JP3227397B2 - Image forming method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming method for heating and fixing a toner image formed on a recording material with toner, and forming an image on the recording material.

[0002]

2. Description of the Related Art Conventionally, in a general full-color image forming method, a photosensitive member of a photosensitive drum is uniformly charged, and first, image exposure is performed by a laser beam modulated by a magenta image signal of an original to form an image on the photosensitive drum. An electrostatic latent image is formed on the photosensitive drum, the magenta developing device develops the electrostatic latent image, a magenta toner image is formed on the photosensitive drum, and the developed magenta toner is conveyed by the transfer charger. The image is transferred onto a recording material that has been subjected to magenta image formation.

Next, the photosensitive drum after the above-mentioned development and transfer is neutralized by a neutralizing charger, cleaned, and then charged again by a primary charger. Formation of a cyan toner image, and transfer of the cyan toner image onto a recording material to which the magenta toner image has been transferred, and further, yellow,
In the same manner as for the black color, the four color toner images are transferred onto the recording material. Further, the recording material on which the four color toner images are formed is fixed by the action of heat and pressure by a fixing unit such as a fixing roller to form a full-color image.

[0004] In recent years, such image forming apparatuses have been used not only in office work copying machines for copying original documents, but also in printers as output devices of computers or personal copies for individuals. It is starting to be used. In addition to the field represented by such a laser beam printer, the development of plain paper fax using a basic engine is also rapidly developing.

[0005] Therefore, in the image forming apparatus as described above, smaller, lighter, faster, higher image quality, and higher reliability have been sought, and the machine is composed of simpler elements in various points. It is becoming like. As a result, the performance required of the toner has become higher, and if the performance of the toner is not improved, a better machine cannot be realized.

[0006] In recent years, demand for color copying has rapidly increased along with various copying needs, and even higher image quality and higher resolution are desired in order to copy original color images more faithfully. From these viewpoints, the toner used in the color image forming method needs to have good melting property and color mixing property when heat is applied, has a low softening point, and has a low melting temperature and a sharp melt property. A high toner is required. By using such a toner having a high sharp melt property, the color reproduction range of a copy can be widened, and a color copy faithful to the original image can be obtained.

However, such a color toner having a high sharp melt property generally has a high affinity with a fixing roller and tends to be easily offset to the fixing roller.
Particularly, in the case of a fixing unit in a color image forming apparatus, since a plurality of toner layers of magenta, cyan, yellow, and black are formed on a recording material, further offset occurs due to an increase in toner layer thickness. It tends to be easy.

Conventionally, in order to improve the releasability of the toner from the fixing roller, for example, the surface of the fixing roller is formed of a material having excellent releasability from the toner (for example, silicone rubber or fluorine resin). And, furthermore, in order to prevent the offset and the fatigue of the roller surface,
Coating with a thin film of a highly releasable liquid such as silicone oil or fluorine oil has been performed. This method
Although it is extremely effective in preventing toner offset, a device for supplying an anti-offset liquid is required, and the fixing device becomes complicated, and the applied oil is used between the layers constituting the fixing roller. This causes peeling, which results in a problem of shortening the life of the fixing roller.

On the other hand, in response to various needs of copying in recent years,
As the recording material, various papers, coated papers, plastic films, and the like are used. Above all, an overhead projector (OH
The need for an OHP sheet for utilizing P) has attracted attention. In particular, the OHP sheet, unlike paper, has a low oil absorption capacity, so that the oil used in the above method adheres to the surface of the recording material, and as a result, the resulting copied OHP sheet becomes sticky by applying oil. Inevitably, the quality of the image is degraded. In addition, silicone oil etc. evaporates due to heat and contaminates the inside of the machine.
There is also a possibility that a problem such as treatment of the recovered oil may occur.

Therefore, there is a great expectation for establishing a fixing system which does not require oil application at the time of fixing an image, which solves the above problems, and for developing a new toner for achieving the same.

Further, in the case of the above-described oil application fixing system, the roller surface may be roughened or the oil application may be uneven due to the durability of a large number of sheets. Along with this, if a conventional toner having a high sharp melt property having a high affinity with the fixing roller is used, the image surface is roughened even if the offset is not performed. As a result, as in the OHP apparatus, When observing or projecting a toner image on a screen with transmitted light, a decrease in transparency due to light scattering may be observed.

[0012]

SUMMARY OF THE INVENTION An object of the present invention is to provide an image forming method which solves the above problems.

That is, an object of the present invention is to provide a color image projected on an overhead projector (OHP) which is not durable, especially in a halftone portion where the image density is low, and is excellent in durability. An object of the present invention is to provide an image forming method capable of forming a color image or a full-color image having color tone reproducibility.

Further, another object of the present invention is to provide a heat and pressure fixing member to which no oil is applied, or a method in which the amount of oil to be applied is 0.1 to 0.1.
An object of the present invention is to provide a method for forming a color image without stickiness or a full-color image by using a heating and pressing fixing member coated with a releasing oil so as to have a density of 04 mg / sheet (A4 size) or less.

Still another object of the present invention is to provide an image forming method capable of forming a color or full-color image imaging sheet having excellent transparency and good quality.

[0016]

The above objects are achieved by the present invention described below.

That is, according to the present invention, a toner image formed by toner is heat-fixed on a laminate sheet having at least a base layer mainly composed of a heat-resistant resin and a surface coat layer mainly composed of a thermoplastic resin. In the image forming method for forming an image on the laminate sheet, the toner contains at least a binder resin, a colorant, and a substance having a low softening point, and has a storage elastic modulus (G′6) at a temperature of 60 ° C.
0) and the storage modulus (G′80) at a temperature of 80 ° C. (G′60 / G′80) are 80 or more,
Storage modulus (G'155) at 5 ° C and temperature 190 ° C
(G'155) to the storage modulus (G'190)
/ G'190) is 0.95 to 5.0, and the solubility parameter (SP-A) of the thermoplastic resin of the surface coat layer is
The absolute value (| (SP-A)-(SP-B) |) of the difference between the solubility parameter (SP-B) of the binder resin is 5 [J /
m ³ ] ^1/2 · 10 ⁻³ or less.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The present inventor has proposed a toner image formed by toner on a laminate sheet having at least a base layer mainly composed of a heat-resistant resin and a surface coat layer mainly composed of a thermoplastic resin. In the image forming method of forming an image on the laminate sheet by heating and fixing the toner, a study was conducted on the transparency of the imaging sheet on which the image was formed on the laminate sheet and the projected image characteristics by OHP. By controlling the difference between the solubility parameter of the thermoplastic resin in the surface coat layer of the laminate sheet and the solubility parameter of the binder resin of the toner, the projected color image becomes durable when used for OHP. The color space area can be maintained without dulling, and the transparency is excellent. It has been found that it is possible to form an imaging sheet of good color image or full-color image quality.

Regarding the definition of the viscoelasticity of the toner, see
Japanese Unexamined Patent Application Publication Nos. 128071, Hei 4-353866, and Hei 6-5904 exist, but are not satisfactory.

The toner used in the present invention has a temperature of 60 ° C.
(G'60 / G'80) of the storage elastic modulus (G'60) at 80 ° C. to the storage elastic modulus (G'80) at a temperature of 80 ° C.
Is 80 or more, preferably 100 to 400, and more preferably 150 to 300. The storage elastic modulus (G′155) at a temperature of 155 ° C. and the temperature 1
The ratio (G ′) to the storage elastic modulus at 90 ° C. (G′190)
155 / G′190) is 0.95 to 5.0, preferably 1.0 to 5.0, and more preferably 1.1 to 4.8.

The storage elastic modulus (G'60) at a temperature of 60 ° C. and the storage elastic modulus (G'8) at a temperature of 80 ° C.
The ratio (G'60 / G'80) to (0) indicates the storage elastic physical properties of the binder resin in the process of changing from a glassy state or a glass transition state that is hardly deformed even when an external force is applied to a deformable state. . When the ratio (G'60 / G'80) is 80 or more, it means that the viscoelasticity of the toner sharply decreases in the process of being heated from a temperature of 60 ° C. to a temperature of 80 ° C. Thereby, low-temperature fixing can be performed favorably in the heating and pressing fixing step.

Therefore, the toner layer formed on the laminate sheet is easily melted and deformed quickly at the time of fixing, the surface of the fixed image is smoothed, and the color mixing between the color toners is improved.

The storage elastic modulus (G'60) at a temperature of 60 ° C. and the storage elastic modulus (G'8) at a temperature of 80 ° C.
When the ratio (G'60 / G'80) to (0) is less than 80, no sharp viscoelastic properties of the toner are observed in the process of heating from 60 ° C to 80 ° C, and the surface of the fixed image Since the smoothing is impaired and the color mixing between the color toners is impaired, the transparency and color reproducibility of the OHP projected image become difficult.

In the present invention, the storage modulus (G'60) of the toner at a temperature of 60 ° C. is preferably 1 × 10
^{8 to} 1 × 10 ¹⁰ dyn / cm ² , more preferably 2
× 10 ^{8 to} 9 × 10 ⁹ dyn / cm ² , more preferably 2.5 × 10 ^{8 to} 7 × 10 ⁹ .

If the storage modulus (G'60) of the toner at a temperature of 60 ° C. is less than 1 × 10 ⁸ dyn / cm ² , the toner is susceptible to pressure and rubbing force in the developing device, and adversely affects durability development. When it exceeds 1 × 10 ¹⁰ dyn / cm ² , it is difficult to obtain a sharp melt toner,
P transparency is not good.

In the present invention, the storage elastic modulus (G'80) at a temperature of 80 ° C. of the toner is preferably 1 × 10
^{5 to} 1 × 10 ⁷ dyn / cm ² , more preferably 2
It is preferably from 10 ^{5 to} 9 × 10 ⁶ dyn / cm ² , more preferably from 3 × 10 ^{5 to} 8 × 10 ⁶ dyn / cm ² .

When the storage modulus (G'80) at a temperature of 80 ° C. of the toner is less than 1 × 10 ⁵ dyn / cm ² , the heat resistance is weak and the blocking property is reduced.
When it exceeds 1 × 10 ⁷ dyn / cm ² , image smoothness after fixing cannot be obtained, and OHP transparency is not good.

The ratio (G'155 / G'190) of the storage elastic modulus (G'155) at a temperature of 155 ° C. to the storage elastic modulus (G'190) at a temperature of 190 ° C. is 0.95 to 5.0. As a result, a moderate elasticity term is obtained in the toner, the influence of the deterioration of the fixing roller surface due to durability and the like is hardly affected, and the change in the surface property of the fixed image can be reduced. A color projection image with less dullness of the projected color image due to durability and little deterioration in transparency can be obtained.

Further, a change in the color space area of the projected color image due to durability is small, and a color projected image with little color space deterioration can be obtained.

When the ratio (G′155 / G′190) of the storage elastic modulus (G′155) at a temperature of 155 ° C. to the storage elasticity (G′190) at a temperature of 190 ° C. is less than 0.95, Is too large in cross-linking of the resin, resulting in impaired color mixing properties. If it exceeds 5.0, it is apt to be affected by deterioration of the fixing roller surface due to durability and the like, since it has rich sharp melt properties. As a result, the transparency of the OHP projected image may be reduced in durability.

In the present invention, the storage elastic modulus (G'155) at a temperature of 155 ° C. of the toner is preferably 8.
5 × 10 ^{3 to} 9 × 10 ⁴ dyn / cm ² , more preferably 9 × 10 ^{3 to} 8 × 10 ⁴ dyn / cm ² , still more preferably 9 × 10 ^{3 to} 7 × 10 ⁴ dyn / cm ^2.
Good to be.

If the storage elastic modulus (G'155) at a temperature of 155 ° C. of the toner is less than 8.5 × 10 ³ dyn / cm ² , the sharp melt property of the toner is too large, so that the OHP transparency due to durability is high. Is difficult to maintain, and 9 ×
If it exceeds 10 ⁴ dyn / cm ² , the elasticity term of the toner is weak, and OHP transparency, particularly the dullness of the halftone portion is large.

