JP3210247B2 - Image forming method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an image forming method for transferring a fixed image of a toner image formed on a first image carrier to a second image carrier.

[0002]

2. Description of the Related Art It is known to transfer an image to a three-dimensional object using a technique called transfer picture. For example, a water-soluble glue such as dextrin is applied on a base material such as paper to form a first image carrier, and an image is formed on this coating film using acrylic ink by a method such as screen printing. A water pressure transfer method is known in which a first image carrier having this image is immersed in water, dextrin is dissolved, and an acrylic ink image floating in water is transferred to a three-dimensional object such as pottery by water pressure. As a transfer paper for electrophotography used for transfer picture, there is Templin manufactured by Mutoh Kogyo Co., Ltd. This transfer paper is a film in which dextrin is formed on rice paper. After forming a fixed image of the toner image on the surface of the dextrin layer of the transfer paper using an electrophotographic apparatus, an organic solvent capable of softening the resin of the fixed image is applied to the transfer paper, and the target of retransfer to the fixed image is applied. To provide an adhesive force to the second image carrier. Next, after the transfer paper and the second image carrier are brought into close contact with each other so as to face each other, water is applied from the back surface of the transfer paper to dissolve the dextrin film and transfer the fixed image to the second image carrier. Is what you do. However, transfer paper with a water-soluble coating film formed on such an opaque paper is not only difficult to line up at the time of retransfer, but also the surface of the transfer paper before image formation is affected by moisture in the air. Will soften. A problem such that the softened dextrin adheres to the photoreceptor in the electrophotographic apparatus is likely to occur. Further, as described above, since the transfer paper is sensitive to the moisture in the air, it greatly expands or contracts in response to a change in the amount of water, and the transfer paper is curled, and the transferability of the transfer paper in the apparatus is likely to be reduced.

On the other hand, Japanese Patent Application Laid-Open No. Hei 4-36086 proposes a retransfer material using polyvinyl alcohol, which is a saponified product of polyvinyl acetate (polyvinyl acetate), instead of dextrin. The retransfer material proposed here is a material obtained by coating a silicone resin on paper and then mixing a silicone antifoaming agent with Casesol O-5 manufactured by Nikka Chemical Co., Ltd.
The retransfer itself, after forming a fixed image of the toner image on this coating film with an electrophotographic apparatus, peeling the coating film from the substrate, and superimposed so that the fixed image is directly opposite the retransfer body,
By applying heat and pressure, the resin of the fixed image is softened to obtain an adhesive force to the retransfer body, and after cooling, 20% aqueous ethyl alcohol is applied from the back surface of the coating to bond the coating to the fixed image. The force is reduced and retransfer is performed. According to this method, since a thin film-like coating film having a fixed image is peeled off from the substrate, it becomes an almost transparent film, and there is an advantage that it can be easily lined up.

However, since the coating material used is a partially saponified polyvinyl acetate, it is sensitive to moisture in the air, as in Templin, and tends to curl before image formation. The problem, and even
The coating film remains due to dissolution of the coating film at the time of peeling off the coating film. Since silicone is used for the release film, a problem that the coating film peels off during the transfer of the transfer material in the electrophotographic apparatus is likely to occur.

[0005]

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

It is a further object of the present invention to provide an image forming method for transferring images well under various environments.

It is a further object of the present invention to provide an image forming method for performing a transfer picture using a first image carrier having a fixed image which does not easily curl.

Another object of the present invention is to provide an image forming method for performing a transfer picture using a first image carrier having improved water resistance and improved release properties of a release layer. It is in.

It is a further object of the present invention to provide an image forming method for performing a transfer picture using a first image carrier which does not contaminate a photosensitive member or causes less contamination.

It is a further object of the present invention to provide an image forming method in which the fixing of a toner image is good and the transfer of the fixed image from the first image bearing member to the second image bearing member can be favorably performed. It is in.

[0011]

A toner image is formed on a laminate surface of a first image carrier having a laminate having a release layer formed on a substrate, using a toner having toner particles and an external additive. image forming a first fixed image fixed on the surface of the image bearing member, a release layer having the fixed image is peeled from the first image bearing member, a second image bearing the fixed image from the release layer was transferred to the body, an image forming method for forming an image on the second image bearing member, a stack of the first image bearing member, having at least an adhesive layer and a release layer, the release layer is a transfer layer At least have
The release layer has the following formula

[Outside 2] Wherein, S _L is releasing the release layer from the first image bearing member, warm
Release layer under low temperature and low humidity environment of 15 ° C and 10% RH
Shows the area after leaving for 2 days, S _H temperatures the peel layer
Released for 24 hours in a high-temperature, high-humidity environment of 30 ° C and 80% RH
2 shows the area of the release layer after being placed. Area expansion ratio calculated from] is 102 - 106% relates to an image forming method characterized by transferring the fixed image while swelling the peeling layer to the second image bearing member.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION After fixing the fixed image on the release layer of the first image carrier on the surface of the second image carrier, the present inventors peel off the fixed image from the release layer to obtain a second image carrier. It has been found that when transferring to the surface of the image carrier, the fixed image can be quickly and uniformly separated from the release layer by adjusting the area expansion coefficient of the release layer to a specific range.

The area expansion coefficient of the release layer is 102 to 106%.
(More preferably, from 102 to 105%), when the release layer swells, the fixed image can be satisfactorily self-separated and transferred to the second image bearing member. Even if the first image carrier is left, curling is less likely to occur, and dimensional fluctuation is less.

The area expansion coefficient of the release layer can be measured as follows.

The release layer is peeled off from the first image bearing member, and the release layer is removed under a low temperature and low humidity environment at a temperature of 15 ° C. and a humidity of 10% RH.
After leaving for days, the area (S _L ) of the release layer is measured. Next, after leaving the release layer in a high-temperature and high-humidity environment at a temperature of 30 ° C. and a humidity of 80% RH for one day (24 hours), the area (S _H ) of the release layer is measured.

The area expansion rate is calculated from the following equation.

[0017]

[Outside 1]

A specific example of the first image carrier used in the present invention will be described below with reference to FIG.

FIG. 1 is a longitudinal sectional view schematically showing a layer structure of a first image carrier 1 for transfer picture. Base material 11
Is a medium- or high-quality plain paper; a coated paper in which one or both surfaces of these papers are coated with a resin for filling; a heat-resistant film such as polyethylene terephthalate. When the base material 11 is paper, the weight of the paper is 30 to 200 g.
/ M ² , more preferably 45 to 150 g /
m ² . If the paper weight is less than 30 g / m ² , the transportability in the electrophotographic apparatus is reduced. When the weighing exceeds 200 g / m ² , the paper has too high rigidity, and conveyability is reduced.
It is preferably 45 to 150 g / m ² as coated paper. In order to maintain good image transferability in an electrophotographic apparatus, 0.2 to 4% by weight of an inorganic salt such as sodium chloride is added to the coated paper, and the volume resistivity of the coated paper is set at a temperature of 2%.
10 ^{8 in} the environment of 0 ° C and 65% RH for 24 hours
It is preferably adjusted to に 10 ¹⁰ Ω · cm. When a heat-resistant film is used for the substrate 11, a biaxially stretched heat-resistant polyethylene terephthalate film is preferable from the viewpoint of transportability. The thickness of the polyethylene terephthalate is preferably 50 to 200 μm, more preferably 75 to 150 μm. In addition, heat-resistant films
An antistatic layer having a cationic or nonionic surfactant is applied to the B surface, and the surface specific resistance is 10 ^{8 to} 10
It may be adjusted to ¹² Ω (temperature 20 ° C., humidity 65% RH).

The adhesive layer 12 includes a release layer 13 and a transfer layer 14.
Is provided in order to prevent the peeling layer formed by the above from peeling off in the electrophotographic apparatus. The adhesive layer 12 includes an acrylic resin soluble in an organic solvent, an aqueous acrylic resin emulsion, a water-soluble acryl, a water-soluble polyester, 6.6 nylon, polyacrylonitrile, and the like. If necessary, an amorphous silicon dioxide fine powder having an oil absorbing property (fine silica powder) may be mixed into the adhesive layer 12.

The silicon dioxide fine powder is mixed with the upper release layer 13.
Has the ability to increase the adhesive strength of the base material, and further has the ability to absorb moisture evaporated from the inside of the base material.

Next, the release layer 13 is preferably formed of polyvinyl alcohol which is a saponified product of polyvinyl acetate. The saponification degree is preferably 90% or more, more preferably 95% or more. When polyvinyl alcohol having a saponification degree of less than 90% is used, it is preferable to use a mixture containing a small amount of water-soluble silicone (commonly used as an antifoaming agent or a surfactant) as a release agent. Polyvinyl alcohol having a degree of saponification of less than 70% is not preferred because water resistance is reduced. When silicone (organic silicon compound) is mixed in the transfer layer 14,
As shown in FIG. 2, the release layer may be one layer of the transfer layer 14.

The mutual material selection of the release layer 13 and the adhesive layer 12 is also affected by the adhesive force, and it is preferable that the material is not separated at least by the respective transport forces in the electrophotographic apparatus. 90 ° peeling as adhesive strength 1.
It is preferably at least 5 g / cm, and more preferably at most 6 g / cm so that the peeling layer formed of the transfer layer 14 and the release layer 13, which will be described later, is not broken when the peeling layer is peeled off from the substrate 11 side.

