JP2002169321A - Image receiving material for color electrophotography - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide image receiving material for color electrophotography on either surface of which a color electrophotographic image excellent in glossiness and good in color reproducibility is formed and on the opposite surface of which an excellent distinct non-blotting image is formed in the case of recording the image by an ink jet system. SOLUTION: In the image receiving material for electrophotography which is provided with a supporting body, the image receiving layer of toner including polymer provided on either surface of the supporting body and a particle layer including particulates provided on the other surface of the supporting body, the flow starting temperature of the image receiving layer is equal to or under the flow starting temperature of the toner and the particle layer includes two or more kinds of particulates different in average particle size by >=5 μm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic image-receiving material for forming a reflection image. In particular, the present invention relates to an image receiving material whose front surface is suitable for recording by an electrophotographic method and whose rear surface is suitable for recording by ink jet.

[0002]

2. Description of the Related Art A color electrophotographic method is a dry process, has a high printing speed, and can output to general-purpose paper (plain paper or high-quality paper). However, when image information of a face, a landscape, and the like is output for photographic use, sufficient performance cannot be obtained with general-purpose paper or the like due to particularly poor gloss. In order to obtain gloss, the surface of the image receiving material needs to be smooth. Further, it is necessary that the toner is embedded in the image receiving layer at the time of fixing after the transfer of the toner, so that the surface becomes smooth. On the other hand, with the spread of ink jet printers in recent years, print output by ink jet can be easily obtained even in ordinary households. As a result, printing of postcard addresses and the like by ink jet has become popular. For this reason, it is required from a practical point of view that the glossy photo-like front print is recorded by an electrophotographic method and printed on the back surface by ink jet to produce various cards and postcards.

In a fixing step of an electrophotographic image forming process, toner is fixed on an image receiving paper by applying temperature and pressure. To make the image receiving surface glossy, the toner is embedded in an image receiving layer and the surface is smoothed. There is a need. JP-A-63-929
No. 65 discloses that a polymer layer is provided on the surface for embedding the toner in the image receiving layer. Japanese Patent Application Laid-Open No. 4-212168 discloses that an image receiving layer is provided in which the flow start temperature of a polymer is specified. These techniques have made it possible to obtain a certain degree of gloss on the image receiving surface. On the other hand, although it was possible to print on the back surface of these receiving papers by inkjet,
There has been a problem that remarkable curl is generated or a toner image is cracked due to a change in temperature or humidity. This occurs when the paper of the support absorbs moisture and expands and contracts. In order to address this problem, U.S. Pat. No. 5,691,039 discloses that an anti-curl layer having a melting point of 115 ° C. or higher is provided on the surface opposite to the image receiving layer of the toner. However, it has been found that the provision of such a coating layer on a paper support hinders the absorption of ink-jet ink, making it impossible to perform normal printing or rubbing the ink. Further, it has been found that there is a drawback that when the prints on the image receiving surface are continuously output in an electrophotographic manner, the image receiving papers stacked on the stacking portion are adhered.

[0004] Further, when an image receiving layer for ink jet is provided on the side opposite to the image receiving surface of the toner, there arises a problem that the image receiving paper is wound around the fixing roller or is offset depending on the temperature at the time of fixing the electrophotographic print. . It has also been found that, when image receiving papers are stacked and stored in a high temperature environment, problems such as adhesion of the toner image receiving surface to the ink jet image receiving surface overlaid thereon occur.

[0005]

SUMMARY OF THE INVENTION In view of these problems of the prior art, the present invention is capable of forming a color electrophotographic image having excellent gloss and excellent color reproducibility on one surface. It is another object of the present invention to provide a color electrophotographic image-receiving material which can form a clear and good image without blur when recorded on the opposite surface by ink jet. It is another object of the present invention to provide a color electrophotographic image receiving material which does not adhere to each other even when stored in an overlapping manner before recording, and furthermore, does not adhere to the accumulation portion even when electrophotography is continuously printed. .

[0006]

An object of the present invention is to provide a support, an image-receiving layer of a toner containing a polymer provided on one surface of the support, and fine particles provided on the other surface of the support. In an electrophotographic image receiving material having a particle layer containing
An image receiving material for color electrophotography, characterized in that the flow start temperature of the image receiving layer is equal to or lower than the flow start temperature of the toner, and the particle layer contains two or more kinds of fine particles having an average particle diameter different by 5 μm or more. Has been solved by the present invention. Also,
The above object is to provide an electrophotographic apparatus having a support, an image receiving layer of a toner containing a polymer provided on one surface of the support, and a particle layer containing fine particles provided on the other surface of the support. In the image receiving material, the flow start temperature of the image receiving layer is 98 ° C.
Or less, wherein the particle layers differ in average particle diameter by 5 μm or more.
This problem has been solved by another invention which provides an image receiving material for color electrophotography, wherein the image receiving material contains more than one kind of fine particles. In the color electrophotographic image-receiving material of the present invention, the particle layer contains at least one kind of fine particles having an average particle diameter of 5 μm or less, and has an average particle diameter of 5 μm or more than the fine particles.
It is preferable to include at least one type of other fine particles having a size of m or more. Further, it is preferable that the particle layer contains at least one kind of fine particles having an average particle diameter of 10 μm or more and at least one kind of other fine particles having an average particle diameter smaller than the fine particles by 5 μm or more. Further, the thickness of the image receiving layer of the toner is 6 μm or more, the thickness of the particle layer is 1 μm or more,
Preferably, the particle layer contains porous silica particles. Further, among two or more kinds of fine particles having an average particle diameter different from each other by 5 μm or more, 1 part by weight of the fine particles having a large average particle diameter,
It is preferable that fine particles having a small average particle diameter be contained in an amount of 1 to 10 parts by weight. Further, the coating amount of the binder in the particle layer is preferably equal to or more than the total coating amount of the particles in the particle layer. In this specification, “to” indicates a range that includes numerical values described before and after it as a minimum value and a maximum value.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The color electrophotographic image-receiving material of the present invention will be described below in detail. The color electrophotographic image-receiving material of the present invention comprises a support, an image-receiving layer of a toner containing a polymer provided on one surface of the support, and particles containing fine particles provided on the other surface of the support. It has a layer. The color electrophotographic image-receiving material of the present invention is characterized in that the flow start temperature of the toner image-receiving layer is lower than the flow start temperature of the toner, or the flow start temperature of the toner image-receiving layer is lower than 98 ° C. . At least one of these conditions must be satisfied, but both may be satisfied. The flow start temperature can be measured using, for example, a flow tester CFT-500 manufactured by Shimadzu Corporation. If the flow start temperature of the toner image receiving layer is simply lower than the flow start temperature of the toner, or if the flow start temperature of the toner image receiving layer is 98 ° C. or less, it becomes easy to adhere. May cause blocking. As an anti-adhesion technique for avoiding such a problem, it is well known to incorporate fine particles called a matting agent. However, when the electrophotographic method is used, since there is a transfer step of transferring the toner by applying a high voltage, there is a disadvantage that these matting agents disturb the transferred image or lower the transfer efficiency. In particular, when particles having a size of 10 μm or more were filled, it was found that a phenomenon in which a toner image was removed in a spot shape occurred. On the other hand, when particles of 10 μm or less were used, there was a dilemma that the functions of blocking and preventing adhesion were not sufficiently obtained. Under such circumstances, the present inventor prevents the above-described blocking by providing a particle layer containing two or more types of particles having an average particle diameter different by at least 5 μm on the back surface opposite to the image receiving layer, and It has been found that a good image without transfer failure can be obtained. That is, the color electrophotographic image-receiving material of the present invention has a flow start temperature of the toner image-receiving layer lower than a flow start temperature of the toner, or a flow start temperature of the toner image-receiving layer of 98 ° C. or lower, and an average particle size. It is characterized in that a particle layer containing two or more kinds of fine particles different by 5 μm or more is formed on the back surface.