In the present invention, the storage elastic modulus (G′190) at a temperature of 190 ° C. of the toner is preferably 8 ×.
10 ^{2 to} 8.4 × 10 ³ dyn / cm ² , more preferably 1 × 10 ^{3 to} 8.2 × 10 ³ dyn / cm ² ,
Even more preferably, 1.5 × 10 ^{3 to} 8 × 10 ³
dyn / cm ² is preferable.

If the storage elastic modulus (G'190) at a temperature of 190 ° C. of the toner is less than 8 × 10 ² dyn / cm ² , the high-temperature offset resistance in fixing is weak, and the influence of the roller surface deteriorated due to durability is reduced. Easy to receive, OHP
The effect on transparency is large, and 8.4 × 10 ³ dyn / cm
If it exceeds ² , the elasticity of the toner is large, so that the smoothness of the surface of the fixed image is insufficient, and the OHP transparency, particularly the dullness of the halftone portion, becomes large.

Further, in the toner used in the present invention, in the loss elastic modulus curve, the temperature range of 40 to 70 ° C. is 1 × 10 ⁹ (dyn / cm ² ) or more [more preferably, 1 × 10 ^{9 to} 1 × 10 ¹⁰ (dyn / cm ² )]
It is preferable in order to improve blocking resistance and a large number of sheets of the toner having the maximum value (G _"max).
More preferably, the maximum value (G ″ _max ) of the loss modulus at a temperature of 40 to 70 ° C. of the toner and a temperature of 40 ° C. of the toner
(G ″ _max / G ″) with the loss modulus (G ″ ₄₀ )
₄₀ ) is preferably 1.50 or more, more preferably 1.
52 to 5.00, more preferably 1.55 to 4.
00 is better.

Temperature 40 in loss elasticity curve of toner
The maximum value (G ″ _max ) in the region from to 70 ° C. is 1 × 10 ⁹
If it is less than (dyn / cm ² ), blocking tends to occur due to heat generated by rubbing in the developing device.

The maximum value (G ″ _max ) of the loss elastic modulus at a toner temperature of 40 to 70 ° C. and the toner temperature 40
Ratio to the loss modulus (G ″ ₄₀ ) at (° C.) (G ″ _max /
When G ″ ₄₀ ) is less than 1.5, the effect on the storage elastic modulus is large, and the above storage elastic modulus (G ′) at a temperature of 60 ° C.
60) and temperature 80. Storage elastic modulus at ℃ (G'80)
(G'60 / G'80) is reduced, resulting in a dull image with a halftone portion in the projected image.

Measurement of Rheological Properties of Toner Using a viscoelasticity measuring device (rheometer) RDA-II type (manufactured by Rheometrics) under the following conditions, from 30 to 2
The storage elastic modulus G 'and the intersection (Tc) of the storage elastic modulus (G') and the loss elastic modulus (G ") in a temperature range of 00 ° C. are measured. Uses a parallel plate having a diameter of 7.9 mm and a low elastic modulus of 25 mm when the elastic modulus is low Measurement sample: After heating and melting the toner, the diameter is about 8 mm.
Cylindrical sample with height of 1.5 to 5mm, or diameter of about 25m
m and a disk-shaped sample with a height of 1.5 to 3 mm are 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 25 ° C to 210 ° C at a rate of 2 ° C per minute.

Further, in the present invention, the absolute value of the difference between the solubility parameter (SP-A) of the thermoplastic resin of the surface coat layer of the laminate sheet (SP-A) and the solubility parameter (SP-B) of the binder resin of the toner (| (SP-A)-(S
P-B) |) is not more than 5 [J / m ³ ] ¹ / 2.10 ^-3 (0
5 [J / m ³ ] ^1/2 · 10 ^-3 ), preferably ³ [J / m ³ ]
³ ] ¹ / 2.10 ^-3 or less (0-3 [J / m ³ ] ¹ / 2.10
^-3 ), more preferably 1.5 [J / m ³ ] ^1/2 · 10
^-3 or less (0 to 1.5 [J / m ³ ] ¹ / 2.10 ^-3 ).

The absolute value of the difference between the solubility parameter (SP-A) of the thermoplastic resin of the surface coat layer of the laminate sheet (SP-A) and the solubility parameter (SP-B) of the binder resin of the toner (| (SP-A)-( SP-B) |) is 5 [J / m
³ ] When the ^ratio is not more than ^1/2 · 10 ⁻³ , the compatibility between the resins of the surface coat layer and the toner layer is improved when the toner image is fixed on the laminate sheet by the heating and pressing member, and the OHP When an image formed on a laminate sheet is projected on a screen with transmitted light using the method described above, light scattering is reduced, and a color projection image having excellent transparency and high quality is obtained.

The absolute value of the difference between the solubility parameter (SP-A) of the thermoplastic resin of the surface coat layer of the laminate sheet (SP-A) and the solubility parameter (SP-B) of the binder resin of the toner (| (SP-A)-( SP-B) |) is 5.0 [J /
m ³ ] ^1/2 · 10 ^-3 , the compatibility between the thermoplastic resin of the surface coat layer and the toner at the fixing temperature of the binder resin is poor. When an image formed on a laminate film is projected on a screen by the method described above, irregular reflection of light increases, and the transparency of a color projection image decreases.

In the present invention, the solubility parameter (SP- B ) of the binder resin of the toner is preferably 12 to 32 [J / m ³ ] ^1/2 · 10 ^-3 , more preferably 14 [J / m ³ ] ^1/2 · 10 ^-3 .
To 30 [J / m ³ ] ^1/2 · 10 ^-3 .

When the solubility parameter (SP- B ) of the binder resin of the toner is less than 12 [J / m ³ ] ^1/2 · 10 ^-3 , the polarity of the resin is weak, and the toner charging ability by a durability test is determined. Decreased to 32 [J / m ³ ] ¹ / 2.10
If it exceeds ^-3 , the dispersibility of the colorant will be reduced.

In the present invention, the solubility parameter of the thermoplastic resin (SP-
A ) is preferably from 12 to 32 [J / m ³ ] ^1/2
10 ^-3 , more preferably 14 to 30 [J / m ³ ] ^1/2
・ It is good to be 10 ^-3 .

The solubility parameter (SP- A ) of the thermoplastic resin in the surface coat layer of the laminate sheet is 12 [J /
When m ³ ] ^1/2 · 10 ^{-3 is} less, the polarity of the resin is weak, and the toner charging ability in a durability test is reduced, and 32 [J / m ³ ] ^1/2 · 10 ^-3 is reduced. If it exceeds,
It is difficult to uniformly coat the surface with the antistatic agent, resulting in non-uniform surface resistance.

The solubility parameter of the thermoplastic resin (SP
Value) is a polymer handbook

[0047]

[Outside 1] by John Wiley & Sons. ln
c. Iv), pages 349 to 359, and the solubility parameter of the resin.

Further, in the toner used in the present invention, the low softening point substance is preferably 1 to 40 parts by weight, more preferably 5 to 40 parts by weight, and still more preferably 10 to 40 parts by weight, based on 100 parts by weight of the binder resin. More than 35 parts by weight, which is more than the usual toner for fixing under heat and pressure, it is preferable that the release oil is not applied or the amount of the release oil applied is 0.04 mg / sheet (A4) or less. Certain heating and pressing members allow the toner image to be fixed on the laminate sheet.

When the content of the low softening point substance contained in the toner is less than 1 part by weight, the release oil is not applied, or the application amount of the release oil is 0.04 mg / sheet (A4 It is difficult to fix without offset by the heat and pressure fixing member of the following size.
If the amount exceeds the weight part, the transparency of the projected image by the OHP is likely to be reduced.

In the present invention, the binder resin of the toner has a toluene-soluble component and a toluene-insoluble component, and the toluene-insoluble component is preferably 0.1% based on the weight of the binder resin.
To 30% by weight, more preferably 0.5 to 25% by weight
Good to be.

The binder resin of the toner has a toluene insoluble content of 0.1.
When the amount is less than 1% by weight, the ratio (G'155 / G'19) of the storage elastic modulus (G'155) at a temperature of 155 ° C. to the storage elastic modulus (G'190) at a temperature of 190 ° C.
0) is difficult to be 0.95 or more, and 30
If the amount exceeds the weight percent, the ratio (G'155 / G'19) of the storage elastic modulus (G'155) at a temperature of 155 ° C. to the storage elastic modulus (G'190) at a temperature of 190 ° C.
It is difficult to make 0) 5.0 or less.

In the present invention, the binder resin for the toner includes polystyrene; a styrene-substituted homopolymer such as poly-p-chlorostyrene and polyvinyltoluene; a styrene-p-chlorostyrene copolymer, and styrene-vinyltoluene. Copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene -Vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, etc. Styrene-based copolymer; Le resin, methacrylic resin, polyvinyl acetate, silicone resins, polyester resins, polyamide resins, furan resins, epoxy resins, xylene resins.

These resins are used alone or in combination. As a main component of the binder resin, a styrene copolymer, which is a copolymer of styrene and another vinyl monomer, is preferable in terms of developability and fixability.

As comonomers for the styrene monomer of the styrene copolymer, acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, methacrylic Acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, methacrylonitrile, monocarboxylic acid having a double bond such as acrylamide or a substituent thereof; maleic acid, butyl maleate, methyl maleate, A dicarboxylic acid having a double bond such as dimethyl maleate and a substituted product thereof; a vinyl ester such as vinyl chloride, vinyl acetate and vinyl benzoate; an ethylene olefin such as ethylene, propylene and butylene; Sulfonyl methyl ketone, such as vinyl vinyl hexyl ketone, vinyl methyl ether, vinyl ethyl ether, such as vinyl ether vinyl isobutyl ether. These vinyl monomers are used alone or in combination of two or more.

The styrene copolymer is preferably cross-linked with a cross-linking agent such as divinylbenzene in order to widen the fixing temperature range of the toner and improve the offset resistance.

As the crosslinking agent, a compound having two or more polymerizable double bonds is used. For example, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; carboxylic acid esters having two double bonds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol dimethacrylate; divinylaniline; Divinyl ether,
Divinyl compounds such as divinyl sulfide and divinyl sulfone; and compounds having three or more vinyl groups. These are used alone or as a mixture.

When the binder resin is mainly composed of a crosslinked styrene copolymer, the binder resin has a molecular weight of 3,000 in the molecular weight distribution by gel permeation chromatography (GPC) of the THF-soluble portion of the binder resin. It is preferable to have a main peak in a region of from 50,000 to 50,000 and a subpeak or shoulder in a region of a molecular weight of 100,000 or more. More preferably, it is preferable to have two or more subpeaks, two or more shoulders or two or more subpeaks or two or more subpeaks and shoulders in a region having a molecular weight of 100,000 or more. further,
As described above, the binder resin containing a styrene copolymer as a main component preferably contains 0.1 to 30% by weight (more preferably, 1 to 15% by weight) of a toluene-insoluble component.

The term "toluene-insoluble content" refers to the polymerization ratio of the ultra-high molecular weight polymer component (substantially crosslinked polymer) insoluble in the toluene solvent in the resin composition in the toner. The toluene-insoluble matter is defined by a value measured as follows.

0.5 to 1.0 g of the toner sample is weighed (W ₁ g), and the filter paper (for example, No. 86 manufactured by Toyo Roshi Kaisha, Ltd.) is used.
R), subjected to a Soxhlet extractor, extracted with 100 to 200 ml of toluene as a solvent for 6 hours, evaporated the soluble components extracted with the toluene solvent, dried under vacuum at 100 ° C. for several hours, and dissolved in toluene. The resin component is weighed (W ₂ g). The weight of components other than the resin component such as the pigment and wax in the toner is defined as (W ₃ g). The toluene-insoluble content is obtained from the following equation.

[0060]

[Outside 2]

When the binder resin is a polyester resin, the molecular weight distribution of the toluene-soluble component by GPC is preferably in the range of 3,000 to 50,000, more preferably
At least one peak exists in the region of molecular weight of 5,000 to 30,000, and a binder resin having a molecular weight of 100,000 or less is preferably 60 to 100% by weight, more preferably 65 to 95%. preferable.

If there is no peak in the molecular weight region of 3,000 to 50,000 and there is a peak in the molecular weight region of less than 3,000, the blocking resistance at high temperatures is weak, and this adversely affects the developing characteristics.

