Asker C was 60 degrees. As the rubber for the fixing roller and the pressure roller, methylphenyl silicone rubber may be used. Fixing temperature is 16
The ripple should be within ± 3 ° C at 0 ° C, and the applied pressure should be 392-58
8N (40-60 kgf).

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

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

0.5 g of a measurement sample of the THF-insoluble component was weighed, and the filter paper (for example, No. 86R)
(Size 28 × 10 mm, manufactured by Toyo Roshi Kaisha, Ltd.) and then subjected to a Soxhlet extractor. Using 200 ml of THF as a solvent, extraction is performed at 8 hours and 24 hours, and insolubles A, B and B / A are calculated.

At this time, the THF extraction cycle is about 4 to 5
The extraction is performed at a reflux rate of once a minute. After completion of the extraction, the cylindrical filter paper is taken out and weighed to obtain an insoluble content of the sample.

Measurement of Dynamic Elastic Modulus of Toner Using a viscoelasticity measuring device (rheometer) RDA-II type (manufactured by Rheometrics) under the following conditions under the following conditions:
The dynamic elastic modulus G ′ is measured in a temperature range of 10 ° C. Measurement jig: Use a flat circular plate with a diameter of 7.9 mm when the elastic modulus is high, and use a flat circular plate with a diameter of 40 mm when the elastic modulus is low. A shallow cup corresponding to the circular plate is used on the side of the actuator. The gap between the bottom of the shallow cup and the circular plate is about 2 mm. Measurement sample: about 8 mm in diameter after heating and melting the toner,
A cylindrical sample having a height of 2 mm or a disk-shaped sample having a diameter of about 40 mm and a height of about 2 mm is used. -Measurement frequency: 6.28 radians / sec-Measurement distortion setting: After setting the initial value to 0.1%, perform measurement in the automatic measurement mode. -Sample extension correction: Adjust in the automatic measurement mode. Measurement temperature: The temperature is raised from 60 ° C to 210 ° C at a rate of 2 ° C per minute.

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

The column was stabilized in a heat chamber at 40 ° C., and tetrahydrofuran (THF) was passed through the column at this temperature 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.

The maximum endothermic peaks and
Fine semi-width of the measured differential thermal analysis measuring apparatus (DSC measuring device), DSC-7
(Perkin Elmer).

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

In this heating process, an endothermic peak of a main peak in a temperature range of 30 to 160 ° C. is obtained.

The half width of the maximum endothermic peak is the temperature width at which the peak exists at a half or more of the height from the base line to the peak top of the maximum endothermic peak. The peak does not have to be continuous over half the height in all the half widths.

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

As the channels, 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; 25.40-32.00 μm;
13 channels of 00 to 40.30 μm are used.

[0173]

EXAMPLES Hereinafter, the toner production examples and examples of the present invention will be described, but the present invention is not limited to these examples.

Toner Production Example 1 Binder Resin: Polyester Resin No. 1 100 parts by mass Wax: paraffin wax (A) 3 parts by mass Charge control agent: aromatic oxycarboxylic acid Al compound (I) 6 parts by mass Pigment: copper phthalocyanine 5 parts by mass

The polyester resin N as the binder resin
o. The monomer composition ratio used in No. 1 is shown below.

[0176]

Embedded image In the above structure, the diol component represented by (x + y = 3.0) 59 mol% fumaric acid 21 mol% terephthalic acid 11 mol% trimellitic acid 9 mol% 1 means Tg is 6
0 ° C., GPC of a THF-soluble component, Mn was 3300, Mw was 33000, Mw / Mn
Was 10.0.

The above materials were sufficiently premixed with a Henschel mixer, melt-kneaded at an arbitrary barrel temperature using a twin-screw extruder, cooled, roughly crushed about 1 to 2 mm using a hammer mill, and then crushed. It was pulverized by 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 prepare a cyan toner 1. Table 1 shows a list of the type of binder resin, the type of wax and the endothermic peak and the half width, the type and number of charge control agents, and the barrel setting temperature in the kneader used for the cyan toner 1. Table 2 shows the physical properties.

