KR101011712B1 - Electrophotographic image-receiving sheet and image-forming process using the same - Google Patents

Abstract

(Problem) By forming a toner aqueous layer containing a thermoplastic resin on a support, and employing an aqueous sheet in which the peeling force is optimized between the fixing belt surface and the surface of the aqueous sheet on the side of the toner aqueous layer on the support, It is an object of the present invention to provide a fixing belt type electrophotographic award sheet which realizes stable paper feeding without sacrificing aptitude and without being offset, and has good glossiness, abundant photo appreciation, and a good image.

(Solution means) A fixing belt type electrophotographic award sheet in which a toner aqueous layer containing a polymer is formed on a support, wherein the support belt is formed from the surface of the fixing belt on the surface of the electrophotographic award sheet on the side of the toner aqueous layer with respect to the support. The peeling force of 1-20N / m in the said electrophotographic waterborne sheet surface temperature 50 degreeC, or the peeling force from the fixing belt surface is 1-20N in 90 degreeC of the said electrophotographic waterborne sheet surface temperature. / m is a fixing belt type electrophotographic award sheet.

Description

ELECTTROPHOTOGRAPHIC IMAGE-RECEIVING SHEET AND IMAGE-FORMING PROCESS USING THE SAME}

1 is a schematic view showing an example of the fixing belt type electrophotographic apparatus of the present invention.

Fig. 2 is a schematic diagram showing a measurement state of peeling force in the present invention.

It is a schematic sectional drawing which shows an example of the electrophotographic award sheet of this invention.

(Explanation of the sign)

1 Award Sheet 1a Award Sheet Surface

2 Toner Water Layer 3 Support

4 backing layer 12 toner

13 fixing belt 13a fixing belt surface

14 Heating roller 15 Pressing roller

16 Chiller 17 Tension Roller

TECHNICAL FIELD The present invention relates to an image forming method using a fixing belt type electrophotographic water sheet and the electrophotographic water sheet. In particular, the long term aptitude is greatly improved and is used in fixing belt type electrophotographic. A suitable fixing belt type electrophotographic award sheet and an image forming method using the award sheet.

The electrophotographic method is a printing method which has a quick printing speed by a dry process and is used as an output machine of a copying machine or a personal computer. This electrophotographic method is accomplished by transferring a toner image to an aqueous material, and fixing the toner image to the aqueous material by passing it through a fixing unit heated, and / or pressurized, such as a fixing roller or a fixing belt. As the water-receiving material, in addition to general-purpose paper (normal paper, good-quality paper, etc.), in order to improve the glossiness and bring it closer to the photographic sense, the water-receiving material for electrophotography in which a toner aqueous layer containing a thermoplastic resin was formed on a support was used. It is proposed (for example, refer patent document 1 and 2).

Such a water phase material has a drawback that it is easy to be offset when peeled from the fixing unit, and is likely to cause a conveyance failure. Therefore, a constant release effect such as a silicone-based compound, a fluorine compound, and a wax is applied to the toner water layer or the outermost layer. Adding the release agent which has is proposed (for example, refer patent documents 3-6).

However, the quantity of the mold release agent conventionally is optimized with respect to the fixing roller type electrophotographic method, and does not necessarily correspond with the quantity calculated | required by the water sheet used by the fixing belt type electrophotographic method. That is, in the electrophotographic method of a fixing roller type | mold, a water phase sheet is a thing peeled from a fixing roller immediately after heating with a fixing roller. Therefore, in order to improve the release property of a fixing roller and a water phase sheet, a large amount of mold release agent was added to the layer which comprises the surface of the water phase sheet which contact | connects a fixing roller (for example, refer patent document 6).

In addition, in the fixing belt type electrophotographic method, it is necessary that the surface of the water sheet and the fixing belt surface are in close contact with each other during the passage of the fixing unit. Therefore, incompatibility arises because only the peelability of the fixing belt which is a fixing part, and a water phase sheet is high. The fixing belt type electrophotographic method is because a glossy image cannot be obtained if the fixing belt and the water sheet are not in contact with each other while passing through the fixing unit. Therefore, the peelability of the fixing belt and the water sheet can be adjusted to such an extent that the fixing belt and the water sheet are brought into close contact with each other during the passage of the fixing unit, and that the peeling of the water sheet from the fixing belt can be performed without causing an offset. There is a need. Therefore, the amount of the release agent added to the layer constituting the surface of the water-phase sheet in contact with the fixing belt is also an electrophotographic method of the fixing belt system, and therefore it is necessary to optimize it.

(Patent Document 1)

Japanese Patent Laid-Open No. 4-212168

(Patent Document 2)

Japanese Patent Laid-Open No. 8-211645

(Patent Document 3)

Japanese Patent Laid-Open No. 11-52604

(Patent Document 4)                         

Japanese Patent Laid-Open No. 11-52605

(Patent Document 5)

Japanese Patent Laid-Open No. 11-52606

(Patent Document 6)

Japanese Patent Laid-Open No. 11-212292

This invention solves all the problems in the said prior art, and makes it a subject to achieve the following objectives. That is, the first object of the present invention is a fixing sheet type electrophotographic award sheet in which a toner aqueous layer containing a thermoplastic resin is formed on a support, wherein the surface of the fixing belt and the support are on the side of the toner aqueous layer. By adopting the water sheet which optimizes the peeling force between the surface of the water sheet, it realizes stable paper feeding without being offset, and has a good glossiness, is rich in photographic feeling, and realizes a good image. It is to provide the award sheet for photography.

Further, a second object of the present invention is to optimize the amount of the releasing agent added to the layer constituting the surface of the water sheet for the fixing belt type electrophotographic, without offsetting the fixing roller and the fixing belt, The long term aptitude is greatly improved, and an object of the present invention is to provide a glossy fixable belt type electrophotographic award sheet.

Further, the third object of the present invention is to achieve stable paper feeding without being offset by the fixing roller and the fixing belt even when using an oilless machine without fixing oil, and has excellent glossiness so far, It is to provide an image forming method which is rich in photographic sensation and can form a good image.

As a means for solving the said subject, it is as follows.

A fixing belt type electrophotographic award sheet in which a toner aqueous layer containing a polymer is formed on a <1> support, wherein the peeling from the surface of the fixing belt of the surface of the electrophotographic award sheet on the side of the toner aqueous layer with respect to the support A force is 1-20 N / m in said electrophotographic water sheet surface temperature of 50 degreeC, The fixing belt type electrophotographic water sheet of Claim 1 characterized by the above-mentioned.

<2> A fixing belt type electrophotographic award sheet in which a toner aqueous layer containing a polymer is formed on a support, wherein the peeling from the surface of the fixing belt on the surface of the electrophotographic award sheet on the side of the toner aqueous layer with respect to the support. A force is 1-20 N / m in the said electrophotographic water sheet surface temperature of 90 degreeC, The fixing sheet type electrophotographic water sheet of Claim 1 characterized by the above-mentioned.

<3> The surface tension (γ _p ) (mN / m) and the toner fixing temperature of the polymer according to <1> or <2>, wherein the toner aqueous layer contains a polymer, and is measured at a toner fixing temperature. The surface tension γ _t of the toner measured in (mN / m) satisfies the condition of the following formula (I), characterized in that the fixing sheet type electrophotographic award sheet.

γ _p -γ _t ≥8 (I)

<4> In <1> or <2>, the electrophotographic award sheet is used in an electrophotographic apparatus having a fixing belt, and the contact angle (θ) of the molten toner at the toner fixing temperature to the surface of the toner aqueous layer ₁ ) (.) And a contact angle (θ ₂ ) (.) With respect to the surface of the fixing belt of the molten toner at the toner fixing temperature satisfy the condition of the following formula (II). Award sheet for electrophotography.

θ ₂ -θ ₁ ≥10 (II)

<5> The <1> or <2>, wherein the electrophotographic award sheet is used in an electrophotographic apparatus having a fixing belt, and the surface free energy G ₁ (mN / m) of the surface of the toner aqueous layer and the fixing belt surface the surface free energy _{(G 2) (mN / m} ) the image-receiving sheet for the formula fixing belt type electrophotographic, characterized in that to satisfy the condition of (III) a.

G ₁ -G ₂ ≥10 (III)

<6> The polar component value (g ^p ₁ ) (mN) of the surface free energy of the surface of the toner aqueous layer is used in an electrophotographic apparatus having a fixing belt, wherein the electrophotographic award sheet is used in <1> or <2>. / m) and the polar component value (g ^p ₂ ) (mN / m) of the surface free energy on the surface of the fixing belt satisfy the condition of the following formula (IV). Sheet.

g ^p ₁ -g ^p ₂ ≥0.3 (IV)

<7> The belt type electrophotographic film according to <1> or <2>, wherein the material of the surface of the fixing belt is at least one member selected from the group consisting of silicone rubber, fluororubber, silicone resin and fluororesin. Award sheet.

<8> The fixing sheet type electrophotographic water receiving sheet according to <1> or <2>, wherein a layer made of a fluorocarbon siloxane rubber having a uniform thickness is formed on the surface of the fixing belt.

<9> The <1> or <2>, which has a layer of silicone rubber of uniform thickness on the surface of the fixing belt, and forms a layer of fluorocarbon siloxane rubber on the surface of the silicone rubber layer A fixing belt type electrophotographic award sheet, comprising:

<10> The fixing sheet type electrophotographic water receiving sheet according to <8>, wherein the fluorocarbon siloxane rubber has a perfluoroalkyl ether group and / or a perfluoroalkyl group in the main chain.

<11> At least one mold release agent according to <1> or <2>, wherein the layer constituting the surface of the aqueous sheet on the side of the toner aqueous layer with respect to the support is selected from the group consisting of a silicone compound, a fluorine compound, a wax and a mat agent. An award sheet for fixing belt type electrophotographic, characterized in that it contains a.

<12> The fixing belt type electron according to <11>, wherein the content of the release agent is 0.1 to 20% by mass with respect to the mass of the layer constituting the surface of the aqueous sheet on the side of the toner aqueous layer with respect to the support. Award sheet for photos.

<13> The fixing sheet type electrophotographic water receiving sheet according to <11>, wherein the release agent is a wax, the wax is a natural wax, and the natural wax is at least one of a vegetable wax and a mineral wax.

<14> The fixing sheet type electrophotographic water receiving sheet according to <13>, wherein the natural wax is a plant wax, and the plant wax is a carnauba wax having a melting point of 70 to 95 ° C.

<15> The fixing sheet type electrophotographic water receiving sheet according to <13>, wherein the natural wax is a mineral wax, and the mineral wax is montan wax having a melting point of 70 to 95 ° C.

<16> The fixing sheet type electrophotographic water receiving sheet according to <1> or <2>, wherein the polymer is a self-dispersing water-based polyester resin emulsion that satisfies the following characteristics (1) to (4).

(1) Number average molecular weight (Mn) = 5000-10000

(2) Molecular weight distribution (weight average molecular weight / number average molecular weight) ≤ 4

(3) Glass transition temperature (Tg) = 40-100 degreeC

(4) Volume average particle diameter = 20-200 nmφ

<17> The fixing sheet type electrophotographic water receiving sheet according to <1> or <2>, wherein the support is selected from base paper, synthetic paper, synthetic resin sheet, coated paper, and laminated paper.

<18> The toner housed in <1> or <2> contains at least a binder resin and a colorant, and the volume average particle diameter of the toner is 0.5 µm or more and 10 µm or less, and the volume average. An award sheet for fixing belt type electrophotographic, characterized in that the particle size distribution index (GSDv) is 1.3 or less.

<19> The fixing belt type electrophotograph according to <18>, wherein the ratio (GSDv / GSDn) of the volume average particle size distribution index GSDv and the number average particle size distribution index GSDn is 0.95 or more. Dragon award sheet.

<20> The fixing sheet type electrophotographic water receiving sheet according to <18>, wherein an average value of a shape coefficient represented by the following formula is 1.00 to 1.50.

Shape factor = (π × L ² ) / (4 × S)

(Where L is the maximum length of the toner particles and S is the projection area of the toner particles).

<21> The process according to <18>, wherein the toner accommodated in the toner aqueous layer forms agglomerated particles in a dispersion formed by dispersing at least (i) resin particles to prepare agglomerated particle dispersions, (ii) the agglomerated particles. Adding and mixing a fine particle dispersion obtained by dispersing fine particles in the dispersion to adhere the fine particles to the aggregated particles to form adherent particles; and (iii) heating the fuse particles to fuse the attached particles to form toner particles. It is obtained by the manufacturing method of the toner containing, The fixing belt type electrophotographic award sheet characterized by the above-mentioned.                     

<22> An image forming method using the fixing belt type electrophotographic award sheet according to <1> or <2>, wherein a toner image is formed on the electrophotographic award sheet, and then the award sheet for electrophotography The image forming surface of the image forming method is heated and pressed by a fixing belt and a roller, cooled, and then peeled from the fixing belt.

<23> An image forming method using the fixing belt type electrophotographic award sheet according to <1> or <2>, wherein after forming a toner image on the electrophotographic award sheet, the sheet is fixed with a thermal roller And the image forming surface of the electrophotographic water-receiving sheet is further heated and pressed by a fixing belt and a roller, cooled, and then peeled from the fixing belt.

<24> The image formation according to <22>, wherein the formed toner image is cooled to a state below a softening point or a glass transition point of + 10 ° C. or lower of the binder resin used in the toner, and then peeled from the fixing belt. Way.

<25> The image formation according to <23>, wherein the formed toner image is cooled to a state below a softening point or a glass transition point of + 10 ° C or lower of the binder resin used in the toner, and then peeled from the fixing belt. Way.

<26> The fixing sheet type electrophotographic water receiving sheet according to <9>, wherein the fluorocarbon siloxane rubber has a perfluoroalkyl ether group and / or a perfluoroalkyl group in the main chain.

<27> The <17> above, wherein the support is a base paper, and the base paper has a ratio (Ea / Eb) between the longitudinal Young's modulus (Ea) and the transverse Young's modulus (Eb) in the range of 1.5 to 2.0. Award sheet for fixing belt type electrophotographic.

<28> The fixing sheet type electrophotographic water receiving sheet according to <17>, wherein the support is a base paper, and the oken smoothness of the surface of the toner aqueous layer side of the base paper is 210 seconds or more.

<29> The fixing sheet electrophotographic award sheet according to <1> or <2>, wherein the toner aqueous layer has a light transmittance of 78% or less.

The electrophotographic award sheet of the present invention is formed by forming a toner aqueous layer containing a thermoplastic resin on a support, and a peel force from the surface of the fixing belt on the surface of the electrophotographic award sheet on the side of the toner aqueous layer with respect to the support. The surface temperature of the said electrophotographic water image sheet is 1-20 N / m in 50 degreeC, and the surface temperature of the said electrophotographic water image sheet is 1-20 N / m in 90 degreeC, The said An electrophotographic award sheet in which the peeling force between the fixing belt surface and the surface of the electrophotographic award sheet on the side of the toner award layer is optimized can be employed, whereby the long-term aptitude is greatly improved and offset. It is possible to realize stable paper feeding without using the present invention, to have good glossiness, to have a rich photographic sense, and to realize a good image.

In the image forming method of the present invention, after the toner image is formed on the electrophotographic award sheet using the electrophotographic award sheet of the present invention, the image forming surface of the electrophotographic award sheet is fixed. The belt and the roller are heated and pressurized, cooled, and then peeled from the fixing belt. This makes it possible to prevent peeling of the electrophotographic award sheet and toner, or offset of the electrophotographic award sheet and toner components even when using an oilless machine without fixing oil, thereby realizing stable paper feeding. In addition, it has excellent glossiness so far, is rich in photographic sense, and a good image is realized.

(Example)

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

<Relationship between the fixing belt surface and the support sheet surface on the toner aqueous layer side>

The fixing belt type electrophotographic award sheet of the present invention requires that the peeling force between the fixing belt surface and the support body on the surface of the electrophotographic award sheet on the toner aqueous layer side is within a certain range. In the image forming method using the fixing sheet electrophotographic award sheet, not only improving the peelability of the electrophotographic award sheet from the fixing belt which is the fixing unit but also improving the surface of the fixing belt and the electrophotographic image during the passage of the fixing unit. This is because the sheet surface needs to be in close contact. Hereinafter, the image forming method using the fixing belt type electrophotographic water-receiving sheet shown in FIG. 1 is taken as an example, and it demonstrates concretely. In addition, the method of this invention is not limited to the method shown in FIG.

First, the electrophotographic award sheet 1 to which the toner is adhered is heated and pressurized in the heat presser A capable of melting and pressurizing the toner 12, and is in close contact with the fixing belt 13. Thereafter, the water sheet 1 is cooled in the cooling section B, and further peeled from the fixing belt 13 in the peeling section C. While passing through the fixing parts A to C, the surface of the fixing belt 13 and the surface of the water sheet 1 are kept in close contact.

Thus, the surface of the fixing belt and the surface of the water sheet have a certain adhesiveness and pass through the fixing parts A to C, whereby the toner adhered to the toner water layer is finely fixed without spreading on the water sheet, and the toner Since it is pressurized by the fixing belt and completely cooled and solidified in the toner aqueous layer, there is no image step and a smooth and smooth toner image can be obtained.

On the other hand, in the peeling part (C), when the surface of the fixing belt and the surface of the water sheet are peeled off with a certain degree or more of peelability, a part of the image or a part of the material constituting the water sheet is attached to the fixing belt to be offset or offset. It is attached to the fixing belt itself, which can prevent the case where the medium is broken.

In order to satisfy both of these advantages, in a fixing belt type electrophotographic award sheet in which a toner aqueous layer containing a thermoplastic resin is formed on a support of the present invention, fixing of the surface of the aqueous sheet on the toner aqueous layer side with respect to the support When the said water sheet surface temperature is 50 degreeC, the peeling force from a belt surface is 1-20 N / m, Preferably it is 2-20 N / m.

Moreover, the peeling force from the fixing belt surface of the surface of the water sheet on the toner water layer side with respect to the support, the surface temperature of the water sheet is 1 to 20 N / m at 90 ° C, preferably 1 to 18 N / m, 1-15 N / m is more preferable.                     