Next, a toner image is transferred onto the surface of the transfer layer 14 by an electrophotographic apparatus as shown in FIG. 3 to be described later, and the toner image is fixed on the transfer layer 14 by a fixing unit until the re-transfer process is started. It is required to hold the fixed image for a while, and to have sufficient release performance for the fixed image at the time of retransfer. FIG. 4 shows a first image carrier having a fixed image 15 on the transfer layer 14.

Further, the transfer layer is also required to have sufficient water resistance. It is necessary that the water resistance is excellent while ensuring the permeability of the swelling liquid during retransfer. Specifically, polyvinyl acetate (A) produced by saponifying 90% or more of polyvinyl acetate is added with 90% of polyvinyl acetate.
%, It is preferable to form the transfer layer 14 with a composition in which polyvinyl alcohol (B) produced by saponification is mixed. The mixing ratio is preferably such that the content of polyvinyl alcohol (A) having a high degree of saponification of 90% or more is 10% by weight or more, more preferably 25% by weight or more and less than 75% by weight, as a solid content ratio. is there. If it is less than 10% by weight, polyvinyl alcohol (B) having a low saponification degree of less than 90%
The water-soluble property of the transfer layer easily appears, and the transfer layer easily melts out under a high temperature environment. Further, when the polyvinyl alcohol (A) has a high degree of saponification of 75% by weight or more, the arrangement of the linear polymer forming the transfer layer becomes highly regular like a cellulose film. The dimensional change of the may be large. The polyvinyl alcohol (A) having a high degree of saponification is more preferably 25% by weight or more and less than 75% by weight as a solid content ratio. If necessary, a cationic or nonionic antistatic agent may be added to the transfer layer 14 to improve electrophotographic transferability. The addition amount of the antistatic agent is preferably adjusted so that the surface specific resistance of the transfer layer is 10 ⁸ to 10 ¹² Ω.

Conventionally known antistatic agents can be used. For example, quaternary ammonium salt compounds,
Pyridinium salt compounds, phosphonium salt compounds, alkyl betaine compounds, alkyl imidazoline compounds, alkyl alanine compounds, polyoxyethylene type nonionic compounds, polyhydric alcohol type nonionic compounds, polyvinylbenzyl type cations and polyacryls Examples thereof include a conductive resin such as an acid-type cation and a dispersion of ultrafine metal oxide particles such as SnO ₂ and SnO ₂ —Sb in a binder resin. It is preferable that these antistatic agents are mixed in a coating solution for forming the transfer layer and applied simultaneously.

Further, an inorganic white pigment such as silicon dioxide fine powder may be mixed in order to improve the paper transport property and the toner fixing property. When the transfer layer is formed together with the release layer, it is preferable to increase the amount of the silicon dioxide fine powder and to mix the silicone compound.

Regarding the thickness of each layer, the adhesive layer 12 is preferably a thin layer so as not to cause splitting of the film.
μm to 10 μm are preferred. If it is less than 2 μm, unevenness tends to occur, and if it exceeds 10 μm, in-layer peeling tends to occur. However, if silicon dioxide fine powder is mixed in the adhesive layer, the film thickness may be increased to 15 μm because the film strength increases.

The release layer 13 has a role of a primer layer of the transfer layer 14 and a role of achieving sufficient peeling at the interface between this layer and the adhesive layer 12, and preferably has a thickness of 2 μm to 6 μm. . If it exceeds 6 μm, the dimensional change due to the increase and decrease of the water content of the release layer is large, and the first image carrier tends to curl.

The thickness of the transfer layer 14 is preferably 3 to 50 μm. If the thickness is smaller than this, the strength of the release layer is reduced, and the release layer is likely to be broken when peeled from the substrate. 50μ
When the thickness is larger than m, the release layer after peeling becomes hard, and the reproducibility of the curved surface at the time of retransfer tends to decrease. More preferably, the thickness of the transfer layer is 4 μm to 40 μm.

Next, as shown in FIG. 5, the release layer having the fixed image 15 (lamination of the transfer layer 14 and the release layer 13) is released from the adhesive layer 12, and as shown in FIG. The surface is brought into close contact with the surface of the second image bearing member, and is pressed from the surface of the release layer 13 while heating, so that the fixed image 15
And the second image carrier are heated and fixed. After fixing the fixed image 15 and the second image carrier, the release layer is swollen with a swelling agent that does not substantially dissolve the fixed image and does not substantially swell. Due to the swelling force when the release layer swells, a dissociation action acts on the interface between the fixed image fixed on the surface of the second image carrier and the release layer. Therefore, as shown in FIG. 7, the release layer can be peeled off from the fixed image while the fixed image remains on the second image carrier 16 by swelling the release layer. You can transfer pictures.

It is preferable that the second image carrier is formed of a material which is not or hardly deteriorated or deformed by heat. For example, pottery, tile, wood, glass, metal, plastic, and plates, sheets, molded products, pressed products, etc. constituted by combining these are mentioned.

In the present invention, after the retransfer, a curable transparent resin may be applied and cured to cover the surface of the image on the second image carrier.

Next, the toner used in the image forming method will be described.

In the case of a toner, a carrier and a two-component developer, the toner is charged to a required charge amount and charge polarity by friction with the carrier, and an electrostatic charge image is developed using electrostatic attraction to develop the toner. Form an image. Therefore, in order to obtain a good toner image, it is important that the toner has good triboelectricity, which is determined mainly by the relationship with the carrier.

In particular, the color toner preferably satisfies the following characteristics.

(1) The fixed color toner is almost completely melted so that the shape of the color toner particles cannot be distinguished so that the color toner does not diffusely reflect light and hinder color reproduction. Is preferred.

(2) A color toner having transparency which does not hinder the toner layers of different colors below the toner layer is preferable.

(3) Each of the constituent color toners preferably has a well-balanced hue and spectral reflection characteristics and a sufficient saturation.

As a result of intensive studies on color toners satisfying the characteristics required for the above-described electrophotographic color toner and preferably applicable to the transfer picture forming method, the following organic pigment was uniformly dispersed in the toner particles using a polyester resin. The color toner dispersed therein satisfactorily satisfies charge stability, fixability, and characteristics required for transfer picture formation.

A color toner applicable to a transfer picture forming method using a color electrophotographic apparatus preferably has good melting properties and color mixing properties when heat is applied, and has a low softening point and a short melting time for sharp melt properties. Color toners are preferred. By using a color toner having sharp-melting properties, the color reproduction range of a copy or print can be widened, and a color image faithful to a multicolor image or a full-color image of a document can be satisfactorily obtained.

Further, the color toner is used for transfer picture formation in which a once obtained fixed image is retransferred to a second image carrier (final transfer material) to form a picture, so that the surface of the fixed image has irregularities. The adhesion between the toner and the second image carrier decreases, and the fixed image is easily peeled off, which is not preferable. On the other hand, at the time of re-transfer, for example, an alcohol-based solvent is applied from the back surface of the first image carrier, penetrates to the interface with the fixed image, and separates the fixed image and the transfer layer 14. Adhering and fixing are not preferable because they cannot be retransferred.

Accordingly, it is preferable to use a toner binder resin which satisfies both good adhesion to the transfer layer 14 at the time of fixing and release performance from the transfer layer at the time of retransfer.

The color toner preferably uses a polyester resin as the binder resin in consideration of the fixing property and the sharp melt property. In particular, the following equation (1)

[0045]

[Outside 2] (Wherein R is an ethylene or propylene group, x and y are each an integer of 1 or more, and the average value of x + y is 2 to 10). A carboxylic acid component comprising a divalent or higher carboxylic acid or an acid anhydride thereof or a lower alkyl ester thereof (for example, fumaric acid, maleic acid, maleic anhydride, phthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, etc.) Polyester resins obtained by co-condensation polymerization of the above are more preferable because they have sharp melting characteristics.

Further, the acid value of the polyester resin is 2 to 2
When it is 5 mgKOH / g, excellent charging stability can be obtained in each environment, and the adhesion to the transfer layer 14 at the time of fixing and the peelability from the transfer layer 14 at the time of retransfer can be sufficiently satisfied. .

When the acid value is less than 2 mgKOH / g, the toner tends to charge up, the stability of charging decreases, and the adhesion to the transfer layer 14 decreases.
Offset is likely to occur during fixing. In particular, a transfer layer 1 composed of a mixture of polyvinyl acetate saponified at 90% or more and polyvinyl acetate saponified at less than 90%.
When the first image bearing member having No. 4 is used, the effect is remarkable.

On the other hand, the acid value of the polyester resin is 25 mg.
When it is larger than KOH / g, the stability over time of charging decreases, and the charge amount of the toner tends to decrease along with the durability of a large number of sheets. Particularly in a high-temperature and high-humidity environment, image defects such as toner scattering and fog tend to occur. .

When the acid value is larger than 25 mgKOH / g, the adhesiveness to the transfer layer 14 becomes too strong, and the offset resistance at the time of heat and pressure fixing to the first image carrier is improved. In addition, the releasability at the time of retransfer decreases. Therefore, a large amount of alcohol solvent may need to be used at the time of peeling, and a fixed image may remain on the transfer layer 14 at the time of partial retransfer, and a good transfer picture may not be obtained.