The anti-blocking properties of the sample toners in Table 2 were evaluated by being left in an oven at 50 ° C. for one week. As the evaluation, the level of cohesiveness was visually determined.

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

Toner Production Examples 2 and 3 Aromatic oxycarboxylic acid Al added as a charge control agent
Cyan Toners 2 and 3 were prepared in the same manner as in Toner Production Example 1 except for the amount of compound (I) added. Tables 1 and 2 show a list of the prescription and the physical properties of the toner.

Toner Production Examples 4 and 5 Ester wax was used in place of paraffin wax (A), and kneading (barrel) in a twin screw extruder
Cyan toners 4 and 5 were prepared in the same manner as in toner production example 1 except that the set temperature was changed from 120 ° C. to 100 ° C. and 180 ° C., respectively. Tables 1 and 2 show a list of the prescription and the physical properties of the toner.

Toner Production Example 6 The charge controlling agent was an aromatic oxycarboxylic acid Al compound (I)
Was replaced with Cr compound (I), and a cyan toner 6 was prepared in the same manner as in Toner Production Example 5. Tables 1 and 2 show a list of the prescription and the physical properties of the toner.

Toner Production Example 7 A cyan toner 7 was prepared in the same manner as in Toner Production Example 1, except that paraffin wax (B) was used instead of paraffin wax (A). Tables 1 and 2 show a list of the prescription and the physical properties of the toner.

Toner Production Example 8 A cyan toner 8 was prepared in the same manner as in Toner Production Example 1, except that paraffin wax (C) was used instead of paraffin wax (A). Tables 1 and 2 show a list of the prescription and the physical properties of the toner.

Toner Production Example 9 Polyester resin no. In place of 1, Tg is 53 ° C., and GPC of a THF-soluble component has Mn of 3000
, Mw is 9300, and Mw / Mn is 3.1. A cyan toner 9 was prepared in the same manner as in Toner Production Example 1 except that No. 2 was used. Tables 1 and 2 show a list of the prescription and the physical properties of the toner.

Toner Production Example 10 Polyester resin No. In place of 1, the Tg was 66 ° C., and the GPC of the THF-soluble component showed that Mn was 6000.
And Mw is 24000 and Mw / Mn is 4.0.
Polyester resin No. A cyan toner 10 was prepared in the same manner as in Toner Production Example 1 except that No.3 was used.
Tables 1 and 2 show a list of the prescription and the physical properties of the toner.

Toner Production Example 11 Magenta Toner 1 was prepared in the same manner as in Toner Production Example 1 except that 5 parts by mass of quinacridone was used instead of 5 parts by mass of copper phthalocyanine. Yellow toner 1 and copper phthalocyanine in the same manner as in Toner Production Example 1 except that 5 parts by mass of Pigment Yellow 17 was used instead of 5 parts by mass instead of 5 parts by mass. Black toner 1 was prepared in the same manner as in Production Example 1.

Comparative Toner Production Example 1 Aromatic oxycarboxylic acid Al added as charge control agent
Cyan Toner 11 was prepared in the same manner as in Toner Production Example 1 except for the amount of compound (I) added. Tables 1 and 2 show a list of the prescription and the physical properties of the toner.

Comparative Toner Production Example 2 A cyan toner 12 was prepared in the same manner as in Toner Production Example 1, except that the charge control agent was not used. Tables 1 and 2 show a list of the prescription and the physical properties of the toner.

Comparative Toner Production Examples 3 and 4 Instead of the Al compound of aromatic oxycarboxylic acid, a Zn compound (III) or a Fe compound (I
Cyan toners 13 and 14 were prepared in the same manner as in toner production example 1 except that V) was used. Tables 1 and 2 show a list of the prescription and the physical properties of the toner.

[0192]

Embedded image

Tables 1 and 2 show a list of prescriptions and physical properties of the toner.

Comparative Toner Production Examples 5 and 6 Cyan toners 15 and 1 were produced in the same manner as in Comparative toner production example 2 except that paraffin wax (D) and paraffin wax (E) were used instead of paraffin wax (A).
6 was prepared. Tables 1 and 2 show a list of the prescription and the physical properties of the toner.