When a particle layer containing fine particles having an average particle size of not more than 5 μm is formed, two or more particles having a relatively large size, for example, about 10 μm, must be used to prevent blocking. However, in this case, the occurrence of the transfer failure described above cannot be avoided. In the present invention, the difference between the average particle diameters is 5 μm or more, preferably 6 μm.
To 20 μm, and more preferably 7 to 15 μm. When the difference between the average particle diameters is 20 μm or more, the above-described transfer failure occurs.

It has been found that the particle layer formed on the back surface that satisfies the above conditions further shows good performance for ink-jet printing. When two or more kinds of particles having a difference in average particle diameter of less than 5 μm are used, when the front side is printed with an electrophotograph and then printed on the back side with an ink jet, the offset prevention oil used for the electrophotographic fixing roller is used. It was clarified that the ink was repelled and the characters were blurred by the adhesion. However, if a particle layer containing two or more types of particles having a difference in average particle size of 5 μm or more is formed according to the present invention, a clearer and better printing state can be obtained.

From the viewpoint of the clarity and resolution of ink-jet printing, the particle layer has relatively small particles having an average particle diameter of preferably 5 μm or less, more preferably 0.1 to 4 μm.
m, more preferably at least one particle having a particle size of 0.5 to 3 μm. The particle layer preferably contains at least one kind of relatively large particles having an average particle diameter of preferably 10 μm or more, more preferably 10 to 30 μm, and still more preferably 10 to 20 μm. That is, the most preferred embodiment has an average particle size of 10 to 10.
Relatively large particles of 20 μm and an average particle size of 0.5 to 3
The use of at least two particles of relatively small particles of μm. According to this aspect, it is possible to obtain an image receiving paper having no offset or abnormal transfer during electrophotographic printing and excellent in printing performance by the ink jet on the back surface.

In a preferred embodiment of the present invention, the thickness of the toner image receiving layer is from 6 to 20 μm, and the thickness of the ink jet receiving particle layer on the back surface is from 1 to 20 μm. In addition, the thickness of the particle layer in this specification means the thickness of the binder layer formed after applying and drying the coating liquid for forming the particle layer. Particles (matting agent) from the binder layer surface
However, such protruding particles are not considered as the thickness of the particle layer. The particle layer has an average particle size of 5 μm
Of the two or more types of fine particles different from the above, one part by weight of fine particles having a large average particle diameter corresponds to one fine particle having a small average particle size.
It is preferably contained in an amount of 10 to 10 parts by weight, more preferably 2 to 8 parts by weight. By using more particles having a smaller average particle size than fine particles having a larger average particle size, not only the resolution of ink printing can be improved but also the unexpected effect of improving the image quality of electrophotography can be obtained. The coating amount of the binder in the particle layer is preferably equal to or more than the total coating amount of the particles in the particle layer.
More preferably, it is 5 times. When the coating amount of the binder is less than the total particle coating amount, particles (matting agent)
Are easily spilled from the image receiving material, and there is a concern that the equipment may be contaminated. On the other hand, if the binder coating amount exceeds 5 times the total particle coating amount, the particles sink into the binder, failing to exert a sufficient anti-adhesion effect, and tending to reduce writing suitability.

The support for the electrophotographic image-receiving material used in the present invention can withstand the fixing temperature, and has such properties as smoothness, whiteness, slipperiness, friction, antistatic properties, and dents after fixing. Any material that can satisfy the requirements can be used. Generally, papers and synthetic polymers (films) described in "Basics of Photographic Engineering-Silver salt photography-" edited by the Photographic Society of Japan, pages 223 to 240 of Corona Co., Ltd. (1979). And other photographic supports. Specifically, synthetic paper (polyolefin-based, polystyrene-based synthetic paper, etc.), high-quality paper, art paper, coated paper, cast-coated paper, mixed paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper , Baryta paper, wallpaper,
Paper support such as backing paper, synthetic resin or emulsion impregnated paper, synthetic rubber latex impregnated paper, synthetic resin internal paper, paperboard, cellulose fiber paper, polyolefin-coated paper (especially paper coated on both sides with polyethylene), polyolefin,
Various plastic films or sheets such as polyvinyl chloride, polyethylene terephthalate, polystyrene methacrylate, polyethylene naphthalate, polycarbonate polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose), and treatment for giving white reflectivity to the plastic. For example, a film or sheet, cloth, metal, glass, or the like which has been subjected to a treatment (for example, a treatment such as incorporating a pigment such as titanium oxide in the film) is used. These can be used alone or can be used as a support laminated on one or both sides with a synthetic polymer such as polyethylene. Also, a laminate of any combination of the above supports can be used. In addition, JP-A-62-253159, pages (29) to (31), JP-A-1-61236, pages (14) to (17), JP-A-63-316848, and JP-A-2- Supports described in Japanese Patent Nos. 22651, 3-56955, and US Pat. No. 5,001,033 can be used.