When the said peeling force is 20 N / m or less in 50 degreeC, even when peeling from a fixing belt, it can peel, maintaining favorable glossiness. Moreover, when peeling force is 1 N / m or more in 90 degreeC, even if it passes through a fixing part, the fixing belt surface and the water surface sheet surface can be maintained in close contact, without peeling.

Here, peeling force is measured as follows, for example, referring FIG.

First, the sample which cut out the electrophotographic award sheet 1 and the part of the fixing belt 13 to arbitrary size is prepared. In the actual fixing belt type electrophotographic method, the surface of the fixing belt 13 in contact with the water sheet 1, that is, the fixing belt surface 13a and the fixing belt 13 of the water sheet 1 The surface of the contact sheet, i.e., the support, is brought into contact with the surface of the image sheet 1a on the side of the toner image layer. Next, the water sheet is heated for 10 seconds to 1 minute so that the temperature of the fixing belt and the surface of the water sheet is 30 to 150 ° C. Thereafter, one end (the left end in FIG. 2) of the fixing belt 13 is held, and the fixed angle of the fixing belt 13 and the peeling direction X is set at a constant of 20 to 60 mm / sec so that the angle θ is always 90 °. Peel off at speed. At this time, the force applied to the peeling direction X is the peeling force.

In order to adjust the peeling force of the fixing belt surface and the water sheet surface as described above, it is also important to select the material of the fixing belt surface and the material of the water sheet surface.

EMBODIMENT OF THE INVENTION Hereinafter, in order to achieve the peeling force of this invention, the preferable fixing belt, the material of the surface of a fixing belt, the water sheet, and the material of the surface of a water sheet are demonstrated.

<Fixing belt>

The fixing belt used here is suitably an endless belt formed by using polyamide, electroforming nickel, aluminum, etc. as a base material. In addition, the material of the surface of the fixing belt is preferably a silicone-based or fluorine-based material, more specifically, at least one selected from the group consisting of silicone rubber, fluororubber, silicone resin, and fluororesin. It is desirable to. Such a material is generally a material which is low in adhesiveness with a polymer appearing as the surface of the water sheet and is easily peeled off, and therefore is preferable in order to make the peeling force between the fixing belt and the surface of the water sheet in a desired range.

As the material of the surface of the fixing belt, for example, silicone crosslinked fluorinated poly such as silicone rubber, polytetrafluoroethylene perfluoroalkyl vinyl ether copolymer (PFA), and SIFEL (registered trademark) manufactured by Shin-Etsu Chemical Co., Ltd. Ethers, polytetrafluoroethylene (PTFE), ethylene tetrafluoride hexafluoropropylene copolymer (FEP), perfluoroalkoxyalkanes, silicone modified acrylic polymers and the like.

Among these, it has the form which formed the layer of the fluorocarbon siloxane rubber of the uniform thickness on the surface of the fixing belt, the layer of the silicone rubber of the uniform thickness on the surface of the said fixing belt, and also the surface of the said silicone rubber layer The form which formed the layer of fluorocarbon siloxane rubber is preferable.

As said fluorocarbon siloxane rubber, what has a perfluoroalkyl ether group and / or a perfluoroalkyl group in a principal chain is preferable.

As such a fluorocarbon siloxane rubber, (A) the fluorocarbon polymer which has a fluorocarbon siloxane of following General formula (1) as a main component, and has an aliphatic unsaturated group, and (B) two or more ≡SiH groups in 1 molecule. Organopolysiloxane and / or fluorocarbonsiloxane, (C) filler, and (D) an effective amount, containing 1 to 4 times the molar amount of said SiSi group relative to the amount of aliphatic unsaturated groups in said fluorocarbon siloxane rubber composition. Hardened | cured material of the fluorocarbonsiloxane rubber composition containing a catalyst is used preferably.

The fluorocarbon polymer of the said (A) component has a fluorocarbonsiloxane which has a repeating unit represented by following General formula (1) as a main component, and has an aliphatic unsaturated group.

In the above formula (1), R ¹⁰ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 3 carbon atoms, particularly methyl. It is preferable. a and e are each 0 or 1, b and d are the integers of 1-4, respectively, and c is an integer of 0-8. In addition, x is an integer of 1 or more, Preferably it is 10-30.

As such (A) component, what is represented by following formula (2) can be mentioned.

As organopolysiloxane which has a (Si) group in the said (B) component, the organohydrogen polysiloxane which has 2 or more of hydrogen atoms couple | bonded with the silicon atom in a molecule | numerator is mentioned.

Moreover, in the fluorocarbon siloxane rubber composition used by this invention, when the fluorocarbon polymer of (A) component has an aliphatic unsaturated group, the organohydrogen polysiloxane mentioned above can be used as a hardening | curing agent. That is, in this case, hardened | cured material is formed by the addition reaction which generate | occur | produces between the aliphatic unsaturated group in fluorocarbon siloxane, and the hydrogen atom couple | bonded with the silicon atom in organohydrogen polysiloxane.

As such an organohydrogen polysiloxane, various organohydrogen polysiloxanes used for the addition-curable silicone rubber composition can be used.

The above-mentioned organohydrogenpolysiloxane is generally formulated in a proportion such that the number of? SiH groups is one or more, in particular 1 to 5, relative to one aliphatic unsaturated hydrocarbon group in the fluorocarbon siloxane of the component (A). It is preferable to make it.

In addition, as a fluorocarbon which has a SiSi group, in the unit of Formula (1) or Formula (1), R <^10> is a dialkyl-hydrogen siloxy group, and the terminal is a dialkyl-hydrogen siloxy group, a silyl group, etc. It is preferable that it is a SiH group, and what is represented by following formula (3) can be enumerated.

As a filler of the said (C) component, the various filler used for the general silicone rubber composition can be used. For example, reinforcing fillers such as fumed silica, precipitated silica, carbon powder, titanium dioxide, alumina, quartz powder, talc, sericite and bentonite, fibrous fillers such as asbestos, glass fibers, organic fibers, etc. Can be illustrated.

As the catalyst of the component (D), a chlorinated chloroplatinic acid, alcohol-modified chloroplatinic acid, a complex of chloroplatinic acid and an olefin, platinum black or palladium supported on a carrier such as alumina, silica or carbon, Group VIII elements or compounds of the periodic table such as rhodium and olefin complexes, chloro tris (triphenylphosphine) rhodium (Wilkinson catalyst), rhodium (III) acetylacetonate, and the like are exemplified, but the complexes thereof are alcohol-based, ether It is preferable to dissolve and use in solvents, such as a system and a hydrocarbon.

In the fluorocarbon siloxane rubber composition used in the present invention, various compounding agents can be added within a range not impairing the object of the present invention of improving solvent resistance. For example, dispersing agents such as diphenylsilanediol, low-molecular-molecular chain hydroxyl group-blocked dimethylpolysiloxane, hexamethyldisilazane, heat resistance improving agents such as ferrous oxide, ferric oxide, cerium oxide and iron octylate, and coloring agents such as pigments, etc. Can be blended as needed.

The fixing belt of the present invention can be obtained by coating the surface of a belt body made of a heat resistant resin or a metal with the fluorocarbon siloxane rubber composition and heating and curing, but if necessary, m-xylene hexafluoride, Dilution with a solvent such as benzotrifluoride to give a coating solution can be applied by general coating methods such as spray coat, dip coat and knife coat. In addition, heat hardening temperature and time can be selected suitably, Usually, it selects according to the kind of a belt main body, a manufacturing method, etc. in the range of 100-500 degreeC and time 5 second-5 hours.

10-100 micrometers is preferable and, as for the material of the said fixing belt surface, it is preferable to apply on the said base material with the film thickness of 20-50 micrometers especially. Such surface treatment can prevent the peelability of the electrophotographic award sheet and toner, or the offset of the award sheet and toner components.                     

<Evaluation Sheet for Electrophotography>

The electrophotographic award sheet of the present invention, for example, as shown in Fig. 3, has a toner aqueous layer 2 on the support 3, optionally has a backing layer 4, and other layers suitably selected as necessary. For example, a protective layer, an intermediate layer, a servant layer, a cushion layer, an antistatic layer (reflective) layer, a reflective layer, a color tone adjusting layer, a storage stability improvement layer, an anti-adhesion layer, an anti-curl layer, a smoothing layer, and the like. Each of these layers may have a single layer structure or a laminated structure.

[Support]

As said support body, it is preferable that it is a support with a low transparency with 30% or less of light transmittance from the point which makes the electrophotographic award sheet of this invention closer to a photograph, and it is more preferable that the said light transmittance is 20% or less. It is more preferable that it is 15% or less.

In addition, the said light transmittance can be measured with a direct reading haze meter (Suga tester HGM-2DP).

As the said support body, 0.01-5 micrometers of center line average roughness of the surface are preferable, and 0.05-3 micrometers is more preferable.

By adjusting the said center line average roughness to the said numerical range, the electrophotographic award sheet which has the outstanding characteristic etc. is provided.

There is no restriction | limiting in particular as said support body, Although it can select suitably according to the objective, For example, a base paper, a synthetic paper, a synthetic resin sheet, a coated paper, a laminated paper, etc. are mentioned. These supports may have a single layer structure or a laminated structure of two or more layers.

-Original-

As a raw material of the said base paper (including synthetic paper), what is used for a well-known base paper as what is used for a support body can be selected from various materials, without restrict | limiting in particular. Examples include natural pulp selected from conifers and hardwoods, synthetic pulp made of plastic materials such as polyethylene and polypropylene, or a mixture of natural pulp and synthetic pulp.

As a pulp that can be used as a raw material of the base paper, the hardwood bleached graft pulp (LBKP) is used in that it improves the surface smoothness, rigidity and dimensional stability (curlity) of the base paper with good balance and to a sufficient level. Although preferred, conifer bleached graft pulp (NBKP), hardwood sulfite pulp (LBSP), and the like may be used.

As for pulp fiber, it is suitable to use hardwood pulp originally short in fiber length.

A beater, a refiner, or the like can be used for pulverization of the pulp. In the pulp slurry obtained after beating the pulp (hereinafter sometimes referred to as "pulp feed material"), various additives such as fillers, dry strength enhancers, size agents, wet strength enhancers, fixatives, and pH adjusters may be necessary. And other drugs are added.

Examples of the filler include calcium carbonate, clay, kaolin, clay, talc, titanium oxide, diatomaceous earth, barium sulfate, alumina hydroxide, magnesium hydroxide and the like.                     

Examples of the dry strength enhancer include cationized starch, cationized polyacrylamide, anionic polyacrylamide, amphoteric polyacrylamide, carboxy modified polyvinyl alcohol and the like.

As said size agent, For example, rosin derivatives, such as a fatty acid salt, rosin, maleinized rosin, paraffin wax, etc., or higher fatty acids, such as an alkyl ketene dimer, alkenyl anhydride succinic acid (ASA), and epoxidized fatty acid amide, are contained, for example. Compounds and the like.

Examples of the wet strength enhancer include polyamine polyamide epichlorohydrin, melamine resins, urea resins, epoxidized polyamide resins, and the like.

Examples of the fixing agent include polyvalent metal salts such as aluminum sulfate and aluminum chloride, cationic polymers such as cationic starch, and the like.

As said pH adjuster, a caustic soda, a soda carbonate, etc. are mentioned, for example. Examples of other drugs include antifoaming agents, dyes, slime control agents, optical brighteners and the like.

Moreover, a softening agent etc. can also be added as needed. The softening agent is described in, for example, pages 554 to 555 (issued in 1980) of the New Paper Processing Handbook (compiled by Chiyaku Time Co., Ltd.).

The treatment liquid used for the surface size treatment may contain, for example, a water-soluble polymer, a size agent, a water-resistant substance, a pigment, a pH adjuster, a dye, a fluorescent brightener, and the like. As the water-soluble polymer, for example, cationized starch, polyvinyl alcohol, carboxy modified polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, cellulose sulfate, gelatin, casein, sodium polyacrylate, sodium styrene-maleic anhydride copolymer Salts, sodium polystyrene sulfonate and the like.

Examples of the water-resistant substance include latex emulsions such as styrene-butadiene copolymer, ethylene-vinyl acetate copolymer, polyethylene, and vinylidene chloride copolymer, and polyamide polyamine epichlorohydrin.

Examples of the pigment include calcium carbonate, clay, kaolin, talc, barium sulfate, titanium oxide and the like.

As an example of a base paper material, in addition to the natural pulp paper mentioned above, synthetic pulp paper, the mixed paper of natural pulp and synthetic pulp, or various super immersion papers can be mentioned.

In order to improve the stiffness and dimensional stability (curlability) of the electrophotographic image paper, the above-described base paper has a ratio (Ea / Eb) of 1.5 to 12 in the longitudinal Young's modulus (Ea) and the transverse Young's modulus (Eb). It is preferable to exist in the range of 2.0. In the range where the Ea / Eb value is less than 1.5 or more than 2.0, the rigidity and curlability of the electrophotographic image receiving paper tend to be deteriorated, and it is not preferable because it causes a problem in the runability at the time of conveyance.

In the present invention, the oken smoothness of the surface of the toner aqueous layer side of the base paper is 210 seconds or more, preferably 250 seconds or more. If the oken smoothness is less than 210 seconds, the image quality of the toner image is poor, which is not preferable. In addition, an upper limit is although it does not specifically limit, In fact, about 600 second, Preferably about 500 second will be suitable.

In the present invention, the problem of the present invention is achieved by employing 210 seconds or more, which is a much larger Oken smoothness than the conventionally used Oken smoothness.                     

Here, the Oken type smoothness is JAPAN TAPPI No. It is the smoothness prescribed by law 5B.

In general, it is known that the "elasticity" of the paper varies based on the difference in the style of the confession, and the elastic force (rate) of the paper made after the confession can be used as an important factor indicating the "elasticity" of the paper. . In particular, the elastic modulus of the paper can be obtained from the following equation by using the relationship between the dynamic modulus and the density showing the physical properties of the viscoelastic material of the paper, and by using the ultrasonic vibration element to measure the sound velocity propagating in the paper. Can be.

E = ρc ² (1-n ² )

[E: dynamic modulus, ρ: density, c: sound velocity in paper, n: Poisson's ratio]

In addition, in the case of a normal paper, since n is about 0.2, even if it calculates by the following formula, it can calculate without large difference.

E = ρc ²

That is, the elastic modulus can be easily obtained as long as the density and the sound velocity of the paper can be measured. In the above formula, when measuring the sound velocity, various well-known apparatuses, such as Sonic Tester SST-110 type (made by Nomura Shoji Co., Ltd.), can be used.

The thickness of the base paper is usually 30 to 500 µm, preferably 50 to 300 µm, more preferably 100 to 250 µm. The weight of the base paper is, for example, preferably in the range of 50 to 250 g / m ² , more preferably in the range of 100 to ²⁰⁰ g / m ² .

In the original paper, specifically, it is a good-quality paper, for example, the Japanese Photographic Society published "Basic of Photo Engineering-Silver Dye Photographs", a paper of Koronashi Co., Ltd. (Showa 54) (223) to (240) pages. Etc. are listed as preferable.

In order to impart the desired centerline average roughness to the surface, the base paper has a fiber length distribution (e.g., 24 mesh screen residues and 42 mesh screen residues, for example, as disclosed in Japanese Patent Application Laid-Open No. 58-68037). It is preferable to use the pulp fiber whose sum total is 20 mass%-45 mass%, and 24 mesh screen residues are 5 mass% or less). Moreover, center line average roughness can be adjusted by surface-treating by applying heat and pressure with a machine calendar, a super calendar, etc.

Synthetic Resin Sheet

As said synthetic resin sheet (film), what shape | molded synthetic resin in the sheet form, etc. are mentioned, For example, polyester resins, such as polyolefin resin, such as a polypropylene resin, or polyethylene terephthalate resin, were extrusion-molded in the sheet form. Can be obtained by.

-Coated paper-

The coated paper is a paper or sheet obtained by coating various resins, rubber latex or polymer materials on one side or both sides of a sheet such as a base paper, and the coating amount varies depending on the use. Examples of such coated paper include art paper, cast coated paper, yankee paper, and the like.

As thickness of the said thermoplastic resin layer, 5-100 micrometers is preferable and 15-50 micrometers is more preferable. The thermoplastic resin layer formed on the surface and the thermoplastic resin layer formed on the back surface may be the same as or different from the components, the physical properties, the thickness, and the configuration.

As the resin coated on the surface of base paper or the like, it is suitable to use a thermoplastic resin. As such a thermoplastic resin, the following (a)-(a) thermoplastic resin can be illustrated, for example.

(A) Polyolefin resins, such as a polyethylene resin and a polypropylene resin, copolymer resin of olefins, such as ethylene and a propylene, and other vinyl monomers, an acrylic resin, etc. are mentioned.

(B) A thermoplastic resin having an ester bond. For example, polyester resin obtained by condensation of a dicarboxylic acid component (The sulfonic acid group, a carboxyl group etc. may be substituted by these dicarboxylic acid components), and an alcohol component (The hydroxyl group etc. may be substituted by these alcohol components.), Polyacrylic acid ester resins such as polymethyl methacrylate, polybutyl methacrylate, polymethyl acrylate and polybutyl acrylate or polymethacrylate ester resin, polycarbonate resin, polyvinyl acetate resin, styrene acrylate Resin, styrene-methacrylic acid ester copolymer resin, vinyltoluene acrylate resin and the like.

Specifically, what was described in Unexamined-Japanese-Patent No. 59-101395, 63-7971, 63-7972, 63-7973, 60-294862, etc. can be mentioned.

Moreover, as a commercial item, Byron 290, Byron 200, Byron 280, Byron 300, Byron 103, Byron GK-140, Byron GK-130; Tufton NE-382, tufton U-5, ART-2009, ART-2010 from Khao; Eritel UE3500, UE3210, XA-8153, KZA-7049, KZA-1449 from UNICHIKA; Polyester TP-220, R-188 from Nippon Gosei Chemical Co., Ltd .; The various thermoplastic resins of the Hiros series of Sekogagaku Kogyo Co., Ltd. are mentioned.

(C) polyurethane resins;

(D) polyamide resins, urea resins and the like.

(E) polysulfone resins;

(F) polyvinyl chloride resin, polyvinylidene chloride resin, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl propionate copolymer resin and the like.