Comparative Toner Production Example 7 A cyan toner 17 was prepared in the same manner as in Toner Production Example 1, except that polyethylene wax was used instead of paraffin wax (A). Table 1 shows a list of prescriptions and physical properties of the toner.
And 2.

Comparative Toner Production Example 8 A cyan toner 18 was prepared in the same manner as in Toner Production Example 1 except that a polypropylene wax was used instead of the paraffin wax (A). Tables 1 and 2 show a list of the prescription and the physical properties of the toner.

Comparative Toner Production Example 9 Polyester Resin No. In place of 1, the Tg is 50 ° C., and the GPC of the THF-soluble component has Mn of 1500
Polyester No. having an Mw of 2900 and an Mw / Mn of 1.9. A cyan toner 19 was prepared in the same manner as in Comparative Toner Production Example 2 except that No. 4 was used. Tables 1 and 2 show a list of the prescription and the physical properties of the toner.

Comparative Toner Production Example 10 Polyester Resin No. In place of 1, the Tg is 70 ° C., and the GPC of the THF-soluble component
0, Mw is 220,000, and Mw / Mn is 2
Polyester No. 2.0 A cyan toner 20 was prepared in the same manner as in Comparative Toner Production Example 2 except that No. 5 was used. Tables 1 and 2 show a list of the prescription and the physical properties of the toner.

Comparative Toner Production Example 11 Polyester Resin No. In place of 1, Tg is 60 ° C., and in GPC of a THF-soluble component, Mn is 1000
0, Mw is 300,000, and Mw / Mn is 3
A cyan toner 21 was prepared in the same manner as in Comparative Toner Production Example 2, except that a styrene-n-butyl acrylate copolymer of 0.0 was used. Tables 1 and 2 show a list of the prescription and the physical properties of the toner.

<Example 1> Prepared according to Production Example 1 of toner.
Using the obtained cyan toner 1, the basis weight is 75 g / m ^TwoNote
1.2mg / cm of toner carried on recording paper^TwoToner painting
An image is formed, and the process speed is adjusted using the fixing device shown in FIG.
The image was fixed at 120 mm / sec. In addition,
Using the toner 1, the amount of toner carried on the OHP sheet
0.2 to 1.0 mg / cm^TwoBand-shaped cyant changed to
After forming a toner image, the fixing device shown in FIG.
Was set to 30 mm / sec, and the image was fixed.

The gloss (gloss) of the fixed image was measured using a VG-10 type gloss meter (manufactured by Nippon Denshoku Co., Ltd.) using each solid image used for the chromaticity measurement as a sample.
First, the voltage is set to 6 V by a constant voltage device. Next, the light projection angle and the light reception angle are each adjusted to 60 °. Using the zero point adjustment and the standard plate, after the standard setting, the sample image is placed on the sample table, three white papers are superimposed and measured, and the numerical value indicated on the mark is read in%. 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 was used.

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

Table 3 shows a list of the fixing test results and the evaluation results of the OHP permeability.

The gloss in the table is a measurement result obtained by fixing at a fixing temperature of 160 ° C. and by the gloss measuring method.

By controlling the viscoelastic properties of the toner and the change with time of the THF-insoluble component to the values specified by the present invention, good fixing properties can be ensured. It was confirmed that by performing heat fixing using a pressure roller, it was possible to form a fixed image having excellent OHP transparency and a wide temperature range with high gloss (gloss).

<Example 2> Using cyan toner 1, the surface material of the fixing roller and the pressure roller used in Example 1 was changed to P.
Evaluation was performed in the same manner as in Example 1 except that FEP was replaced with FEP. As shown in Table 3, very good results were obtained.

<Examples 3 to 9> Evaluations were made in the same manner as in Example 1 using cyan toners 2 to 8 in place of cyan toner 1, and good results were obtained as shown in Table 3. Was.

Example 10 Evaluation was performed in the same manner as in Example 1 except that a roller of 53 degrees was used in place of the roller having a product rubber hardness of 60 degrees, and a cyan toner 9 was used in place of the cyan toner 1. As a result, good results were obtained as shown in Table 3.