Among these supports, particularly preferred is a support having one or both sides laminated with a synthetic polymer such as polyethylene which can suppress the influence of temperature and humidity. In the present invention, a remarkable effect is exhibited particularly when a support having both surfaces laminated is used. Since the laminated support has almost no water absorption, good printing by ink jet could not be performed until now, but it was found that good printing suitability can be obtained by manufacturing an image receiving material according to the constitution of the present invention. The thickness of the support is usually 25 to 300.
μm, preferably about 50 to 360 μm, and more preferably about 75 to 250 μm.

Various additives appropriately selected can be added to the above-mentioned constituent layers of the support within a range that does not impair the object of the present invention. For example, a brightener, a conductive agent, a filler, a pigment or a dye such as titanium oxide, ultramarine blue, carbon black or the like can be contained as necessary. One or both surfaces of these supports can be subjected to various surface treatments or undercoats for the purpose of improving the adhesion to a layer provided thereon. As the surface treatment, for example, a glossy surface or JP-A-55-26507
JP-A No. 5-2,049, and the like, and the activation treatment such as corona discharge treatment, flame treatment, glow discharge treatment, or plasma treatment. As the undercoat, for example, a method described in JP-A-61-846443 can be used. Further, these may be used alone, or may be used in combination with an arbitrary combination, such as performing an activation treatment after performing molding or the like, or performing an undercoat after performing a surface treatment such as activation treatment. it can. During the construction of these supports or the front and back surfaces, and during the combination thereof, a hydrophilic binder and a semiconductive metal oxide such as alumina sol or tin oxide, carbon black or other antistatic agent may be applied. Good. Specifically, supports described in JP-A-63-220246 can be used.

On one side of the support, a toner receiving layer is formed. The toner receiving layer contains a toner receiving substance. Although the type of the toner receptive substance is not particularly limited, typical examples thereof include those having an ester bond; polyurethane resins; polyamide resins such as urea resins; polysulfone resins; polyvinyl chloride resins, polyvinylidene chloride resins, and vinyl chloride resins. Vinyl acetate copolymer resin, vinyl chloride-vinyl propionate copolymer resin; polyol resin such as polyvinyl butyral, cellulose resin such as ethyl cellulose resin, cellulose acetate resin; polycaprolactone resin, styrene-maleic anhydride resin, polyacrylonitrile resin , Polyether resins, epoxy resins, phenolic resins; polyolefin resins such as polyethylene resins and polypropylene resins, copolymer resins of olefins such as ethylene and propylene with other vinyl monomers, and acrylic resins. It can be. The acceptor substance may be used alone, or two or more kinds may be used in combination as a mixture or a copolymer.

Preferably, the receptive resin contains a polyester resin. Particularly preferred are those containing 20% by weight or more of a polyester resin. Examples of the resin having an ester bond include terephthalic acid, isophthalic acid,
Dicarboxylic acid components such as maleic acid, fumaric acid, phthalic acid, adipic acid, sebacic acid, azelaic acid, abietic acid, and succinic acid (these dicarboxylic acid components may be substituted with a sulfonic acid group, a carboxyl group, or the like) ), Ethylene glycol, diethylene glycol, propylene glycol, bisphenol A, bisphenol S,
Polyester resin, polymethyl methacrylate, polybutyl methacrylate, polymethyl acrylate obtained by condensation with an alcohol component such as ethylcyclohexyl dimethanol, neopentyl glycol or the like (these alcohol components may be substituted with a hydroxyl group or the like) Examples thereof include a polyacrylate resin or polymethacrylate resin such as polybutyl acrylate, a polycarbonate resin, a polyvinyl acetate resin, a styrene acrylate resin, a styrene-methacrylate copolymer resin, and a vinyl toluene acrylate resin. it can. Specific examples are described in JP-A-59-101395, JP-A-63-7971, JP-A-63-7972, JP-A-63-7973, and JP-A-60-294882. Things can be mentioned. In addition, commercially available products include Byron 290 and Byron 20 manufactured by Toyobo.
0, Byron 280, Byron 300, Byron 10
3. Byron GK-140, Byron GK-130, Kao-made Tufton NE-382, Tufton U-5, ATR
-2009, ATR-2010, Unitika's Elitel UE3500, UE3210, XA-8153, Nippon Synthetic Chemical's Polyester TP-220, R-188 and the like can be used.

The image receiving layer containing such a receptive substance may be formed by dispersing the receptive substance in a water-soluble binder and carrying it. It is preferable to use a water-soluble polymer having a group capable of undergoing a cross-linking reaction with a hardener, and among them, polyvinyl alcohol and gelatins are preferably used. In addition, the receptive substance may form a coating film in a water-soluble binder so as to maintain a granular shape, in which case, select from a coating film formed at a temperature at which the toner is thermally fixed. Is preferred. As the water-soluble binder used in this case, a known water-soluble polymer can be used.

As the method for dispersing the receptive substance in the water-soluble binder, any of the known dispersion methods for dispersing a hydrophobic substance in a water-soluble polymer can be used. Typically, a method in which a solution in which a receptive substance is dissolved in an organic solvent immiscible with water is mixed with an aqueous solution of a water-soluble binder and emulsified and dispersed, and a latex of the receptive substance (polymer) is mixed with an aqueous solution of a water-soluble binder And the like.