When there is no peak in the region having a molecular weight of 3,000 to 50,000 and there is a peak in the region having a molecular weight of more than 50,000, the fixability in a low temperature portion tends to be improved.

When the content of the component having a molecular weight of 100,000 or less is less than 60% by weight, the OHP transparency is deteriorated due to the large amount of the high molecular weight component.

It is also preferable to use a mixture of a styrene copolymer and a polyester resin as the binder resin. For example, a combination of a cross-linked styrene copolymer and a non-cross-linked polyester resin, and a combination of a cross-linked styrene copolymer and a cross-linked polyester resin are preferable in terms of toner fixing properties, offset resistance, and color mixing.

The polyester resin has excellent fixability and transparency, and is suitable for a color toner requiring good color mixing. In particular,

[0067]

[Outside 3] (Wherein, R ₁ and R _{2 each} represent an ethylene or propylene group, x and y each represent an integer of 1 or more, and x +
The average value of y is 2-10. A) a bisphenol derivative or a substituted product thereof as a diol component;
Carboxylic acid component comprising a carboxylic acid having a valency or higher or an acid anhydride thereof or a lower alkyl ester thereof (for example, fumaric acid, maleic acid, maleic anhydride, phthalic acid, terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid, etc.) )) Is preferable.

Further, the polyester resin preferably has an acid value of 1 to 35 mgKOH / g, more preferably 1 to 35 mgKOH / g.
To 20 mgKOH / g, more preferably 3 to 15 mgKOH / g.
mgKOH / g, and the hydroxyl value is preferably
2 to 45 mgKOH / g, more preferably 3 to 4
0 mgKOH / g, more preferably 4 to 30 mg
Those having KOH / g are preferred from the viewpoint of environmental stability of the charging characteristics of the toner.

The acid value of the polyester resin is 1 mg KOH /
When the value is less than 2 g or less than 2 mgKOH / g, the toner has a low charge-imparting ability and generates a lot of fog in a high-temperature and high-humidity environment. Further, the acid value of the polyester resin exceeds 35 mgKOH / g or the hydroxyl value is 45 mgKOH / g.
When it exceeds mgKOH / g, the charge is increased in a low-temperature and low-humidity environment, and the image density is significantly reduced.

The acid value and hydroxyl value of the polyester resin are as follows:
It is measured by the following measuring method.

[Acid Value] The number of mg of potassium hydroxide required to neutralize free fatty acids, resin acids and the like contained in 1 g of a sample is called an acid value, and the test is carried out as follows.

(1) Reagent (a) Solvent Ethyl ether-ethyl alcohol mixed liquid (1 + 1 or 2 + 1) or benzene-ethyl alcohol mixed liquid (1 + 1 or 2 + 1), and these solutions were prepared using phenolphthalein as an indicator immediately before use. / 1
0 Neutralize with potassium hydroxide ethyl alcohol solution.

(B) Phenolphthalein solution 1 g of phenolphthalein was added to ethyl alcohol (95 v / v).
%) Dissolve in 100 ml.

(C) N / 10 potassium hydroxide-ethyl alcohol solution 7.0 g of potassium hydroxide was dissolved in as little water as possible, and ethyl alcohol (95 v / v%) was added to make 1 liter. I do. The orientation is JIS
K 8006 (basic matter concerning titration during reagent content test).

(2) Procedure Correctly weigh 1 to 20 g of a sample, add 100 ml of a solvent and a few drops of a phenolphthalein solution as an indicator, and shake thoroughly until the sample is completely dissolved. In the case of a solid sample, dissolve by heating on a water bath. After cooling, the mixture is titrated with an N / 10 potassium hydroxide ethyl alcohol solution, and the end point of neutralization is defined as the point at which the indicator continues to be reddish for 30 seconds.

(3) Calculation formula The acid value is calculated by the following formula.

[0077]

[Outside 4] Where A: acid value B: amount of N / 10 potassium hydroxide ethyl alcohol solution used (ml) f: factor of N / 10 potassium hydroxide ethyl alcohol solution S: sample (g)

[Hydroxyl value] When 1 g of a sample is acetylated by a specified method, the number of mg of potassium hydroxide required to neutralize acetic acid bound to a hydroxyl group is called a hydroxyl value, and the following reagent, operation and calculation formula Perform the test by

(1) Reagent (a) Acetylation reagent 25 g of acetic anhydride was put into a 100 ml measuring flask, and pyridine was added to make a total amount of 100 ml.
And shake thoroughly.

The acetylating reagent is kept away from moisture, carbon dioxide and acid vapors, and is stored in a brown bottle.

(B) Phenolphthalein solution 1 g of phenolphthalein was added to ethyl alcohol (95 v / v).
%) Dissolve in 100 ml.

(C) N / 2 Potassium Hydroxide-Ethyl Alcohol Solution 35 g of potassium hydroxide is dissolved in as little water as possible, and ethyl alcohol (95 v / v%) is added to make 1 liter. . The orientation is JIS
K 8006.

(2) Procedure 0.5 to 2.0 g of a sample was weighed correctly in a round bottom flask, and the acetylation reagent 5
Add ml correctly. Place a small funnel over the mouth of the flask and heat the bottom about 1 cm in a glycerin bath at 95-100 ° C. At this time, in order to prevent the temperature of the neck of the flask from rising due to the heat of the bath, a cardboard disc with a round hole is placed over the base of the neck of the flask. After 1 hour, the flask is taken out of the bath, allowed to cool, 1 ml of water is added from the funnel and shaken to decompose acetic anhydride. In order to further complete the decomposition, the flask was again heated in a glycerin bath for 10 minutes, allowed to cool, and then the funnel and the wall of the flask were washed with 5 ml of ethyl alcohol, and N / 2 potassium hydroxide ethyl alcohol was added using a phenolphthalein solution as an indicator. Titrate with solution.

A blank test is performed in parallel with the main test.

(3) Calculation Formula The hydroxyl value is calculated by the following formula.

[0086]

[Outside 5] A: hydroxyl value B: amount of N / 2 potassium hydroxide ethyl alcohol solution used in blank test (ml) C: amount of N / 2 potassium hydroxide ethyl alcohol solution used in main test (ml) f: N / Factor of potassium dihydroxide ethyl alcohol solution S: Sample (g) D: Acid value

In the present invention, the low softening point substance used in the toner for developing an electrostatic image includes polymethylene wax such as paraffin wax, polyolefin wax, microcrystalline wax, Fischer-Tropsch wax, amide wax, higher fatty acid, Derivatives such as long-chain alcohols, ester waxes, and their graft compounds and block compounds are mentioned, and those having a sharp endothermic peak in a DSC endothermic curve from which low molecular weight components have been removed are preferred.

The wax preferably used is a linear alkyl alcohol having 15 to 100 carbon atoms,
Examples include linear fatty acids, linear acid amides, linear esters, and montan derivatives. It is also preferable that impurities such as liquid fatty acids are previously removed from these waxes.

Further, preferably used wax is
Low-molecular-weight alkylene polymer obtained by radical polymerization of alkylene under high pressure or Ziegler contact under low-pressure or other catalyst; alkylene polymer obtained by thermally decomposing high-molecular alkylene polymer; A product obtained by separating and purifying a low-molecular-weight alkylene polymer produced as a by-product; from a distillation residue of a hydrocarbon polymer obtained by the Age method from a synthesis gas composed of carbon monoxide and hydrogen, or from a distillation residue of the obtained hydrocarbon polymer as hydrogen. A polymethylene wax obtained by extracting and separating a specific component from a synthetic hydrocarbon obtained by addition is mentioned. An antioxidant may be added to these waxes.

The low softening point substance used in the present invention is DS
The C endothermic curve preferably has an endothermic main peak in a temperature range of preferably 40 to 90 ° C, more preferably 45 to 85 ° C. Further, the endothermic main peak is preferably a sharp-melting, low softening point substance having a half width of preferably within 10 ° C, more preferably within 5 ° C. In particular, an ester wax whose low softening point substance is mainly an ester compound of a long-chain alkyl alcohol having 15 to 45 carbon atoms and a long-chain alkyl carboxylic acid having 15 to 45 carbon atoms is preferable.

In the DSC endothermic curve of the low softening point substance,
When the endothermic main peak exists in a temperature range of less than 40 ° C., the strength of the toner particles is reduced, and the development characteristics during a durability test are likely to be reduced. Also, the blocking resistance is weak.

[0092] In the case where the temperature is higher than 90 ° C, the fixing start point at a low temperature becomes higher. Further, for example, when used in a polymerization method toner, the granulation property deteriorates.

In the present invention, as the endothermic main peak of the low softening point substance, a DSC measurement is performed in accordance with ASTM D3418-8, and the maximum endothermic peak value in the measured DSC endothermic curve is used.

In the present invention, particularly preferred low softening point substances have the following structures.

[0095]

[Outside 6] (Wherein, R ₁ and R ₂ represent an organic group having 1 to 40 carbon atoms, the difference in the number of carbon atoms between R ₁ and R ₂ is 3 or more, and a and b
Represents an integer of 0 to 4, a + b is 4, c and d each represent an integer of 0 to 25, and m and n do not become 0 at the same time. )

[0096]

[Outside 7] (Wherein, R ₃ and R ₄ represent an organic group having 1 to 40 carbon atoms, the difference in the number of carbon atoms between R ₃ and R ₄ is 3 or more, and R ₅ is
A hydrogen atom or an organic group having 1 or more carbon atoms, e and f
Represents an integer of 0 to 3, e + f represents an integer of 1 to _3, and when e + f is 2, one of R ₃ and R ₄ is
It represents an organic group having 1 or more carbon atoms, g and h each represent an integer of 0 to 25, g and h do not become 0 at the same time, i represents an integer of 1 to 3, and e + f + i represents 4 is there.

[0097]

[Outside 8] (Wherein, R ₆ and R ₈ represents an organic group having from 6 to 32 carbon atoms, R ₆ and R ₈ are same and or different, R ₇
Represents an organic group having 1 to 20 carbon atoms. )

[0098]

[Outside 9] (Wherein, R ₉ and R ₁₁ represents an organic group having from 6 to 32 carbon atoms, R ₉ and R ₁₁ are same and or different, R ₁₀
Is

[0099]

[Outside 10] (Where j and k represent an integer of 1 to 10, and 1 represents 1
Represents an integer of up to 20. ))

[0100]

[Outside 11] (Wherein, R ₁₁ represents an organic group having 1 to 40 carbon atoms;
Represents an integer of 0 to 4, n represents an integer of 1 to 4,
m + n is 4, o and p each represent an integer of 0 to 25, and o and p do not become 0 at the same time. )

In the above structural formula, specific examples of the organic group include an alkyl group, an acyl group, an acyloxy group, an aryl group, an alkoxyl group and an aldoketene group.

As the black colorant used in the present invention, carbon black, a magnetic substance, and those toned to black using the following yellow colorant, magenta colorant and cyan colorant are used.

Examples of the yellow colorant include condensed azo compounds, isoindolinone compounds, anthraquinone compounds,
A compound represented by an azo metal complex, a methine compound or an allylamide compound is used. Specifically, C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 6
2, 74, 83, 93, 94, 95, 97, 109, 1
10, 111, 120, 127, 128, 129, 14
7, 168, 174, 176, 180, 181, 191
Etc. are preferably used.

As the magenta coloring agent, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindico compounds and berylen compounds are used. Specifically, C.I.
I. Pigment Red 2, 3, 5, 6, 7, 23, 4
8: 2, 48: 3, 48: 4, 57: 1, 81: 1, 1
44, 146, 166, 169, 177, 184, 18
5, 202, 206, 220, 221, 254 are particularly preferred.

As the cyan coloring agent, copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds and the like can be used. Specifically, C.I. I.
Pigment Blue 1, 7, 15, 15: 1, 15: 2,
15: 3, 15: 4, 60, 62, 66, etc. can be particularly preferably used.