<Example 11> Evaluation was performed in the same manner as in Example 1 except that a roller of 72 degrees was used in place of the roller having a product rubber hardness of 60 degrees, and a cyan toner 10 was used in place of the cyan toner 1. As a result, good results were obtained as shown in Table 3.

<Example 12> A roller having a surface layer of PFA and a rubber hardness of 60 degrees was used as a toner. As toner, cyan toner 1, magenta toner 1 and yellow toner 1 obtained in Production Example 11 were used. , 4-2, 4-3, 4-4 shown in FIG.
To obtain a full-color image fixed at 160 ° C. by the heat fixing device shown in FIG. Since the image has a sufficiently high gloss and a sufficiently wide color reproduction range, it is particularly suitable when pictorial expression is required. Also, since the toner after fixing is sufficiently melted, OHP
Also has excellent permeability.

<Comparative Examples 1 to 11> Evaluations were made in the same manner as in Example 1 except that cyan toners 11 to 21 were used in place of cyan toner 1.
A combination of a toner and a fixing device satisfying all of high-temperature offset resistance, high gloss reproducibility and OHP transparency was not obtained.

<Comparative Example 12> Instead of a roller having a product rubber hardness of 60 degrees, a roller having a degree of 48 degrees was used.
The evaluation was carried out in the same manner as in Example 1 by using, but it was inferior to that of Example 1, but high gloss (gloss)
However, there was a problem in the durability of the rubber roller as the fixing test for many sheets was continued.

<Comparative Example 13> Instead of the roller having the product rubber hardness of 60 degrees, a 77 degree roller was used.
Was evaluated in the same manner as in Example 1, and there was no problem in fixing performance.
The glossiness (gloss) was too high compared to the case of the degree, and the pictorial image was good, but it was felt that letters were hard to see due to light reflection.

<Comparative Example 14> Using cyan toner 1,
The evaluation was performed in the same manner as in Example 1 except that the outermost layer material of the fixing roller and the pressure roller used in Example 1 was changed from FEP to RTV silicone rubber. Did not.

[0216]

[Table 1]

[0219]

[Table 2]

[0218]

[Table 3]

[0219]

According to the present invention, good fixability can be ensured by controlling the viscoelastic properties of the toner and the change with time of THF-insoluble components to the values specified by the present invention. By performing heat fixing using a fixing roller and a pressure roller with specified hardness, it is possible to obtain a fixed image having excellent OHP transparency and a wide temperature range with high gloss (gloss).

[Brief description of the drawings]

FIG. 1 is a schematic explanatory view of a conventional image heat fixing device.

FIG. 2 is a diagram illustrating an example of a dynamic elastic modulus curve of the toner of the present invention.

FIG. 3 is a diagram illustrating an example of a dynamic elastic modulus curve of a conventional toner.

FIG. 4 is a schematic explanatory view showing an example of an image forming apparatus to which the present invention can be applied.

FIG. 5 is a schematic explanatory view showing an example of an apparatus unit of the image forming apparatus shown in FIG.

FIG. 6 is a schematic explanatory view of an image heating and fixing device to which the toner of the present invention can be applied.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Image carrier (photoreceptor) 4 Developing device 16 Developing sleeve 20 Cyan toner 25 Fixing device 51 Core metal 52 Elastic layer 53 Fixing roller 54 Pressure roller 55 Halogen heater 58 Thermistor 60 Transfer paper (recording material) 61 Unfixed color toner 63 Fluorine resin layer (surface layer)

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03G 9/097 G03G 15/20 107 15/20 103 109 107 9/08 331 109 346 (72) Inventor Sugawara Yonyoshi 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Yojiro Hotta 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. F-term (reference) 2H005 AA01 AA06 CA08 CA14 CA25 DA02 EA03 EA06 EA07 2H033 AA01 AA47 BA30 BA58 BB05 BB14 BB34 CA07 CA27 CA39 3J103 AA02 AA15 AA24 AA33 AA41 AA51 BA03 BA31 BA41 FA05 FA12 FA18 FA19 GA02 GA66 HA03 HA04 HA05 HA12 HA15 HA37 HA43

Claims (12)