The water-soluble polymer does not specify its composition, bonding structure, molecular structure, molecular weight, molecular weight distribution, or form as long as it is a water-soluble polymer. Examples of water-solubilizing groups of the polymer include a hydroxyl group, a carboxylic acid group,
Examples include an amino group, an amide group, and an ether group. Examples of the water-soluble polymer include Research Disclosure (hereinafter referred to as “RD”) No. 17,643, 2
6, page 651 of RD18,716, RD307,1
No. 05, pages 873-874 and JP-A-64-13,5.
No. 46, pages (71) to (75). Specifically, for example, vinylpyrrolidone-vinyl acetate copolymer, styrene-vinylpyrrolidone copolymer, styrene-maleic anhydride copolymer, water-soluble polyester, water-soluble polyurethane, water-soluble nylon, water-soluble epoxy resin Can be used.

Water-dispersible resins such as water-dispersed acrylic resins, water-dispersed polyester resins, water-dispersed polystyrene resins, and water-dispersed urethane resins; acrylic resin emulsions, polyvinyl acetate emulsions, SBR (styrene / butadiene / rubber) emulsions, etc. Emulsion or
Any of these copolymers, mixtures, and aqueous solutions such as those modified with a cation can be appropriately selected and used in combination of two or more. Further, the gelatin may be selected from lime-processed gelatin, acid-processed gelatin, and so-called demineralized gelatin having a reduced content of calcium and the like according to various purposes,
It is also preferable to use them in combination.

Commercially available water-dispersed polyesters include, for example, Toyobo Vironal MD-1250, MD-1
930, plus coat Z-446, Z-4 made by Kaoru Kagaku
65, RZ-96, Nippon Nippon Ink's ES-611, ES
-670, Takamatsu Yushi Pesresin A-160P, A-2
10, A-620 and the like. The film forming temperature of the polymer to be used is preferably room temperature or higher for storage before printing, and is preferably 100 ° C. or lower for fixing toner particles.

Various plasticizers can be used in the image receiving material of the present invention to control the elongation. The thermophysical properties of the plasticizer used are appropriately selected according to the binder and other components of the constituent layers. For example, considering the melting point, the temperature is preferably 300 ° C. or lower, more preferably 250 ° C. or lower, and particularly preferably 200 ° C. or lower. The amount of the plasticizer added is 0.1% when the total weight of the binder, other components and the plasticizer constituting the layer is 100% by weight.
It is preferably from 001 to 90% by weight, more preferably from 0.1 to 60% by weight, particularly preferably from 1 to 40% by weight.

Examples of the plasticizer include "Chemical Handbook" (edited by The Chemical Society of Japan, Maruzen), "Plasticizer-Its Theory and Application-" (edited by Koichi Murai, Koshobo), and "Research on Plasticizers: Top". "Research on plasticizers, 2" (edited by the Society of Polymer Chemistry) and "Handbook
It can be selected by referring to "Plastic compounding chemicals" (edited by Rubber Digest).

Also, JP-A-59-83154, JP-A-59-178451, and JP-A-59-1784 describe plasticizers under the names of high-boiling organic solvents and hot solvents.
Nos. 53, 59-178454 and 59-1
Nos. 78455, 59-178457 and 6
2-174754, 62-245253, 61-209444, and 61-20053
No. 8, No. 62-8145, No. 62-9348
JP, JP-A-62-30247, JP-A-62-1366
No. 46, No. 62-174754, No. 62-2
Nos. 45253, 61-209444, 6
Esters such as those described in 1-200538, 62-8145, 62-9348, 62-30247, 62-136646 and JP-A-2-235694. (Eg, phthalates, phosphates, fatty acid esters, abietic esters, adipic esters,
Sebacates, azelates, benzoates, butyrates, epoxidized fatty acids, glycolates, propionates, trimellitates, citrates, sulphonates , Carboxylic esters, succinic esters, maleic esters, fumaric esters, phthalic esters, stearic esters, etc.), amides (eg, fatty acid amides, sulfoamides, etc.), ethers, alcohols , Paraffins,
Examples include compounds such as lactones, polyethyleneoxys, silicone oils, and fluorine compounds.

Further, low-molecular-weight polymers such as those described below can also be used. As commercial products, Asahi Denka Kogyo Adecaizer PN-170, PN-1430, C.I.
P. HALL company products PARAPLEX-G-25, G-
30, G-40, Rika Hercules product ester gum 8
L-JA, ester R-95, pentaline 4851, F
K115, 4820, 830, Luizol 28-JA,
Picolastic A75, Picotex LC, Crystallex 3085 and the like can be mentioned. These include adjustment of slipperiness (improvement of transportability due to reduction of frictional force), improvement of fixing portion offset (peeling of toner and layer to fixing portion),
It may be used for purposes such as curl balance adjustment and charge adjustment (formation of a toner electrostatic image).

The electrophotographic image-receiving material of the present invention can contain a charge control agent in at least one layer for the purpose of controlling transfer and adhesion of toner. As the charge control agent, any of conventionally known antistatic agents can be used,
In addition to surfactants such as cationic surfactants, anionic surfactants, amphoteric surfactants, and nonionic surfactants, polymer electrolytes, conductive metal oxides, and the like can be used.
For example, cationic antistatic agents such as quaternary ammonium salts and polyamine derivatives; anionic antistatic agents such as cation-modified polymethyl methacrylate, cation-modified polystyrene, and alkyl phosphate; nonionic antistatic agents such as anionic polymers and fatty acid esters. Agents, but are not limited to these.

As the conductive metal oxide, ZnO, Ti
O ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , Mg
O, BaO and MoO ₃ can be mentioned. These may be used alone or a composite oxide of these may be used. Further, the metal oxide may further contain a different element, for example, Al, In with respect to ZnO.
Etc., Nb relative to TiO _2, Ta or the like, for SnO _2, containing Sb, Nb, halogen elements etc. (doping)
Can be done. The toner image receiving layer is 1 × 10 ⁶ to 1
× 10 ¹⁵ range (under conditions of 25 ° C and 65% relative humidity)
It is preferable to have a surface electric resistance of 1 × 10 ⁶ Ω
If it is less than 1, the amount of toner when the toner is transferred to the image receiving layer is insufficient, and the density of the obtained toner image is low. On the other hand, if it exceeds 1 × 10 ¹⁵ Ω, an unnecessary charge is generated during transfer. Therefore, the toner is not sufficiently transferred, and the density of the image becomes low. Electrostatic charges occur during the handling of electrophotographic image-receiving materials, and dust easily adheres to them.
This is not preferable because double feeding, discharge marks, toner transfer dropping, and the like are likely to occur. Further, it is not always necessary to adjust the charge of the heat-resistant layer containing the water-soluble polymer.