These black colorant, yellow colorant, magenta colorant and cyan colorant can be used alone or as a mixture or in the form of a solid solution. In the present invention, the colorant is selected from the viewpoints of hue angle, saturation, lightness, weather resistance, transparency on an OHP film, and dispersibility in toner particles. In the present invention, the content of carbon black, yellow colorant, magenta colorant and cyan colorant as the black colorant in the toner is preferably 1 to 20 parts by weight per 100 parts by weight of the binder resin.

When a magnetic material is used as the black colorant, the content of the colorant in the toner is different from other colorants, and is preferably 40 to 150 parts by weight per 100 parts by weight of the binder resin.

As the charge control agent used to stabilize the triboelectric charging characteristics of the toner, a charge control agent that is colorless, has a high toner charging speed, and can stably maintain a constant charge amount is preferable. Further, in the case of using a polymerized toner production method in which a toner composition is formed by polymerizing a monomer composition containing a polymerizable monomer in an aqueous medium as a method for producing toner particles, there is no polymerization inhibitory effect, Charge control agents that are free of solubilizers in the medium are particularly preferred. Specifically, examples of the negative control agent include salicylic acid, alkyl salicylic acid, dialkyl salicylic acid, naphthoic acid, a metal compound of dicarboxylic acid, sulfonic acid, a polymer compound having a carboxylic acid in a side chain, a boron compound, and a urea compound. , Silicon compounds, carrick's arenes, etc., and the quaternary ammonium salt, a polymer compound having the quaternary ammonium salt in the side chain, a guanidine compound, an imidazole compound, etc. are preferably used as the positive control agent. . The content of these charge control agents in the toner is as follows.
0.5 to 10 parts by weight per 100 parts by weight is preferred. However, in the present invention, the addition of the charge control agent to the toner is not essential, and in the case of using the two-component developing method, the case of using the non-magnetic one-component blade coating developing method utilizing frictional charging with the carrier. In the above, toner particles need not necessarily contain a charge control agent by positively utilizing frictional charging with the blade member or the sleeve member.

As one of the methods for producing the toner for developing an electrostatic image of the present invention, a binder resin, a colorant, a low softening point substance, and a charge control agent and other internal additives as optional components are added. After kneading using a pressure kneader, extruder, or media disperser to uniformly disperse the mixture, the mixture is crushed mechanically or under a jet stream to a target to pulverize to a desired toner particle size, and further classified. There is a toner production method by a pulverization method for producing a toner particle by sharpening the particle size distribution through the above. In addition to this,
6-10231, JP-A-59-53856, and JP-A-59-61842, in which a monomer composition is polymerized in an aqueous medium to form toner particles. A method for producing toner particles using
JP-A-62-106473 and JP-A-63-186.
No. 253, an interface association method for aggregating at least one kind of fine particles to obtain toner particles having a desired particle size; the monomer is soluble and the monomer is polymerized. A dispersion polymerization method in which the produced polymer is obtained by polymerizing the monomer composition in an insoluble organic solvent to form toner particles; a toner particle is produced by polymerizing the monomer composition in the presence of a water-soluble polymerization initiator. And the production of toner particles by an emulsion polymerization method typified by a soap-free polymerization method.

When the toner particles used in the present invention are produced by a pulverization method, a high molecular weight binder resin and a low molecular weight binder resin are used by blending, and if necessary, the type of low softening point substance may be used. It is preferable to control the viscoelastic properties of the toner by changing the amount and the amount of addition. In particular, it is possible to use a binder resin having a hydroxyl group or a carboxyl group as a binder resin and to add an organometallic compound or a derivative thereof at the time of kneading to cause metal crosslinking, thereby producing a THF-insoluble substance. When the toner particles used in the present invention are produced by a polymerization method, an appropriate crosslinking agent and / or a resin component are added to the polymerizable monomer, and a low softening point substance and a polymerization initiator are further added and dissolved. It is preferable to granulate the obtained monomer composition in an aqueous medium, further carry out a polymerization reaction, encapsulate a low softening point substance in the toner particles with the polymerized polymer, and form a sea-island structure. .

A substance having a low softening point is encapsulated with a binder resin,
As a method of constructing the sea-island structure, the polarity of the substance having a low softening point is set to be smaller than that of the main monomer in an aqueous medium, and a small amount of a resin or monomer having a large polarity is added to the polymerizable unit. A method of obtaining toner particles having a core-shell structure in which a low softening point substance is coated with a binder resin by polymerizing the monomer is exemplified. The toner particles having the core-shell structure may be directly used as the toner particles, or the toner particles having the sea-island structure may be generated by aggregating and assembling the ultrafine toner particles to a desired particle size. . In constructing a sea-island structure using these methods, at least one of the low softening point substances is:
The melting point (the maximum endothermic peak temperature in the DSC endothermic curve) is preferably lower than the polymerization temperature.

By encapsulating the low softening point substance in the toner particles, even if the toner particles contain a relatively large amount of the low softening point substance, a decrease in the blocking resistance of the toner can be suppressed. By using a low softening point substance having a sharp melt property, toner particles having strong mechanical impact and capable of producing toner particles having a low-temperature fixability and a good mixing property at the time of heat and pressure fixing can be produced.

In the present invention, a vinyl polymerizable monomer capable of undergoing radical polymerization is used as the polymerizable monomer used for producing a toner by a polymerization method. As the vinyl polymerizable monomer, a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used. As the monofunctional polymerizable monomer, styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimerstyrene, pn-butylstyrene , P-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p- Styrene derivatives such as phenylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate,
n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl Acrylate, diethyl phosphate ethyl acrylate,
Acrylic polymerizable monomers such as dibutyl phosphate ethyl acrylate and 2-benzoyloxyethyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert- Methacrylic polymerizable monomers such as butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, diethyl phosphate ethyl methacrylate, dibutyl phosphate ethyl methacrylate; methylene Aliphatic monocarboxylic acid esters; vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, benzoate Vinyl acids, such as vinyl esters of vinyl formate, vinyl methyl ether, vinyl ethyl ether, vinyl propionate blanking dust ethers; vinyl methyl ketone, vinyl hexyl ketone, and such vinyl vinyl isopropyl ketone.

Examples of the polyfunctional polymerizable monomer include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, and 1,6.
-Hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, 2,2'-bis [4- (acryloxydiethoxy) phenyl] propane, trimethylolpropane triacrylate, tetramethylolmethane Tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate,
1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2'-bis [4- (methacryloxydiethoxy) phenyl] propane, 2,
2'-bis [4- (methacryloxypolyethoxy) phenyl] propane, trimethylolpropane trimethacrylate, tetramethylolmethanetetramethacrylate, divinylbenzene, divinylnaphthalene, divinylether and the like.

In the present invention, the above-mentioned monofunctional polymerizable monomers may be used alone or in combination of two or more.
The monofunctional polymerizable monomer and the polyfunctional polymerizable monomer described above are used in combination. Polyfunctional polymerizable monomers can also be used as crosslinking agents.

As the polymerization initiator used in the polymerization of the above-mentioned polymerizable monomer, an oil-soluble initiator and / or a water-soluble initiator are used. For example, as the oil-soluble initiator, 2,2'-azobisisobutyronitrile, 2,2 '
-Azobis-2,4-dimethylvaleronitrile, 1,
Azo compounds such as 1'-azobis (cyclohexane-1-carbonitrile) and 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile; acetylcyclohexylsulfonyl peroxide, diisopropyl baroxycarbonate, decanolyl par oxide,
Lauroyl peroxide, stearoyl peroxide, propionyl peroxide, acetyl peroxide, t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, t-butylperoxyisobutyrate, cyclohexanone peroxide, methyl ethyl ketone peroxide, Peroxide initiators such as dicumyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide and cumene hydroperoxide are exemplified.

Examples of the water-soluble initiator include ammonium persulfate, potassium persulfate, and 2,2'-azobis (N, N'-
Dimethyleneisobutyroamidine) hydrochloride, 2,2'-azobis (2-aminodinopropane) hydrochloride, azobis (isobutylamidine) hydrochloride, sodium 2,2'-azobisisobutyronitrile sulfonate, sulfuric acid Ferrous or hydrogen peroxide.

In the present invention, in order to control the degree of polymerization of the polymerizable monomer, a chain transfer agent, a polymerization inhibitor and the like may be further added and used.

In the present invention, as a method for producing a toner, the shape of the toner particles can be controlled uniformly, a sharp particle size distribution can be easily obtained, and toner particles having a small particle size of 3 to 8 μm can be easily obtained. The suspension polymerization method used is particularly preferred. Further, a seed polymerization method in which a monomer is further adsorbed on the polymer particles once obtained and then polymerized using a polymerization initiator can also be suitably used in the present invention. At this time, it is also possible to use a compound having polarity dispersed or dissolved in the monomer to be adsorbed. When suspension polymerization is used as a method for producing toner particles, toner particles can be produced directly from the monomer composition by the following production method. Low softening point substance such as wax in the monomer, colorant, polymerization initiator,
A monomer composition obtained by adding a crosslinking agent and other additives and uniformly dissolving or dispersing with a homogenizer, an ultrasonic disperser, or the like, in an aqueous medium containing a dispersion stabilizer, using a normal stirrer or a homomixer, a homogenizer. And so on. Preferably, the stirring speed and time are adjusted so that the droplets of the monomer composition have a desired toner particle size,
Granulate. Thereafter, by the action of the dispersion stabilizer, the particles may be stirred to such an extent that the particle state is maintained and the particles are prevented from settling. Polymerization temperature is 40 ° C or higher, usually 50 to 90 ° C
(Preferably 55-85 ° C.) at a temperature of polymerization. The temperature may be raised in the latter half of the polymerization reaction, and may be further increased in the latter half of the reaction or after the end of the reaction to remove unreacted polymerizable monomers and by-products that cause odor at the time of fixing the toner. The partial aqueous medium may be distilled off. After the reaction, the generated toner particles are collected by washing and filtration, and dried.

In the suspension polymerization method, it is usually preferable to use 300 to 3000 parts by weight of water as a dispersion medium with respect to 100 parts by weight of the monomer composition. As the dispersant used, for example, as inorganic oxides, tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide,
Examples include magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, alumina and the like. Examples of organic compounds include polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose,
Ethyl cellulose, sodium salts of carboxymethyl cellulose, starch and the like are used. These dispersants are
It is preferable to use 0.2 to 2.0 parts by weight based on 100 parts by weight of the polymerizable monomer.

As these dispersants, commercially available ones may be used as they are, but in order to obtain finely dispersed particles having a uniform particle size, it is necessary to form an inorganic oxide in a dispersion medium under high-speed stirring. You can also. For example, in the case of tricalcium phosphate, a dispersant suitable for a suspension polymerization method can be obtained by mixing an aqueous solution of sodium phosphate and an aqueous solution of calcium chloride under high-speed stirring. For the purpose of making these dispersants finer, a surfactant of 0.001 to 0.1% by weight may be used in combination. Specifically, commercially available nonionic, anionic and cationic surfactants can be used. For example, sodium dodecyl sulfate, sodium tetradecyl sulfate,
Sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, calcium oleate and the like are preferably used.

The toner of the present invention has a shape factor SF-
The value of 1 is 100 to 160, more preferably 100 to 15
0, and more preferably 100 to 125 toner.

In the present invention, SF-1 indicating the shape factor is used.
Means, for example, FE-SEM (S-800) manufactured by Hitachi, Ltd.
, 100 toner images enlarged at a magnification of 500 times are sampled at random, and the image information is transmitted via an interface to, for example, an image analyzer (Luzex I, manufactured by Nicole).
Introduced in II) and analyzed, the value calculated by the following equation is defined as shape factor SF-1.

[0124]

[Outside 12] [Wherein, MXLNG indicates the absolute maximum length of the toner particles,
AREA indicates the projected area of the toner particles. ] Shape factor S
F-1 indicates the degree of roundness of the toner particles.

A toner having a toner shape factor SF-1 larger than 160 gradually changes from a spherical shape to an irregular shape, and a decrease in transfer efficiency is observed.

The toner of the present invention includes a lubricant powder such as Teflon powder, zinc stearate powder and polyvinylidene fluoride powder; an abrasive such as cerium oxide, silicon carbide, strontium silicate, calcium titanate and strontium titanate. It is preferable to externally add a fluidity improver such as silica, titanium oxide and aluminum oxide; a caking inhibitor; and a conductivity imparting agent such as carbon black, zinc oxide and tin oxide.