(Ol) Polyol resins, such as polyvinyl butyral, cellulose resins, such as ethyl cellulose resin and cellulose acetate resin, etc. are mentioned.

(A) Polycaprolactone resin, styrene-maleic anhydride resin, polyacrylonitrile resin, polyether resin, an epoxy resin, a phenol resin, etc. are mentioned.

In addition, the said thermoplastic resin may be used individually by 1 type, and may use 2 or more types together.

Laminate paper

The said laminated paper laminated | stacked various resin, rubber | gum, a polymer sheet, a film, etc. on the sheet | seats, such as a base paper. As such a material to laminate, polyolefin, polyvinyl chloride, polyethylene terephthalate, polystyrene, polymethacrylate, polycarbonate, polyamide, triacetyl cellulose, etc. are mentioned, for example. These resin may be used individually by 1 type, and may use 2 or more types together.

Although the said polyolefin is generally formed using low density polyethylene, in order to improve the heat resistance of a support body, it is preferable to use polypropylene, the mixture of polypropylene and polyethylene, the high density polyethylene, the mixture of high density polyethylene and low density polyethylene, etc. desirable. In particular, it is most preferable to use a mixture of high density polyethylene and low density polyethylene from the viewpoint of price and laminate suitability.

Mixing of the said high density polyethylene and the said low density polyethylene is used, for example by mixing ratio (mass ratio) 1/9-9/1. As said mixing ratio, 2 / 8-8 / 2 are preferable and 3 / 7-7 / 3 are more preferable. When forming a thermoplastic resin layer on both surfaces of the said support body, it is preferable to form the back surface of a support body, for example using high density polyethylene or the mixture of a high density polyethylene and a low density polyethylene. Although it does not restrict | limit especially as molecular weight of polyethylene, It is preferable that a melt index is between 1.0-40 g / 10min also in any of a high density polyethylene and a low density polyethylene, and it has an extrusion ability.

In addition, you may perform the process which adds white reflectivity to these sheets or films. As such a processing method, the method of mix | blending pigments, such as a titanium oxide, in these sheets or films is mentioned, for example.

The resin to be coated or laminated is not limited to a thermoplastic resin. For example, a resin obtained by reacting a monomer or a thermoplastic resin with heat or light, a film-forming agent, a crosslinking agent, or the like, or a thermosetting resin may be used.

Moreover, one or more layers of the said resin layer to coat or laminate may harden | cure the monomer containing a photoinitiator, and the resin composition by ultraviolet irradiation.

The resin composition used in this case enumerates an electron beam curable organic compound as a main component. There is no restriction | limiting in particular in the kind of the said electron beam curable organic compound. These may be monomers or oligomers. These may be used individually by 1 type and may use 2 or more types together.

The electron beam curable unsaturated compound can be selected from, for example, the following compounds.

(1) Acrylic compounds of monohydric alcohols and polyalkylene glycols of aliphatic, alicyclic, or aromatic aliphatic groups

(2) Acrylate compounds of which alkylene oxide is added to an aliphatic, alicyclic, or aromatic aliphatic monohydric alcohol.

(3) polyacryloylalkyl phosphate esters

(4) Reaction products of carboxylic acid, polyol and acrylic acid

(5) Reaction product of isocyanate, polyol and acrylic acid

(6) Reaction product of epoxy compound and acrylic acid

(7) Reaction product of epoxy compound, polyol and acrylic acid

As these compounds, as an electron beam curable unsaturated organic compound, a polyoxyethylene epicrohydrin modified bisphenol A diacrylate, a dicyclohexyl acrylate, an epichlorohydrin modified polyethylene glycol diacrylate, 1,6- Hexanediol diacrylate, hydroxybiphosphate ester neopentyl glycol diacrylate, nonylphenoxypolyethylene glycol acrylate, ethylene oxide modified phenoxylated phosphate acrylate, ethylene oxide modified phthalic acrylate, polybutadiene acrylate, Caprolactam modified tetrahydrofurfuryl acrylate, trisacryloxyethyl) isocyanurate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol pentaa Relate, dipentaerythritol hexaacrylate, polyethylene glycol diacrylate, 1,4-butadiene diol diacrylate, neopentyl glycol diacrylate, neopentyl glycol modified trimethylolpropane diacrylate, and the like Can be enumerated.

In this invention, these organic compounds can be used individually or in combination of 2 or more types.

In addition, as a resin layer to coat or laminate, it does not restrict | limit especially to the kind of ultraviolet curable organic compound hardened | cured by ultraviolet irradiation. This ultraviolet curable resin composition is prepared by adding a suitable quantity of photoinitiators to the electron beam curable resin mentioned above. In this invention, it is preferable to use in the range which the photoinitiator may or may not contain and the odor does not arise in the resin composition provided for electron beam hardening.                     

As said photoinitiator, well-known photoinitiators are mentioned, For example, aceto, such as ethyl anthraquinone, methylbenzoylformate, 1-hydroxycyclohexylphenyl ketone, anthraphenone, diethoxyacetophenone, and trichloroacetophenone Phenones, o-benzoylmethylbenzoate, benzophenone, Michler's ketone, benzyl, benzoin, benzoin alkyl ether, benzyldimethyl ketal, tetramethylthirammonosulfite, xanthone, thioxanthones, benzophenones, and Azo compounds and the like. These photoinitiators may be used individually by 1 type, and may use 2 or more types together.

As addition amount of the said photoinitiator, about 0.1-10 mass% is preferable normally with respect to the mass of ultraviolet curable resin. For example, using a well-known photoinitiator, such as N-methyl diethanolamine and bisdiethylamino benzophenone together with the said photoinitiator, is preferable for the improvement of a cure rate. The amount of the photopolymerization accelerator to be added is not particularly limited as long as the effect is exerted, but is generally 0.5 to 2 times the mass of the photopolymerization initiator.

There is no restriction | limiting in particular as an electron beam accelerator used for the said electron beam irradiation, For example, electron beam irradiation apparatuses, such as a van degraf type scanning system, a double scanning system, and a curtain beam system, can be used.

There is no restriction | limiting in particular as the ultraviolet irradiation apparatus used for the said ultraviolet irradiation, For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, etc. can be used.

The support may be any combination of the above various supports to form a laminate.

As a method of coating resin etc. on the said base paper etc., the method of apply | coating, impregnating, or spraying a resin solution or suspension etc. to these base papers is mentioned preferably, for example.

On both sides or one side of the base paper before coating or laminating, for the purpose of improving the adhesiveness with the resin coated on the base paper or the like, it is necessary to perform activation treatment such as corona discharge treatment, flame treatment, glow discharge treatment or plasma treatment. desirable.

After forming a coat layer or a laminate layer on the base paper, synthetic paper, or synthetic resin sheet, or on these sheets, surface treatment such as corona discharge treatment for the purpose of improving the adhesiveness with the layer thereon, for example, the toner aqueous layer. Alternatively, the lower layer may be applied to the surface.

The surface of the thermoplastic resin layer or the like used for the coated paper may be printed with a gloss surface or a fine surface, a mat surface or a matt surface of JP-A-55-26507, as necessary. Therefore, printing of a matte surface may be performed on the surface of the thermoplastic resin layer etc. on the opposite side (back surface) from the side in which the formed conductive layer is formed. In addition, these surfaces after being printed can be subjected to activation treatments such as corona discharge treatment and flame treatment, and can also be subjected to undercoating treatment as described in JP-A 61-846443 after the activation treatment. have.

In addition, these may be used alone, or may be used in any combination, such as performing an activation treatment after performing printing or the like, or performing a bottom coating after surface treatment such as an activation treatment.

Moreover, various additives suitably selected can be added to a thermoplastic resin layer etc. in the range which does not impair the objective of this invention.

As thickness of the said support body, 25 micrometers-300 micrometers are preferable, 50 micrometers-260 micrometers are more preferable, 75 micrometers-220 micrometers are still more preferable. As strength of the said support body, various things can be used according to the objective, and as a support body for the electrophotographic water receiving sheet of photographic image quality, what is close to the support body for color silver salt photography is preferable.

As the support, from the viewpoint of fixing performance, the thermal conductivity of the support under the condition that the relative humidity is 65% at 20 ° C is preferably 0.50 Kcal / m · h · ° C or higher. Here, thermal conductivity can be measured according to the method of Unexamined-Japanese-Patent No. 53-66279 with the transcription | transfer paper whose humidity was adjusted based on JISP 8111. Moreover, as a density of the said support body, 0.7 g / cm <3> or more is preferable from a said viewpoint.

In the said support body, various additives suitably selected can be mix | blended within the range which does not impair the objective of this invention. As such additives, for example, brighteners, conductive agents, fillers, pigments such as titanium oxide, ultramarine blue, carbon black, dyes and the like can be contained as necessary.

The hydrophilic binder and semiconducting metal oxides such as alumina sol and tin oxide, carbon black, and other antistatic agents may be blended or applied to the surface, the back surface, and a combination thereof among the supports. Specifically, the support described in JP-A-63-220246 can be used. It is preferable that the said support body can endure fixing temperature, and can satisfy a request | requirement from the point of whiteness, slipperiness | lubricacy, friction property, antistatic property, and dent after fixation.

[Layers constituting the water sheet surface]

The surface of the water sheet on the toner water layer side with respect to the support means the surface of the water sheet in contact with the fixing belt. As the layer constituting the surface of the award sheet, specifically, a layer appearing on the surface of the award sheet may be enumerated as a toner aqueous layer, surface protective layer or the like formed on the support. For example, in FIG. 3, the toner aqueous layer 2 corresponds to this.

<Toner Winner>

When the toner award layer is shown on the surface of the award sheet, the layer constituting the surface of the award sheet becomes the toner award layer. The toner aqueous layer is mainly composed of a polymer, preferably a thermoplastic resin. Specifically, the amount of polymer contained in the toner aqueous layer is preferably 90 to 99.5 mass%, more preferably 93 to 99 mass%, based on the mass of the toner aqueous layer.

The toner aqueous layer is formed on at least one surface of the support, and accommodates toners which form an image from a developing drum or an intermediate transfer member by (positive) electricity, pressure, or the like in a transfer process, and heat, pressure or the like in a belt fixing process. It has a function that can be immobilized.

As the toner aqueous layer, since the electrophotographic award sheet of the present invention has a texture close to photographs, it is necessary to be a low transparency toner aqueous layer having a light transmittance of 78% or less, and the light transmittance preferably 73% or less. And, 72% or less is more preferable. In addition, the said light transmittance can form the coating film of the same thickness on a polyethylene terephthalate film (100 micrometers) separately, and can measure it using a direct reading haze meter (Suga tester HGM-2DP).

As a material of the toner aqueous layer, at least a thermoplastic resin and a releasing agent are contained, and other components as necessary.

Thermoplastics

The thermoplastic resin is not particularly limited as long as it can be deformed under temperature conditions at the time of fixing and can accommodate the toner. The thermoplastic resin can be appropriately selected depending on the purpose, but a resin of the same series as the binder resin of the toner is preferable. In most of the toners, polyester resins, copolymer resins such as styrene and styrene-butyl acrylate are used, and in this case, polyester resins, styrene, It is preferable to use copolymerized resins, such as styrene-butylacrylate, It is more preferable to contain 20 mass% or more of copolymerized resins, such as polyester resin, styrene, and styrene- butyl acrylate, Furthermore, styrene , Styrene-butyl acrylate copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer and the like are also preferable.

As a specific example of the said thermoplastic resin, (V) polyvinyl chloride, such as (A) resin which has ester bond, (B) polyurethane resin, (C) polyamido resin, such as (D) polysulfone resin, etc. (A) polyolefin resin, such as (ca) polycaprolactone resin, such as (ba) polyvinyl butyral, such as resin, etc. are mentioned.

Examples of the resin having the (a) ester bond include terephthalic acid, isophthalic acid, maleic acid, fumaric acid, phthalic acid, adipic acid, sebacic acid, azelaic acid, abietinic acid, succinic acid, trimellitic acid, pyromellitic acid, and the like. Dicarboxylic acid components (sulfonic acid groups, carboxyl groups and the like may be substituted for these dicarboxylic acid components), and diether derivatives of ethylene glycol, diethylene glycol, propylene glycol, bisphenol A, bisphenol A (for example, ethylene of bisphenol A). Alcohol adducts such as oxide adducts, propylene oxide adducts of bisphenol A, and the like, bisphenol S, 2-ethylcyclohexyl dimethanol, neopentyl glycol, cyclohexyl dimethanol, glycerin, and the like. Polyester resin, polymethyl methacrylate, polybutyl methacrylate obtained by condensation of Polyacrylic acid ester resin or polymethacrylic acid ester resin, polycarbonate resin, polyvinyl acetate resin, styrene acrylate resin, styrene-methacrylic acid ester copolymer such as polymethyl acrylate and polybutyl acrylate Resin, vinyltoluene acrylate resin, and the like.

Specific examples include those described in Japanese Patent Application Laid-Open Nos. 59-101395, 63-7971, 63-7972, 63-7973, and 60-294862.

As a commercial item of the said polyester resin, For example, Byron 290, Byron 200, Byron 280, Byron 300, Byron 103, Byron GK-140, Byron GK-130; Tufton NE-382, tufton U-5, ART-2009, ART-2010 from Khaoze; Eritel UE3500, UE3210, XA-8153 from UNICHIKA; Nippon Gosei Chemical Co., Ltd. polyester TP-220, R-188, etc. are mentioned.

As a commercial item of the said acrylic resin, Daisal SE-5437, SE-5102, SE-5377, SE-5649, SE-5466, SE-5482, HR-169, 124, HR- of Mitsubishi Rayon Co., Ltd. make, for example. 1127, HR-116, HR-113, HR-148, HR-131, HR-470, HR-634, HR-606, HR-607, LR-1065, 574, 143, 396, 637, 162, 469, 216, BR-50, BR-52, BR-60, BR-64, BR-73, BR-75, BR-77, BR-79, BR-80, BR-83, BR-85, BR-87, BR-88, BR-90, BR-93, BR-95, BR-100, BR-101, BR-102, BR-105, BR-106, BR-107, BR-108, BR-112, BR- 113, BR-115, BR-116, BR-117; Sekisui Chemical Co., Ltd. Esrek P SE-0020, SE-0040, SE-0070, SE-0100, SE-1010, SE-1035; Sanyo-Casegoyo Higher ST95, ST120; Sansei Chemical Co., Ltd. FM 601, etc. are listed.

Examples of the (e) polyvinyl chloride resin and the like include polyvinylidene chloride resin, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl propionate copolymer resin and the like.

Examples of the above (bar) polyvinyl butyral include cellulose resins such as polyol resin, ethyl cellulose resin, cellulose acetate resin and the like. As a commercial item, the Denki Chemical Co., Ltd. product, the Sekisui Chemical Co., Ltd. product, etc. are mentioned. It is preferable that the said polyvinyl butyral content is 70 mass% or more and average polymerization degree 500 or more, It is more preferable that it is average polymerization degree 1000 or more, As a commercial item, Denka Chemical Co., Ltd. Denka Beauty 3000 -1, 4000-2, 5000A, 6000C; Sekisui Gaku's Esrek BL-1, BL-2, BL-3, BL-S, BX-L, BM-1, BM-2, BM-5, BM-S, BH-3 , BX-1, BX-7 and the like.

As said (ca) polycaprolactone resin etc., styrene-maleic anhydride resin, polyacrylonitrile resin, polyether resin, an epoxy resin, a phenol resin etc. are mentioned further.

As said (a) polyolefin resin etc., copolymer resin, acrylic resin, etc. of polyethylene resin, polypropylene resin, etc., olefins, such as ethylene and a propylene, and another vinyl monomer are mentioned.

The said thermoplastic resin may be used individually by 1 type, and 2 or more types may be sufficient, In addition, these mixture, these copolymers, etc. can also be used.

As said thermoplastic resin, it is preferable that the toner aqueous layer physical property mentioned later can be satisfied in the state which formed the said toner aqueous layer, and it is more preferable that even the resin alone can satisfy the toner aqueous layer physical properties mentioned above, It is also preferable to use two or more resins with different toner aqueous layer physical properties.

As the thermoplastic resin, one having a higher molecular weight than the thermoplastic resin used in the toner is preferable. However, the molecular weight does not necessarily mean that the above-described molecular weight relation is necessarily preferred depending on the relationship between the thermodynamic properties of the thermoplastic resin used for the toner and the resin used for the toner aqueous layer. For example, when the softening temperature of the resin used for the toner aqueous layer is higher than the thermoplastic resin used for the toner, it may be desirable that the molecular weight is the same or that the molecular weight of the resin used for the toner aqueous layer is small.

As said thermoplastic resin, it is also preferable to use the mixture of resin of the same composition, and having a different average molecular weight from each other. Moreover, as a relationship of the molecular weight of the thermoplastic resin used for toner, the relationship disclosed by Unexamined-Japanese-Patent No. 8-334915 is preferable.

As molecular weight distribution of the said thermoplastic resin, it is preferable that it is wider than the molecular weight distribution of the thermoplastic resin used for the said toner.

As said thermoplastic resin, Unexamined-Japanese-Patent No. 5-127413, Unexamined-Japanese-Patent No. 8-194394, Unexamined-Japanese-Patent No. 8-334915, Unexamined-Japanese-Patent No. 8-334916, Unexamined-Japanese-Patent No. 9 It is preferable to satisfy the physical properties disclosed in Japanese Patent Laid-Open No. 171265, Japanese Patent Laid-Open No. 10-221877, and the like.

As a thermoplastic resin used for the said toner aqueous layer, it is especially preferable that it is water-based resin, such as a water-soluble resin and a water-dispersible resin, for the following (i)-(ii) reasons.

(i) There is no discharge of organic solvent in coating drying process, and it is excellent in environmental suitability and workability.

(ii) Release agents, such as wax, are difficult to dissolve in a solvent at room temperature, and in many cases, they are dispersed in a solvent (water, an organic solvent) when used. In addition, the water dispersion form is stable and the manufacturing process aptitude is excellent. In addition, waxes tend to spread on the surface in the process of coating and drying, and effects of a releasing agent (offset resistance, adhesive resistance, etc.) are easily obtained.