In the present invention, a base paper, a water-resistant layer, a base paper coating layer, a protective layer, an image receiving layer, a cushion layer, an undercoat layer, a heat insulating layer, a porous layer, a heat resistant layer, an adhesive layer, and a curl which constitute an electrophotographic image receiving material. Photographic additives can be used for the adjustment layer and the like. For example, RD1764 is used as a photographic additive.
3 (December 1978), RD18716 (November 1979) and RD307105 (November 1989)
The relevant parts are summarized below.

[0029]

[Table 1]

The image receiving material for electrophotography of the present invention has anti-blocking properties, improved slipperiness, antistatic properties, improved releasability,
Organic and / or inorganic fine particles (hereinafter abbreviated as a matting agent) can be added to the constituent layers for the purpose of white background, curl, moisture adjustment of the whole image receiving material, and the like. The matting agent preferably has a particle size of 0.001 to 50 μm.
Those having a thickness of from 0.5 to 30 μm are more preferred. The average particle size of the matting agent depends on the thickness of the heat-resistant layer.
When it is 0, it is preferably 0.01 to 500,
It is more preferably from 0.1 to 300, particularly preferably from 0.5 to 100. The matting agent may appear on the surface of the heat-resistant layer or may enter the inside. The amount of the matting agent applied is 0.001
-20 g / m ^2, more preferably 0.003-10 g
/ M ² , particularly preferably 0.005 to 5 g / m ² .

As the matting agent, conventionally known matting agents can be used. For example, organic and / or inorganic fine particles described in JP-A-5-262055 can be used as a matting agent. Specifically, as an organic matting agent, for example, in addition to the compounds described in JP-A-63-274944 and JP-A-63-274952, such as benzoguanamine resin particles, polycarbonate resin particles, and ABS resin particles,
Melamine resin particles, melamine-formaldehyde copolymer particles, polymethyl methacrylate particles of compounds described in JP-A-61-88256, page (29), polyolefin resin particles such as polyethylene particles, styrene resin particles, and heat resistance by crosslinking. And crosslinked polymethyl methacrylate particles and crosslinked polystyrene particles having improved abrasion resistance. Examples of the inorganic matting agent include oxides (titanium dioxide, silicon dioxide, etc.), alkaline earth metal salts (eg, sulfates and carbonates, specifically barium sulfate, calcium carbonate, etc.), and images. Examples include silver halide grains (silver chloride, silver bromide, etc.) that do not form, glass, and the like.

In the particle layer of the present invention, it is preferable to use solid particles having an average particle size of 5 μm or less. Average particle size is 5μ
As the solid particles having a particle size of m or less, an inorganic pigment is preferably used. Examples of inorganic pigments include silica pigments, alumina pigments, titanium dioxide pigments, zinc oxide pigments, zirconium oxide pigments, mica iron oxide, lead white, lead oxide pigments, cobalt oxide pigments, strontium chromate, molybdenum pigments, smectites, Mention may be made of magnesium oxide pigments, calcium oxide pigments, calcium carbonate pigments and mullite. Among them, silica pigments and alumina pigments are preferred. Two or more of these inorganic pigments may be used in combination. Silica pigments include spherical silica and amorphous silica. The silica pigment can be prepared by a dry method, a wet method, or an airgel method. The surface of the hydrophobic silica particles may be surface-treated with a trimethylsilyl group or silicone. The silica pigment is preferably porous. The average pore size of the porous silica pigment is preferably from 0.1 to 5 μm. The average pore volume per weight of the porous silica pigment is preferably 0.5 to 3 ml / g.

The alumina pigment 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 preferred over anhydrous alumina. Monohydrate or trihydrate can be used as the alumina hydrate. Monohydrates include pseudoboehmite, boehmite and diaspore. Trihydrate includes gibbsite and bayerite. The average particle size of the alumina pigment is preferably from 4 to 300 nm, more preferably from 4 to 200 nm. The alumina pigment is preferably porous. The average pore size of the porous alumina pigment is preferably from 50 to 500 nm. The average pore volume per weight of the porous alumina pigment is preferably 0.3 to 3 ml / g. Alumina hydrate can be prepared by a sol-gel method in which ammonia is added to an aluminum salt solution for precipitation, or a method in which alkali aluminate is hydrolyzed. Anhydrous alumina can be obtained by dehydrating alumina hydrate by heating. The amount of the inorganic pigment to be used is preferably 5 to 2000% by weight in terms of a dry weight ratio to the binder in the layer to be added.

The layer constituting the electrophotographic image-receiving material of the present invention may be cured by a hardener. In the case of curing an organic solvent-based polymer, JP-A-61-19999
No. 7, No. 58-215398 and the like can be used. It is particularly preferable to use an isocyanate-based hardening agent for the polyester resin. In the case of a water-soluble polymer, the compounds specified as hardeners in Table 1 can be used. Further, the electrophotographic image-receiving material of the present invention may contain an organic fluoro compound for the purpose of coating aid, improving slipperiness, preventing static charge, and improving releasability. Representative examples of the organic fluoro compound include Japanese Patent Publication No. 57-90.
No. 53, column 8-17, fluorinated surfactants described in JP-A-61-20944, JP-A-62-135826, etc., or oily fluorine compounds such as fluorine oil, or tetrafluoride A hydrophobic fluorine compound such as a solid fluorine compound resin such as an ethylene resin is exemplified.