Particularly, inorganic fine powders include silica fine powder, titanium oxide fine powder, aluminum oxide fine powder, strontium silicate fine powder, calcium titanate fine powder,
An inorganic fine powder such as a strontium titanate fine powder is preferred. The inorganic fine powder is preferably hydrophobized with a hydrophobizing agent such as a silane coupling agent, silicone oil, or a mixture thereof. The external additive is preferably used in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the toner particles.

Next, an example of a laminate sheet used in the present invention will be described with reference to FIG.

In FIG. 1, A indicates a base layer mainly composed of a heat-resistant resin, and B indicates a surface coat layer mainly composed of a thermoplastic resin.

In the present invention, the main component refers to a component contained in an amount of 50% by weight or more based on all components. The base layer A needs to have a heat resistance that does not cause significant thermal deformation due to heating during heat fixing or heat and pressure fixing. The base layer A used in the present invention has a heat distortion temperature of 4.6 kg / cm ² described in ASTM D684, preferably 145 ° C.
Above, more preferably those at 150 ° C. or higher. More specifically, the base layer A used in the present invention has a heat distortion temperature of 145 ° C. or higher under the above measurement conditions, and a resin having a maximum use temperature of 100 ° C. or higher, such as polyethylene. Terephthalate (PE
T), polyester, polyamide or polyimide. Among them, polyethylene terephthalate is particularly preferred in terms of heat resistance and transparency.

The thickness of the base layer A made of the above-mentioned material needs to be such that wrinkles do not occur even when the film is softened by heating during image fixing. For example, in the case of polyethylene terephthalate, Is 50 μm
I just need more. Further, even in the case of a light-transmitting film, since the light transmittance decreases as the thickness increases, the thickness of the base layer A is preferably 50 to 300 μm, more preferably 70 to 300 μm.
It is preferable to use those having a thickness of about 200 to 200 μm, more preferably about 100 to 150 μm.

In the laminate sheet used in the present invention, a coat layer B mainly composed of a thermoplastic resin is formed on the base layer A as described above. In the present invention,
As a method for forming the coat layer B, a coating liquid comprising a material for forming the coat layer B dissolved in an organic solvent is light-transmitted by a coating method such as a bar coating method, a dipping method, a spray method, and a spin coating method. Coating on the surface of the base layer A and drying at room temperature or by heating. Further, in order to improve the adhesion between the heat-resistant resin A as the base layer and the coat layer B, a surface treatment such as a plasma treatment or a corona discharge treatment is performed, or the heat-resistant resin layer A and the coat layer B It is also preferable to form an easily adhesive layer between them.

Here, examples of the resin which can be used as the easy-adhesion layer include polyester resin, acrylate resin, methacrylate resin, styrene-acrylate copolymer, and styrene-methacrylate copolymer. Resins such as polymers are exemplified.

Next, the constituent materials of the coat layer B of the laminate sheet of the present invention will be described in detail. First, the thermoplastic resin used in the present invention will be described. As described above, the thermoplastic resin, which is a material for forming the coat layer B, has the solubility parameter (SP-A) that is different from the solubility parameter (SP-B) of the binder resin of the toner in absolute value (| (SP-
It is important that A)-(SP-B) |) is 5 or less. For example, conventionally known polyester resins, polymethyl methacrylate resins, acrylic resins, styrene resins, styrene-acryl resins, Various thermoplastic resins such as a rubber-based resin, an epoxy-based resin, a vinyl chloride-based, a vinyl acetate-based resin, and a polyurethane-based resin, and those using a crosslinking agent for them.

In the present invention, the number average molecular weight is from 3,000 to
A thermoplastic resin in the range of 500,000, more preferably 5,000 to 200,000 is suitably used. That is, if it is less than 3,000, the lamination sheet sticks to the surface of the fixing means remarkably, and if it is more than 500,000, the softening property of the coat layer B at the time of heat fixing is insufficient, and the toner particles are buried in the coat layer. As a result, the effect of reducing the granularity of the toner is impaired, the image quality is reduced, and the coating liquid used for forming the coating layer B has a high viscosity. It is not preferable because it lowers the workability.

In the present invention, the number average molecular weight of the thermoplastic resin was determined from the molecular weight distribution measured by GPC.
The GPC was measured under the following conditions using GPC-150C (manufactured by Waters). That is, the column is stabilized in a heat chamber at 40 ° C., and THF (tetrahydrofuran) as a solvent is flown into the column at this temperature at a flow rate of 1 ml per minute, and the sample concentration is 0.05 to
The THF sample solution of the resin prepared to 0.6% by weight is 50 to
Measure by injecting 200 μl. Then, the molecular weight distribution of the sample is determined from the relationship between the logarithmic value of the calibration curve prepared from several types of monodisperse polystyrene standard samples and the count number, and the molecular weight is calculated. As a standard polystyrene sample for preparing a calibration curve, a commercially available standard polystyrene manufactured by Tosoh Corporation was used, and the molecular weight was 6 × 10 ² , 2.1 × 10 ³ , and 4 × 10 ³ .
³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10
⁵ , 3.9 × 10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ ,
4.48 × 10 ⁶ was used. The detector used was a RI (refractive index) detector, and the column was TSKgel manufactured by Tosoh.
A combination of G1000H, G2000H, G3000H was used.

The optimum thickness of the coating layer B made of the above constituent materials varies depending on the particle size of the toner to be fixed, but is preferably 2 to 50 μm, more preferably 3 to 30 μm. Good to do. The optimum thickness of the coat layer B is also limited by the translucency and blur of the image, but since the coat layer has flexibility, there is no fear that the image cracks even if the coat layer becomes thick.

The laminate sheet used in the present invention is:
It is preferable to mix an antistatic agent or apply an antistatic agent in the surface coat layer B, and to adjust the surface resistivity to 10 ^{7 to} 13 ¹³ Ω / port, which is a region suitable for toner transfer.

The surface resistivity was measured according to JIS K69.
Measured according to 11. In the present invention, using R8340A and R12702A manufactured by Advantest,
The measurement was performed at 20 ° C., 60% RH, and a voltage of 100 V.

As the antistatic agent used at this time, any of conventionally known antistatic agents can be used. For example, quaternary ammonium salt compounds, pyridinium salt compounds,
Phosphonium salt compounds, alkyl betaine compounds,
Conductive resins such as alkyl imidazoline compounds, alkyl alanine compounds, polyoxyethylene type nonionic compounds, polyhydric alcohol type nonionic compounds, polyvinylbenzyl type cations and polyacrylic acid type cations, S
Ultrafine particles of metal oxide such as nO ₂ or SnO ₂ —Sb are dispersed in a binder resin. These antistatic agents can be mixed in a coating solution for forming the surface coat layer and applied simultaneously, or after forming the surface coat layer, a solution obtained by dissolving the above antistatic agent in alcohol or the like can be applied to prevent the formation of the antistatic agent. Preferably, a layer is formed. The antistatic layer may be formed on the surface coat layer B or between the base layer A and the surface coat layer B.

The laminate sheet used in the present invention comprising the above constituent materials is required to have excellent transparency, and has a light transmittance of at least 80% or more, preferably at least 80%, as a total light transmittance as an OHP sheet. It is preferably 85% or more, and the haze is at least 10 or less, preferably 7 or less, more preferably 3 or less.

The measurement of the transparency in the present invention was carried out according to JI
Performed according to SK-7105.

The image forming method of the present invention comprises a color copier,
The present invention can be applied to all the electrophotographic systems using the toner described above, such as a color printer and a color fax. or,
The image forming method of the present invention can be preferably applied to a fixing unit that does not apply a releasing property such as oil to the fixing unit, but using a toner prepared by a conventional pulverizing method,
The present invention can also be applied to an electrophotographic system using a conventional fixing means for separately applying a release agent such as oil.

Hereinafter, an image forming apparatus capable of performing the image forming method of the present invention will be described in detail with reference to FIGS.

The color electrophotographic apparatus shown in FIG. 6 includes a transfer material transport system I provided from the right side of the apparatus main body to a substantially central portion of the apparatus main body, and the transfer material transport system I provided at a substantially central portion of the apparatus main body. A latent image forming unit II provided in the vicinity of the transfer drum 615 constituting the image forming apparatus I; and a developing unit (that is, a rotary developing device) III provided in the vicinity of the latent image forming unit II. Are roughly divided into

The transfer material transport system I has the following configuration. An opening is formed in a right wall (the right side in FIG. 6) of the apparatus main body, and detachable transfer material supply trays 602 and 603 are provided in the opening so as to partially protrude outside the apparatus. Feed rollers 604 and 605 are disposed almost directly above the trays 602 and 603, and are linked to the feed rollers 604 and 605 and a transfer drum 605 disposed to the left and rotatable in the direction of arrow A. For this purpose, a paper feed roller 606 and paper feed guides 607 and 608 are provided. In the vicinity of the outer peripheral surface of the transfer drum 615, the contact roller 609, the gripper 610, the transfer material separating charger 611, and the separating claw 61 from the upstream to the downstream in the rotation direction.
2 are sequentially arranged.

On the inner peripheral side of the transfer drum 615, a transfer charger 613 and a transfer material separating charger 614 are provided. A transfer sheet (not shown) made of a polymer, such as polyvinylidene fluoride, is attached to a portion of the transfer drum 615 around which the transfer material is wound, and the transfer material is electrostatically placed on the transfer sheet. It is stuck on. At the upper right side of the transfer drum 615, a conveyor belt unit 616 is disposed in close proximity to the separation claw 312. At the end (right side) of the conveyor belt unit 616 in the transfer material transport direction (right side), a fixing device 618 is disposed. I have. A discharge tray 617 that extends to the outside of the apparatus main body 601 and is detachable from the apparatus main body 601 is provided further downstream of the fixing device 618 in the transport direction.

Next, the configuration of the latent image forming section II will be described. A photosensitive drum (for example, an OPC photosensitive drum) 619, which is a latent image carrier rotatable in the direction of the arrow in FIG. 6, is provided with its outer peripheral surface in contact with the outer peripheral surface of the transfer drum 615. Above the photosensitive drum 619 and in the vicinity of the outer peripheral surface thereof, from the upstream side to the downstream side in the rotation direction of the photosensitive drum 619, the charge removing charger 620 and the cleaning unit 621 are arranged.
And a primary charger 623 are sequentially arranged. Further, an image exposure unit 624 such as a laser beam scanner for forming an electrostatic latent image on the outer peripheral surface of the photosensitive drum 619 and an image exposure reflection unit 625 such as a mirror are provided. It is arranged.

The construction of the rotary developing device III is as follows. A rotatable housing (hereinafter referred to as a “rotating body”) 6 is provided at a position facing the outer peripheral surface of the photosensitive drum 619.
, And four types of developing devices are mounted in the rotating body 626 at four positions in the circumferential direction.
Are visualized (that is, developed) on the electrostatic latent image formed on the outer peripheral surface of the. The above four types of developing devices are:
Each has a yellow developing device 627Y, a magenta developing device 627M, a cyan developing device 627C, and a black developing device 627BK.

The sequence of the entire image forming apparatus having the above configuration will be described by taking a full color mode as an example. When the above-described photosensitive drum 619 rotates in the direction of the arrow in FIG.
Charged by In the apparatus shown in FIG. 6, the peripheral speed of the photosensitive drum 619 (hereinafter referred to as process speed) is 1
00 mm / sec or more (for example, 130 to 250 mm /
sec). Photosensitive drum 6 by primary charger 623
When charging of the document 19 is performed, image exposure is performed by the laser beam E modulated by the yellow image signal of the document 628, an electrostatic latent image is formed on the photosensitive drum 619, and development is performed in advance by the rotation of the rotating body 626. The electrostatic latent image is developed by the yellow developing device 627Y fixed at the position, and a yellow toner image is formed.