As said water-based resin, if it is a water-soluble resin and a water-decomposable resin, the composition, a bonding structure, molecular structure, molecular weight, molecular weight distribution, and a form are not specifically determined. As an example of the water-based group of a polymer, a sulfonic acid group, a hydroxyl group, a carboxylic acid group, an amino group, an amide group, an ether group, etc. are mentioned. Examples of the above water-soluble resins include those described in Research Disclosure 17,643, page 26, 18,716, 651, 307,105, 873 to 874, and Japanese Patent Publication No. 64-13546, pages 71 to 75. Can be listed.

Specifically, for example, vinylpyrrolidone-vinyl acetate copolymer, styrene-vinylpyrrolidone copolymer, styrene-maleic anhydride copolymer, water-soluble polyester, water-soluble acrylic, water-soluble polyurethane, water-soluble nylon, water-soluble epoxy Resin can be used. Moreover, gelatin should just be chosen from what is called degreased gelatin which reduced content of lime gelatin, acid gelatin, calcium, etc. according to various objectives, It is also preferable to use it in combination. Commercially available products include various coats from Kaou Kagaku Kogyo Co., Ltd. as water-soluble polyesters, Finetex ES series from Dainippon Ink Kagaku Kogyo Co., Ltd., Jurima AT series from Nippon Kayaku Co., Ltd. Fine Tex 6161, K-96 from Ku Kogyo Co., Ltd., Hyros NL-1189, BH-997L from Sekogaku Kogyo Co., etc. are listed.

As the water-dispersible resin, water-dispersible resins such as water-dispersible acrylic resins, water-dispersed polyester resins, water-dispersed polystyrene resins, and water-dispersed urethane resins; Emulsions such as an acrylic resin emulsion, a polyvinyl acetate emulsion, an SBR (styrene butadiene rubber) emulsion, a resin or emulsion obtained by dispersing the thermoplastic resins of (A) to (A), or their air It is suitably selected from among a mixture, a mixture, and a cation modification, and 2 or more types can be combined.

Commercially available products of the water-dispersible resins include, for example, polyester-based bironal series from Toyobo, Pesresin A series from Takamatsu Yuji, Toughton UE series from Kao, Nippon Gosei Polyester WR series, and Uni The Elair series of acrylic products and acryl series of Chika products include Hirose XE, KE, PE series of Sekogaku Kogyo Co., Ltd., and Jurima ET series of Nippon Juyaku.

The film formation temperature (MFT) of the polymer to be used is preferably room temperature or more for storage before printing, and 100 ° C. or less for fixing of toner particles.

In this invention, it is preferable to use the self-dispersion type water-based polyester resin emulsion which satisfy | fills the characteristic of following (1)-(4) as said thermoplastic resin. Since this is a self-dispersing type which does not use a surfactant, the hygroscopicity is low even in a high humidity atmosphere, the softening point decreases due to moisture, and the occurrence of offset during fixing and generation of inter-sheet adhesion failure during storage can be suppressed. Moreover, since it is an aqueous system, it is excellent in environment and workability. In addition, since the polyester resin which is easy to have a molecular structure with high cohesive energy is used, it has sufficient hardness in a storage environment, and becomes a low elasticity (low viscosity) molten state in the electrophotographic fixing process, and a toner is an aqueous layer It can be filled in to achieve sufficient high image quality.                     

(1) 5000-10000 are preferable and, as for a number average molecular weight (Mn), 5000-7000 are more preferable.

(2) ≤ 4 is preferable and, as for molecular weight distribution (weight average molecular weight / number average molecular weight), Mw / Mn ≤ 3 is more preferable.

(3) 40-100 degreeC is preferable and, as for glass transition temperature (Tg), 50-80 degreeC is more preferable.

(4) 20-200 nm (phi) is preferable and, as for a volume average particle diameter, 40-150 nm (phi) is more preferable.

As content in the said toner aqueous layer of the said thermoplastic resin, 10 mass% or more is preferable and 30 mass% or more is more preferable.

Release Agent

The release agent of this invention is mix | blended with a toner aqueous layer in order to prevent the offset of a toner aqueous layer. The release agent used in the present invention is heated and melted at a fixing temperature, precipitates on the surface of the toner aqueous layer, is unevenly distributed on the surface of the toner aqueous layer, and is cooled and solidified to form a layer of the release agent material on the surface of the toner aqueous layer. If it is made, the kind is not limited.

As a mold release agent which exhibits such an effect, 1 or more types of mold release agents chosen from the group which consists of a silicone compound, a fluorine compound, a wax, and a mat agent can be mentioned. Preferably, at least one release agent selected from the group consisting of silicone oil, polyethylene wax, carnauba wax and silicone particles and polyethylene wax particles is listed.

Specifically, as the mold release agent used in the present invention, for example, a compound described in "Similar Wax Properties and Applications" of Saiwai Shobo and a silicone handbook based on the daily paper company publication can be used. In addition, Japanese Patent Publication No. 59-38581, Japanese Patent Publication No. 4-32380, Japanese Patent No. 2838498, No. 2949558, Japanese Patent Publication No. 50-117433, No. 52-52640, No. 57-148755 61-62056, 61-62057, 61-118760, Japanese Patent Laid-Open No. 2-42451, 3-41465, 4-212175, 4-214570, 4-263267 No. 5-34966, No. 5-119514, No. 6-59502, No. 6-161150, No. 6-175396, No. 6-219040, No. 6-230600, No. 6-295093, East 7-36210, East 7-43940, East 7-56387, East 7-56390, East 7-64335, East 7-199681, East 7-223362, East 7-287413, East 8 -184992, East 8-227180, East 8-248671, East 8-248799, East 8-248801, East 8-278663, East 9-152739, East 9-160278, East 9-185181 No. 9-319139, No. 9-319143, No. 10-20549, No. 10-48889, No. 10-198069, No. 10-207116, No. 11-2917, No. 11-44969, Silicon compounds and fluorine compounds used in the toners described in Japanese Patent Publications Nos. 11-65156, 11-73049 and 11-194542. Water or wax can also be used preferably. Moreover, these compounds can also be used in combination.

Specifically, the silicone compound is a silicone oil as a silicone oil (specifically, dimethylsiloxane oil, methylhydrogensilicone oil, phenylmethylsilicone oil, commercially available products of Shin-Etsu Chemical Co., Ltd. KF-96, KF -96L, KF-96H, KF-99, KF-50, KF-54, KF-56, KF-965, KF-968, KF-994, KF-995, HIVAC F-4, F-5; Toray Dow Corning Silicon Products SH200, SH203, SH490, SH510, SH550, SH710, SH704, SH705, SH7028A, SH7036, SM7060, SM7001, SM7706, SH7036, SH8710, SH1107, SH8627; TSF400, TSF401, TSF404, TSF405, TSF431, TSF433, TSF434, TSF437, TSF450 Series, TSF451 Series, TSF456, TSF458 Series, TSF483, TSF484, TSF4045, TSF4300, TSF4600, YF33 Series, YF-3057, YF-3800, YF-3802, YF-3804, YF-3807, YF-3897, XF-3905, XS69-A1753, TEX100, TEX101, TEX102, TEX103, TEX104, TSＷ831, etc., amino modified silicone oil (KF-857, KF from Shin-Etsu Chemical Co., Ltd. as a commercially available product) -858, KF-859, KF-861, KF-864, KF-880, SF8417, SM8709 from Toray Dow Corning Silicon, TSF4700, TSF4701, TSF4702, TSF4703, TSF4704, TSF4705, TSF4706, TEX150 from Toshiba Silicon , TEX151, TEX154, etc.), carboxy modified silicone oil (BY16-880 from Toray Dow Corning Silicone, TSF4770 from Toshiba Silicone, XF42-A9248, etc.), carbinol modified silicone oil from Toshiba Silicone as commercially available XF42-B0970 etc.), vinyl modified silicone oil (XF40-A1987 by Toshiba Silicone, etc. as a commercial item), epoxy modified silicone oil (SF8411, SF8413 by Toray Dow Corning Silicone as a commercial item); TSF3965, TSF4730, TSF4732, XF42-A4439, XF42-A4438, XF42-A5041, XC96-A4462, XC96-A4463, XC96-A4464, TEX170, etc. from Toshiba Silicone Co., Ltd., Shin-Etsu Chemical Co., Ltd. Product KF-351 (A), KF-352 (A), KF-353 (A), KF-354 (A), KF-355 (A), KF-615 (A), KF-618, KF- 945 (A); SH3746, SH3771, SF8421, SF8419, SH8400, SF8410 from Toray Dow Corning Silicon; TSF4440, TSF4441, TSF4445, TSF4446, TSF4450, TSF4452, TSF4453, TSF4460, etc.) Silicone oil, methacryl modified silicone oil, mercapto modified silicone oil, alcohol modified silicone oil (commercially available products such as SF8427, SF8428 from Toray Dow Corning Silicon, TSF4750, TSF4751, XF42-B0970 from Toshiba Silicone, etc.), alkyl modified Silicone oil (SF8416 from Toray Dow Corning Silicon, TSF410, TSF411, TSF4420, TSF4421, TSF4422, TSF4450 from Toshiba Silicone, XF42-334, XF42-A3160, XF42-A3161, etc.), fluorine-modified silicone oil (commercially available FS1265 from Toray Dow Corning Silicon, FQF501 from Toshiba Silicone, etc.), silicone rubber and silicone microparticles (Toray Dow as commercially available) Corning silicon products SH851U, SH745U, SH55UA, SE4705U, SH502UA & B, SRX539U, SE6770U-P, DY38-038, DY38-047, Trefil F-201, F-202, F-250, R-900, R-902A , E-500, E-600, E-601, E-506, BY29-119; Tospur 105, 120, 130, 145, 240, 3120, etc. from Toshiba Silicone; Silicone modified resins (specifically, olefin A compound obtained by modifying a silicone resin of a resin, a polyester resin, a vinyl resin, a polyamide resin, a cellulose resin, a phenoxy resin, a vinyl chloride-vinyl acetate resin, a urethane resin, an acrylic resin, a styrene-acrylic resin, or a copolymer resin thereof. DIAROMA SP03V, SP712, SP2105, SP3023 by Dainichi Seika Corp. as a commercial item etc .; Moda FS700, FS710, FS720, FS730, FS770 from Nippon Maintenance products; Doua Kousea Kagaku's Cymac US-270, US-350, US-352, US-380, US-413, US-450, Regeda GP-705, GS-30, GF-150, GF- 300; Toray Dow Corning Silicon SH997, SR2114, SH2104, SR2115, SR2202, DCI-2577, SR2317, SE4001U, SRX625B, SRX643, SRX439U, SRX488U, SH804, SH840, SR2107, SR2115; YR3370, TSR1122, TSR102, TSR108, TSR116, TSR117, TSR125A, TSR127B, TSR144, TSR180, TSR187, YR47, YR3187, YR3224, YR3232, YR3270, YR3286, YR3340, YR3365, TEX152, TEX152, TEX152, TEX152, etc. ), Reactive silicone compounds (specifically, there are addition reaction type, peroxide curing type, and ultraviolet curing type) and are commercially available TSR1500, TSR1510, TSR1511, TSR1515, TSR1520, YR3286, YR3340, PSA6574, TPR6500, TPR6501, TPR6600, TPR6702, TPR6604, TPR6700, TPR6701, TPR6705, TPR6707, TPR6708, TPR6710, TPR6712, TPR6721, TPR6722, UV9300, UV9315, UV9425, UV9430, XS56-A2775, XS56-A2982, XS56-A5675, XS56-A5675 XS56-A8012, XS56-B1794, SL6100, SM3000, SM3030, SM3200, # SR3022, etc.) are mentioned.

Examples of the fluorine compound include fluorine oil (Difluoroyl # 1, # 3, # 10, # 20, # 50, # 100, Unidyne TG-440, TG-452, TG-490, available from Daikin Kogyo Co., Ltd. as a commercially available product). TG-560, TG-561, TG-590, TG-652, TG-670U, TG-991, TG-999, TG-3010, TG-3020, TG-3510; MF-100 from Tochemprodakutsu, MF-110, MF-120, MF-130, MF-160, MF-160E; Safron S-111, S-112, S-113, S-121, S-131, S-132, from Asahi Glass S-141, S-145; Sansei Fluoro Chemical's FC-430, FC-431, etc.), Fluoro rubber (commercially available as Toray Dow Corning Silicon, LS 63U, etc.), Fluorine-modified resin (Nippon Oil as a commercially available product) Product Modpa F200, F220, F600, F2020, F3035; Diaroma FF203, FF204 from Dainichi Seika; Sufron S-381, S-383, S-393, SC-101, SC-105 from Asahi Glass , KH-40, SA-100; EF-351, EF-352, EF-801, EF-802, EF-601, TFE, TFEA, TFEMA, PDFOH from Tochemprodakuts; THV- from Sumitomo 3M 200P etc.), fluoride Acid compounds (commercially available products such as EF-101, EF-102, EF-103, EF-104, EF-105, EF-112, EF-121, EF-122A, EF-122B, and EF-122C available from Tochem Produk. , EF-123A, EF-123B, EF-125M, EF-132, EF-135M, EF-305, FBSA, KFBS, LFBS, etc., fluorosulfonic acid, fluoric acid compounds or salts (specifically fluoric anhydride) , Dihydrofluoric acid, boric acid, zinc fluoride, nickel fluoride, tin fluoride, lead fluoride, copper fluoride, silicic acid, potassium titanate, perfluorocaprylic acid, ammonium perfluorophthalate, etc.), inorganic fluoride Specifically, aluminum fluoride, potassium silicate, potassium zirconate fluoride, zinc fluoride tetrahydrate, calcium fluoride, lithium fluoride, barium fluoride, tin fluoride, potassium fluoride, acidic potassium fluoride, magnesium fluoride, titanic fluoride, zirconium fluoride, Ammonium hexafluorophosphate, potassium hexafluorophosphate, etc.);

Examples of the waxes include petroleum waxes, synthetic hydrocarbons, modified waxes, hydrogenated waxes, natural waxes, and the like.

As said petroleum wax, paraffin wax (paraffin wax 155, 150, 140, 135, 130, 125, 120, 115, HNP-3, HNP-5, HNP-9, HNP-10, HNP from Nippon Shiroi as a commercial item) -11, HNP-12, HNP-14G, SP-0160, SP-0145, SP-1040, SP-1035, SP-3040, SP-3035, NPS-8070, NPS-L-70, OX-2151, OX -2251, EMUSTAR-0384, EMUSTAR-0136; Cerrozol 686, 428, 651-A, A, H-803, B-460, E-172, 866, K-133, Hydrin D- 337, E-139; 125 ° paraffin, 125 ° FD, 130 ° paraffin, 135 ° paraffin, 135 ° H, 140 ° paraffin, 140 ° N, 145 ° paraffin, paraffin wax M from Nippon Seki Yumitsubishi Sekiyu ), Microcrystal wax (commercially available as Hi-Mic-2095, Hi-Mic-3090, Hi-Mic-1080, Hi-Mic-1070, Hi-Mic-2065, Hi-Mic-1045, Hi-Mic-2045, EMUSTAR-0001, EMUSTAR-042X; Cerrozol 967, M of Nakagyo oil and fat products; 155 microwax, 180 microwax of Nippon Seki Yumitsubishi Sekiyu product), petorolatam (as a commercial item) OX-1749, OX-0450, OX-0650B, OX-0153, OX-261BN, OX-0851, OX-0550, OX-0750B, JP-1500, JP-056R, JP-011P, etc. from Nippon Seiro. And the like.

Examples of the synthetic hydrocarbons include polyethylene wax (polyone A, 393, H-481 from Nakagyo Oil Co., Ltd., acid wax E-310, E-330, E-250P, LEL-250, LEL-800, LEL-400P, etc.), polypropylene wax (commercially available Biscol 330-P, 550-P, 660-P from Sanyo Kasei), Fischer Tropsch wax (FT100, FT-0070 from Nippon Seiro, etc.) , Acid amide compounds or acid imide compounds (specifically, commercially available products such as stearic acid amide and phthalic anhydride) such as Cerazole 920, B-495, Hi-micron G-270, G-110, and hydrin D of Nakagyo Oil & Fat Products. -757 and the like).

Examples of the modified wax include amine-modified polypropylene (QN-7700 from Sanyokasei Co., Ltd. as a commercially available product), acrylic acid-modified and fluorine-modified wax, olefin-modified wax, and urethane type wax (NPS-6010, HAD-5090 from Nippon Seiro Co., Ltd. as a commercially available product). ), Alcohol waxes (NPS-9210, NPS-9215, OX-1949, XO-020T, etc., available from Nippon Shiroi, etc.).

Examples of the hydrogenated wax include hardened castor oil (such as castor wax of Itosei oil as a commercial product), castor oil derivative (dehydrated castor oil DCO, DCO Z-1, DCO Z-3, and castor oil fatty acid of Itosei oil products as a commercial product). CO-FA, ricinoleic acid, dehydrated castor oil fatty acid DCO-FA, dehydrated castor oil fatty acid epoxy ester D-4 ester, castor oil-based urethane acrylate CA-10, CA-20, CA-30, castor oil derivative MINERASOL S -74, S-80, S-203, S-42X, S-321, special castor oil condensed fatty acid MINERASOL RC-2, RC-17, RC-55, RC-335, special castor oil condensed fatty acid ester MINERASOL LB- 601, LB-603, LB-604, LB-702, LB-703, # 11, L-164, etc.), stearic acid (commercially available 12-hydroxy stearic acid from Itosei Oil, etc.), lauric acid, myristic Acid, palmitic acid, behenic acid, sebacic acid (commercially available sebacic acid from Itosei oil, etc.), undecylenic acid (commercially available Itosei oil products) Undecylenic acid, etc.), heptyl acid (commercially available from Itosei oil, heptyl acid, etc.), maleic acid, highly maleated oil (commercially available from Itosei Oil, HIMALEIN DC-15, LN-10, 00-15, DF- 20, SF-20, etc.), suction oil (selbonol # 10, # 30, # 60, R-40, S-7, etc. of Itosei oil as a commercial item), cyclopentadienized oil (Itosei oil as a commercial item) Synthetic waxes, such as CP oil, CP oil-S, etc. of a product, etc. are mentioned.