The adhesion and release properties of the toner to the transfer layer 14 are such that the residual hydroxyl groups of the polyvinyl acetate forming the transfer layer 14 and the carboxyl groups of the binder resin forming the toner strongly interact with each other. The degree of saponification,
The balance with the acid value of the polyester binder is important. The acid value of the polyester resin is 2 to 25, preferably 3
-22, more preferably 5-20 (mgKOH / g).

The weight average molecular weight (M
w) is 3,000 to 150,000 (more preferably, 6,0
00 to 100,000, more preferably 7,000 to 8
And most preferably 8,000 to 50,000), and the number average molecular weight (Mn) of the binder resin is 1,5
00 to 15,000 (more preferably 1,500 to 10,000, and still more preferably 1,500 to 1
000, most preferably 2,000 to 8,000
0), and the value of Mw / Mn is preferably 2 to 10 (more preferably 3 to 8, more preferably 3 to 6). If the Mw of the binder resin is larger than 150,000, the fixability of the toner is reduced, and the color mixing property is reduced. If the Mw of the binder resin is less than 3,000, the retransferability of the fixed image to the second image carrier decreases. Similarly, when the Mn of the binder resin is 15,
If it is larger than 000, the fixability and color mixing property of the toner will decrease, while if Mn is less than 1,500, the blocking resistance of the toner will decrease. When the binder resin has an Mw / Mn of 2 to 10, it is possible to satisfactorily achieve color mixing property, fixing property of the toner, prevention of winding around the fixing roller, and prevention of contamination of the fixing roller surface.

In the chromatic toner, the cyan toner contains at least a binder resin and a copper phthalocyanine-based organic pigment, the magenta toner contains at least the binder resin and a quinacridone-based organic pigment, and the yellow toner contains It is preferable that the toner contains at least a binder resin and an isoindolinone-based organic pigment because good chargeability, good fluidity of toner, good spectral reflection characteristics, and light resistance can be obtained.

The copper phthalocyanine organic pigments include
C. I. Pigment Blue 15; 15: 1; 15: 2;
15: 3; 15: 4. Further, a phthalocyanine pigment having a phthalocyanine skeleton having a structure represented by the formula (2) and substituting 1 to 5 phthalimidomethyl groups is exemplified. A copper phthalocyanine pigment having another substituent may be used.

[0054]

[Outside 3]

The content is 0.1 to 12 parts by weight, preferably 0.5 to 10 parts by weight, and more preferably 1 to 8 parts by weight based on 100 parts by weight of the binder resin. If the amount exceeds 12 parts by weight, the saturation and lightness of the cyan toner decrease, and the color reproducibility decreases.

The quinacridone organic pigments include C.I.
I. Pigment Red 122 is preferred, and C.I. I. Pigment Red 202, 206, 207 are also preferred. C.
I. Pigment Red 122 as a base pigment may be used in combination with other coloring agents. Examples of the pigment used at that time include C.I. I. Pigment Red 1, 2, 3, 4, 5,
6,7,8,9,10,11,12,13,14,1
5,16,17,18,19,21,22,23,3
0, 31, 32, 37, 38, 39, 40, 41, 4
8,49,50,51,562,53,54,55,5
7, 58, 60, 63, 64, 68, 81, 83, 8
7,88,89,90,112,114,123,14
6,150,163,184,185,209,23
8; I. Pigment Violet 19; I. Butt Red 1,2,10,13,15,23,29,3
5 and the like. A dye such as a xanthene dye may be partially used in combination.

The content is 0.1 to 15 parts by weight, preferably 1 to 12 parts by weight, based on 100 parts by weight of the binder resin.
Parts by weight, more preferably 1 to 10 parts by weight.

Even when used in combination with another dye / pigment, the other dye / pigment is preferably not more than 50 parts by weight, more preferably not more than 25 parts by weight, per 100 parts by weight of the quinacridone pigment.

Examples of the isoindolinone-based organic pigment include:
C. I. Pigment Yellow 109, 110, 139,
173, 185 are preferred, and C.I. I. Pigment Yellow 173 or 109 is preferred in terms of charge stability and color reproducibility.

The content is 0.1 to 15 parts by weight, preferably 2 to 12 parts by weight, more preferably 3 to 10 parts by weight, based on 100 parts by weight of the binder resin.

An external additive such as a fluidity improver may be added to the toner, and any toner can be used as long as the fluidity can be increased before and after the addition. For example, as external additives, fine powders of metal oxides such as silicic acid fine powder, alumina fine powder, titanium oxide fine powder, zirconium oxide fine powder, magnesium oxide fine powder or hydrophobized substances thereof; boron nitride fine powder, Nitride such as aluminum nitride fine powder and carbon nitride fine powder; and resin fine particles such as silicone resin fine particles.

In the present invention, calcium titanate, strontium titanate, barium titanate, magnesium titanate, cerium oxide, zirconium oxide, aluminum oxide, titanium oxide, zinc oxide, calcium carbonate and the like are preferably used. It is particularly preferable to use a hydrophobic titanium oxide fine powder having an average primary particle diameter of 0.01 to 2 μm.

It is preferable that the additives not only increase the fluidity of the toner but also do not hinder the chargeability of the toner. In the toner used in the present invention, the titanium oxide fine powder subjected to the hydrophobic treatment has an excellent fluidity-imparting property while maintaining a stable chargeability of the toner.

The average primary particle diameter of titanium oxide is 0.01 to
When the thickness is 0.2 μm, the fluidity is good and the toner is uniformly charged, and as a result, toner scattering and fogging hardly occur. Further, the titanium oxide particles are less likely to be embedded on the surface of the toner particles, and the toner is less likely to deteriorate.
Multi-sheet durability is improved. This tendency is more remarkable in the sharp-melt toner. The particle size of the titanium oxide particles was measured with a transmission microscope.

Furthermore, since the titanium oxide particles have been subjected to a hydrophobic treatment, the influence of moisture, which is a factor that affects the charge amount, is eliminated, and the difference in charge amount between high and low humidity is reduced, thereby reducing environmental impact. The characteristics can be further improved, and the toner can be uniformly charged.

When the toner and the above-mentioned titanium oxide are used in combination, the amount of titanium oxide to be added is 0.5 to
5.0 wt%, preferably 0.7 to 3.0 wt%, more preferably 1.0 to 2.5 wt%. When the above range is satisfied, the fluidity of the toner is good, a stable charge amount can be maintained, and toner scattering is unlikely to occur.

The toner has a weight average particle diameter of 3 to 12 μm.
(More preferably 4 to 10 μm), containing 15 to 45% by number of toner particles having a particle size of 5 μm or less, and having a particle size of 12.
0.1 to 5% by volume (preferably 0.1 to 4% by volume) of toner particles having a particle size of 7 to 16.0 μm, and 1.0% by volume or less of toner particles having a particle size of 16 μm or more. preferable.

The toner having the above particle size distribution can further enhance the effect of obtaining a stable charging ability in the characteristics of the material itself. The toner has the above-mentioned particle size distribution, so that the charge distribution of the toner itself becomes very sharp, thereby not only improving the development efficiency, but also significantly reducing the "fogging" in the background portion of the image. can get.

As a further effect, it is possible to faithfully reproduce the electrostatic charge image formed on the photoreceptor, and it is excellent in the reproducibility of halftone dots and minute dot latent images such as digital images. The toner having the above-mentioned particle size distribution can give a toner image excellent in gradation and resolution of the light portion.

The toner particles having a particle size of 5 μm or less have been considered to be difficult to control the charge amount, to reduce the fluidity of the toner, and to be a fogging component on an image background portion. This is important for forming a high quality image.

The toner developed on the photosensitive member at the potential portion of the electrostatic image was collected and its particle size distribution was measured.
m or less, especially toner particles having a particle size of about 5 μm in the fine dot portion. This is true to the electrostatic image when toner particles having a particle size of about 5 μm are smoothly supplied to the development of the electrostatic image on the photoreceptor, and the electrostatic image is well reproduced without protruding from the electrostatic image. The resulting image is obtained. Further, by using the toner having the above-mentioned specific particle size distribution, it is possible to satisfactorily achieve the fixability of the fixed image to the first image carrier and the adhesion to the second image carrier.

When the toner has negative chargeability, it is preferable to add a charge control agent for the purpose of further stabilizing the negative charge characteristics. Examples of the negative charge control agent include a colorless or pale-colored organic metal complex such as a metal complex of an alkyl-substituted salicylic acid (for example, a chromium complex or a zinc complex or an aluminum complex of di-tert-butylsalicylic acid).

When the toner is positively chargeable, it is preferable to contain a charge control agent exhibiting positive chargeability. For example, a triphenylmethane-based compound, a rhodamine-based dye, and polyvinylpyridine can be mentioned, and it is particularly preferable to use a colorless or light-colored positive charge control agent that does not affect the color tone of the toner.

When these charge control agents are contained in the toner particles, the content thereof is not necessarily limited as long as it does not affect the color tone of the color toner. Suitably the range is from 10% to 10% by weight, preferably from 4% to 8% by weight.

When the charge control agent is used in the above content, the initial variation of the charge amount is small, and the absolute charge amount required at the time of development is easily obtained. As a result, "fog" and reduction in image density are favorably suppressed.

Further, if necessary, metal salts of fatty acids (eg, zinc stearate, aluminum stearate, etc.), fine powders of fluorine-containing polymer (eg, polytetrafluoroethylene,
A lubricant such as fine powder of polyvinylidene fluoride or tetrafluoroethylene-vinylidene fluoride copolymer, or a conductivity-imparting agent such as tin oxide or zinc oxide may be added.