The transfer material conveyed via the paper feed guide 607, the paper feed roller 606, and the paper feed guide 608 is held by the gripper 610 at a predetermined timing, and is brought into contact with the contact roller 609 and the corresponding contact roller. 609 and the opposing electrode electrostatically wind the transfer drum 615. The transfer drum 615 rotates in the direction of the arrow in FIG. 6 in synchronization with the photosensitive drum 619, and
The yellow toner image formed by 27Y is transferred onto the transfer material by the transfer charger 613 at a position where the outer peripheral surface of the photosensitive drum 619 and the outer peripheral surface of the transfer drum 615 are in contact. The transfer drum 615 continues to rotate, and prepares for transfer of the next color (magenta in FIG. 6).

The photosensitive drum 619 is provided with
After being removed by the cleaning device 20 and cleaned by the cleaning means 621 using a cleaning blade, it is charged again by the primary charger 623, image exposure is performed by the next magenta image signal, and an electrostatic latent image is formed. The rotary developing device rotates while an electrostatic latent image is formed on the photosensitive drum 619 by image exposure using a magenta image signal, and places the magenta developing device 627M at the above-described predetermined developing position. Develop with magenta toner. Subsequently, the above-described process is also performed for cyan and black, respectively. When the transfer of the four-color toner image is completed, the three-color visual image formed on the transfer material is transferred to each of the chargers 622 and 614. , The gripping of the transfer material by the gripper 610 is released, and the transfer material is separated from the transfer drum 615 by the separation claw 612.
18 and is fixed by heat and pressure to complete a series of full-color print sequences, and a required full-color print image is formed on one surface of the transfer material.

Next, another image forming method will be described more specifically with reference to FIG.

In the apparatus system shown in FIG. 7, the developing units 74-1, 74-2, 74-3, and 74-4 respectively include a developer having a cyan toner, a developer having a magenta toner, and a developing device having a yellow toner. A developer having a developer and a black toner is introduced, and the electrostatic charge image formed on the photoconductor 71 is developed by a magnetic brush development system or a non-magnetic-component development system, etc., so that a toner image of each color is formed on the photoconductor 71. You. The photoreceptor 71 is made of a-Se, Cds, ZnO
_2. A photosensitive drum or a photosensitive belt having a photoconductive insulating material layer such as OPC and a-Si. The photoconductor 71 is rotated in a direction indicated by an arrow by a driving device (not shown).

As the photosensitive member 71, 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 transport performance in the same layer.
The charge transport layer may be a single layer type, or may be a function separation type photosensitive layer having a charge generation layer as a component. 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, and poor cleaning, fusion of a toner to a photoreceptor, and filming of an external additive. Less likely.

In the charging step, there are a system that is not in contact with the photoreceptor 71 using a corona charger, and a contact system that uses a roller or the like, and either system is used. For efficient uniform charging, simplification, and low ozone generation, a contact type as shown in FIG. 7 is preferably used.

The charging roller 72 basically has a core 72b at the center and a conductive elastic layer 72a formed on the outer periphery thereof. The charging roller 72 is pressed against the surface of the photoconductor 71 with a pressing force, and is rotated by the rotation of the photoconductor 71.

A preferable process condition when the charging roller is used is that the contact pressure of the roller is 5 to 500 g / cm.
When a DC voltage with an AC voltage superimposed thereon is used, an AC voltage = 0.5 to 5 kVpp and an AC frequency = 50
Hz to 5 kHz, DC voltage = ± 0.2 to ± 1.5 kV, and when DC voltage is used, DC voltage = ± 0.2 to
± 5 kV.

Other charging means include a method using a charged 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 a conductive rubber, and a release coating 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 toner image on the photosensitive member is applied with a voltage (for example, ±
(0.1 to ± 5 kV). The surface of the photoconductor after the transfer is cleaned by cleaning means 79 having a cleaning blade 78.

The intermediate transfer member 75 includes a pipe-shaped conductive core 75b and a medium-resistance elastic layer 75 formed on the outer peripheral surface thereof.
a. The core metal 75b may be formed by applying a conductive plating to a plastic pipe.

The medium resistance elastic layer 75a is made of silicon rubber, Teflon 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 to adjust the electric resistance (volume resistivity) to a medium resistance of 10 ⁵ to 10 ¹¹ Ω · cm. It is a solid or fired fleshy layer.

The intermediate transfer member 75 is provided in parallel with the photosensitive member 71 so as to be in contact with the lower surface of the photosensitive member 71, and is rotated at the same peripheral speed as the photosensitive member 71 in the counterclockwise direction indicated by the arrow. I do.

The first color toner image formed and carried on the surface of the photosensitive member 71 is transferred by a transfer bias applied to the intermediate transfer member 75 while passing through a transfer nip portion where the photosensitive member 71 and the intermediate transfer member 75 are in contact with each other. The intermediate transfer is sequentially performed on the outer surface of the intermediate transfer body 75 by the electric field formed in the nip castle.

If necessary, the surface of the intermediate transfer member 75 is cleaned by the detachable cleaning means 80 after the transfer of the toner image onto the transfer material. When there is a toner image on the intermediate transfer member, the cleaning unit 80 is separated from the surface of the intermediate transfer member so as not to disturb the toner image.

A transfer means is provided in parallel with the intermediate transfer body 75 and is brought into contact with the lower surface of the intermediate transfer body 75. The transfer means 77 is, for example, a transfer roller or a transfer belt. It rotates clockwise with the same peripheral speed as the arrow. The transfer unit 77 may be disposed so as to directly contact the intermediate transfer body 75, or a belt or the like may be disposed so as to contact between the intermediate transfer body 75 and the transfer unit 77.

In the case of the transfer roller, it has a basic structure of a central core 77b and a conductive elastic layer 77a formed on the outer periphery thereof.

For the intermediate transfer member and the transfer roller, general materials can be used. By setting the volume resistivity of the elastic layer of the transfer roller smaller than the volume resistivity of the elastic layer of the intermediate transfer body, the voltage applied to the transfer roller can be reduced, and a good toner image can be formed on the transfer material. In addition, it is possible to prevent the transfer material from being wound around the intermediate transfer member. In particular, it is particularly preferable that the volume resistivity of the elastic layer of the intermediate transfer member is at least 10 times the volume resistivity of the elastic layer of the transfer roller.

The hardness of the intermediate transfer member and the transfer roller is determined by JI
It is measured according to SK-6301. The intermediate transfer member used in the present invention is preferably composed of an elastic layer belonging to the range of 10 to 40 degrees. On the other hand, the hardness of the elastic layer of the transfer roller is higher than the hardness of the elastic layer of the intermediate transfer member.
Those having a value of from -80 degrees are preferred in order to prevent the transfer material from winding around the intermediate transfer member. When the hardness of the intermediate transfer member and that of the transfer roller are reversed, a concave portion is formed on the transfer roller side, and the winding of the transfer material around the intermediate transfer member is likely to occur.

The transfer means 77 rotates the intermediate transfer member 75 at a constant speed or at a different peripheral speed. The transfer material 76 is conveyed between the intermediate transfer body 75 and the transfer means 77,
The toner image on the intermediate transfer body 75 is transferred to the surface of the transfer material 76 by applying a bias having a polarity opposite to the frictional charge of the toner to the transfer unit 77 from the transfer bias unit.

As the material of the transfer rotary member, the same material as that of the charging roller can be used. The preferable transfer process condition is that the contact pressure of the roller is 5 to 500 g / c.
m and the DC voltage is ± 0.2 to ± 10 kV.

For example, the conductive elastic layer 77b of the transfer roller
Is polyurethane, ethylene-propylene-diene terpolymer (EPDM) in which conductive material such as carbon is dispersed
It is made of an elastic material having a volume resistance of about 10 ⁶ to 10 ¹⁰ Ωcm. A bias is applied to the core 77a from a constant voltage power supply. The bias condition is ± 0.2 ~
± 10 kV is preferred.

Next, the transfer material 76 is conveyed to a fixing device 81 having a heating roller having a built-in heating element such as a halogen heater, and an elastic pressure roller pressed against the heating roller with a pressing force. The toner image is heated and pressed and fixed on the transfer material by passing between the roller and the pressure roller. A fixing method using a heater via a film may be used.

The toner image formed by the toner on the laminate sheet by the image forming apparatus shown in FIGS. 6 and 7 is heated and fixed on the laminate sheet by the heat fixing means shown in FIGS. 2 and 3, and the image is formed on the laminate sheet. Is formed.

FIG. 2 is a schematic diagram showing an example of the heat-pressure fixing device used in the present invention. In FIG. 2, reference numeral 1 denotes a heat-pressure fixing unit having a fixing roller 2 and a pressure roller 3. The fixing roller 2 and the pressure roller 3 are pressed against each other with a predetermined pressure, and an unfixed toner image 6 is formed.
Is passed between the fixing roller 2 and the pressure roller 3, heat and pressure are applied to the recording material 5, and the unfixed toner image 6 is placed on the recording material 5. As a result, a toner image 7 is formed. The fixing roller 2 is provided with a heating means 4 such as a halogen heater.

The surface of the fixing roller 2 is made of a fluorine-based resin such as ethylene tetrafluoride resin (PTFE), perfluoroalkoxy fluororesin (PFA) or fluoroethylene-propylene copolymer (FEP).

On the other hand, the heating and pressurizing device of the film heating type is a heating roller press, a hot plate type, a belt heating and pressurizing type, a flash heating type, an open heating type, etc. In comparison with a device or an image heat fixing device, the following advantages are provided and the device is effective.

(1) In the heating and pressurizing and fixing device of the film heating type, since a heating element having a low heat capacity in which a linear heating element having a low heat capacity is formed into a film-shaped thin film can be used, power consumption can be reduced. It is possible to shorten the wait time (quick start property), and it is also possible to raise the temperature inside the machine.

(2) In the heat-press fixing device of the film heating type, since the fixing point and the separation point can be set separately, the offset can be effectively prevented. In addition, various disadvantages of other system devices can be solved.

FIG. 3 is a schematic diagram of a film heating type heating / pressing fixing device (image heating fixing device) having the above-described features.

In FIG. 3, reference numeral 203 denotes a heater (ceramic heater) fixedly supported by a support.
3, a heat-resistant film (fixing film) 201 is brought into close contact with a pressure roller 202 as a pressure rotating body and is slid and conveyed. Then, the heating element 20 is sandwiched by the heat-resistant film 201.
A recording material P on which an image as a material to be heated is to be fixed between the heat-resistant film 201 and the pressure roller 202 in a pressure-contact nip portion (fixing nip portion) N formed by the pressure roller 3 and the pressure roller 202. The heat is applied to the surface of the recording material P through the heat-resistant film 201 by conveying the pressure-contact nip N while being held together with the heat-resistant film 201, and the recording material P The upper unfixed visible image (toner image) T is heated and fixed on the surface of the recording material P. The recording material P that has passed through the pressure nip N is separated from the surface of the film 201 and transported to the left in the drawing.
204 is a felt-like pad impregnated with a release oil as a release agent, and is in contact with the heat-resistant film 201. In the apparatus shown in FIG. Oil is being supplied.
The heat and pressure fixing device used in the present invention may be a heat and pressure fixing device for separately applying releasable oil as shown in FIG. 3, but an oilless heating and heating device which does not separately apply oil. A pressure fixing device may be used. In the case of this oilless type heat and pressure fixing device, the pad 20
No. 4 is not impregnated with a release oil.

In the present invention, in the heat and pressure fixing apparatus having the above-described structure, it is not necessary to separately supply a releasable oil such as silicone oil in order to prevent the recording material after fixing from sticking. preferable. However, if the releasable oil is in such an amount that the stickiness of the recording material after fixing is not a problem, the fixing unit between the heating and pressing fixing means and the unfixed toner image on the recording material is used. It is also possible to fix by heating and pressing while supplying a releasing oil to the toner. The release oil is supplied by an application member such as an oil pad (not shown) on the surface of the fixing roller 2 in the pressure fixing device shown in FIG. This is carried out by impregnating a coating member such as an oil pad 204 with a release oil such as silicone oil. The amount of release oil separately supplied to the fixing unit is preferably 0.04 mg / sheet (A4 size) or less, more preferably 0.04 mg / sheet (A4 size). , 0.02 mg / sheet (A4
It is preferable that the amount is not larger than (size).