As said natural wax, it is preferable that it is any one or more of a vegetable wax and a mineral wax, and especially a plant wax is preferable. Moreover, as said natural wax, especially water-dispersible wax is preferable at the point of compatibility, when an aqueous thermoplastic resin is used as a thermoplastic resin of the said toner aqueous layer.

Examples of the plant-based waxes include carnauba wax (EMUSTAR-0413 from Nippon Shiroi, Nakagyo oil from Cerrozole 524, etc.), castor oil (from Itosei oil refined castor oil, etc.) and vegetable oils. (Rape Seed Oil), soybean oil, wax, cotton lob, rice wax, sugar cane wax, candelilla wax, Japan wax, jojoba oil, animal wax, beeswax, lanolin, sperm, steep (whale oil), and wool wax This is listed. Among them, in particular, in terms of being able to provide an electrophotographic award sheet which is excellent in offset resistance, adhesion resistance, noticeability, glossiness, is hard to be cracked, and can form a high quality image. Carnauba wax having a melting point of 70 to 95 ° C is particularly preferred.

Examples of the mineral waxes include natural waxes such as montan wax, montan ester wax, ground wax and ceresin, and fatty acid esters (oxygen sizers DOA, AN-800, DINA, DIDA, DOZ, DOS from Shin-Nipponica as commercially available products). , TOTM, TITM, E-PS, nE-PS, E-PO, E-4030, E-6000, E-2000H, E-9000H, TCP, C-1100, etc., polyethylene wax (Naka as a commercially available product) Polyons A, 393, H-481 from the cross-linked products; Sanwax E-310, E-330, E-250P, LEL-250, LEL-800, LEL-400P, etc., from Sanyo Kasei; As a commercial item, Biscol 330-P, 550-P, and 660-P of Sanyo Kasei products are mentioned. Among them, in particular, in terms of providing offset photoresist, adhesiveness, noticeability, glossiness, hardly cracking, and providing an electrophotographic award sheet capable of forming a high-quality image. Montan wax having a melting point of 70 to 95 ° C is particularly preferable.

As content (g / m <^2> ) in the said toner aqueous layer (surface) of the said natural wax, 0.1-4 g / m <^2> is preferable and 0.2-2 g / m <^2> is more preferable. If the content is less than 0.1 g / m ² , the offset resistance and the adhesion resistance may be particularly insufficient, while if the content is more than 4 g / m ² , the amount of wax is too large, resulting in poor image quality. There is a case to be done.

Especially as melting | fusing point (degreeC) of the said natural wax, 70-95 degreeC is preferable and 75-90 degreeC is more preferable at the point of offset resistance and noticeability.

Various well-known things can be mentioned as said mat agent. Solid particles used as a mat agent can be classified into inorganic particles and organic particles. Specific examples of the inorganic mat material include oxides (eg, silicon dioxide, titanium oxide, magnesium oxide, alumina), alkaline earth metal salts (eg, barium sulfate, calcium carbonate, magnesium sulfate), silver halides (eg, silver chloride, silver bromide) And glass.

As the inorganic mat agent, for example, German Patent 2529321, British Patent 760775, 1260772, US Patent 1201905, 2192241, 3053662, 3030649, 3232206, 3333555, 3333958 And those described in the specifications of Nos. 3370951, 3411907, 3437484, 33523022, 3615554, 3635714, 3769020, 4040245 and 4029504.

The organic mat material includes starch, cellulose esters (e.g., cellulose acetate propionate), cellulose ethers (e.g., ethyl cellulose), and synthetic resins. It is preferable that synthetic resin is water-insoluble or poorly water-soluble. Examples of water-insoluble or poorly water-soluble synthetic resins include poly (meth) acrylic acid esters (e.g., polyalkyl (meth) acrylates, polyalkoxyalkyl (meth) acrylates, polyglycidyl (meth) acrylates), Poly (meth) acrylamide, polyvinylester (e.g. polyvinyl acetate), polyacrylonitrile, polyolefin (e.g. polyethylene), polystyrene, benzoguanamine resin, formaldehyde condensation polymer, epoxy resin, polyamide, poly Carbonates, phenol resins, polyvinylcarbazole and polyvinylidene chloride.

You may use the copolymer which combined the monomer used for the above polymer.

In the case of the copolymer, a small amount of hydrophilic repeating unit may be included. Examples of the monomer forming the hydrophilic repeating unit include acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, and hydroxyalkyl (meth). Acrylates, sulfoalkyl (meth) acrylates and styrenesulfonic acids.

As an organic mat agent, for example, British Patent No. 105713, US Patent No. 1939213, No. 22227373, No. 22268662, No. 223237, No. 2376005, No. 22391181, No. 2701245, No. 2992101, No. 3079257 No. 3262782, No.3443946, No.3516832, No.3539344, No.3591379, No.3754924, No.3767448, Japanese Patent Publication No. 49-106821, Japanese Patent Publication No. 57-14835 The things described in can be enumerated.

Moreover, you may use together 2 or more types of solid particle. The average particle diameter of the solid particles is, for example, preferably 1 to 100 µm, preferably 4 to 30 µm. 0.01-0.5 g / m <^2> is preferable and, as for the usage-amount of a solid particle, 0.02-0.3 g / m <^2> is more preferable.

As the release agent added to the toner aqueous layer of the present invention, these derivatives, oxides, tablets, and mixtures may be used. In addition, these may have a reactive substituent.

Especially as melting | fusing point (degreeC) of the said mold release agent, 70-95 degreeC is preferable and 75-90 degreeC is more preferable at the point of offset resistance and noticeability.

As the mold releasing agent, a water-dispersing mold releasing agent is particularly preferable from the viewpoint of compatibility with the case of using an aqueous thermoplastic resin as the thermoplastic resin of the toner aqueous layer.

As content in the said toner aqueous layer of a mold release agent, 0.1-20 mass% is preferable, 0.3-10.0 mass% is more preferable, 0.5-8.0 mass% is more preferable.

-Other Ingredients-

Examples of the other components include various additives added for the purpose of improving the thermodynamic properties of the toner aqueous layer, such as colorants, plasticizers, fillers, crosslinking agents, charge control agents, emulsions, and dispersions. The other components contained in these toner aqueous layers are preferably hollow particles in that they are excellent in thermal conductivity (low thermal conductivity) of the toner aqueous layers upon image fixing, and in particular, the pigments are hollow particle shapes. Is preferably.

--coloring agent--

Examples of the colorant include fluorescent brighteners, white pigments, colored pigments, and dyes.

The fluorescent brightener is a compound having absorption in the near ultraviolet and fluorescing at 400 to 500 nm, and various known fluorescent brighteners can be used without particular limitation. As said fluorescent brightener, the compound described in K.VeenRataraman compilation "The Chemistry of Synthetic Dyes" V volume 8 can be mentioned preferably. Specific examples thereof include a stylbene compound, a coumarin compound, a biphenyl compound, a benzooxazoline compound, a naphthalimide compound, a pyrazoline compound, a carbostyryl compound, and the like. Examples thereof include Howiteftpa-PSN, PHR, HCS, PCS, B from Sumitomogagaku Co .; And UVITEX-OB from Ciba-Geigy.

As said white pigment, the inorganic pigment (for example, titanium oxide, calcium carbonate, etc.) demonstrated by the part of the filler mentioned later can be used. As the colored pigment, various pigments and azo pigments described in JP-A-63-44653 and the like (for example, azo lake; carmine 6B, red 2B, insoluble azo; monoazo yellow, disazo yellow, pyrazole orange, balkan) Orange, condensed azo; chromophthal yellow, chromophthaled), polycyclic pigments (e.g., phthalocyanine; copper phthalocyanine blue, copper phthalocyanine green, dioxazine; dioxazine violet, isoindolinone; isoindolinone Yellow, styrene-based, perylene, flavantron, thioindigo, lake pigments (e.g. malachite green, rhodamine B, rhodamine G, victoria blue B) and inorganic pigments (e.g. oxides, titanium dioxide, bengara, Sulfates, precipitated barium sulfate, carbonates, precipitated calcium carbonates, silicates; hydrous silicates, anhydrous silicates, metal powders, aluminum powders, bronze powders, zinc powder, carbon black, sulfur lead, rusted blue and the like.

These may be used individually by 1 type and may use 2 or more types together. Among these, titanium oxide is particularly preferable as the pigment.                     

Although there is no restriction | limiting in particular as a shape of the said pigment, It is preferable that it is a hollow particle shape from the point which is excellent in the heat transfer property (low thermal conductivity) at the time of image fixation.

As the dye, various known dyes can be used.

Examples of the oil-soluble dyes include anthraquinone compounds and azo compounds.

Specific examples of the water-insoluble dye include CIVata violet 1, CIVata violet 2, CIVata violet 9, CIVata violet 13, CIVata violet 21, CIVata blue 1, CIVata blue 3, CIVata blue 4, and CIVata blue. 6, vat salt dyes such as CIVat Blue 14, CIVat Blue 20, CIVat Blue 35, CI Disperse Violet 1, CI Disperse Violet 4, CI Disperse Violet 10, CI Disperse Blue 3, CI Disperse Blue 7 , Disperse dyes such as CI Disperse Blue 58, CI Solvent Violet 13, CI Solvent Violet 14, CI Solvent Violet 21, CI Solvent Violet 27, CI Solvent Blue 11, CI Solvent Blue 12, CI Solvent Blue 25, CI Solvent Blue 55 Oil-soluble dyes such as;

Moreover, the coloring coupler used by the silver salt photograph can also be used preferably.

As content (g / m <^2> ) in the said toner aqueous layer (surface) of the said coloring agent, 0.1-8 g / m <^2> is preferable and 0.5-5 g / m <^2> is more preferable.

If the content of the colorant does not satisfy 0.1 g / m ² , the light transmittance in the toner aqueous layer is increased. On the other hand, if the content of the colorant exceeds 8 g / m ² , the gold cracks, cracks, adheres, and the like. The handleability may deteriorate.

--Plasticizer--

As said plasticizer, it can use without restrict | limiting especially the plasticizer for well-known resin. The plasticizer has a function of adjusting the flow or softening of the toner aqueous layer by heat and / or pressure when fixing the toner.

As said plasticizer, "Kagaku manual" (the Japanese chemical society compilation, Maruzen) and "plasticizer-the theory and application-" (Murai Koichi compilation, Saiwaishoboy) and "research prize of plasticizer" of "plasticizer It can be selected with reference to "Research" (composed by the Polymer Chemistry Association), and "Handbook Rubber / Plastic Combination Drug" (Compiled by Rubber Digest Co., Ltd.).

Although the said plasticizer is described as a high boiling point organic solvent, a thermal solvent, etc., For example, Unexamined-Japanese-Patent No. 59-83154, 59-178451, 59-178453, 59-178454, 59 -178455, 59-178457, 62-174754, 62-245253, 61-209444, 61-200538, 62-6145, 62-9348, 62-2247 No. 62-136646, No. 62-174754, No. 62-245253, No. 61-209444, No. 61-200538, No. 62-8145, No. 62-9348, No. 62-30247, Esters as described in Japanese Patent Application Laid-Open No. 62-136646, Japanese Patent Laid-Open No. 2-235694, etc. (for example, phthalic acid esters, phosphate esters, fatty acid esters, abietinic acid esters, adipic acid esters, Sebacic acid esters, azelaic acid esters, benzoic acid esters, butyric acid esters, epoxidized fatty acid esters, glycolic acid esters, propionic acid esters, trimellitic acid esters, citric acid esters, Sulfonic acid esters, carboxylic acid esters, succinic acid esters, maleic acid esters, fmaric acid esters, phthalic acid esters, stearic acid esters, etc.), amides (e.g. fatty acid amides, sulfoamides, etc.), ethers And compounds such as alcohols, lactones and polyethyleneoxy.

The said plasticizer can be used in mixture with resin.

As the plasticizer, a relatively low molecular weight polymer can be used. In this case, the molecular weight of the plasticizer is preferably lower than the molecular weight of the binder resin to be plasticized, the molecular weight is preferably 15000 or less, and more preferably 5000 or less. In the case of the polymer plasticizer, the binder to be plasticized It is preferable that it is a polymer of the same kind as resin. For example, polyester of low molecular weight is preferable for plasticization of polyester resin. Oligomers can also be used as plasticizers. In addition to the above-listed compounds, commercially available products include, for example, Adekasaiza PN-170 and PN-1430 from Asahi Denka Kogyo; PARAPLEX-G-25, G-30, G-40 from C.P.HALL; Ester gum 8L-XA, Ester R-95, Fentarin 4851, FK115, 4820, 830, Ruizol 28-XA, Picolastic A75, Picotex LC, Crytarex 3085, etc., manufactured by Rika Hacures.

The plasticizer is used to mitigate stresses or misalignments (physical misalignment such as elastic force or viscosity, misalignment due to material resin such as molecular or binder backbone or pendant portion) that occur when toner particles are embedded in the toner aqueous layer. Can be used arbitrarily.                     

The plasticizer may be in a very finely dispersed state in a toner aqueous layer, may be in a very fine phase separation in a sea island shape, or may be sufficiently mixed and dissolved with other components such as a binder.

As content in the said toner aqueous layer of the said plasticizer, 0.001-90 mass% is preferable, 0.1-60 mass% is more preferable, 1-40 mass% is more preferable.

The plasticizers include adjustment of slipperiness (improvement of conveyability by lowering friction), improvement of fixing unit offset (separation of toner or layer in the fixing unit), adjustment of curl balance, charging adjustment (formation of toner electrostatic image), and the like. It may be used for the purpose.

--filler--

As said filler, an organic or inorganic filler can be mentioned, A well-known thing can be used as a reinforcing agent for binder resin, a filler, and a reinforcing material. Examples of the filler include "hand rubber and plastic compounding chemicals" (compiled by Rubber Digest Co., Ltd.), "new plastic compounding bases and applications" (Taisei Chemical Co., Ltd.), "filler handbook" (Taisei Chemical Co., Ltd.), etc. Can be selected by reference.

In addition, various inorganic fillers (or pigments) can be used as the filler. Examples of the inorganic pigments include silica, alumina, titanium dioxide, zinc oxide, zirconium oxide, mica-shaped iron oxide, ceruse, lead oxide, cobalt oxide, strontium chromate, molybdenum pigment, smectite, magnesium oxide, calcium oxide and carbonate. Calcium, mullite and the like. As a filler, silica and aluminum oxide are especially preferable. These fillers may be used individually by 1 type, and may use 2 or more types together. Moreover, as said filler, a thing with a small particle size is preferable. If the particle size is large, the surface of the toner aqueous layer is likely to be roughened.

The silica includes circular silica and amorphous silica. The silica may be synthesized by a dry method, a wet method or an aerogel method. The surface of the hydrophobic silica particles may be surface treated with trimethylsilyl group or silicon. As silica, colloidal silica is preferable. As an average particle diameter of a silica, 200-5000 nm is preferable.

It is preferable that the said silica is porous. 4-120 nm is preferable and, as for the average diameter of porous silica, 4-90 nm is more preferable. In addition, the average diameter per mass of the porous silica is preferably, for example, 0.5 to 3 ml / g.

The alumina includes anhydrous alumina and alumina hydrate. As the crystal form of anhydrous alumina, α, β, γ, δ, ζ, η, θ, κ, ρ or χ can be used. Alumina hydrate is more preferable than anhydrous alumina. As the alumina hydrate, monohydrate or trihydrate can be used. Monohydrates include pseudo-boehmite, boehmite and diaspores. Examples of trihydrates include jib sites and vialites. As an average particle diameter of alumina, 4-300 nm is preferable and 4-200 nm is more preferable. It is preferable that alumina is porous. As an average diameter of porous alumina, 50-500 nm is preferable. As average pore volume per mass of porous alumina, about 0.3-3 ml / g is preferable.

The alumina hydrate can be synthesized by a sol-gel method in which ammonia is added to an aluminum salt solution to precipitate, or a method of hydrolyzing an alkali aluminate. Anhydrous alumina can be obtained by dehydrating an alumina hydrate by heating.

It is preferable that the said filler is 5-2000 mass% based on the dry mass of the binder of the layer to add.

--Bridge

The said crosslinking agent can be mix | blended in order to adjust the storage stability of a toner aqueous layer, thermoplastics, etc. As such a crosslinking agent, a compound having an epoxy group, an isocyanate group, an aldehyde group, an active halogen group, an active methylene group, an acetylene group, and other known reactors in two or more molecules is used as the reactor.

As said crosslinking agent, the compound which has 2 or more groups which can form a bond by a hydrogen bond, an ionic bond, a coordination bond etc. can also be used unlike these.

As said crosslinking agent, a well-known compound can be used as a coupling agent for resins, a hardening | curing agent, a polymerization agent, a polymerization promoter, a coagulant, a film composition agent, a film composition auxiliary agent, etc. Examples of the coupling agent include, for example, chlorosilanes, vinylsilanes, epoxysilanes, aminosilanes, alkoxyaluminum chelates, titanate coupling agents, and the like. The known ones listed in (Rubber Digest Co., Ltd.) or the like can be used.

--Charge control agent--

In order to adjust transfer of a toner, adhesion | attachment, etc., or to prevent the charge adhesion of a toner aqueous layer, it is preferable to contain a charge regulator in the toner aqueous layer of this invention. As the charge regulator, various conventionally known charge regulators can be used. As such a charge regulator, a polymer electrolyte, a conductive metal oxide, etc. can be used, for example, surfactants, such as a cationic surfactant, anionic surfactant, amphoteric surfactant, and a nonionic surfactant. For example, quaternary ammonium salts, cationic antistatic agents such as polyamine derivatives, cationic modified polymethylmethacrylates, cationic modified polystyrenes, anionic antistatic agents such as alkyl phosphates and anionic polymers, fatty acid esters, polyethylene oxides, and the like Although an ionic antistatic agent is enumerated, it is not limited to these.

In the case where the toner has a negative charge, for example, a cation or a nonionic is preferable as the charge control agent blended in the toner aqueous layer.

Examples of the conductive metal oxide include ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, MoO _3, and the like. These conductive metal oxides may be used alone, or may be used as these complex oxides. In addition, the metal oxide may further contain a dissimilar element, for example, ZbO, Al, In, etc., TiO ₂ , Nb, Ta, etc., SnO ₂ , Sb, Nb, a halogen element, etc. (doping )can do.