A heat-resistant layer may be provided on the back surface of the electrophotographic image-receiving material of the present invention. As the material of the heat-resistant layer, any material can be used as long as it can withstand the fixing temperature, but it preferably contains a water-soluble polymer, and more preferably contains 10% by weight or more of a water-soluble polymer. . As the binder or the main component constituting the layer, the above-mentioned polymer for an image receiving layer or a water-soluble polymer, or another organic solvent-soluble polymer or a water-soluble polymer can be used. As the water-soluble polymer, a water-soluble polymer having a group capable of undergoing a cross-linking reaction with a hardener is preferable, and among them, polyvinyl alcohol and gelatins are preferably used. The heat-resistant layer may be composed of two or more layers. Moreover, the thickness of the heat-resistant layer is 0.01 to 50 μm in total,
Particularly, a range of 0.05 to 20 μm is preferable.

In the present invention, the layers constituting the electrophotographic image receiving material are prepared by using the above-mentioned materials and further adding various auxiliaries as necessary, or by dissolving or dispersing in an appropriate solvent. Is formed using a conventionally known coating method such as a blade coating method, an air knife coating method, a gravure coating method, a squeeze coating method, a roll coating coating method, a spray coating method, a dip coating method, and a bar coating method. Can be.

The shape of the electrophotographic image receiving material is not particularly limited as long as it can be used for recording by an electrophotographic method. It may be in the form of a sheet or a band, or may be in the form of a long roll. From the viewpoint of printing efficiency, a roll-shaped long winding is preferable. In the case of a long roll, it is preferable to cut the final product inside the printer, and it is preferable to use a printer having that function. Other specific examples of the electrophotographic image-receiving material of the present invention include L-size and 2L-size photographic prints, photographs and nouns with pictures, tickets, calendars, photographic prints with border decorations, and the like. It is. Further, when the electrophotographic image-receiving material of the present invention is used, a print having no blank portion which is not printed on the edge can be produced by an electrophotographic printing method.

As the toner used in the color electrophotographic method, known toners can be used, and yellow, magenta,
It is preferable to form a color image with three or four colors of cyan or black. Further, two or more toners having different color densities may be used. Also, a transparent or white toner may be used. However, a toner having a flow start temperature higher than the flow start temperature of the image receiving layer of the color electrophotographic image receiving material of the present invention must be selected.
Further, a toner having UV absorption or a toner containing various additives mentioned as additives for the image receiving layer may be used. For example, a toner containing an anti-fading agent can form a toner image having excellent image storability. Two or more kinds of toners may react and exhibit a function. A toner having a higher softening point than other toners may be used in combination and used as a so-called matting agent. Further, the toner may have a different contact angle with the image receiving layer in a molten state, and the spread of each toner at the time of fixing may be controlled to change the effective density to form a part of the gradation. . The present invention is not particularly limited as an electrophotographic method that can be used. For example, "Basic and application of electrophotographic technology" and "Basic and application of electrophotographic technology" edited by the Electrophotographic Society of Corona Publishing, Inc. The method described in “Application / Continuation” can be used, and the type and method of the toner are not limited.

[0039]

The present invention will be described more specifically below with reference to examples and comparative examples. Materials, reagents, ratios, operations, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples. In addition,
The structures of compound-1 and surfactant-1 used in the following examples are as follows.

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Example 1 Polyethylene having a density of 0.96 g / m ² was laminated on both sides of a high-quality paper having a basis weight of 160 g to a thickness of 15 μm to obtain a support. On one surface of this support, the following image-receiving layer composition was applied by a wire coater so as to have a dry film thickness of 10 μm, and dried to form a toner image-receiving layer. <Image-receiving layer composition> Polyester resin (Tafton U-5, manufactured by Kao Corporation) 100 g of titanium dioxide (Tipaque ^R A-220, manufactured by Ishihara Sangyo Kaisha) 15 g Compound -1 10 g of methyl ethyl ketone 400g

Further, on the surface opposite to the image receiving layer, a particle layer composition having the following composition was dried with a bar coater to a dry film thickness of 9%.
It was coated to a thickness of μm and dried to form a particle layer, and an image receiving material for color electrophotography was obtained. <Composition for particle layer> Polyester resin (Vylonal MD-1930, manufactured by Toyobo) 130 g Particle A (benzoguanamine resin, see Table 2 for average particle size) 10 g Particle B (silica particles, see Table 2 for average particle size) 31 g Water 320g

Next, the prepared color electrophotographic image receiving material is cut into A4 paper, set in a color laser printer (Docucolor DC1250, manufactured by Fuji Xerox), and a photographic image previously captured by a scanner is applied to the image receiving layer surface. Recorded. Subsequently, using a color inkjet printer (PM3000, manufactured by Epson Corporation), Chinese characters were printed on the particle layer surface by changing the font type from 5 points to 14 points. Regarding the image quality of the toner image formed on the image receiving layer, the uniformity of solid gray and the loss of toner were evaluated. Regarding the ink jet printing on the back surface, the printed portion was rubbed with a dry cloth immediately after recording, and the degree of ink flow and the resolution of the font of each size were evaluated.
Further, 50 sheets of the color electrophotographic image receiving material before recording were stacked and left for 1 week in an environment of 40 ° C., and the adhesion state of the image receiving paper was confirmed. Table 2 shows the results. The flow start temperature of the toner was measured with a flow tester CFT-500 manufactured by Shimadzu Corporation using a color toner commercially available for the above color laser printer. The flow start temperature of the image receiving layer was measured by scraping and collecting the image receiving layer and similarly using a flow tester CFT-500. As a result, the flow start temperature of the image receiving layer was 3 ° C. lower than the flow start temperature of the toner.

[0043]

[Table 2]

As can be seen from Table 2, when the difference in particle size is 5 μm or less, defects tend to occur in the toner image when particles having a relatively large particle size are used (No. 1), and particles having a relatively small particle size are used. It can be seen that when is used, the ink-jet characters are blurred and easily adhered (No. 8). On the other hand, it can be seen that the use of the color electrophotographic image-receiving material that satisfies the conditions of the present invention provides a good electrophotographic image and good printing by inkjet (numbers 2, 4 to 4).
7, 9, 10).