Further, the toner particles may contain a release agent as a fixing aid. For example, aliphatic hydrocarbon wax,
Oxides of aliphatic hydrocarbon waxes, waxes containing fatty acid esters as main components, saturated linear fatty acids, unsaturated fatty acids, saturated alcohols, polyhydric alcohols, fatty acid amides, saturated fatty acid bisamides, Examples thereof include saturated fatty acid amides and aromatic bisamides. The release agent is 0.1 to 20 parts by weight per 100 parts by weight of the binder resin,
Preferably, it is 0.5 to 10 parts by weight. When the amount of the release agent exceeds 20 parts by weight, blocking resistance and high-temperature offset resistance are liable to decrease, while when the amount is less than 0.1 part by weight, the release effect is small.

These release agents are preferably contained in the binder resin by a method in which the resin is dissolved in a solvent, the temperature of the resin solution is increased, and the mixture is added and mixed while stirring, or a method of mixing at the time of kneading. .

The toner is preferably mixed with a carrier and used as a two-component developer. As the carrier, for example, metals such as iron, nickel, copper, zinc, cobalt, manganese, chromium, calcium, magnesium, rare earth and the like, and their alloys, oxides, and magnetic ferrites which are not oxidized or surface oxidized can be used. As a material of the magnetic particles used as the carrier, 98% or more of Cu-Zu
-Fe (metal composition ratio (5 to 20): (5 to 20): (3
Ferrite particles having a composition of 0 to 80)) are preferable for easy surface uniformization and stable charging ability. However, the present invention is not particularly limited, and in addition, flat, spongy, coin-like, spherical, spherical and other various forms of iron oxide powder, copper, manganese, nickel, zinc, tin, magnesium, lead, strontium, Ferrite containing one or more of barium, lithium, calcium, etc.,
Particles composed of a mixture of various resins and magnetic powder are used.

A coat carrier in which the surface of the carrier core particles is coated with a resin is particularly preferred. As a method for producing the coated carrier, a method of dissolving or suspending a coating material such as a resin in a solvent, applying the applied material to adhere to the surface of the carrier core particles, a method of simply mixing with a powder, and a conventionally known method can be applied.

As a coating substance on the surface of the carrier core particles, an electrically insulating resin is used and is appropriately selected according to the toner material and the carrier core material. It is preferable to use a resin having a small surface energy in order to prevent the toner from being spent on the carrier due to fusing or the like. For example, a silicone resin or a fluororesin may be used. In order to enhance the adhesion to the carrier core particles, it is preferable to use various additives in combination to enhance the toughness of the coating. In particular, when the silicone resin is coated, the durability and charging characteristics of the obtained coated carrier are further improved by adding water to the coating resin diluting solvent used.

This is because the crosslinking point of the curable silicone resin and the hydrolysis of the silane coupling agent are promoted, and the curing reaction proceeds, and although the surface energy of the silicone resin increases for a short time, the carrier core particles This is due to the improvement in the adhesion to the substrate.

The applied amount of the coating resin to the carrier core particles is such that the resin solid content is 0.05% by weight to 10% by weight, preferably 0.1% by weight to 5% by weight.

The average particle size of the carrier is 27 to 100 μm,
Preferably 25 to 70 μm, more preferably 25 to 65
It is preferred to have μm.

When a two-component developer is prepared by mixing a toner and a carrier, the mixing ratio is 1% by weight to 12% by weight, preferably 2% by weight, as the toner concentration in the developer.
Good results are usually obtained with ９9% by weight. If the toner concentration is less than 1% by weight, the image density tends to be low,
If it exceeds 12% by weight, fogging and scattering in the machine are liable to occur, and the useful life of the developer tends to decrease.

Next, a method for forming a fixed image of a toner image on the first image carrier by electrophotography using a sheet-like transfer material as the first image carrier will be described with reference to FIG. explain.

FIG. 3 is a schematic diagram showing an example of an image forming apparatus for forming a fixed image on a first image carrier. The image forming apparatus shown in FIG. 3 is used as a full-color copying machine or a full-color printer. In the case of a full-color copying machine, as shown in FIG. 4, a digital color image reader unit is provided at the upper part, and a digital color image printer unit is provided at the lower part.

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

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

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

[0091] The printer unit is provided with a photosensitive drum 1 for forming an image.
Is rotated in the direction of the arrow, and after the charge is removed by the pre-exposure lamp 11, the photosensitive drum 1 is uniformly negatively charged by the charger 2 to irradiate a light image E for each separation color, and the electrostatic charge on the photosensitive drum 1 Form an image.

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

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

The transfer sheet is conveyed from the transfer sheet cassette 7a, 7b or 7c, which is the first image carrier, to the transfer drum 5 through the transfer sheet conveying system, and is carried on the transfer drum 5.
The recording material carried on the transfer drum 5 is repeatedly conveyed to a transfer position facing the photosensitive drum 1 with the rotation of the transfer drum 5, and passes through the transfer position while transferring through the transfer position.
By the operation of b, the toner image on the photosensitive drum 1 is transferred onto the transfer sheet.

As shown in FIG. 4, the toner image may be directly transferred from the photosensitive drum to a transfer sheet, or the toner image on the photosensitive member may be transferred to an intermediate transfer member, and the toner image may be transferred from the intermediate transfer member. It may be transferred to a sheet.

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

The transfer sheet onto which the toner images of four colors have been transferred in this manner is separated from the transfer drum 5 by the action of the separation claw 8a, the separation push-up roller 8b and the separation charger 5h, and is heated and fixed by the fixing device. 9, where the toner is heated and pressurized and fixed to perform color mixing and color development of the toner and fixation to the transfer sheet. After forming a full-color fixed image, the sheet is discharged to the tray 10 and one full-color copy is made. finish. On the other hand, the photosensitive drum 1 is subjected to the image forming process again after the residual toner on the surface is cleaned and removed by the cleaning device 6.

An electrode roller 14 and a fur brush 15, and an oil removing roller 16 and a backup brush 17, which are opposed to each other via the transfer sheet, are provided on the transfer drum 5. Cleaning is performed to remove the attached powder and the attached oil on the transfer sheet. Such cleaning is performed before or after image formation, and at any time when a jam, that is, a paper jam occurs.

The eccentric cam 25 is operated at a desired timing, and the 29 cam follower 5 integrated with the transfer drum 5 is operated.
i, the transfer sheet and the photosensitive drum 1
And the gap between them can be set arbitrarily.
For example, the interval between the transfer drum and the photosensitive drum can be increased during standby or when the power is off.

By the image forming apparatus, a full-color fixed image is formed on the transfer layer 14 of the transfer sheet as the first image carrier. In the above-described image forming apparatus, a single-color fixed image or a multi-color fixed image may be used depending on the single-color mode and the multi-color mode.

The fixed image thus formed on the transfer sheet is transferred to the second image carrier by the above-described method and painted.

The method for measuring each physical property will be described below.

Measurement of Particle Size Distribution of Toner A Coulter Counter TA- or Coulter Multisizer (manufactured by Coulter Inc.) is used. The electrolyte is about 1% N using primary grade sodium chloride.
Prepare aCl aqueous solution. For example, ISOTON, R-
(Coulter Scientific Japan) can be specified. As the measuring method, the electrolytic aqueous solution 100 to
In 150 ml, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant, and 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample was suspended was subjected to a dispersion treatment for about 1 to 3 minutes with an ultrasonic
Using a μm aperture, the volume and number of toner particles are measured for each channel, and the volume distribution and number distribution of the toner are calculated. Then, the weight average particle diameter (D4) of the toner on a weight basis determined from the volume distribution of the toner particles.
(The central value of each channel is set as a representative value for each channel).

The channels are 2.00 to 2.52
μm; 2.52 to 3.17 μm; 3.17 to 4.00 μm
m; 4.00 to 5.04 μm; 5.04 to 6.35 μm
m; 6.35 to 8.00; 8.00 to 10.08 μm;
10.08 to 12.70 μm; 12.70 to 16.00
μm; 16.00-20.20 μm; 20.20-2
5.40 μm; 25.40 to 32.00 μm; 32 to 4
13 channels of 0.30 μm are used.

Method for Measuring Average Particle Size of Titanium Oxide Fine Particles The primary particle diameter was determined by observing the titanium oxide fine particles with a transmission electron microscope and enlarging 300,000 to 50,000 times in the field of view, 300 pieces of 0.005 μm or more. The average particle diameter is determined by measuring the particle diameter, and the dispersed particle diameter on the toner particles is observed with a scanning electron microscope, and 300 titanium oxide fine particles enlarged in the visual field by 30,000 to 50,000 times are qualitatively determined by XMA. The average particle diameter is determined by measuring the particle diameter.

Measurement method of oxidation 2 to 10 g of a sample is weighed in a 200 to 300 ml Erlenmeyer flask, and about 50 ml of a mixed solvent of methanol: toluene = 30: 70 is added to dissolve the resin. If solubility is poor, a small amount of acetone may be added. 0.1%
Is titrated with a previously standardized N / 10 potassium hydroxide-alcohol solution using a mixed indicator of promthymol blue and phenol red, and the acid value is calculated by the following calculation from the consumption of the alcoholic potassium solution.