-Other additives--

The material that can be used for the toner aqueous layer of the present invention may contain various additives for improving the stability of the output image and also for improving the stability of the toner aqueous layer itself. Examples of additives for this purpose include various known antioxidants, anti-aging agents, anti-aging agents, ozone anti-aging agents, ultraviolet absorbers, metal complexes, light stabilizers, preservatives, mold inhibitors, and the like.

As said antioxidant, a chromman compound, a coumaran compound, a phenol compound (for example, a hindered phenol), a hydroquinone derivative, a hindered amine derivative, a spiroindan compound is mentioned, for example. On the other hand, about antioxidant, it is described in Unexamined-Japanese-Patent No. 61-159644.

As said anti-aging agent, the thing of "76 rubber | gum rubber compounding chemicals revision 2nd edition" (1993, Rubber Digest Co., Ltd.) p76-121 is mentioned, for example.

As the ultraviolet absorber, for example, a benzotriazole compound (described in the specification of US Patent No. 3533794), a 4-thiazolidonate compound (described in the specification of U.S. Patent No. 3352681), and a benzophenone compound (Japanese Patent Publication No. 46-2784) Substrate) and an ultraviolet absorbing polymer (described in Japanese Patent Application Laid-Open No. 62-260152).

Examples of the metal complex include, for example, US Pat. Nos. 4241155, 4245018, and 4254195, Japanese Patent Laid-Open Nos. 61-88256, 62-174741, 63-199248, and Japanese Patent Laid-Open No. 1- It is suitable to be described in the publications of No. 75568 and No. 1-74272.

In addition, the ultraviolet absorber and light stabilizer as described in "the handbook rubber / plastic compound chemical revision 2nd edition" (Rubber Digest Inc., 1993) p122-137 are used suitably.

To the material that can be used for the toner aqueous layer of the present invention, a known photo additive may be added as described above. As photographic additives, for example, research and closure record (hereinafter abbreviated as RD) No.17643 (December 1978), No.18716 (November 1979) and No.307105 (November 1989) The part described in the above is collectively shown below.

 Type of additives RD17643 RD18716 RD307105

Brightener 24p. 648p. Right i 868p.

2. Stabilizer 24-25p. 649p. Right side I 868-870p.

3. Light absorbing agent 25 to 26p. 649p. Right i 873p.

(UV absorber)

4. Pigment stabilizer 25p. 650p. Right i 872p.

5. Scleral 26p. 651 p. Left column 874-875p.

6. Binder 26p. 651 p. Left column 873-874p.

7. Plasticizer, lubricant 27p. 650p. Right i 876p.

8. Coating aid 26-27p. 650p. Right I 875-876p.

(Surfactants)

9. Static inhibitor 27p. 650p. Right I 876-877p.

10. Mat 878-879 p.

The toner aqueous layer of this invention is formed by apply | coating the coating liquid containing the polymer used for a toner aqueous layer on a said support body with a wire coater, etc., and drying. Coating liquid is prepared by dissolving additives, such as a thermoplastic polymer and a plasticizer, in organic solvents, such as alcohol and a ketone, or disperse | distributing uniformly, for example. As an organic solvent used here, methanol, isopropyl alcohol, methyl ethyl ketone, etc. are mentioned, for example. If the polymer used for the toner aqueous layer is water-soluble, the toner aqueous layer can be prepared by coating an aqueous polymer solution on the support. Moreover, about the polymer which is not water-soluble, it is also possible to apply | coat on a support body with an aqueous dispersion.

The film formation temperature of the polymer used in the present invention is preferably room temperature or more for storage before printing, and 100 ° C. or less for fixing toner particles.

The toner aqueous layer of the present invention is applied such that the coating mass after drying is, for example, 1 to 20 g / m ² , more preferably 4 to 15 g / m ² .

Although there is no restriction | limiting in particular as thickness of the said toner aqueous layer, 1-30 micrometers is preferable and 2-20 micrometers is more preferable.

<All Properties of Toner Water Layer>

It is preferable that the toner aqueous layer has a high whiteness. As said whiteness, it is measured by the method of JIS P8123, and 85% or more is preferable. In the wavelength region of 440 nm to 640 nm, the spectral reflectance is preferably 85% or more, and the difference between the maximum spectroscopic reflectance and the lowest spectroscopic reflectance in the same wavelength region is preferably within 5%. Alternatively, it is more preferable that the spectral reflectance is 85% or more in the wavelength region of 400 nm to 700 nm, and the difference between the maximum spectroscopic reflectance and the lowest spectroscopic reflectance in the same wavelength region is within 5%.                     

As the whiteness, specifically, in the CIE 1976 (L ^* a ^* b ^* ) color space, the L ^* value is preferably 80 or more, more preferably 85 or more, and even more preferably 90 or more. As for the white color tone, the value of (a ^* ) ² + (b ^* ) ² is preferably 50 or less in L ^* a ^* b ^* space, as long as possible. The following is more preferable and 5 or less are more preferable.

As the toner aqueous layer, a high gloss is preferable. As glossiness, the 45 degree glossiness is preferable in the whole area | region from white without a toner to black of maximum density | concentration, 60 or more are preferable, 75 or more are more preferable, and 90 or more are more preferable.

However, the glossiness is preferably 110 or less. If it exceeds 110, it is not preferable as image quality such as metallic gloss.

In addition, the glossiness can be measured based on JIS Z 8741.

It is preferable that the toner aqueous layer has high smoothness. As the smoothness, the arithmetic mean roughness Ra is preferably 3 μm or less, more preferably 1 μm or less, and even more preferably 0.5 μm or less in the entire region from white without toner to black of maximum concentration.

In addition, arithmetic mean roughness can be measured based on JIS B 0601, B 0651, and B 0652.

It is preferable that the toner aqueous layer has the physical properties of one item in the following items, more preferably a plurality of items, most preferably all items.

(1) The Tg (glass transition temperature) of the toner aqueous layer is 30 ° C or more and the Tg + 20 ° C or less of the toner.

(2) T1 / 2 (1/2 method softening point) of the toner aqueous layer is 60 to 200 占 폚, preferably 80 to 170 占 폚. Here, the 1/2 method softening point uses a specific apparatus, and under certain conditions, adds a predetermined extrusion weight, at a predetermined constant temperature (for example, 50 ° C.), after a predetermined time, for example, 300 seconds, at a predetermined constant velocity temperature increase. It evaluates at the temperature which becomes a half of the difference of the outflow starting point in each temperature at the time of heating up at the speed | rate, and the piston stroke at the end.

(3) The Tfb (outflow start temperature) of the toner aqueous layer is 40 to 200 占 폚, preferably the Tfb of the toner aqueous layer is Tfb + 50 占 폚 or less of the toner.

(4) The temperature at which the viscosity of the toner aqueous layer becomes 1 × 10 ⁵ CP is lower than that of the toner at 40 ° C. or higher.

(5) The storage elastic modulus G 'at the fixing temperature of the toner aqueous layer is 1 × 10 ^{2 to} 1 × 10 ⁵ Pa, and the loss modulus G ″ is 1 × 10 ^{2 to} 1 × 10 ⁵ Pa.

(6) Loss tangent (G "/ G ') which is a ratio of loss elasticity modulus G" and storage elastic modulus G' at the fixing temperature of a toner aqueous layer is 0.01-10.

(7) The storage elastic modulus G 'at the fixing temperature of the toner aqueous layer is -50 to +2500 with respect to the storage elastic modulus G "at the fixing temperature of the toner.

(8) The inclination angle of the molten toner on the toner aqueous layer is 50 ° C or less, particularly 40 ° C or less.

As the toner receiving layer, it is preferable to satisfy the physical properties disclosed in Patent No. 2788358, Japanese Patent Laid-Open Nos. 7-248637, 8-305067, 10-239889, and the like.

The physical property of said (1) can be measured by a differential scanning calorimeter (DSC). The physical property of said (2)-(3) can be measured using the flow tester CFT-500 or 500D by Shimadzu Corporation. The physical property of said (5)-(7) can be measured using a rotatable rheometer (for example, the dynamic analyzer RAD II by the Leometric Co., Ltd. product). The physical property of said (8) can be measured by the method disclosed in Unexamined-Japanese-Patent No. 8-334916 using the contact angle measuring apparatus of the Kyowa Chemicals Co., Ltd. product.

As the toner aqueous layer, one having a surface electrical resistance in the range of 1 × 10 ^{6 to} 1 × 10 ¹⁵ Ω / cm ² (at 25 ° C. and 65% RH) is preferable.

When the surface resistance is less than 1 × 10 ⁶ Ω / cm ² , the toner amount at the time of transferring the toner to the toner receiving layer is not sufficient, and the density of the toner image obtained is likely to be low, while the surface electrical resistance is high. When it exceeds 1 × 10 ¹⁵ Ω / cm ² , more than necessary charges are generated during transfer, the toner is not sufficiently transferred, the density of the image is low, and static electricity is generated during handling of the electrophotographic award sheet. It is easy to adhere, and may cause miss feed, heavy feeding, discharge display, toner transfer omission, etc. at the time of copying.

Further, with respect to the support, as the surface electrical resistance on the side opposite to the toner aqueous layer, 5 × 10 ^{8 to} 3.2 × 10 ¹⁰ Ω / cm ² is preferable, and 1 × 10 ^{9 to} 1 × 10 ¹⁰ Ω / cm ² is More preferred.

In the present invention, the measurement of the surface electrical resistance is based on JIS K 6911, the sample is humidified for 8 hours or more under an environment of a temperature of 20 ° C. and a humidity of 65%, and under the same environment, R8340 manufactured by Advancedist. It is obtained by measuring after passing an electric current for 1 minute on condition of 100V of applied voltages using the following.

[Other layers]

As said other layer, a surface protection layer, a back surface layer, an adhesion | attachment improvement layer, an intermediate | middle layer, a servant layer, a cushion layer, an antistatic (prevention) layer, a reflection layer, a color tone preparation layer, a storage stability improvement layer, an adhesion prevention layer, an anti-coal layer, for example , And smoothing layers and the like. These layers may be single layer structure, and may be comprised by two or more layers.

Surface protective layer

The surface protective layer is the toner award for the purpose of protecting the surface of the electrophotographic award sheet of the present invention, improving storage properties, improving handleability, imparting handwriting property, improving device permeability, and imparting anti-offset property. It can be formed on the surface of the layer. One surface may be sufficient as the said surface protection layer, and it may consist of two or more layers. Various thermoplastic resins, heat-changeable resins, etc. can be used for a surface protection layer as a binder, It is preferable to use resin of the same kind as the said toner aqueous layer. However, the thermodynamic characteristics, the electrostatic characteristics, and the like do not have to be the same as the toner aqueous layer, and can be optimized respectively.

The above-mentioned various protective additives usable for the toner aqueous layer can be blended into the surface protective layer. In particular, the said surface protection layer can mix | blend other additives, for example, a mat agent, etc. with the mold release agent used by this invention. Moreover, various well-known things are mentioned as said mat agent.

As the outermost surface layer (for example, a surface protection layer, etc., when a surface protection layer is formed) in the electrophotographic award sheet of the present invention, it is preferable that compatibility with toner is good in terms of fixability. Specifically, it is preferable that the contact angle with the melted toner is, for example, 0 to 40 degrees.

-Back layer-

In the electrophotographic award sheet of the present invention, the back layer is formed on the opposite side of the toner aqueous layer with respect to the support for the purpose of imparting back output aptitude, improving back output image quality, improving balance, and improving device permeability. It is preferable to be.

Although there is no restriction | limiting in particular as a color of the said back layer, In the case of the double-sided output type award sheet in which the electrophotographic image receiving sheet of this invention forms an image also in the back surface, it is preferable that a back layer is also white. As for the whiteness and the spectral reflectance, 85% or more is preferable similarly to the surface.

In addition, in order to improve double-sided output aptitude, the structure of the back layer may be the same as that of the toner receiving layer side. The various additives demonstrated above can be used for a back surface layer. Especially as such an additive, it is suitable to mix | blend a mat agent, a charge regulator, etc. Single layer structure may be sufficient as a back surface layer, and a laminated structure of two or more layers may be sufficient as it.

In addition, in order to prevent the offset at the time of fixing, when using mold release oil etc. for a fixing roller, a back surface layer may be made oil absorption.

-Adhesive improvement layer

It is preferable to form the said adhesion | attachment improvement layer in order to improve the adhesiveness of a support body and a toner aqueous layer in the electrophotographic award sheet of this invention. It is preferable to mix | blend the various additives mentioned above with an adhesive improvement layer, and to mix | blend a crosslinking agent especially. Moreover, in order to improve the water solubility of a toner, it is preferable to form a cushion layer etc. further between the said adhesion improvement layer and the toner aqueous layer in the electrophotographic water-receiving sheet of this invention.

Middle layer

The intermediate layer can be formed, for example, between the support and the adhesion improving layer, between the adhesion improving layer and the cushion layer, between the cushion layer and the toner aqueous layer, between the toner aqueous layer and the storage improvement layer, and the like. Of course, in the case of the electrophotographic award sheet composed of the support, the toner aqueous layer, and the intermediate layer, the intermediate layer can be present, for example, between the support and the toner aqueous layer.

(The property of the electrophotographic award sheet)

When the surface tension of the polymer contained in the toner award layer of the electrophotographic award sheet is greater than the surface tension of the toner, and the difference is not less than a certain level, transfer of the toner to the award sheet is performed satisfactorily, and thus to the toner award layer. It is preferable because the adhesion of the toner is improved. Specifically, the surface tension of the polymer and the surface tension of the toner are measured at the toner fixing temperature. Under the measurement conditions, the polymer and the toner are in a molten state, and the surface tension is measured by the pendant drop method, the bubble pressure method, or the like. For example, in the case of the pendant drop method, the polymer and the toner are melted at the toner fixing temperature to form a liquid phase, and this is discharged from the needle tip to analyze and measure the shape of the droplet. In this case, the surface tension (γ _p) of the polymer (mN / m) (mN / m) and the surface tension of the toner (γ _t) is, the following equation (I):

γ _p -γ _t ≥8 (I)

Satisfactory, preferably satisfies γ _p -γ _t ≧ 9.

Herein, the polymer is one or more polymers contained in the toner aqueous layer, and means that no toner aqueous layer additive is included.

Here, when the contact angle on the surface of the fixing belt is larger than the contact angle of the surface of the toner aqueous layer on the award sheet, and the difference is more than a certain level, the award sheet and the fixing belt are peeled off satisfactorily, and the offset of the toner and the aqueous layer Since offset can be prevented and glossiness improves, it is preferable. The measurement of the contact angle is performed by a static method, for example, using a toner melted at the toner fixing temperature. That is, a toner fixed in a cube of approximately 2 mm square is placed on the surface of the aqueous layer heated at the toner fixing temperature, and the contact angle when melting is measured. In this case, the contact angle θ ₁ (°) with respect to the surface of the toner aqueous layer and the contact angle θ ₂ (°) with respect to the fixing belt surface are represented by the following formula (II);

θ ₂ -θ ₁ ≥10 (II)

Satisfactory, preferably satisfying θ ₂ -θ ₁ ≧ 13.

In addition, when the surface free energy of the surface of the toner aqueous layer in the award sheet is larger than the surface free energy on the surface of the fixing belt, and the difference is more than a certain level, the toner aqueous layer and the fixing belt are peeled off satisfactorily. It is preferable because no offset of the non-image portion which is not attached occurs and the glossiness is improved. Specifically, the surface free energy measures the contact angles (θ _i ) and (θ _j ) on the surface of the toner aqueous layer and the fixing belt surface for two kinds of liquids i and j, and the dispersible component from the following expanded Fowks equation. (g ^d ), the polar component (g ^P ), and the surface free energy (G) of the solid are obtained.

G = g ^d + g ⁰

only,

(Wherein γ _li and γ _lj are surface tensions of liquids i and j, γ ^d _li and γ ^d _lj are dispersion force components of surface tensions of liquids i and j, and γ ^p _li and γ ^p _lj are liquid i And the polar force component of the surface tension of j, and are intrinsic values of the liquids i and j. Θ _i and θ _j represent the contact angles of the liquids i and j.)

At this time, the toner-receiving layer surface of the surface free energy _{(G 1) (mN / m} ) , and a surface free energy of the surface of the fixing belt _{(G 2) (mN / m} ) of the following formula (III);

G ₁ -G ₂ ≥10 (III)

Satisfactory, and preferably, G ₁ -G ₂ ≧ 15.

Further, the value of the polar component (g ^p ₁ ) (mN / m) of the surface free energy on the surface of the toner water layer and the value of the polar component (g ^p ₂ ) of the surface free energy on the surface of the fixing belt (mN / m). ) Is the following formula (IV);

g ^p ₁ -g ^p ₂ ≥ 0.3 (IV)

Satisfactory, and preferably, g ^p ₁ -g ^p ₂ ≧ ₂ .

The toner aqueous layer surface mentioned here means the surface of the side in which the toner aqueous layer is formed among the electrophotographic award sheets of this invention.                     

Moreover, there is no restriction | limiting in particular as thickness of the said electrophotographic water receiving sheet of this invention, Although it can select suitably according to the objective, For example, 50-350 micrometers is preferable and 100-280 micrometers is more preferable.

<Toner>

The electrophotographic award sheet of the present invention is used by accommodating toner in a toner aqueous layer when printing or copying.

The toner contains at least a binder resin and a colorant, and a mold release agent and other components as necessary.

Toner binding resin

As said binder resin, Styrene, such as styrene and parachloro styrene; Vinyl esters such as vinyl naphthalene, vinyl chloride, vinyl boride, vinyl fluoride, vinyl acetate, vinyl propionate, vinyl benzoate and vinyl butyrate; Methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, n-octyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, α-chloroacrylate, methyl methacrylate, ethyl methacrylate, meta Methylene aliphatic carboxylic acid esters such as butyl acrylate; Vinyl nitriles such as acrylonitrile, methacrylonitrile and acrylamide; Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; N-vinyl compounds such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole and N-vinylpyrrolidone; Homopolymers and copolymers of vinyl monomers such as vinyl carboxylic acids such as methacrylic acid, acrylic acid and cinnamic acid, copolymers thereof, and various polyesters can be used, and various waxes can also be used in combination.                     