[0186]

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

Example 1 (Production of Cyan Toner No. 1) 710 parts by weight of ion-exchanged water and 0.1 mol / l were placed in a 21-liter four-necked flask equipped with a high-speed stirrer TK-Homomixer. Na ₃ P
450 parts by weight of an O ₄ aqueous solution was added, the number of revolutions was adjusted to 12,000, and the mixture was heated to 70 ° C. It was prepared here 1.0 mol / 1-CaCl ₂ aqueous solution 68 parts by weight was gradually added fine sparingly water-soluble dispersing agent Ca ₃ (PO ₄₎ dispersant system comprising _2. -Styrene monomer 162 parts by weight-2-ethylhexyl acrylate 22 parts by weight-n-butyl acrylate monomer 16 parts by weight-C.I. I. Pigment Blue 15: 3 14 parts by weight ・ Linear polyester 10 parts by weight (phthalic acid-propylene oxide modified bisphenol A) ・ Dialkylsalicylic acid metal compound 2 parts by weight ・ Divinylbenzene 0.5 part by weight ・ C 22 alkyl carboxylic acid Low-softening substance mainly composed of an ester compound of alkyl alcohol having 22 carbon atoms and 30 parts by weight

After the above mixture was dispersed for 3 hours using an attritor, a dispersion to which 3.0 parts by weight of lauryl peroxide as a polymerization initiator was added was poured into the dispersion medium prepared above, and the mixture was stirred at 10,000 rpm for 10 minutes. Granulated. Then change the stirrer from a high-speed stirrer to a propeller stirring blade,
The polymerization was continued at 0 rpm for 10 hours. After the polymerization was completed, the slurry was cooled, and diluted hydrochloric acid was added to remove the dispersant.

After further washing and drying, cyan toner particles having a weight average diameter of 6.5 μm (binder resin SP value 1
8.0). 100 parts by weight of the above-mentioned cyan particles and 1.5 parts by weight of hydrophobic silica were mixed with a Henschel mixer, and cyan toner No. 1 was mixed. 1 was obtained.

The obtained cyan toner No. Viscoelastic properties of No. 1 (storage modulus G ′ loss modulus G ″ and tan (δ))
Is shown in FIG. 4 and the values of the storage elastic modulus G 'at each temperature are shown in Table 1.

(Production of Laminate No. 1) 100 μm
A polyester resin (thermal deformation temperature: 152 ° C./SP value: 18.8) is coated to a thickness of 15 μm on a base layer made of polyethylene terephthalate having a thickness of 15 μm to form a surface coat layer. Coated with a quaternary ammonium salt compound, and the surface resistance value is 5 × 10 ¹⁰ Ω.
/ □ (20 ° C., 60% RH). 1 was obtained.

The obtained laminated sheet No. Table 1 shows various configurations and physical properties of No. 1.

(Image formation and evaluation)
1 and the laminate sheet No. 1 1 was developed using a commercially available full-color copier (CLC500; manufactured by Canon Inc.) and a developing contrast of 320 V under an environment of a temperature of 23 ° C. and a humidity of 65% RH to form a toner image. The image was transferred onto a laminate sheet to obtain an unfixed toner image having a gradation. The unfixed toner image formed on the laminate sheet is fixed at a temperature of 180 degrees and a process speed of 30 mm by an external fixing device (no oil coating function; roller diameter 40φ) in which the surface of the fixing roller is a fluororesin shown in FIG. / Sec, a heat-press fixing was performed to obtain a fixed image (imaging sheet).

The image density of the obtained fixed image was 0.4-0.
6 (halftone portion) and the image temperature of 1.1-1.3 (solid portion) were measured for transmittance and haze.

The transmittance was measured using a Shimadzu self-spectrophotometer UV.
2200 (manufactured by Shimadzu Corporation) was used for the measurement. The transmittance of the laminated sheet alone is set to 100%, and the transmittance at the maximum absorption wavelength at magenta toner: 650 nm, cyan toner: 500 nm, yellow toner: 600 nm is measured and evaluated based on the following evaluation criteria. did.

(Evaluation criteria for transmittance) Image density 0.4-0.6 (halftone portion) Image density 1.1-1.3 (solid portion) A: transmittance is 80% or more A: transmittance is 70% or more B: transmittance The transmittance is 70% or more and less than 80%. 〇: The transmittance is 60% or more and less than 70%. Δ: The transmittance is 60% or more and less than 70%. Δ: The transmittance is 50% or more and less than 60%. X: The transmittance. But less than 60% ×: transmittance is less than 50%

The haze was measured using a haze meter NDH-
Measurement was performed using 300A (manufactured by Nippon Shika Kogyo Co., Ltd.), and the difference from the haze of the laminate sheet alone was measured, and evaluated based on the following evaluation criteria.

(Evaluation criteria for haze) Image density 0.4-0.6 (halftone portion) Image density 1.1-1.3 (solid portion) A: Haze is less than 20% A: Haze is less than 25% B: Haze is 20 % To less than 25% 〇: Haze is 25% to less than 30% △: Haze is 25% to less than 35% △: Haze is 30% to less than 40% ×: Haze is 35% or more ×: Haze But more than 40%

Further, in the above-described measuring method, the change in the transmittance and the haze of the image at the initial stage and after 2,000 sheets of durability were evaluated for each of the halftone portion and the solid portion.

The difference between the initial image transmittance and the haze after 2,000 sheets of durability was evaluated based on the following evaluation criteria.

(Evaluation Criteria for Difference between Transmittance of Initial Image and Transmittance of Image after Durability of 2,000 Sheets) 未 満: Less than 8% 〇: 8% or more and less than 13% Δ: 13% or more and less than 18% ×: 18 % Or more (Evaluation standard for difference between haze of initial image and haze of image after 2,000 sheets of durability) ：: less than 8% 〇: 8% or more and less than 13% Δ: 13% or more and less than 18% ×: 18% or more The transportability of the laminate sheet was evaluated as follows.

The cyan toner No. 1 and the laminate sheet No. 1 1 is a commercially available full-color copying machine (CLC500;
Using a remodeling machine (manufactured by Canon Inc.), the temperature was 23 degrees and the humidity was 65.
In an environment of% RH, a toner image was formed by developing at a development contrast of 320 V, and the obtained toner image was transferred onto a laminate sheet to obtain an unfixed toner image having an image area ratio of 5%. FIG. 2 shows an unfixed image formed on the laminate sheet. An external fixing device in which the surface of the fixing roller is made of a fluororesin (no oil application function; roller diameter 4
0Fi), heat and pressure fixing was performed at a fixing temperature of 180 degrees and a process speed of 30 mm / sec. At this time, the transportability of the laminate sheet in the external fixing device as the heat fixing device was evaluated based on the following evaluation criteria.

(Evaluation Criteria for Transportability) 〇: The laminate sheet passed without being wound around the fixing roller.

Δ: The first part of the laminate sheet was slightly wrapped around the fixing roller, but passed without any problem by using a separation claw pressed against the roller at a pressure of about 10 gf.

X: The laminate sheet was wound around the fixing roller by using a separation claw pressed against the roller at a pressure of about 10 kf.

Table 2 shows the evaluation results.

Example 2 The cyan toner N of Example 1 was used except that a yellow colorant (CI Pigment Yellow 17) was used as the colorant.
o. The yellow toner N shown in Table 1 in the same manner as in the production of
o. 1 was produced. Cyan toner N used in Example 1
o. No. 1 in place of Yellow Toner No. 1 and image formation and evaluation were performed in the same manner as in Example 1. Table 2 shows the evaluation results.

Example 3 The cyan toner No. 1 of Example 1 was used except that a magenta colorant (CI Pigment Red 122) was used as the colorant. Magenta toner No. 1 shown in Table 1 in the same manner as in the production of 1 was produced. Cyan toner No. 1 used in Example 1 Magenta toner no. 1 and image formation and evaluation were performed in the same manner as in Example 1. Table 2 shows the evaluation results.

(Example 4) The cyan toner No. 1 of Example 1 was used except that a black colorant (carbon black) was used as the colorant. Table 5 in the same manner as in the manufacture of Table 1.
The black toner No. shown in FIG. 1 was produced.

In the cyan toner No. used in Example 1, 1,
In the yellow toner No. used in Example 2, 1, magenta toner No. 1 used in Example 3 1 and the black toner No. 1 obtained above. A full-color toner was used on a laminate sheet under the same developing conditions as in Example 1 in full-color mode using a commercial full-color copier (CLC500; manufactured by Canon Inc.) modified machine using the four toners of Example 1. An image was formed, and the obtained full-color toner image was transferred onto a laminate sheet to obtain an unfixed full-color toner image having an image density of 5%. The unfixed full-color toner image formed on the laminate sheet was heated and pressed and fixed by the external fixing device shown in FIG. 2 in the same manner as in Example 1 in the same manner as in Example 1. An image free of stickiness with excellent sheet transportability and color mixing was obtained.

The following method was used to show color mixing due to durability. First, the color space of the projected image of the OHP based on the measurement of the spectral radiance meter PR650 (manufactured by Photo Research) is obtained. Next, the area of the color space (a ^* , b ^* ) of the initial projection image of the embodiment is set to 100, and the color space area of the durable projection image of the embodiment and the color space of the initial and durable projection images of the comparative example are obtained.

It should be noted that 100 indicates that the color mixing property is good, and that the color mixing property deteriorates as the numerical value decreases.

Example 5 Cyan toner No. 1 of Example 1 was used except that the amount of divinylbenzene used as a crosslinking agent was changed to 1.0 part by weight. Table 1 in the same manner as in the manufacture of Table 1.
The cyan toner No. shown in FIG. 2 was produced. Cyan toner No. 1 used in Example 1 1 in place of cyan toner No.
2, and image formation and evaluation were performed in the same manner as in Example 1.

(Embodiment 6) The cyan toner N of Embodiment 1
o. The cyan toner of Example 1 except that the low softening point substance used in the production of Example 1 was replaced with a low softening point substance containing a diester compound of an alkyl dicarboxylic acid having 18 carbon atoms and an alkyl alcohol having 18 carbon atoms as a main component. No. No. 1 in the same manner as in the production of 3 was adjusted. Cyan toner No. 1 used in Example 1 1 in place of cyan toner No. 3, and image formation and evaluation were performed in the same manner as in Example 1. Table 2 shows the evaluation results.

(Example 7) The laminate sheet No. of Example 1 was used. In the same manner as in Example 1 except that a styrene-acrylic resin was used instead of the polyester resin used in the production of Laminated Sheet No. 1 shown in Table 1, 2 was produced.

In the laminate sheet No. used in Example 1,
No. 1 in place of the laminate sheet No. 1 Example 1 using 2
Image formation and evaluation were performed in the same manner as described above. Table 2 shows the evaluation results.

(Example 8) The laminate sheet No. of Example 1 was used. The thickness of the surface coat layer in the production of No. 1 was 10 μm
Except that the laminate sheet No. 1 in the same manner as in the production of Laminated Sheet No. 1 shown in Table 1. 3 was produced.

The laminate sheet No. used in Example 1
No. 1 in place of the laminate sheet No. 1 Example 1 using 3
Image formation and evaluation were performed in the same manner as described above. Table 2 shows the evaluation results.

Example 9 The cyan toner N of Example 1 was used except that the amount of the low softening point substance was 8 parts by weight.
o. Cyan toner N shown in Table 1 in the same manner as in the production of
o. 4 was produced. Cyan toner N used in Example 1
o. 1 in place of cyan toner No. Example 1 using Example 4
Image formation and evaluation were performed in the same manner as described above. Table 2 shows the evaluation results.

Example 10 The amount of the low softening point substance was 9
Except for using 0 parts by weight, the cyan toner No. of Example 1 was used. 1 in the same manner as in the production of cyan toner No. 1 shown in Table 1. 5 was produced. Cyan toner N used in Example 1
o. 1 in place of cyan toner No. Example 1 using 5
Image formation and evaluation were performed in the same manner as described above. Table 2 shows the evaluation results.

(Comparative Example 1) The laminate sheet No. 1 used in Example 1 was used. Table 3 not forming a surface coat layer in place of 1
Sheet No. shown in FIG. Image formation and evaluation were performed in the same manner as in Example 1 except that Sample No. 4 was used. Table 4 shows the evaluation results.