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

Measurement method of molecular weight of binder resin Mw and Mn of the binder resin are measured by gel permeation chromatography (GPC). The column was stabilized in a heat chamber at 40 ° C. and the column at this temperature was loaded with tetrahydrofuran (TH
F) at a flow rate of 1 ml / min.
Inject 00 μl and measure. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the count number. As a standard polystyrene sample for preparing a calibration curve, for example, one having a molecular weight of about 10 ² to 10 ⁷ manufactured by Tosoh Corporation or Showa Denko KK, and it is appropriate to use a standard polystyrene sample having at least about 10 points. is there. An RI (refractive index) detector is used as the detector. As the column, a combination of a plurality of commercially available polystyrene gel columns is preferably used.

For example, Shodex G manufactured by Showa Denko KK
PC KF-801,802,803,804,80
5,806,807,800P, TSKgel G1000H (H _XL ), G2000
H (H _XL ), G3000H (H _XL ), G4000H (H
_{XL), G5000H (H XL)} , G6000H (H XL),
G7000H (H _XL ), TSKguardcolumn
Can be cited.

A sample is prepared as follows.

After placing the sample in THF and leaving it to stand for several hours, it is shaken well, mixed well with THF (until the sample is no longer united), and allowed to stand still for 12 hours or more. Then T
The time of leaving in HF is set to 24 hours or more.
After that, the sample processing filter (pore size 0.45
0.5 μm, for example, Myshoridisk H-25
-5 (manufactured by Tosoh Corporation, Exiclodisk 25CR manufactured by Germanic Science Japan) can be used as a GPC sample. The sample concentration is adjusted so that the resin component is 0.5 to 5 mg / ml.

Measurement method of surface resistance value The surface resistance value of the first image bearing member and the surface resistance value of the transfer layer are measured according to JIS K6911.

As the measuring apparatus, for example, R8340A and R12702A manufactured by Advanced Test Co., Ltd. are used, and the measurement is performed at a voltage of 100 V in an atmosphere at a temperature of 20 ° C. and a temperature of 65% RH.

[0114]

EXAMPLES Example 1 of Transfer Sheet Production Example 1 A single-coated paper obtained by subjecting one side of a medium paper weighing 64 g / m ^{2 to} a cohesive treatment with a mixture of starch and talc was used as a base material 11 (base paper), and the following formulation was used. Transfer sheet N for transfer picture
o. 1 was prepared.

Adhesive layer Acrylic resin (Cover coat resin LO-316, manufactured by Ryo Kagaku Co., Ltd.) 100 parts by weight Toluene 100 parts by weight

A coating solution containing the above materials was applied to the surface of the substrate 11 by a lip coater, and the adhesive layer 1 having a thickness of 7 μm was applied.
2 was formed on the substrate 11.

Release layer Highly saponified polyvinyl alcohol solution (98% saponification degree, solid content: 14% by weight) 10 parts by weight Water 90 parts by weight

A coating liquid obtained by mixing the above materials was applied to the surface of the adhesive layer 11 with a comma coater, and a release layer 13 having a thickness of 3 μm was formed on the adhesive layer 12.

Transfer layer: High saponified polyvinyl alcohol solution (98% saponification, solid content: 14% by weight) 50 parts by weight Low saponified polyvinyl alcohol solution (Saponification degree: 85%, solid content: 14% by weight) 50 parts by weight Inhibitor (cationic surfactant) 2.5 parts by weight Water 5 parts by weight

A coating liquid containing the above materials was applied to the surface of the release layer 13 by a screen coater, and dried at a temperature of 60 ° C. and a humidity of 35% RH for 30 minutes to release the transfer layer 14 having a thickness of 16 μm. It was formed on the mold layer 13. Transfer sheet N
o. In 1, the adhesive strength between the release layer composed of the transfer layer 14 and the release layer 13 and the adhesive layer 12 was 2.5 g / cm, the area expansion rate of the release layer was 103.5%, The surface specific resistance was 2 × 10 ¹¹ Ω.

Transfer Sheet Production Example 2 The following formula was used as a base material 11 (base paper) using coated paper obtained by filling both surfaces of a high-quality paper having a basis weight of 80 g / m ² with a coating solution containing starch and calcium carbonate. Then, a transfer sheet for picture N0.2 was obtained.

Adhesive layer Acrylic resin (Covercoat Resin LO-316, manufactured by Ryo Kagaku Co.) 100 parts by weight Toluene 100 parts by weight Silicon dioxide fine powder (BET specific surface area 150 m ² / g) 3 parts by weight

The coating liquid obtained by mixing the above materials was applied to the surface of the substrate 11 by a screen coater to form an adhesive layer 12 having a thickness of 9 μm on the substrate 11.

Release layer Highly saponified polyvinyl alcohol solution (99% saponification degree, solid content: 14% by weight) 20 parts by weight Water 100 parts by weight

The coating liquid obtained by mixing the above materials was applied to the surface of the adhesive layer 12 with a screen coater, and a release layer 13 having a thickness of 4 μm was formed on the adhesive layer 12.

Transfer Layer High Saponified Polyvinyl Alcohol Solution (Saponification Degree 99%, Solids 14% by Weight) 50 parts by weight Low Saponified Polyvinyl Alcohol Solution (Saponification degree 88%, Solids 14% by weight) 50 parts by weight Charge Inhibitor (cationic surfactant) 2.5 parts by weight Silicon dioxide fine powder (BET specific surface area 150 m ² / g) 6 parts by weight Water 5 parts by weight

A coating liquid containing the above materials was applied to the surface of the release layer 13 by a screen coater and dried at a temperature of 60 ° C. and a humidity of 35% RH for 30 minutes to release the transfer layer 14 having a thickness of 7 μm. It was formed on a mold layer. Transfer sheet No. 2, the adhesive strength between the release layer composed of the transfer layer 14 and the release layer 13 and the adhesive layer 12 was 2.0 g / cm, the area expansion coefficient of the release layer was 103.0%, The surface specific resistance was 1 × 10 ¹¹ Ω.

Transfer Sheet Production Example 3 (Comparative Example) Transfer sheet No. 1 was prepared in the same manner as in Transfer Sheet Production Example 1 except that the transfer layer 14 was formed using a coating liquid of the following material.
3 was prepared. Highly saponified polyvinyl alcohol solution (saponification degree 98%, solid content 14% by weight) 100 parts by weight Antistatic agent (cationic surfactant) 2.5 parts by weight Water 5 parts by weight

Transfer sheet No. 3, the transfer layer 14
The adhesive strength between the release layer composed of the release layer 13 and the adhesive layer 12 is 3.0 g / cm, and the area expansion coefficient of the release layer is 10 g / cm.
1.8%, and the surface resistivity of the transfer layer 14 is 2 × 1
It was 0 ¹⁰ Ω.

Transfer Sheet Production Example 4 (Comparative Example) Transfer sheet No. 1 was prepared in the same manner as in transfer sheet production example 1 except that the transfer layer 14 was formed using a coating solution of the following material.
4 was prepared. Low saponified polyvinyl alcohol solution (degree of saponification 85%, solid content 14% by weight) 100 parts by weight Antistatic agent (cationic surfactant) 2.5 parts by weight Water 5 parts by weight

Transfer sheet No. 4, the transfer layer 14
The adhesive strength between the release layer comprising the release layer 13 and the adhesive layer 12 is 2.5 g / cm, and the area expansion coefficient of the release layer is 10 g / cm.
7.0%, and the surface resistivity of the transfer layer 14 is 5 × 1
0 ¹¹ Ω.

Transfer Sheet No. 5 (Comparative Example) Transfer sheet No. 5 was prepared in the same manner as in Transfer Sheet No. 2 except that the transfer layer 14 was formed using a coating liquid of the following material.
5 was prepared. Highly saponified polyvinyl alcohol solution (99% saponification, solid content 14% by weight) 100 parts by weight Antistatic agent (cationic surfactant) 2.5 parts by weight Silicon dioxide fine powder (BET specific surface area 150 m ² / g) 6 parts by weight Water 5 parts by weight

Transfer sheet No. 5, the transfer layer 14
The adhesive strength between the release layer comprising the release layer 13 and the adhesive layer 12 is 2.5 g / cm, and the area expansion coefficient of the release layer is 10 g / cm.
1.6%, and the surface resistivity of the transfer layer 14 is 1 × 1
It was 0 ¹⁰ Ω.

Example of Transfer Sheet Production No. 6 (Comparative Example) Transfer sheet No. 6 was prepared in the same manner as in Transfer sheet manufacturing example 2 except that the transfer layer 14 was formed using a coating liquid of the following material.
6 was prepared. Low saponified polyvinyl alcohol solution (88% saponification, solid content 14% by weight) 100 parts by weight Antistatic agent (cationic surfactant) 2.5 parts by weight Silicon dioxide fine powder (BET specific surface area 150 m ² / g) 6 parts by weight Water 5 parts by weight

Transfer sheet No. 6, the transfer layer 14
The adhesive strength between the release layer composed of the release layer 13 and the adhesive layer 12 is 3.0 g / cm, and the area expansion coefficient of the release layer is 10 g / cm.
6.5%, and the surface resistivity of the transfer layer 14 is 3 × 1
0 ¹¹ Ω.