Among these resins, it is particularly preferable to use resins of the same type as those used for the toner aqueous layer of the present invention.

Toner Colorant

As the coloring agent, those commonly used in toners can be used without limitation, for example, carbon black, chrome yellow, kanji yellow, benzidine yellow, sren yellow, quinoline yellow, permanent orange GTR, pyrazolone orange, balkan orange, watch sheep red , Permanent Tread, Brilliant Carmine 3B, Brilliant Carmine 6B, Dayon Oil Red, Pyrazolone Red, Resolred, Rhodamine B Lake, Lake Red C, Rose Bengal, Aniline Blue, Ultramarine Blue, Calco Oil Blue, Methylene Various pigments, such as blue chloride, phthalocyanine blue, phthalocyanine green, marachite green oxalate, are mentioned. In addition, acridine-based, xanthene-based, azo-based, benzoquinone-based, azine-based, anthraquinone-based, thioindago-based, dioxadine-based, thiazine-based, azomethine-based, indigo-based, thioindigo-based, phthalocyanine-based and aniline black And various dyes such as polymethine, triphenylmethane, dimethylmethane, thiazine, thiazole and xanthene. These coloring agents may be used individually by 1 type, and may be used in combination of multiple types.

As for content of a coloring agent, the range of 2-8 mass% is preferable. If the content of the colorant is 2% by mass or more, the coloring power may not be weakened. On the other hand, if the content is 8% by mass or less, transparency may not be impaired.

Toner Release Agent

As the mold release agent, in principle, all known waxes can be used, but relatively low molecular weight highly crystalline polyethylene waxes, Fischer Ropsch waxes, amide waxes, polar waxes containing nitrogen such as urethane compounds and the like are particularly effective. . About polyethylene wax, it is especially effective that molecular weight is 1000 or less, and the range of 300-1000 is more preferable.

The compound which has the said urethane bond is preferable because even if it is low molecular weight, it can maintain a solid state and can set high melting | fusing point high compared with molecular weight by the intensity | strength of the cohesion force by a polar group. The preferable range of molecular weight is 300-1000. The raw material is a combination of diisocyanic acid compounds and monoalcohols, a combination of monoisocyanic acid and monoalcohol, a combination of dialcohols and monoisocyanic acid, a combination of trialcohols and monoisocyanic acid, and a triisocyanate compound Although various combinations, such as a combination of monoalcohols, can be selected, in order to avoid high molecular weight, it is preferable to combine the compound of a polyfunctional group and a monofunctional group, and it is important to make it equivalent functional group amount.

Examples of monoisocyanate compounds in the specific raw material compounds include, for example, dodecyl isocyanate, phenyl isocyanate and derivatives thereof, naphthyl isocyanate, hexyl isocyanate, benzyl isocyanate, butyl isocyanate and butyl isocyanate. Allyl and the like.

As a diisocyanate compound, diisocyanate tolylene, isocyanate 4, 4 'diphenylmethane, diisocyanate toluene, diisocyanate 1, 3-phenylene, diisocyanate hexamethylene, diisocyanoic acid 4-methyl -m-phenylene, diisocyanate isophorone, etc. are mentioned.

As the mono alcohol, it is possible to use extremely common alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol and the like.

Examples of the dialcohols in the starting compound include a large number of glycols such as ethylene glycol, diethylene glycol, triethylene glycol, trimethylene glycol; As the trialcohols, trimethylolpropane, triethylolpropane, trimethanol ethane and the like can be used, but are not necessarily limited to this range.

These urethane compounds can be mixed with a resin and a coloring agent at the time of kneading like a normal mold release agent, and can also be used as a kneading | pulverization grinder type toner. In addition, when used in the above emulsion polymerization flocculation melting method toner, it is dispersed together with a polymer electrolyte such as an ionic surfactant, a polymer acid or a polymer base in water, heated to a melting point or higher, and subjected to a strong shear with a homogenizer or a pressure discharge type disperser. It is added to make microparticles | fine-particles, the release agent particle dispersion of 1 micrometer or less is prepared, and it can be used with resin particle dispersion, a coloring agent dispersion liquid, etc.

Toner Other Ingredients

The toner of the present invention may also contain other components such as internal additives, charge control agents, and inorganic fine particles. As the internal additive, magnetic bodies such as metals such as ferrite, magnetite, reduced iron, cobalt, nickel, manganese, alloys, or compounds containing these metals can be used.

As the charge control agent, various charge control agents usually used such as quaternary ammonium salt compounds, nigrosine compounds, dyes made of complexes such as aluminum, iron, and chromium, and triphenylmethane pigments can be used. In addition, a material that is less likely to be dissolved in water is preferable from the viewpoint of controlling the ionic strength that affects the stability at the time of aggregation and melting and reducing wastewater pollution.

As the inorganic fine particles, silica, alumina, titania, calcium carbonate, magnesium carbonate, tricalcium phosphate, etc., all external additives on the surface of the toner are usually used, and they are dispersed by ionic surfactant, high molecular acid, and polymer base. It is preferable.

Moreover, surfactant can be used for emulsion polymerization, seed polymerization, pigment dispersion, resin particle dispersion, mold release agent dispersion, aggregation, and their stabilization. For example, anionic surfactants such as sulfuric acid ester salts, sulfonic acid salts, phosphate esters and soaps, cationic surfactants such as amine salts and quaternary ammonium salts, polyethylene glycols, alkylphenol ethylene oxide adducts, and polyvalent compounds. It is also effective to use nonionic surfactant, such as alcohol system, together. As a dispersing means at that time, general things, such as a rotary shear type homogenizer and a ball mill which has a media, a sand mill, and a dynomill, can be used.

Moreover, you may add an external additive further to the said toner as needed. As said external additive, an inorganic powder, organic particle | grains, etc. are mentioned. Examples of the inorganic particles include SiO ₂ , TiO ₂ , Al ₂ O ₃ , CuO, ZnO, SnO ₂ , Fe ₂ O ₃ , MgO, BaO, CaO, K ₂ O, Na ₂ O, ZrO ₂ , CaO · SiO ₂ , K ₂ O · (TiO ₂₎ and the like can be given _{n, Al 2 O 3 · 2SiO} 2, CaCO 3, MgCO 3, BaSO 4, MgSO 4. Moreover, as said organic particle | grains, resin powders, such as fatty acid or its derivatives, powders, such as metal salts, such as this, fluorine resin, polyethylene resin, and acrylic resin, can be used. For example, 0.01-5 micrometers is preferable and, as for the average particle diameter of these powders, 0.1-2 micrometers is more preferable.

Although the manufacturing method of the said toner is not specifically limited, (i) forming agglomerated particles in the dispersion liquid which disperse | distributes resin particle, and preparing a flock | aggregate dispersion liquid, (ii) disperse | distributing microparticles in the said flock | aggregate dispersion liquid Adding and mixing a fine particle dispersion to adhere the fine particles to the aggregated particles to form adhered particles; and (iii) heating the fuse particles to fuse them to form toner particles. It is preferable to be.

Toner properties, etc.

As for the toner volume average particle diameter of this invention, 0.5 micrometer or more and 10 micrometers or less are preferable.

If the volume average particle diameter of the toner is too small, it may adversely affect the handleability (supplyability, cleaning property, fluidity, and the like) of the toner, and the particle productivity may decrease. On the other hand, if the volume average particle diameter of the toner is too large, it may adversely affect the image quality and resolution due to particle shape and transferability.

Further, the toner of the present invention preferably satisfies the volume average particle diameter range of the toner, and the volume average particle size distribution index (GSDv) is preferably 1.3 or less.

The ratio (GSDv / GSDn) of the volume average particle size distribution index GSDv and the number average particle size distribution index GSDn is preferably at least 0.95.

The toner of the present invention preferably satisfies the volume average particle diameter range of the toner, and preferably has an average value of the shape coefficient represented by the following formula: 1.00 to 1.50.

Shape factor = (π × L ² ) / (4 × S)

(Where L is the maximum length of the toner particles and S is the projection area of the toner particles).

When the toner satisfies the above conditions, the toner is effective in image quality, in particular, graininess and resolution, and hardly any missing or uneven color accompanying transfer, and does not adversely affect handleability even if the average particle size is not small.

The storage elastic modulus G '(measured at an angular frequency of 10 rad / sec) at 150 ° C. of the toner itself is preferably 10 to 200 Pa from the viewpoint of improving image quality and preventing offset in the fixing process.

 <Image forming method>

The image forming method of the present invention is, in a first aspect, after the toner image is formed on the electrophotographic award sheet, the image forming surface of the electrophotographic award sheet is heated by a fixing belt and a roller. And pressurized, cooled, and then peeled off from the fixing belt.

Moreover, the image forming method of this invention is a 2nd aspect, after forming a toner image in the said electrophotographic award sheet, and fixing it with a thermal roller, and then fixing the said image forming surface of the said electrophotographic award sheet. The fixing belt and the rollers are further heated and pressurized, cooled, and then peeled off from the fixing belt.

As the transfer method, a method used in a conventional electrophotographic method, for example, a direct transfer method in which a toner image formed on a developing roller is directly transferred onto an electrophotographic award sheet, or an intermediate transfer belt or the like, and then There is an intermediate transfer belt method for transferring to a photographic award sheet. From the standpoint of environmental stability and high image quality, the intermediate transfer belt method is preferably used.

The electrophotographic award sheet of the present invention uses an electrophotographic apparatus having a fixing belt, and the toner transferred onto the electrophotographic award sheet is fixed to the electrophotographic award sheet. As the belt fixing method, for example, the oilless belt fixing method described in Japanese Patent Laid-Open No. 11-352819, the second transfer described in Japanese Patent Laid-Open No. 11-231671 and Japanese Patent Laid-Open No. 5-341666. And a method of simultaneously achieving fixation are known. The electrophotographic apparatus having the fixing belt mentioned in the present invention is, for example, capable of conveying, at least, a heating press unit capable of melting and pressurizing the toner, and a toner-adhered aqueous material in a bonded state with the toner aqueous layer. An electrophotographic apparatus including a belt type toner fixing unit having a fixing belt and a cooling unit capable of cooling while optionally attaching a heated electrophotographic award sheet to the fixing belt is enumerated. By using the electrophotographic award sheet having the toner award layer in the electrophotographic apparatus having such a fixing belt, the toner adhered to the toner award layer is fixed without being enlarged to the award material and the Since the melted toner is cooled and solidified in a state of being in close contact, it is accommodated in the toner aqueous layer while the toner is completely filled in the toner aqueous layer. Therefore, it is possible to obtain a smooth toner image having no glossiness and having a gloss.

The electrophotographic water-receiving sheet formed by the present invention is particularly preferable for an image forming method by an oilless belt fixing method, whereby the offset is greatly improved. However, the same can be used for various other image forming methods.

For example, by using the electrophotographic award sheet of the present invention, a full color image can be preferably formed while improving the image quality and preventing the case of cracking. Formation of a color image can be performed using the electrophotographic apparatus which can form a full color image. A normal electrophotographic apparatus has an image paper conveying part, a latent image forming part, and a developing part disposed in close proximity to the latent image forming part, and depending on the model, the latent image forming part and the image paper conveying part are located in the center of the apparatus main body. It has a toner-like intermediate transfer portion in close proximity.

Moreover, as a method for improving image quality, an adhesive transfer or a heat support type transfer method is known which replaces or uses electrostatic transfer or bias roller transfer. For example, Japanese Patent Application Laid-Open No. 63-113576 and Japanese Patent Laid-Open No. 5-341666 describe specific structures thereof. In particular, the method of using the intermediate | middle transfer belt of a heat support type transfer system is preferable. In addition, it is preferable to provide a cooling device in the intermediate belt after toner transfer to the electrophotographic award sheet or in the latter half of the transfer. By the cooling device, the toner (toner image) is cooled to the softening temperature of the binder resin used therein or the glass transition temperature of the toner at + 10 ° C. or lower, and is efficiently transferred to the electrophotographic water-receiving sheet, from the intermediate belt. Can be peeled off.

Fixation is an important process that influences the gloss and smoothness of the final image. As the fixing method, fixing by a heating pressure roller, belt fixing using a belt and the like are known, but from the viewpoint of image quality such as gloss and smoothness, the belt fixing method is more preferable. As for the belt fixing method, for example, the oilless belt fixing method described in JP-A-11-352819, JP-A-11-231671, JP-A 5-341666, secondary There are known methods for simultaneously achieving transcription and settlement. In addition, before fixing and heating by the fixing belt and the fixing roller, the primary fixing by the heat roller may be performed.

The surface of the fixing belt may be subjected to surface treatment of a silicone-based or fluorine-based or a combination thereof in order to prevent peeling of the toner or offset of the toner component. Moreover, it is preferable to provide a belt cooling apparatus in the latter half of fixation, and to make peeling of the electrophotographic award sheet favorable. It is preferable that cooling temperature shall be below the softening point of the polymer of the toner aqueous layer of a toner binder resin and / or the electrophotographic award sheet, or below +10 degreeC of glass transition points. On the other hand, in the initial stage of fixing, it is necessary to raise the temperature to the temperature at which the toner aqueous layer or toner of the electrophotographic award sheet is sufficiently softened. Specifically, the cooling temperature is preferably 70 ° C. or lower and 30 ° C. or higher, and preferably 180 ° C. or lower and 100 ° C. or higher in the initial stage of fixing.

Hereinafter, a concrete description will be given based on FIG. 1 showing an example of an image forming apparatus having a typical fixing belt. In addition, the form of this invention is not limited to the form shown in FIG.

First, the toner 12 is transferred to the electrophotographic award sheet 1 with an image forming apparatus (not shown). The water-receiving sheet 1 to which the toner 12 is attached is conveyed to point A by a conveying facility (not shown), passes between the heating roller 14 and the pressure roller 15, and receives the electrophotographic water-receiving sheet ( The toner aqueous layer 2 or toner 12 of 1) is heated and pressurized to a temperature (fixing temperature) and pressure at which the toner 12 is sufficiently softened.

Here, the fixing temperature means the temperature of the surface of the toner aqueous layer measured at the positions of the heating roller 14, the pressure roller 15, and the nip at A point, for example, 80 to 190 ° C, more preferably. 100-170 degreeC. In addition, the pressure means the pressure of the surface of the toner aqueous layer measured at the heating roller 14, the pressure roller 15, and the nip, for example, 1 to 10 kg / cm ² , more preferably ² to 7 kg / cm ² . . The release agent which was heated and pressed in this way and was present discretely in the toner aqueous layer 2 while the electrophotographic aqueous sheet 1 was later transported by the fixing belt 13 to the cooling device 16. (Not shown) is sufficiently heated to melt, and moves to the surface of the toner aqueous layer. The released release agent forms a layer (film) of the release agent on the surface of the toner aqueous layer. Thereafter, the electrophotographic award sheet 1 is conveyed to the cooling apparatus 16 by the fixing belt 13, for example, below the softening point of the binder resin used for the polymer of the toner aqueous layer and / or toner or glass. The temperature is below the transition point + 10 ° C, preferably 20 to 80 ° C, more preferably to room temperature (25 ° C). As a result, the layer (film) of the release agent formed on the surface of the toner aqueous layer is cooled and solidified, and a release agent layer is formed by the modification of the release agent in the toner aqueous layer.

The cooled electrophotographic award sheet 1 is carried to the point B by the fixing belt 13, and the fixing belt 13 moves on the tension roller 17. Therefore, the electrophotographic water-receiving sheet 1 and the fixing belt 13 are peeled off at B point. On the other hand, it is preferable to set the diameter of a tension roll small, as the electrophotographic award sheet peels from a belt by its rigidity (strength of elasticity).

The method of forming an image on the electrophotographic award sheet of the present invention is not limited to the above-described method particularly shown in FIG. 1 as long as it is an electrophotographic method using a fixing belt. As long as it is a normal electrophotographic method, all are applicable.

For example, a color image can be preferably formed in the electrophotographic award sheet of the present invention. Formation of a color image can be performed using the electrophotographic apparatus which can form a full color image. A normal electrophotographic apparatus has a water image sheet conveying portion, a latent image forming portion, and a developing portion disposed close to the latent image forming portion, and depending on the model, the latent image forming portion and the water sheet conveying portion are located at the center of the apparatus main body. It has a toner-like intermediate transfer portion in close proximity.

Moreover, as a method for improving the image quality, an adhesive transfer or a heat support type transfer method is known which replaces or uses electrostatic transfer or bias roller transfer. For example, Japanese Patent Laid-Open No. 63-113576 and Japanese Patent Laid-Open No. 5-341666 describe specific structures thereof. In particular, the method using the intermediate transfer belt of the heat support transfer type is preferable when a toner of a small particle size is used.

According to the image forming method of the present invention, even when an oilless machine without fixing oil is used, the peelability of the award sheet and toner, or the offset of the award sheet and toner components can be prevented, and a stable paper feed can be realized. It has good glossiness that has never existed, is rich in photographic sense, and can realize a good image.

Example

Hereinafter, although an Example and a comparative example demonstrate this invention in detail, this invention is not limited to a following example at all. In addition, in the following example and a comparative example, "%" and "part" are mass references | standards.

(Examples 1-14 and Comparative Examples 1-3)

<Support>

Rutin on the back side is used as a base paper using a good quality paper (basic weight of pulp tissue: 160 g / m ² ) prepared by internally adding water-dispersible anatase-type titanium dioxide so as to have a content of 1.1 g / m ² and having a center line average roughness of 1.2 μm. High-density polyethylene (MI = 10 g / 10 min, density 0.950 g / cm 3) containing 1.1 g / m ² of type titanium dioxide was extruded by extrusion coating (310 ° C.) to form a polyethylene layer at a thickness of 15 μm. , Support A was prepared.

In addition, on the surface of the above-mentioned quality paper, 1/1 (mass ratio) of high density polyethylene (MI = 8g / 10min, density 0.950g / cm <3>) and low density polyethylene (MI = 7g / 10min, density 0.923g / cm <3>). ) And a surface polyethylene layer having a thickness of 13 µm were extruded in the same manner by extrusion coating to form a mixture (containing 3.0 g / m ² of anatase-type titanium dioxide) to prepare a support B.