(Comparative Example 2) Cyan toner N of Example 1
o. In the production of Cyan toner No. 1 except that the ester type low softening point substance was replaced with a paraffin type low softening point substance and divinylbenzene as a crosslinking agent was not used. Table 3 shows the results in the same manner as in the production of No. 1. Cyan toner No. 6 was produced. The obtained cyan toner No. 6
Properties (storage modulus G ', loss modulus G "and t
an (δ)) is shown in FIG. 5, and the values of the storage elastic modulus G ′ at each temperature are shown in Table 3.

In the cyan toner No. 1 used in Example 1, 1 in place of cyan toner No. 6 and image formation and evaluation were performed in the same manner as in Example 1. Table 4 shows the evaluation results.

(Comparative Example 3) Cyan toner N of Example 1
o. In the production of Cyan toner No. 1 shown in Table 3 in the same manner as in Example 1 except that the ester type low softening point substance was replaced with the paraffin type low softening point substance in the production of No. 1. 7 was produced. Cyan toner No. 1 used in Example 1 1 in place of cyan toner No. 7 and image formation and evaluation were performed in the same manner as in Example 1. Table 4 shows the evaluation results.

Comparative Example 4 The laminate sheet No. of Example 1 In the same manner as in Example 1 except that a polyvinyl alcohol-based resin (SP value: 25.2) was used instead of the polyester resin used in the production of Laminated Sheet No. 1 shown in Table 3, 5 was produced.

In the laminate sheet No. used in Example 1,
No. 1 in place of the laminate sheet No. 1 Example 1 using 5
Image formation and evaluation were performed in the same manner as described above. Table 4 shows the evaluation results.

(Comparative Example 5) Cyan toner No. 1 used in Comparative Example 1 And a yellow colorant (C.I.
I. Pigment Yellow 17) in Example 2 using No. Pigment Yellow 17). Image formation and evaluation were performed in the same manner as in Comparative Example 1 except that Sample No. 1 was used. Table 4 shows the evaluation results.

(Comparative Example 6) Cyan toner N of Example 1
o. In the production of No. 1, the ester type low softening point substance was replaced with a paraffin type low softening point substance, divinylbenzene as a crosslinking agent was not used, and a cyan colorant was replaced with a yellow colorant (CI Pigment Yellow).
17) except that cyan toner No. 17 is used.
1 in the same manner as in the production of Yellow Toner No.
2 was produced. Cyan toner No. 1 used in Example 1 1
In place of Yellow Toner No. 2, and image formation and evaluation were performed in the same manner as in Example 1. Table 4 shows the evaluation results.
Shown in

(Comparative Example 7) Cyan toner N of Example 1
o. In the production of No. 1, an ester type low softening point substance is replaced with a paraffin type low softening point substance, and a yellow colorant (CI Pigment Yellow) is used instead of a cyan colorant.
ow 17) except that cyan toner N
o. No. 1 in the same manner as in the production of
o. 3 was produced. Cyan toner N used in Example 1
o. No. 1 in place of Yellow Toner No. 3, and image formation and evaluation were performed in the same manner as in Example 1. Table 4 shows the evaluation results.

Comparative Example 8 The cyan toner No. used in Comparative Example 4 The yellow toner No. 1 used in Example 2 using a yellow colorant (CI Pigment Yellow 17) as a colorant instead of No. 1 was used. Image formation and evaluation were performed in the same manner as in Comparative Example 4, except that Sample No. 1 was used. Table 4 shows the evaluation results.

(Comparative Example 9) Cyan toner No. 1 used in Comparative Example 1 Yellow toner No. 1 used in Example 2 using a magenta colorant (CI Pigment Red 122) as a colorant instead of Image formation and evaluation were performed in the same manner as in Comparative Example 1 except that Sample No. 1 was used. Table 4 shows the evaluation results.

(Comparative Example 10) Cyan toner N of Example 1
o. In the production of No. 1, the ester type low softening point substance was replaced with a paraffin type low softening point substance, divinylbenzene as a crosslinking agent was not used, and a magenta colorant (CI Pigment Red 122) was used instead of a colorant. , Except that cyan toner No. is used. In the same manner as in the production of magenta toner No. 1 shown in Table 3, 2 was produced.
Cyan toner No. 1 used in Example 1 Magenta toner no. 2, and image formation and evaluation were performed in the same manner as in Example 1. Table 4 shows the evaluation results.

(Comparative Example 11) Cyan toner N of Example 1
o. In the production of Compound No. 1, an ester type low softening point substance was replaced with a paraffin type low softening point substance, and a magenta colorant (CI Pigment Red 1) was used instead of a cyan colorant.
22), except that cyan toner No. 22 is used.
In the same manner as in the production of magenta toner No. 1 shown in Table 3,
3 was produced. Cyan toner No. 1 used in Example 1 1
In place of magenta toner No. 3, and image formation and evaluation were performed in the same manner as in Example 1. Table 4 shows the evaluation results.
Shown in

(Comparative Example 12) The cyan toner No. used in Comparative Example 4 Magenta toner No. 1 used in Example 3 in which a magenta colorant (CI Pigment Red 122) was used as the colorant. Image formation and evaluation were performed in the same manner as in Comparative Example 4, except that Sample No. 1 was used. Table 4 shows the evaluation results.

(Comparative Example 13) The laminate sheet No. used in Example 4 Sheet No. 1 shown in Table 3 without forming the surface coat layer used in Comparative Example 1 in place of Sheet No. 1 4, except that cyan toner No. 4 was used.
1, yellow toner no. 1, magenta toner No. 1
And black toner No. Using the four types of toners,
Image formation and evaluation were performed. Table 6 shows the evaluation results.

(Comparative Example 14) Cyan toner N of Example 1
o. In the production of No. 1, the ester type low softening point substance is replaced with a paraffin type low softening point substance, divinylbenzene which is a crosslinking agent is not used, and a black colorant (carbon black) is used instead of a cyan colorant. Except for the above, the cyan toner No. Table 5 in the same manner as in the manufacture of Table 1.
The black toner No. shown in FIG. 2 was produced.

In Example 4, the cyan toner No. used in Comparative Example 2 was replaced with the four toners used. 6, Comparative Example 6
Yellow toner No. 2, the magenta toner No. used in Comparative Example 10 2 and the black toner Nos. Except for using the four types of toners 2,
Image formation and evaluation were performed in the same manner as in Example 4. Table 6 shows the evaluation results.

(Comparative Example 15) Cyan toner N of Example 1
o. In the production of No. 1, except that the ester type low softening point substance was replaced with a paraffin type low softening point substance and a black colorant (carbon black) was used instead of the cyan colorant. In the same manner as in the production of Black Toner No. 1 shown in Table 5, 3 was produced.

In Example 4, the cyan toner No. used in Comparative Example 3 was replaced with the four toners used. 7, Comparative Example 7
Yellow toner No. 3, magenta toner No. 3 used in Comparative Example 11 3 and the black toner no. Except for using four kinds of toners of No. 3,
Image formation and evaluation were performed in the same manner as in Example 4. Table 6 shows the evaluation results.

Comparative Example 16 The laminate sheet No. of Example 1 In place of the polyester resin used in the production of No. 1, polytetrafluoroethane heat deformation temperature 150 ° C./SP value:
Except that 12.7 [J / m ³ ] ^1/2 10 ^-3 ) is used, the laminate sheet No. 1 in the same manner as in the production of Laminated Sheet No. 1. 6 was produced. The laminate sheet No. used in Example 4 was used. 1 in place of the laminate sheet No. 1 obtained above. 6, except that cyan toner No. 6 was used. 1, yellow toner no. 1, magenta toner No. 1 and black toner No. 1 Image formation and evaluation were performed in the same manner as in Example 4 using the four toners of No. 1. Table 6 shows the evaluation results.

[0241]

[Table 1]

[0242]

[Table 2]

[0243]

[Table 3]

[0244]

[Table 4]

[0245]

[Table 5]

[0246]

[Table 6]

Example 11 A toner image was formed into a laminate sheet in the same manner as in Example 4 except that the external fixing device used in Example 4 was a heating and pressing fixing device of a film heating type shown in FIG. No. After fixing under heat and pressure to 1,
Good results were obtained as in Example 4.

(Example 12) When outputting an unfixed image, a full-color image forming apparatus using an intermediate transfer member shown in FIG. 7 is used. Further, a toner image was formed on a laminated sheet No. in the same manner as in Example 4 except that a heat-press fixing device of a film heating type shown in FIG. As a result, good results were obtained as in Example 4.

[0249]

According to the image forming method of the present invention, when used in an overhead projector (OHP), the projected color image is not dull even in durability, especially in a halftone portion where the image density is low. A color image or a full-color image having good color tone reproducibility can be obtained.

Further, it is possible to form an imaging sheet of a full-color image without stickiness by applying no oil, or by applying heating and pressing means having an oil application amount of 0.04 mg / sheet (A4 size) or less. .

Further, it is possible to form an imaging sheet of a color or full-color image having excellent transparency and good quality.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating a configuration of a laminate sheet used in the present invention.

FIG. 2 shows a heating and pressing fixing means that can be used in the heating and pressing method of the present invention.

FIG. 3 shows another example of the heating and pressing fixing means that can be used in the heating and pressing method of the present invention.

FIG. 4 shows curves of storage elastic modulus, loss elastic modulus, and tan (δ) of the toner of the present invention.

FIG. 5 shows storage elastic modulus, loss elastic modulus and t of a comparative toner.
3 shows a curve of an (δ).

FIG. 6 is a schematic explanatory view of an image forming apparatus that can carry out the image forming method of the present invention.

FIG. 7 is a schematic explanatory view of another image forming apparatus that can execute the image forming method of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Heat fixing means 2 Fixing roller 3 Pressure roller 4 Heating means 5 Recording material 6 Unfixed toner image 7 Fixed toner image A Base layer (base film) B Toner receiving layer P Recording material T Toner 201 Heat resistance Film 202 pressure roller 203 heating element 204 oil pad

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) G03G 9/087 G03G 7/00

Claims (9)

(57) [Claims] 1. A base layer containing a heat-resistant resin as a main component,
An image forming method in which a toner image formed by toner is heat-fixed on a laminate sheet having at least a surface coat layer containing a thermoplastic resin as a main component and an image is formed on the laminate sheet, the toner comprising: It contains at least a resin, a colorant and a low softening point substance, and has a storage modulus (G ′) at a temperature of 60 ° C.
60) and the storage elastic modulus (G′80) at a temperature of 80 ° C. (G′60 / G′80) are 80 or more, and a temperature of 1
Storage modulus (G'155) at 55 ° C and temperature 190
° C storage modulus (G'190)
5 / G′190) is 0.95 to 5.0, and the solubility parameter (S
PA) and the solubility parameter of the binder resin (SP-B)
The absolute value of the difference (| (SP-A)-(SP-B) |) is not more than 5 [J / m ³ ] ^1/2 · 10 ^-3 . 2. A release oil is applied so that the amount of the release oil applied to the heating / pressing fixing member or the laminate sheet to which the release oil is not applied is 0.04 mg / sheet (A4 size) or less. The image forming method according to claim 1, wherein the toner image is fixed on the laminate sheet by a heated and pressed fixing member. 3. The image forming method according to claim 1, wherein the surface coat layer containing the thermoplastic resin as a main component is coated on one side or both sides of the base layer. 4. The heat-resistant resin has a heat deformation temperature of ASTE.
4. The image forming method according to claim 1, wherein the angle is 145 degrees or more in the measurement described in MD684. 5. The image forming method according to claim 1, wherein the binder resin contains a styrene-acrylic resin or a styrene-methacrylic resin. 6. The binder resin has a toluene insoluble content of 0.1.
6. The image forming method according to claim 1, wherein the content is 1 to 30% by weight. 7. The image forming method according to claim 1, wherein the laminate sheet has a light transmitting property. 8. The image forming method according to claim 1, wherein the toner contains 1 to 40 parts by weight of a low softening point substance based on 100 parts by weight of the binder resin. 9. The image forming method according to claim 1, wherein the toner contains 5 to 40 parts by weight of a low softening point substance based on 100 parts by weight of the binder resin.