Production Example of Transfer Sheet No. No. 7 except that the transfer layer 14 was formed using a coating solution of the following material.
7 was prepared. High saponified polyvinyl alcohol solution (Saponification degree 98%, solid content 14% by weight) 70 parts by weight Low saponified polyvinyl alcohol solution (Saponification degree 85%, solids 14% by weight) 30 parts by weight Antistatic agent (cationic) (Surfactant) 2.5 parts by weight Water 5 parts by weight

Transfer sheet No. 7, the transfer layer 14
The adhesive strength between the release layer composed of the release layer 13 and the adhesive layer 12 is 3.0 g / cm, and the area expansion coefficient of the release layer is 10 g / cm.
2.0%, and the surface resistivity of the transfer layer 14 is 5 × 1
It was 0 ¹⁰ Ω.

Production Example of Transfer Sheet No. 8 except that the transfer layer 14 was formed using a coating solution of the following material.
8 was prepared. High saponified polyvinyl alcohol solution (degree of saponification 99%, solid content 14% by weight) 70 parts by weight Low saponified polyvinyl alcohol solution (saponification degree 88%, solid content 14% by weight) 30 parts by weight Antistatic agent (cationic Surfactant) 2.5 parts by weight Silicon dioxide fine powder (BET specific surface area 150 m ² / g) 6 parts by weight Water 5 parts by weight

Transfer sheet No. 8, the transfer layer 14
The adhesive strength between the release layer composed of the release layer 13 and the adhesive layer 12 is 3.5 g / cm, and the area expansion coefficient of the release layer is 10 g / cm.
2.5%, and the surface resistivity of the transfer layer 14 is 2 × 1
It was 0 ¹⁰ Ω.

Example of Transfer Sheet Production No. 9 except that the transfer layer 14 was formed using a coating solution of the following material.
9 was prepared. High saponified polyvinyl alcohol solution (degree of saponification 99%, solid content 14% by weight) 50 parts by weight Low saponified polyvinyl alcohol solution (saponification degree 88%, solid content 14% by weight) 50 parts by weight Antistatic agent (cationic (Surfactant) 2.5 parts by weight Water 5 parts by weight

The transfer sheet No. 9, the transfer layer 14
The adhesive strength between the release layer comprising the release layer 13 and the adhesive layer 12 is 2.5 g / cm, and the area expansion coefficient of the release layer is 10 g / cm.
3.0%, and the surface resistivity of the transfer layer 14 is 5 × 1
It was 0 ¹⁰ Ω.

Production Example of Transfer Sheet No. The transfer sheet No. 10 was prepared in the same manner as in the transfer sheet manufacturing example 2 except that the transfer layer 14 was formed using a coating solution of the following material.
10 was prepared. High saponified polyvinyl alcohol solution (99% saponification, solid content 14% by weight) 50 parts by weight Low saponified polyvinyl alcohol solution (88% saponification, 14% solids content) 50 parts by weight Silicon dioxide fine powder (BET) Specific surface area 150m ² / g) 6 parts by weight Water 5 parts by weight

Transfer sheet No. In 10, the transfer layer 1
4 and the release layer 13 and the adhesive layer 12 had an adhesive strength of 2.5 g / cm and an area expansion coefficient of 1 for the release layer.
03.0%, and the surface resistivity of the transfer layer 14 is 2 ×
It was 10 ¹² Ω.

Production Example of Transfer Sheet No. The transfer sheet No. 11 was prepared in the same manner as in the transfer sheet manufacturing example 2 except that the transfer layer 14 was formed using a coating solution of the following material.
11 was prepared. High saponified polyvinyl alcohol solution (degree of saponification 99%, solid content 14% by weight) 50 parts by weight Low saponified polyvinyl alcohol solution (saponification degree 88%, solid content 14% by weight) 50 parts by weight Antistatic agent (cationic (Surfactant) 7.5 parts by weight Silicon dioxide fine powder (BET specific surface area 150 m ² / g) 6 parts by weight Water 5 parts by weight

Transfer sheet No. 11, the transfer layer 1
The adhesive strength between the release layer composed of the release layer 4 and the release layer 13 and the adhesive layer 12 is 3.0 g / cm, and the area expansion coefficient of the release layer is 1
03.0%, and the surface resistivity of the transfer layer 14 is 5 ×
It was 10 ⁷ Ω.

Example of Transfer Sheet Production No. The both surfaces of the high-quality paper of 12 basis weight 80 g / m ^2, transfer coated paper that the sealing treatment at coating solution containing starch and calcium carbonate in the following formulation as a substrate 11 (base paper) sheet Production Example 2 In the same manner as in the above, transfer picture transfer sheet N0.12 was obtained.

Adhesive layer Acrylic resin (Covercoat Resin LO-316, manufactured by Ryo Kagaku Co., Ltd.) 100 parts by weight Toluene 100 parts by weight Silicon dioxide fine powder (BET specific surface area 150 m ² / g) 4 parts by weight

A coating solution obtained by mixing the above materials was applied to the surface of the substrate 11 by a screen coater, and an adhesive layer 12 having a thickness of 9 μm was formed on the substrate 11.

Transfer Layer High Saponified Polyvinyl Alcohol Solution (Saponification Degree 99%, Solids 14% by Weight) 50 parts by weight Low Saponified Polyvinyl Alcohol Solution (Saponification degree 88%, Solids 14% by weight) 50 parts by weight Charge Inhibitor (cationic surfactant) 2.5 parts by weight Silicon dioxide fine powder (BET specific surface area 150 m ² / g) 6 parts by weight Silicone (KM73, manufactured by Shin-Etsu Chemical Co., Ltd.) 4 parts by weight Water 5 parts by weight

Transfer sheet No. In 12, the transfer layer 1
The adhesive strength between the adhesive layer 4 and the adhesive layer 12 is 2.0 g / cm,
The area expansion rate of the transfer layer is 103.5%, and the transfer layer 14
Had a surface specific resistance of 5 × 10 ¹⁰ Ω.

[0151]

[Table 1]

Production Example No. of Toner Po Riesuteru resin obtained by condensation reaction with 1 propoxylated bisphenol A and fumaric acid No. 1 (acid value 10.8 mg KOH / g) 100 parts by weight Cyan colorant (CI Pigment Blue 15: 3) 4 parts by weight Negative charge control agent (chromium complex compound) 4 parts by weight

The above materials were sufficiently premixed with a Henschel mixer, melt-kneaded with a twin-screw extruder, cooled, roughly crushed using a hammer mill to about 1-2 mm, and then finely crushed by an air jet method. Finely ground.
Further, the obtained finely pulverized material was strictly removed at the same time by a multi-division classifier to obtain a cyan toner having a predetermined particle size distribution.

On the other hand, as a fluidity improver, n-C ₄ H _{9 was} added to 100 parts by weight of hydrophilic titanium oxide fine powder (primary average particle diameter 0.02 μm, BET specific surface area 140 m ² / g).
Surface treatment was performed using 20 parts by weight of —Si (OCH ₃ ) ₃ to obtain a hydrophobic titanium oxide fine powder having a primary average particle diameter of 0.02 μm and a hydrophobicity of 70%.

100 parts by weight of the cyan toner and 1.5 parts by weight of the hydrophobic titanium oxide fine powder were mixed to form a cyan toner No. 1 having the hydrophobic titanium oxide fine powder on the surface of the toner particles.
1 was prepared.

Production Example of Toner Instead of 2 to 4 cyan colorants, 5 parts by weight of a magenta colorant (CI Pigment Red 122), 6 parts by weight of a yellow colorant (CI Pigment Yellow 173) and 5 parts by weight of a black colorant (carbon black) 5 Except for using parts by weight, toner production example No. Magenta toner N to which hydrophobic titanium oxide fine powder is externally added in the same manner as in Example 1.
o. 1, yellow toner no. 1 and black toner N
o. 1 was prepared.

Production Example of Developer Nos. 1 to 4 cyan toner Nos. 1 and 95 parts by weight of Cu—Zn—Fe-based magnetic ferrite carrier particles (average particle size: 50 μm) coated on the surface with a silicone resin, and mixed with a two-component developer No. for cyan. 1 was prepared. Similarly, magenta toner No. 1, yellow toner no. 1 and black toner No. 1 No. 1 using magenta two-component developer No. 1 1, two-component developer No. for yellow No. 1 and black two-component developer No. 1 1 was prepared.

Production Examples of Toner Nos. 5 to 8 Polyester resin No. 5 obtained by the condensation reaction of propoxylated bisphenol A with fumaric acid. 2 (acid value 1.9 mg KOH / g), except that Nos. Cyan toner No. 1 in the same manner as in Nos. 1 to 4.
2, magenta toner no. 2, yellow toner no. 2
And black toner No. 2 was prepared.

Production Example of Developer Nos. 5 to 8 cyan toner Nos. 2, magenta toner no. 2, yellow toner no. 2 and black toner no. No. 2 except that developer No. 2 was used. In the same manner as in Nos. 1 to 4, two-component developer No. for cyan was used. 2, two-component developer for magenta 2, two-component developer No. for yellow 2 and a two-component developer No. 2 for black. 2 was prepared.

Production Examples of Toner Nos. 9 to 12 Polyester resin No. 9 obtained by a condensation reaction of propoxylated bisphenol A and fumaric acid. 3 (acid value 2
5.4 mg KOH / g), except that toner production example Nos. Cyan toner No. 1 in the same manner as
3, magenta toner no. 3, yellow toner no. 3
And black toner No. 3 was prepared.