[Claims] An image is formed on a recording material with a toner,
The toner formed on the recording material by a heat and pressure fixing unit having a fixing roller having a base layer of a heat-resistant rubber, a surface layer of a fluororesin on the surface of the base layer, and a pressing roller pressed against the fixing roller. In an image forming method of fixing an image by heating and pressing to form a fixed image on the recording material, the toner is a toner having at least a binder resin, a toner particle having a colorant and a wax, and a toner having an external additive. In the DSC endothermic curve, the temperature was 30 to 16
The maximum endothermic peak in the range of 0 ° C. is 55 to 80 ° C., the half width of the maximum endothermic peak is 2 to 7 ° C., the binder resin component is mainly composed of a polyester resin, and the toner has a temperature of 140 ° C. dynamic elastic modulus (G _'140) is a 5 × 10 ² to ^{1 × 10 5 dN / m 2} , dynamic elastic modulus at a temperature of 170 ° C. (G' ratio of ₁₇₀₎ (G _'140 / G ' ₁₇₀ ) is 0.05 to 50, and in Soxhlet extraction of a toner using tetrahydrofuran (THF) as a solvent, the THF-insoluble content A of the binder resin component at 8 hours after the start of the extraction is 10 to 20% by mass. And the THF-insoluble content B of the binder resin component at 24 hours from the start of the extraction is 1 to 10% by mass,
The ratio (B / A) of the F-insoluble component A to the THF-insoluble component B is 0.
Using a toner that satisfies 1 to 0.8, as the heating and pressurizing and fixing means, the product hardness of the fixing roller and the pressurizing roller is set to 50 to 75 degrees by Asker C, The surface temperature was set to 160 ° C., and the pressing force between the fixing roller and the pressing roller was 392 to 588 N (4
0 to 60 kgf), a recording paper having a basis weight of 75 to 130 g / m ² is used as the recording material, and a toner carrying amount formed on the recording paper is 0.7 to 1.3 mg / cm 2.
^When the peripheral speed of the fixing roller is 100 to 130 mm / sec, a fixed image having a glossiness (60 degree gloss) of 15 to 30 is formed. Characteristic image forming method. 2. The image forming method according to claim 1, wherein a rubber hardness of a base layer of the fixing roller and the pressing roller is 5 to 50 degrees with Asker C. 3. The toner has a glass transition temperature of 55 to 7
2 ° C., and a number average molecular weight (Mn) of 1500 in a molecular weight distribution by gel permeation chromatography (GPC) of a tetrahydrofuran (THF) soluble portion.
The image forming method according to claim 1, wherein the image forming method has a weight average molecular weight (Mw) of 3000 to 200000 and a Mw / Mn of 2 to 20. 4. The image forming method according to claim 1, wherein the toner contains an organic metal compound in an amount of 0.1 to 10% by mass based on the mass of the toner. 5. A heat-pressing fixing means having a fixing layer having a base layer of a heat-resistant rubber, a surface layer of a fluororesin on the surface of the base layer, and a pressing roller which presses against the fixing roller, is formed by toner. In a fixing method of fixing an image on a recording material by heating and pressing to form a fixed image on the recording material, the toner is a toner having a binder resin, a toner particle having at least a colorant and a wax, and a toner having an external additive. Yes,
In the DSC endothermic curve of the wax, the temperature was 30-16.
The maximum endothermic peak in the range of 0 ° C. is 55 to 80 ° C., the half width of the maximum endothermic peak is 2 to 7 ° C., the binder resin component is mainly composed of a polyester resin, and the toner has a temperature of 140 ° C. dynamic elastic modulus (G _'140) is a 5 × 10 ² to ^{1 × 10 5 dN / m 2} , dynamic elastic modulus at a temperature of 170 ° C. (G' ratio of ₁₇₀₎ (G _'140 / G ' ₁₇₀ ) is 0.05 to 50, and in Soxhlet extraction of a toner using tetrahydrofuran (THF) as a solvent, the THF-insoluble content A of the binder resin component at 8 hours after the start of the extraction is 10 to 20% by mass. And the THF-insoluble content B of the binder resin component at 24 hours from the start of the extraction is 1 to 10% by mass.