After corona discharge treatment of the polyethylene layers on the front and back surfaces of the supports A and B shown in Table 1, the surface coater was coated and dried by adjusting the thickness of the following composition for the bottom layer to 0.1 µm on the surface with a wire coater. On the back surface, the composition for back layer ^{shown below} was adjusted so that application amount after drying might be 4.5 g / m <^2> , it apply | coated and dried, and the back layer was formed.

<< composition for the surface lower layer >>                     

5 g of gelatin

95 g of water

<< composition for the back layer >>

100 g of polyester resin (by Bilon MD-1200 Toyobo)

Matte (Eposuta L15 Nihon Shokubai product) 30 g

60 g of ethanol

200 g of water

<Toner Water Layer Composition>

On the above-described surface lowering layer, the composition A or B for the toner aqueous layer described below is applied and dried by adjusting the coating amount after drying with a wire coater to be 5.5 g / m ² using a mold release agent shown in Table 1, Examples 1-14 and Comparative Examples 1-3 were created. Therefore, in the said Example and a comparative example, the layer which comprises the electrophotographic award sheet surface is a toner aqueous layer containing a predetermined release agent.

<< composition A for the toner aqueous layer >>

100 g of polyester resin (Tuffon U-5, product of Khao)

Release Agent (Table 1) x g

9 g of triphenyl phosphate

Titanium dioxide (Thai fake (registered trademark) A-220, product of Ishihara Sangyo) 15g

Methyl ethyl ketone (hereinafter abbreviated as MEK) 160 g                     

<< composition B for a toner water layer >>

Water-dispersed polyester resin (KZA-7049, made by UNICHIKA) 100g

Release Agent (Table 1) xg

Titanium Dioxide (Tai Fake (registered trademark) A-220, from Ishihara Sangyo)

30 g of methanol

10 g of water

<Material of the fixing belt surface>

As a fixing belt, the endless belt which used the polyimide film as the base material and coated the following material with the film thickness of 35 micrometers on the said polyimide film was used.

<< fixing belt A >>

Endless belt coated with 35μm thick HTV silicone rubber with hardness 40 ° (JIS-A)

<< fixing belt B >>

Silicone crosslinked fluorinated polyether (SIFEL (registered trademark) Shin-Etsu Chemical Co., Ltd.)

<< fixing belt C >>

Polytetrafluoroethylene perfluoroalkyl vinyl ether copolymer (manufactured by Fujigogyo Co., Ltd.)

Peelability Evaluation

Peeling force was measured as follows. A description with reference to FIG. 2 is as follows.

First, the electrophotographic water-receiving sheet 1 was cut out in width 10 cm in length 20 cm, and the fixing belt 13 was cut out in width 10 cm in length 20 cm. The sample was obtained by making the fixing belt surface 13a and the electrophotographic water-receiving sheet 1 contact with the support body of the electrophotographic water-receiving sheet 1 on the toner water-receiving layer side. Next, this sample was bonded through two pairs of rollers (coated with a perfluoroalkyl vinyl ether copolymer, having a diameter of 40 mm and a length of 30 cm) at a nip pressure of 100 kg and a speed of 30 mm / sec. Thereafter, the bonded sample was fixed on a 90 ° C. or 50 ° C. hot plate with the electrophotographic water-sheet down, and heated for 30 minutes.

After confirming that the surface of the center portion of the sample became 90 ° C or 50 ° C, one end of the fixing belt 13 was gripped by the chuck, and the angle (°) formed between the fixing belt 13 and the peeling direction (X) was always made. It peeled at the constant speed of 30 mm / sec so that it might become 90 degrees. At this time, the force applied to the peeling direction X was measured using FORCE GAGE (FCG-2 manufactured by NIDEC-SIMPO Corporation).

 <Evaluation of photographic image>

The electrophotographic award sheet produced according to each of the above Examples and Comparative Examples was formed by using the fixing belt type electrophotographic apparatus shown in Fig. 1, and the glossiness, offset resistance, running property and gloss of the long term The degradation was measured.

As the image for printing, white solid, clay (R = G = B = 50% of image), black (100%), and portrait image of a female were used. As the electrophotographic apparatus, a color laser printer (Tokyu Print C-620) manufactured by Fuji Xerox was used, except that the apparatus having any one of the fixing belts A to C was used.

In this fixing belt system, the conveyance speed of the fixing belt 13 is 30 mm / sec, the nip pressure between the heating roller 14 and the pressure roller 15 is 0.2 MPa (2 kgf / cm <^2> ), and a heating roller The set temperature of (14) is 155 ° C, which corresponds to the fixing temperature. On the other hand, the set temperature of the pressure roller 15 was 130 degreeC. The electrophotographic water-receiving sheet was cooled at 60 degrees C or less at the time of peeling from the fixing belt 13.

The created electrophotographic award sheet was cut with A4. Then, it was set in a color laser printer (Tokyu Print C-620) manufactured by Fuji Xerox, and printed images from a computer were printed. The image printed four types of white, gray (R = G = B = 50% of image), black, and female portrait.

The obtained electrophotographic image was evaluated according to the following criteria.

<< evaluation of offset resistance >>

The electrophotographic award sheet was passed through the apparatus at 30 ° C. in an 80% RH environment. When passing through the fusing unit normally, whether or not a crust-like stain occurred on the image surface was evaluated by the following evaluation criteria. The results are shown in Table 2. In the present invention, "0 or more" is a practically acceptable level.

〔Evaluation standard〕

  ◎: Smudge-like stains did not occur at all.

  (Circle): Although the stain of the shell-like form generate | occur | produced very weakly, it was a level which was satisfactory practically.

   (Triangle | delta): Smudge-shaped irregularity generate | occur | produced slightly.

   X: Smudge-shaped irregularity generate | occur | produced strongly.

<< Evaluation of Driftiness >>

The electrophotographic award sheet was fed 100 sheets continuously using the printer, and the total number of paper feeding failures, jamming, and stacking failures was counted. The results are shown in Table 2. In the present invention, "2 or less" is a practically acceptable level.

 << evaluation of glossiness >>

Glossiness visually confirmed the surface shape of the toner aqueous layer before and after printing. The thing which showed the favorable gloss surface was 0 and the some stain generate | occur | produced, The thing which does not become a problem after printing and (triangle | delta) and the thing which has the stain which remains even after printing was made into x. The results are shown in Table 2.

<< gloss decrease in long term >>

The following reference | standard evaluated the fall of the glossiness after making 10,000 sheets continuous notification. The results are shown in Table 2.

〔Evaluation standard〕

(Double-circle): There was no fall at all.

0: slightly deteriorated

△: slightly lowered

X: fell reliably

<Surface tension measurement>

The surface tension of the polymer used in each of the toner aqueous layers of Examples or Comparative Examples described in the above section of the toner aqueous layer composition and the surface tension of the toner 1 were determined by PD-Z (manufactured by Kyowa Chemical Co., Ltd.). Thermostatic attachment), and measured by a pendant drop method. Specifically, the polymer and toner were melted at a toner fixing temperature of 130 ° C., 150 ° C. and 180 ° C. to form a liquid phase, and this was removed from the needle line and analyzed by analyzing the shape of the droplets. On the other hand, the density of the polymer and the toner was 1. The results are shown in Table 3. In Table 3, the difference in surface tension is a value of (surface tension of polymer used)-(surface tension of toner) at each toner fixing temperature (mN / m).

<Contact angle measurement>

The contact angle of the surface of the toner aqueous layer and the contact angle of the surface of the fixing belt in the aqueous sheet of the Examples and Comparative Examples were measured using a contact angle meter (CA-A) manufactured by Kyouwa Kaimen Chemical Co., Ltd .. Toners 1 to 4 were placed on the surface of the toner aqueous layer or the surface of the fixing belt, melted at the toner fixing temperatures of 130 ° C and 180 ° C, and the contact angles were measured. The results are shown in Table 4. In Table 4, the difference in contact angle is a value of (contact angle on the surface of the fixing belt)-(contact angle on the surface of the toner receiving layer) at each toner fixing temperature (°).

Surface Free Energy Measurement

The surface free energy of the surface of the toner aqueous layer and the surface free energy of the surface of the fixing belt in the water-receiving sheet of the examples and comparative examples were measured using a contact angle meter (CA-A) manufactured by Kyouwa Kaimen Chemical Co., Ltd. . First, water and methylene iodide were used as probe liquids, these liquids were mounted on the surface of the toner aqueous layer or the fixing belt surface, and the contact angle was measured under a 25 ° C / 55% RH atmosphere. The value of the obtained contact angle was substituted into the equation of the above extended Fowks, and the dispersible component (g ^d ) and the polar component (g ^P ) were required. Here, the dispersion force component and the polarity component of the surface tension of each liquid are values inherent to each liquid, and for example, the values described in the Journal of Textile Society 38 (4) and T-147 (1982) were used. From the obtained dispersible component (g ^d ) and the polar component (g ^P ), the surface free energy (G) of the solid was obtained by the formula of the expanded Fowks. The results are shown in Table 5.

In the table, the difference in surface free energy is a value of (surface free energy on the surface of the toner water layer)-(surface free energy on the surface of the fixing belt) (mN / m).

From the results in Table 2, the surface of the water sheet shown in the examples of the present invention had no stickiness, lack of image, and good softness.

In addition, it was possible to print on the back side again after printing all once.

Commercially available color laser printers, specifically, full-color laser printers from Fuji Xerox (DC-2220, DCC-400CP / 320CP, DCC-500CP), Color Copiers (DocuColor 5750) from Xerox Co., Ltd., Seiko Epson LP-8000C of product, COLOR PAGEPRESTO N4-ST of Casio Dengo, COLOR LASER SHOT LBP-2030 of Canon, magicolor 2 of QM Japan Japan, COLOR LASER Bit KL-2010 of Konica, Sharp When printed on JX-8200, Hitachi Seisakujo, BEAMSTAR-RW, and Minolta Color Page Pro PS, both samples can be notified and the results shown in Table 2 can be obtained. there was.

As described above, according to the present invention, by combining the specific belt material and the wax material of the toner aqueous layer, the transfer contamination on the belt is reduced, the long term aptitude is greatly improved, and even oilless machines without fixing oil can be notified. And a fixing belt type electrophotographic water-receiving sheet having excellent glossiness and having a texture similar to that of a photograph is obtained.

Claims (29)

A fixing belt type electrophotographic award sheet in which a toner aqueous layer containing polymer is formed on a support, comprising: from the surface of the fixing belt on the surface of the electrophotographic award sheet on the side of the toner aqueous layer with respect to the support; Peeling force is 1-20 N / m in said electrophotographic water phase sheet surface temperature 50 degreeC, The surface tension (γ _p ) (mN / m) of the polymer contained in the toner aqueous layer measured at the toner fixing temperature, and the surface tension (γ _t ) (mN / m) measured at the toner fixing temperature. This, the conditions of the following formula (I) satisfy the conditions of the fixing belt type electrophotographic water sheet. γ _p -γ _t ≥8 (I) In the fixing belt type electrophotographic award sheet in which a toner aqueous layer containing a polymer is formed on a support, the peeling force from the surface of the fixing belt on the surface of the electrophotographic receiving sheet on the side of the toner aqueous layer with respect to the support, In 90 degreeC of the said electrophotographic water phase sheet surface temperature, it is 1-20 N / m, The surface tension (γ _p ) (mN / m) of the polymer contained in the toner aqueous layer measured at the toner fixing temperature, and the surface tension (γ _t ) (mN / m) measured at the toner fixing temperature. This, the conditions of the following formula (I) satisfy the conditions of the fixing belt type electrophotographic water sheet. γ _p -γ _t ≥8 (I) delete 3. The electrophotographic award sheet according to claim 1 or 2, wherein the electrophotographic award sheet is used in an electrophotographic apparatus having a fixing belt, and the contact angle? ₁ of the molten toner at the toner fixing temperature to the surface of the toner award layer ( ) And the contact angle θ ₂ (.) With respect to the surface of the fixing belt of the molten toner at the toner fixing temperature satisfy the condition of the following formula (II). Award sheet. θ ₂ -θ ₁ ≥10 (II) 3. The electrophotographic award sheet according to claim 1 or 2, wherein the electrophotographic award sheet is used in an electrophotographic apparatus having a fixing belt, and the surface free energy G ₁ (mN / m) of the surface of the toner aqueous layer and the fixing belt surface. The surface free energy (G ₂ ) of (mN / m) satisfies the conditions of the following formula (III), characterized in that the fixing sheet type electrophotographic award sheet. G ₁ -G ₂ ≥10 (III) 3. The polar component value (g ^p ₁ ) of the surface free energy of the surface of the toner aqueous layer, wherein the electrophotographic award sheet is used in an electrophotographic apparatus having a fixing belt. And a polar component value (g ^p ₂ ) (mN / m) of surface free energy on the surface of the fixing belt satisfies the condition of the following formula (IV). g ^p ₁ -g ^p ₂ ≥0.3 (IV) The material for the surface of the fixing belt is at least one member selected from the group consisting of silicone rubber, fluorine rubber, silicone resin and fluorine resin. . 3. A fixing belt type electrophotographic water receiving sheet according to claim 1 or 2, wherein a layer made of a fluorocarbon siloxane rubber having a uniform thickness is formed on the surface of the fixing belt. 3. A silicone rubber layer having a uniform thickness on the surface of the fixing belt, and a layer of fluorocarbon siloxane rubber formed on the surface of the silicone rubber layer. Award sheet for fixation belt type electrophotography to use. The fixing sheet type electrophotographic water phase sheet according to claim 8, wherein the fluorocarbon siloxane rubber has a perfluoroalkyl ether group and / or a perfluoroalkyl group in the main chain. The layer constituting the surface of the aqueous sheet on the side of the toner aqueous layer with respect to the support contains at least one release agent selected from the group consisting of a silicone compound, a fluorine compound, a wax and a mat agent. An award sheet for fixing belt type electrophotographic, characterized in that: 12. The fixing belt type electrophotographic water phase according to claim 11, wherein the content of the release agent is 0.1 to 20% by mass relative to the mass of the layer constituting the surface of the water sheet on the side of the toner water layer relative to the support. Sheet. 12. The fixing belt type electrophotographic water receiving sheet according to claim 11, wherein the release agent is a wax, the wax is a natural wax, and the natural wax is at least one of a vegetable wax and a mineral wax. The waterborne sheet for fixing belt type electrophotography according to claim 13, wherein the natural wax is a plant wax, and the plant wax is a carnauba wax having a melting point of 70 to 95 ° C. 14. The fixing sheet type electrophotographic water receiving sheet according to claim 13, wherein the natural wax is a mineral wax, and the mineral wax is montan wax having a melting point of 70 to 95 ° C. The fixing sheet type electrophotographic water receiving sheet according to claim 1 or 2, wherein the polymer is a self-dispersing water-based polyester resin emulsion that satisfies the following characteristics (1) to (4). (1) Number average molecular weight (Mn) = 5000-10000 (2) Molecular weight distribution (weight average molecular weight / number average molecular weight) ≤ 4 (3) Glass transition temperature (Tg) = 40-100 degreeC (4) Volume average particle diameter = 20-200 nmφ The fixing sheet type electrophotographic award sheet according to claim 1 or 2, wherein the support is selected from a base paper, a synthetic paper, a synthetic resin sheet, a coated paper and a laminated paper. The toner contained in the toner aqueous layer contains at least a binder resin and a colorant, and the volume average particle size of the toner is 0.5 µm or more and 10 µm or less, and the volume average particle size distribution index. (GSDv) is 1.3 or less, The fixing sheet type electrophotographic award sheet characterized by the above-mentioned. 19. The fixing belt type electrophotographic award sheet according to claim 18, wherein in the toner, a ratio (GSDv / GSDn) of the volume average particle size distribution index (GSDv) and the number average particle size distribution index (GSDn) is 0.95 or more. . The fixing sheet type electrophotographic water receiving sheet according to claim 18, wherein an average value of the shape coefficients represented by the following formulas is 1.00 to 1.50. Shape factor = (π × L ² ) / (4 × S) (Where L is the maximum length of the toner particles and S is the projection area of the toner particles). 19. The process according to claim 18, wherein the toner contained in the toner aqueous layer forms agglomerated particles in a dispersion formed by dispersing at least (i) resin particles to prepare agglomerated particle dispersions, (ii) in the agglomerated particle dispersions, A toner comprising a step of adding and mixing a fine particle dispersion obtained by dispersing fine particles to adhere the fine particles to the agglomerated particles to form adhered particles, and (iii) heating the fused particles to fuse them to form toner particles. It is obtained by the manufacturing method of the fixing belt type electrophotographic award sheet. An image forming method using the fixing belt type electrophotographic award sheet according to claim 1, wherein after forming a toner image on the electrophotographic award sheet, the image of the electrophotographic award sheet The forming surface is heated and pressurized with a fixing belt and a roller, cooled, and then peeled from the fixing belt. An image forming method using the fixing belt type electrophotographic award sheet according to claim 1, wherein a toner image is formed on the electrophotographic award sheet, and then fixed by a thermal roller, And the image forming surface of the electrophotographic water-receiving sheet is further heated and pressed by a fixing belt and a roller, cooled, and then peeled from the fixing belt. 23. The image forming method according to claim 22, wherein the formed toner image is cooled to a state below a softening point or a glass transition point of 10 DEG C or lower of the binder resin used in the toner, and then peeled from the fixing belt. 24. The image forming method according to claim 23, wherein the formed toner image is cooled to a state of a softening point or a glass transition point of +10 DEG C or lower of the binder resin used for the toner, and then peeled from the fixing belt. The said fluorocarbon siloxane rubber has perfluoroalkyl ether group and / or perfluoroalkyl group in a principal chain, The fixing belt type electrophotographic water sheet of Claim 9 characterized by the above-mentioned. 18. The fixing belt type according to claim 17, wherein the support is a base paper, and the base paper has a ratio (Ea / Eb) between the longitudinal Young's modulus (Ea) and the transverse Young's modulus (Eb) in the range of 1.5 to 2.0. Award sheet for electrophotography. 18. The fixing belt type electrophotographic water receiving sheet according to claim 17, wherein the support is a base paper, and the oken smoothness of the surface of the toner water receiving layer side of the base paper is 210 seconds or more. The fixing belt type electrophotographic award sheet according to claim 1 or 2, wherein the toner aqueous layer has a light transmittance of 78% or less.

Images