Example 2 The total amount of particles A (average particle diameter 12 μm) and particles B (average particle diameter 3 μm) of the particle layer on the back surface used in the configuration of No. 5 in Table 2 of Example 1 was calculated. A color electrophotographic image-receiving material was produced by changing the weight ratio of the particles A and B as shown in Table 3 without any change, and the same evaluation as in Example 1 was performed. Table 3 shows the results. When the ratio of the weight of the particles B (average particle size: 3 μm) / the weight of the particles A (average particle size: 12 μm) is smaller than 1, ink jet printing resolution tends to decrease, and when it exceeds 10, the adhesion deteriorates. It turns out that there is a tendency. When the ratio is 1 to 10 (preferable range of the present invention), it can be seen that both the resolution of the ink printing and the quality of the toner image are good.

[0046]

[Table 3]

Example 3 An image receiving material for color electrophotography was prepared in the same manner as in Example 4, except that the thickness of the image receiving layer and the thickness of the particle layer on the back surface were changed as shown in Table 4. The 45-degree glossiness of the toner image formed on the image receiving layer was measured by a digital variable-angle gloss meter (UGV-5D, manufactured by Suga Test Instruments Co., Ltd.). The resolution of characters printed on the particle layer by ink jet was also evaluated. Further, the adhesion state was also tested in the same manner as in Example 1. Table 4 shows the results. From Table 4, it was found that relatively good gloss was obtained when the thickness of the image receiving layer was 6 μm or more, and relatively good ink printing was obtained when the thickness of the particle layer on the back surface was 1 μm or more.

[0048]

[Table 4]

Example 4 The following image-receiving layer composition was coated on one side of a high-quality paper of 160 g in weight as a support with a wire coater to a dry film thickness of 10 μm and dried to form a toner. An image receiving layer was formed. <Image-receiving layer composition> Polyester resin 100 g (Table 5 according to the difference of the flow temperature of the toner as the image receiving layer) of titanium dioxide (Tipaque ^R A-220, manufactured by Ishihara Sangyo Kaisha) 15 g Compound -1 80 g of methyl ethyl ketone 400g

Further, on a surface opposite to the image receiving layer, a composition for a particle layer having the following composition was dried with a bar coater to a dry film thickness of 3 μm.
m to obtain a color electrophotographic image-receiving material. <Composition for Particle Layer> Polyester resin (Vylonal MD-1200, manufactured by Toyobo) 130 g Particle A (benzoguanamine resin, average particle diameter 12 μm) 20 g Particle B (silica particles, average particle diameter see Table 5) 40 g Surfactant— 1 0.5g Water 320g

Next, the prepared color electrophotographic image receiving material is cut into A4 paper, set in a color laser printer (Docucolor DC1250, manufactured by Fuji Xerox), and a photographic image previously captured by a scanner is applied to the image receiving layer surface. Recorded. The gloss of the solid gray portion from the minimum reflection density to D = 2 was measured by reading the value of a gloss meter at 45 °, and the maximum difference was recorded. Then, on the particle layer surface,
Using a color inkjet printer (PM3000, manufactured by Epson Corporation), the kanji was printed by changing the font type from 5 points to 14 points. The image quality of the toner image formed on the image receiving layer (the glossiness difference was measured for an image having no omission), the ink flow of the ink jet printing of the particle layer, and the resolution were evaluated in the same manner as in Example 1. Table 5 shows the results.

[0052]

[Table 5]

As is clear from Table 5, when the average particle size of the particles B (silica particles) is 7 μm or less, that is, particles having an average particle size smaller by 5 μm or more than the particles A having an average particle size of 12 μm are used. In this case, it can be seen that the printing of the ink is of good quality. On the other hand, when the flow start temperature of the image receiving layer is higher than the flow start temperature of the toner (when the flow start temperature of the image receiving layer is higher than 98 ° C.), the gloss uniformity of the toner image is reduced, and the difference between the maximum gloss and the minimum gloss is reduced. It can be seen that increases. It can be seen that all of the color electrophotographic image receiving materials satisfying the conditions of the present invention can obtain good performance (Nos. 32 and 35).

(Example 5) Polyester resin (Vylonal MD-1930, manufactured by Toyobo) 1 used in Example 1
In the same manner as in Example 1, color electrophotographic image receiving was performed using 120 g of an aqueous dispersion of SBR resin (solid content: 43%) having a styrene / butadiene / acrylic acid ratio of 68/29/3 instead of 30 g. Materials were prepared and evaluated. As a result, as in Table 1, good results were obtained for the color electrophotographic image-receiving material satisfying the conditions of the present invention. In particular, with respect to the bleeding resistance of the ink, more favorable results were obtained when SBR was used than when polyester resin (Vylonal MD-1930, manufactured by Toyobo) was used.

Example 6 An electrophotographic image-receiving material was prepared in the same manner as in Example 1 except that the composition for the particle layer used in Example 1 was changed to the following A to C. <Composition A for Particle Layer> Polyester resin (Vylonal MD-1930, manufactured by Toyobo) 30% 188 g Polyester resin (Vylonal MD-1200, manufactured by Toyobo) 34% 166 g Particles A (crosslinked polystyrene resin average particle diameter 17 μm) 38 g Particles B (Silica particles, average particle diameter 3 μm) 97 g water 512 g

<Composition B for Particle Layer> Polyester resin (Vylonal MD-1930, manufactured by Toyobo) 30% 263 g Polyester resin (Vylonal MD-1200, manufactured by Toyobo) 34% 232 g Particle A (crosslinked polystyrene resin, average particle diameter 17 μm) ) 38 g Particle B (silica particles, average particle diameter 3 μm) 97 g Water 512 g

<Composition C for Particle Layer> SBR aqueous dispersion (glass transition point 70 ° C.) 44% 318 g Particle A (crosslinked polystyrene resin, average particle diameter 17 μm) 38 g Particle B (silica particles, average particle diameter 3 μm) 97 g 512g of water

After printing with a color laser printer on the toner receiving surface of the three types of electrophotographic image receiving materials thus prepared, a color ink jet printer (PM8
00C, manufactured by Epson; and BJC F850, manufactured by Canon Inc.), and the performance was evaluated. As a result, in the case of using the particle layer compositions A, B, and C, the ink jet performance was good. Further, a test was conducted in which the ink was printed and then left after leaving a water drop. As a result, when the composition C for a particle layer was used, bleeding was reduced and the composition was particularly good. Further, the three types of electrophotographic image-receiving materials thus prepared were added to a Docucolor DC1250 device, respectively, and stains on the fixing roller were confirmed. As a result, when the composition A for the particle layer is passed, a white deposit is observed particularly on the fixing roller on the side in contact with the back surface,
It was found that the particles on the back surface were transferred. on the other hand,
When the compositions B and C for the particle layer were used, the fixing roller was hardly stained. That is, the solid content of the binder (polyester resin or SBR) is
It was found that better performance was obtained when the amount was larger than the total amount of particles A and B.