The ratio (B / A) of the F-insoluble component A to the THF-insoluble component B is 0.
The toner that satisfies 1 to 0.8 is used. As the heating and pressurizing and fixing unit, the product hardness of the fixing roller and the pressing roller is set to 50 to 75 degrees by Asker C. Is set to 160 ° C., and the pressure contact force between the fixing roller and the pressure roller is set to 392 to 588 N (4
0 to 60 kgf), a recording paper having a basis weight of 75 to 130 g / m ² is used as the recording material, and a toner carrying amount formed on the recording paper is 0.7 to 1.3 mg / cm 2.
^When the peripheral speed of the fixing roller is 100 to 130 mm / sec, a fixed image having a glossiness (60 degree gloss) of 15 to 30 is formed. Characteristic fixing method. 6. The fixing method according to claim 5, wherein a rubber hardness of a base layer of the fixing roller and the pressing roller is 5 to 50 degrees by Asker C. 7. The toner has a glass transition temperature of 55 to 7
2 ° C., and a number average molecular weight (Mn) of 1500 in a molecular weight distribution by gel permeation chromatography (GPC) of a tetrahydrofuran (THF) soluble portion.
7. The fixing method according to claim 5, wherein the fixing method has a weight average molecular weight (Mw) of 3,000 to 200,000 and a Mw / Mn of 2 to 20. 8. The fixing method according to claim 5, wherein the toner contains an organic metal compound in an amount of 0.1 to 10% by mass based on the mass of the toner. 9. An image is formed on a recording material with a toner,
A fixing roller having a base layer of a heat-resistant rubber and a surface layer of a fluorine-based resin on the surface of the base layer, and a heat-pressing fixing unit having a pressing roller pressed against the fixing roller are used. The product hardness is set to 50 to 75 degrees by Asker C, the surface temperature of the fixing roller is set to 160 ° C., and the pressing force between the fixing roller and the pressure roller is set to 392 to
588 N (40 to 60 kgf), and a recording paper having a basis weight of 75 to 130 g / m ² was used as the recording material.
The amount of toner carried on the recording paper is 0.7 to 1.
A toner image of 3 mg / cm ² is heated and pressed and fixed on the recording material. When the peripheral speed of the fixing roller is 100 to 130 mm / sec, a fixed image having a glossiness (60 ° gloss) of 15 to 30 is formed. The toner is a toner having at least a binder resin, a colorant, and a toner particle having a wax, and a toner having an external additive. The toner has a temperature of 30 to 16 in a DSC endothermic curve of the wax.
The maximum endothermic peak in the range of 0 ° C. is 55 to 80 ° C., the half width of the maximum endothermic peak is 2 to 7 ° C., the binder resin component is mainly composed of a polyester resin, and the toner has a temperature of 140 ° C. dynamic elastic modulus (G _'140) is a 5 × 10 ² to ^{1 × 10 5 dN / m 2} , dynamic elastic modulus at a temperature of 170 ° C. (G' ratio of ₁₇₀₎ (G _'140 / G ' ₁₇₀ ) is 0.05 to 50, and in Soxhlet extraction of a toner using tetrahydrofuran (THF) as a solvent, the THF-insoluble content A of the binder resin component at 8 hours after the start of the extraction is 10 to 20% by mass. And the THF-insoluble content B of the binder resin component at 24 hours from the start of the extraction is 1 to 10% by mass.
The ratio (B / A) of the F-insoluble component A to the THF-insoluble component B is 0.
A toner characterized by satisfying 1 to 0.8. 10. The toner according to claim 9, wherein the rubber hardness of the base layer of the fixing roller and the pressure roller is 5 to 50 degrees with Asker C. 11. The toner has a glass transition temperature of 55 to 72 ° C., and has a number average molecular weight (Mn) of 150 in a molecular weight distribution by gel permeation chromatography (GPC) of a tetrahydrofuran (THF) soluble portion.
The toner according to claim 9, wherein the toner has a weight average molecular weight (Mw) of 3,000 to 200,000 and a Mw / Mn of 2 to 20. 12. 12. The toner according to claim 9, wherein the toner contains an organic metal compound in an amount of 0.1 to 10% by mass based on the mass of the toner.