Production Example of Developer Nos. 9 to 12 cyan toner Nos. 3, magenta toner no. 3, yellow toner no. 3 and black toner no. No. 3 except that developer No. 3 was used. In the same manner as in Nos. 1 to 4, two-component developer No. for cyan was used. 3, two-component developer for magenta 3, two-component developer No. for yellow No. 3 and two-component developer No. for black. 3 was prepared.

[0162] Production Example Nos13 to 16 styrene -n- butyl acrylate toner - mono -n- butyl maleate copolymer (copolymerization weight ratio 77: 16: 7) except for using a toner of Preparation the Nos. Cyan toner No. 1 in the same manner as in Nos. 1 to 4. 4, magenta toner No. 4, yellow toner no. 4 and black toner no. 4 was prepared.

Production Example of Developer Nos. 13 to 16 cyan toner No. 4, magenta toner no. 4, yellow toner no. 4 and black toner no. No. 4 except that developer No. 4 was used. In the same manner as in Nos. 1 to 4, two-component developer No. for cyan was used. 4, two-component developer for magenta 4, two-component developer No. for yellow No. 4 and two-component developer No. for black. 4 was prepared.

Production Examples of Toner Nos 17 to 20 Polyester resin No. 17 obtained by a condensation reaction between propoxylated bisphenol A and fumaric acid. 4 (acid value 1
(1.3 mg KOH / g), except that toner production example Nos. Cyan toner No. 1 in the same manner as in Nos. 1 to 4.
5, magenta toner no. 5, yellow toner no. 5
And black toner No. 5 was prepared.

Production Example of Developer Nos. 17-20 cyan toner No. 5, magenta toner no. 5, yellow toner no. 5 and black toner no. No. 5 except that developer No. 5 was used. In the same manner as in Nos. 1 to 4, two-component developer No. for cyan was used. 5, two-component developer for magenta 5, two-component developer No. for yellow 5 and a two-component developer No. 5 for black. 5 was prepared.

Production Examples of Toner Nos 21 to 24 Polyester resin No. 21 obtained by a condensation reaction between propoxylated bisphenol A and fumaric acid. 5 (acid value 9.7 mg KOH / g), except that Nos. In the same manner as in Nos. 1 to 4, cyan toner No.
6, magenta toner no. 6, yellow toner no. 6
And black toner No. 6 was prepared.

Production Example of Developer Nos. Cyan toner Nos. 21 to 24 6, magenta toner no. 6, yellow toner no. 6 and black toner no. No. 6 except that developer No. 6 was used. In the same manner as in Nos. 1 to 4, two-component developer No. for cyan was used. 6, two-component developer No. for magenta 6, two-component developer No. for yellow 6 and a two-component developer No. 6 for black. 6 was prepared.

Production Example No. of Toner C. 25 as a magenta colorant; I. Pigment Red
Magenta Toner No. 57 in the same manner as in Production Example 2 for toner except that 3.5 parts by weight of 57: 1 was used. 7 was prepared.

Production Example No. of Developer 25 magenta toner no. Preparation Example No. 7 of the developer except that No. 7 was used Magenta two-component developer N
o. 5 was prepared.

Production Example No. of Toner C. 26 yellow colorant; I. Pigment Yel
low toner 12 was used in the same manner as in toner production example 3 except that 4 parts by weight of yellow toner No. 12 was used. 7 was prepared.

Production Example No. of Developer 26 yellow toner no. Preparation Example No. 7 of the developer except that No. 7 was used 7, a two-component developer N for yellow
o. 8 was prepared.

Production Example No. of Toner No. 27 Toner Production Example No. 27 Weight average particle diameter 13
μm cyan toner No. 7 was prepared.

Production Example No. of Developer 27 cyan toner no. 7, except that developer No. 7 was used. In the same manner as in No. 1, a two-component cyan developer No. 1 was used. 7
Was prepared.

Production Example No. of Toner Cyan toner No. 28 except that hydrophobic silica fine powder (BET specific surface area: 200 m ² / g) treated with dimethyldichlorosilane was externally added instead of hydrophobic titanium oxide fine powder. In the same manner as in the case of 8 was prepared.

Production Example No. of Developer 28 cyan toner no. Except that No. 8 was used, Production Example No. In the same manner as in the case of developer No. 1 for cyan. 8 was prepared.

[0176]

[Table 2]

Example 1 Two-component developer No. for each color 1 and transfer sheet No. 1 1
Is a full-color laser copying machine (CL) schematically shown in FIG.
C700, manufactured by Canon Inc.). 1
A full-color fixed image having a mirror image relationship with the original was formed on the transfer layer 14 of FIG. A mirror image of the document was formed on the transfer layer 14 without causing offset development or winding of the transfer sheet around the heat and pressure fixing roller, and the color tone of the full-color image of the document was well reproduced.

The transfer layer 14 having the full-color fixed image and the release layer 13 are peeled from the adhesive layer 12, the surface of the full-color fixed image is brought into close contact with coated cardboard, and the release layer is heated with a household iron adjusted to 110 ° C. 13 was heated and pressurized to heat and fix a full-color fixed image on coated cardboard. Next, when the release layer 13 and the transfer layer 14 were swollen with a 10% aqueous ethanol solution, the release layer composed of the release layer 13 and the transfer layer 14 could be easily released from the full-color fixed image, and the original was faithful. The full-color fixed image reproduced in Example 1 was transferred to coated cardboard and painted.

A full-color fixed image fixed on coated cardboard was subjected to a light fastness test according to JIS K 7102. As a result, there was no change in color tone even after 400 hours of light irradiation, and the full-color fixed image showed good light fastness. Had.

Further, it was possible to transfer the fixed image to a second image carrier, such as an iron plate other than coated cardboard, and transfer the image.

The transfer sheet No. When No. 1 was left in a high-temperature and high-humidity environment (temperature: 30 ° C., humidity: 80% RH), good moisture resistance was exhibited. The transfer sheet No. When No. 1 was allowed to stand in a normal temperature and low temperature environment (temperature: 20 ° C., humidity: 10% RH), the dimensional change was small, and no curl occurred or only a slight curl in which the transfer layer surface was convex occurred.

Example 2 Transfer Sheet No. The transfer of the fixed image to coated cardboard was performed in the same manner as in Example 1 except that No. 2 was used. Good results were obtained in the same manner as in Example 1.

Comparative Example 1 Transfer sheet No. The transfer of a full-color fixed image to coated cardboard was performed in the same manner as in Example 1 except that Sample No. 3 was used. Since the area expansion coefficient of the release layer was small, image defects were partially observed in the fine line image portion in the transferred full-color fixed image.

Comparative Example 2 Transfer Sheet No. A transfer picture of a full-color fixed image on coated cardboard was made in the same manner as in Example 1 except that No. 4 was used. Since the area expansion coefficient of the release layer is large, the release force of the release layer to the full-color fixed image is too large, and a part where peeling is partially defective occurs, and a part having a different color tone from the original is seen in the full-color fixed image. Was.

Comparative Example 3 Transfer Sheet No. A transfer picture of a full-color fixed image on coated cardboard was performed in the same manner as in Example 2 except that No. 5 was used. Since the area expansion coefficient of the release layer was small, image defects were partially observed in the fine line image portion in the transferred full-color fixed image.

Comparative Example 4 Transfer Sheet No. The transfer picture of the full-color fixed image to the coated cardboard was performed in the same manner as in Example 2 except that No. 6 was used. Since the area expansion coefficient of the release layer is large, the release force of the release layer to the full-color fixed image is too large, and a part where peeling is partially defective occurs, and a part having a different color tone from the original is seen in the full-color fixed image. Was.

Examples 3 to 8 Transferring a full-color fixed image to coated cardboard was performed in the same manner as in Example 1 except that transfer sheets Nos 7 to 12 were used. The result was obtained.

Example 9 Cyan Toner No. No. 2 for cyan two-component developer No. 2 2, magenta toner no. Magenta two-component developer having yellow toner No. 2 No. 2 two-component developer No. 2 for yellow 2 and black toner N
o. No. 2 for black two-component developer No. 2 Transfer painting to coated cardboard was performed in the same manner as in Example 1 except that No. 2 was used.

Transfer sheet No. When forming a full-color fixed image on No. 1, an offset phenomenon was slightly observed at a ratio of about one out of ten sheets, but the full-color fixed image transferred to coated cardboard and painted was at a practical level.

Example 10 Cyan Toner No. No. 3 for cyan two-component developer No. 3 3, magenta toner no. Magenta two-component developer having yellow toner No. 3 No. 3 and a two-component developer No. 3 for yellow. 3 and black toner N
o. No. 3 for black two-component developer No. 3 A transfer picture to coated cardboard was performed in the same manner as in Example 1 except that No. 3 was used.

Since the fixing property between the full-color fixed image and the transfer layer of the release layer was strong, a larger amount of aqueous ethanol solution was required than in Example 1 when the full-color image was released from the release layer. The full-color fixed image transferred to the coated cardboard and painted was at a practical level.

Example 11 Cyan Toner No. No. 4 for cyan two-component developer No. 4 4, magenta toner no. Magenta two-component developer having yellow toner No. 4 No. 4 for yellow two-component developer No. 4 4 and black toner N
o. No. 4 for black two-component developer No. 4 A transfer picture to coated cardboard was performed in the same manner as in Example 1 except that No.4 was used.