Example 7 As a support, a basis weight of 150 was used.
13 μm of polyethylene on the surface of the high-quality paper on the image receiving layer side,
Laminating was performed on the surface on the back layer side so as to have a thickness of 15 μm, and the following image-receiving layer composition was applied using a wire coater so that the thickness when dried was 8 μm, and dried to form a toner image-receiving layer. . <Composition for Image Receiving Layer> Polyester resin (Tuffton U-5, manufactured by Kao) 400 g Titanium dioxide (Taipec (registered trademark) A-220, manufactured by Ishihara Sangyo) 60 g Compound-1 34.8 g Fluorescent brightener (Uvitex-OB) 2.1g Color control dye 0.17g Methyl ethyl ketone 600g

The structure of the color adjusting dye used in this example is as follows, and the following dyes were selected and adjusted in arbitrary amounts. At this time, the whiteness of the image receiving layer was 81%.
Met.

"Dye for adjusting color tone (yellow)"

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"Dye for adjusting color tone (magenta)"

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"Tint adjusting dye (cyan)"

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Further, a particle layer having the following composition was similarly coated on the surface opposite to the image receiving layer with a bar coater to a dry film weight of 10 g / m ^2.
And dried. <Particle layer> Ethanol 52 g Particle A (see Table 6) 12.2 g Water 139 g Polyester resin (Vylonal MD-1930, manufactured by Toyobo) 123 g Polyester resin (Vylonal MD-1200, manufactured by Toyobo) 109 g Particle B (see Table 6) 64 g

(Table 6) Particles AMBX20 (manufactured by Sekisui Chemical Co., Ltd.) average particle size 17 μm SBX17 (manufactured by Sekisui Plastics Industry Co., Ltd.) Average particle size 15 μm (Fuji Silysia Chemical Ltd.) Average particle size 2.5 μm The following four types of image receiving sheets were prepared for the particle layer. Particle A + Particle B Particle A + Particle B Particle A + Particle B Particle A + Particle B

The color electrophotographic image receiving sheet prepared above is cut into A4 sheets, set on a color laser printer (Docucolor DC1250) manufactured by Fuji Xerox, and a photographic image previously taken in by a scanner is printed on the image receiving layer surface. Out. Subsequently, printing was performed by changing the font type from 5 points to 14 points on the back surface of the image receiving paper coated with the toner image receiving layer, using a color ink jet printer PM800C manufactured by Epson Corporation. An evaluation was performed. As a result, ink-jet characters could be read well up to 5 points on any of the image receiving sheets. Further, even if the printed portion was rubbed with a dry cloth immediately after printing, no bleeding occurred. The electrophotographic gray solid of the image receiving layer was uniform, and no toner was removed. Also, the receiving paper before printing is 50
The sheets were stacked and allowed to stand for one week in an environment of 40 ° C., and the adhesion of the image receiving paper was confirmed.

[0067]

The color electrophotographic image-receiving material of the present invention comprises:
A color electrophotographic image having excellent gloss and excellent color reproducibility can be formed on one surface, and a clear, unbleeded good image can be formed on the opposite surface when recorded by inkjet. Further, the color electrophotographic image-receiving material of the present invention does not adhere to each other even if it is stored before being recorded before being recorded, and further, it does not adhere at the accumulation portion even when electrophotography is continuously printed.

Claims (7)

[Claims] 1. An electrophotographic apparatus comprising: a support; an image receiving layer of a toner containing a polymer provided on one surface of the support; and a particle layer containing fine particles provided on the other surface of the support. In the image receiving material, the flow start temperature of the image receiving layer is equal to or lower than the flow start temperature of the toner, and the particle layer contains two or more types of fine particles having an average particle diameter different from each other by 5 μm or more. Image receiving material. 2. An electrophotographic apparatus comprising: a support; an image receiving layer of a toner containing a polymer provided on one surface of the support; and a particle layer containing fine particles provided on the other surface of the support. An image receiving material for color electrophotography, wherein a flow start temperature of the image receiving layer is 98 ° C. or lower, and the particle layer contains two or more kinds of fine particles different in average particle size by 5 μm or more. 3. The particle layer contains at least one kind of fine particles having an average particle diameter of 5 μm or less, and at least one other fine particles having an average particle diameter of 5 μm or more than the fine particles.
The color electrophotographic image-receiving material according to claim 1, wherein the material comprises a seed. 4. The particle layer includes at least one kind of fine particles having an average particle diameter of 10 μm or more, and at least one kind of other fine particles having an average particle diameter smaller than the fine particles by 5 μm or more. The image receiving material for color electrophotography according to claim 1. 5. The method according to claim 1, wherein the image receiving layer of the toner has a thickness of 6 μm or more, the particle layer has a thickness of 1 μm or more, and the particle layer contains porous silica particles. 5. The image receiving material for color electrophotography according to any one of 4. 6. A fine particle having a small average particle diameter of 1 to 10 parts by weight per 1 part by weight of a fine particle having a large average particle diameter among two or more kinds of fine particles having an average particle diameter different from each other by 5 μm or more. The image receiving material for color electrophotography according to claim 1, wherein: 7. The color electrophotographic device according to claim 1, wherein the coating amount of the binder in the particle layer is equal to or more than the total coating amount of all the particles in the particle layer. Image receiving material.