The color mixing properties were inferior to those of the respective color toners used in Example 1, and the color tone reproducibility of a full-color image was slightly inferior to Example 1.

Example 12 Cyan Toner No. No. 5 for cyan two-component developer No. 5 5, magenta toner no. Magenta two-component developer having yellow toner No. 5 No. 5 for yellow two-component developer No. 5 5 and black toner N
o. No. 5 for black two-component developer No. 5 Transfer painting to coated cardboard was performed in the same manner as in Example 1 except that No. 5 was used.

The color mixing properties were inferior to those of the color toners used in Example 1, and the color tone reproducibility of a full-color image was slightly inferior to Example 1.

Example 13 Cyan Toner No. No. 6 for cyan two-component developer No. 6 6, magenta toner no. Magenta two-component developer having yellow toner No. 6 No. 6 two-component developer No. 6 for yellow 6 and black toner N
o. No. 6 for black two-component developer No. 6 Transfer painting to coated cardboard was performed in the same manner as in Example 1 except that No. 6 was used.

Although the full-color fixed image transferred to the coated cardboard and painted was at a practical level, the transfer sheet No. was compared with that of Example 1. In No. 1, the surface of a heating roller for forming a full-color fixed image was easily contaminated with toner.

Example 14 Magenta Toner No. No. 7 in a single color mode using a two-component developer for magenta. A magenta-fixed image was formed on Sample No. 1 and the magenta-fixed image was transferred to coated cardboard in the same manner as in Example 1. The magenta two-component developer No. of Example 1 was used. Compared with the case of the single-color mode 1, the highlight (halftone image density and the image portion were rough).

Example 15 Yellow toner no. No. 7 for yellow two-component developer No. 7 No. 7 in the single color mode in the transfer sheet No.
A yellow fixed image was formed on Sample No. 1 and transfer of the yellow fixed image to coated cardboard was performed in the same manner as in Example 1. The two-component developer No. for yellow of Example 1 was used. As compared with the case of the single-color mode 1, the highlight image portion was rough, and the light resistance was poor.

Example 16 Cyan Toner No. No. 7 for cyan two-component developer No. 7 No. 7 in the single color mode in the transfer sheet No. A cyan fixed image was formed on Sample No. 1 and transfer of the cyan fixed image to coated cardboard was performed in the same manner as in Example 1. The two-component cyan developer No. 1 of Example 1 was used. Compared with the case of the single color mode 1, the transfer picture of the coated cardboard has poor reproducibility in the fine line, reproducibility of the highlight portion and gradation, and transfers the fixed image from the release layer to the coated cardboard. In this case, the adhesion between the fixed image and the coated cardboard was inferior to Example 1.

Example 17 Cyan Toner No. No. 8 for cyan two-component developer No. 8 No. 8 in the single color mode in the transfer sheet No. A cyan fixed image was formed on Sample No. 1 and transfer of the cyan fixed image to coated cardboard was performed in the same manner as in Example 1. Under normal environment, low temperature and low humidity environment, and high temperature and high humidity environment,
Compared to the two-component cyan developer of Example 1, the variation in the image density of the fixed image was large, and the reproducibility of the highlight portion was poor.

[0202]

According to the image forming method of the present invention, a fixed image can be satisfactorily fixed and transferred to a predetermined place of a second image carrier.
This has the effect that a transfer picture capable of favorably suppressing damage to a fixed image can be obtained.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view of a specific example of a transfer sheet as a first image carrier used in the present invention.

FIG. 2 is a schematic sectional view of another specific example of a transfer sheet as a first image carrier used in the present invention.

FIG. 3 is a schematic explanatory view of an electrophotographic apparatus for forming a fixed image on a first image carrier.

FIG. 4 is a schematic explanatory view of a transfer sheet having a fixed image on a transfer layer.

FIG. 5 is an explanatory diagram of a step of peeling a release layer having a fixed image from an adhesive layer.

FIG. 6 is an explanatory diagram of a step of adhering and adhering a fixed image to a surface of a second image carrier.

FIG. 7 is an explanatory diagram of a step of transferring a fixed image to a second image carrier.

[Explanation of symbols]

 Reference Signs List 1 first image carrier (transfer sheet) 11 base material 12 adhesive layer 13 release layer 14 transfer layer

──────────────────────────────────────────────────続 き Continuation of front page (51) Int.Cl. ⁷ Identification symbol FI G03G 15/16 101 G03G 9/08 361 (56) References JP-A-3-144657 (JP, A) JP-A-2-198454 (JP, A) JP-A-59-149970 (JP, A) JP-A-7-333882 (JP, A) JP-A-7-209895 (JP, A) JP-A-8-50380 (JP, A) ( 58) Field surveyed (Int.Cl. ⁷ , DB name) G03G 7/00

Claims (18)

(57) [Claims] 1. A toner image comprising a toner having toner particles and an external additive is formed on a layered surface of a first image bearing member having a layer having a release layer formed on a substrate, and the toner image is formed as a first layer. and fixed on the surface of the image bearing member and a fixed image is formed, the peeling layer having the fixed image is peeled from the first image bearing member, and transferring the fixed image from the release layer to the second image carrier Te, an image forming method for forming an image on the second image bearing member, a stack of the first image bearing member, having at least an adhesive layer and a release layer, the release layer having at least a transfer layer, The release layer has the following formula : Wherein, S _L is releasing the release layer from the first image bearing member, warm
Release layer under low temperature and low humidity environment of 15 ° C and 10% RH
Shows the area after leaving for 2 days, S _H temperatures the peel layer
Released for 24 hours in a high-temperature, high-humidity environment of 30 ° C and 80% RH
2 shows the area of the release layer after being placed. ] Is 102 - 106% area expansion ratio calculated from an image forming method, characterized in that, for transferring the fixed image while swelling the peeling layer to the second image bearing member. 2. The image forming method according to claim 1, wherein the toner image is heated and pressed on the first image carrier. 3. The fixing device according to claim 1, wherein the release layer is pressed against the surface of the second image carrier while being heated via the fixed image, and the fixed image is transferred from the release layer to the second image carrier. Image forming method. 4. The transfer layer is formed of a composition of a first polyvinyl acetate having a saponification degree of 90% or more and a second polyvinyl acetate having a saponification degree of less than 90%. Has a polyvinyl acetate content of 25
The image forming method according to any one of claims 1 to 3, wherein the amount is from not less than 75% by weight to less than 75% by weight. 5. The image forming method according to claim 1, wherein the toner has toner particles containing a binder resin and a colorant, and the binder resin is a polyester resin. 6. The polyester resin has an acid value of 2 to 25 mgK.
The image forming method according to claim 5, wherein OH / g is used. 7. The toner image is formed of a toner selected from the group consisting of a cyan toner, a magenta toner, a yellow toner and a black toner. The cyan toner contains a copper phthalocyanine pigment, and the magenta toner is a quinacridone pigment. The image forming method according to claim 1, wherein the yellow toner contains an isoindolinone-based pigment. 8. The toner has a weight average particle diameter of 3 to 12 μm.
m, and 15 to 45% by number of toner particles having a particle size of 5 μm or less in the number distribution of toner, and 0.1 to 5% by volume of toner particles having a particle size of 12.7 to 16.0 μm in the volume distribution of the toner. The image forming method according to any one of claims 1 to 7, wherein the toner contains 1% by volume or less of toner particles having a particle size of 16.0 µm or more. 9. The toner has a weight average particle diameter of 4 to 10 μm.
9. The image forming method according to claim 8, wherein toner particles having a particle size of 12.7 to 16.0 μm are contained in an amount of 0.1 to 4% by volume. 10. The binder resin of the toner has a weight average molecular weight (Mw) of 3,000 to 150,000 and a number average molecular weight (Mn) of 1,500 to 15,000.
10. The image forming method according to any one of claims 1 to 9. 11. A binder resin for toner having Mw of 3,000.
0 to 100,000, and Mn is 1,500 to 10,000.
The image forming method according to claim 10, wherein Mw / Mn is 2 to 10. 12. The toner has a weight average particle diameter of 4 to 10 μm.
And the primary average particle diameter is 0.01 to 0.2 μm.
The image forming method according to any one of claims 1 to 11, further comprising m titanium oxide fine particles. 13. The image forming method according to claim 12, wherein the titanium oxide fine particles are hydrophobic titanium oxide fine particles. 14. The transfer layer has a surface specific resistance value at a temperature of 20.
The image forming method according to claim 1, wherein the temperature is 10 ^{8 to} 10 ¹² Ω in an environment of a temperature of 65 ° C. and a humidity of 65% RH. 15. The image forming method according to claim 1, wherein the transfer layer contains fine powder of silicon dioxide. 16. A first image carrier having a sheet shape,
The image forming method according to claim 1, further comprising a laminate having a release layer on one surface of the substrate. 17. A method in which the release layer is pressed against the surface of the second image carrier while being heated via the fixed image, the fixed image is adhered to the surface of the second image carrier, and then the release layer is swollen and then released. 17. The image forming method according to claim 1, wherein the layer is separated from the fixed image and the fixed image is transferred to a second image carrier. 18. The image forming method according to claim 17, wherein after the release layer is swollen with hydroalcohol, the release layer is released from the fixed image.