JP2000141896A - Image forming material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To undergo no breakage or dropping with respect to calender treatment, and prevent conductivity from deteriorating and cracking by allowing an image forming layer on the first support body and a transferred layer on the second support body to be laminated in face-to-face relation, and including an outermost layer containing fiber-fine particles at the opposite side to the image forming layer. SOLUTION: The image forming material has as fundamental structure an image forming body having an image forming layer on the first support body 1 and a transferred body having a transferred layer on the second support body. In addition, the image forming body has an image forming layer on one surface of the first support body 1, and an antistatic agent-containing layer and a back layer as an outermost layer containing a mat agent on the other surface. The image forming body furnished with the back layer is given a calender treatment before being formed into an image forming material in a manner being adhered with the transferred body. Even in the case where a calender is applied, by the use of fiber fine particles at the outermost layer, stickiness to the calender roller never occurs; hence this leads to good slippage, and an effect of making no flaws on the image forming layer, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] 1. Field of the Invention [0002] The present invention relates to an abrasion type image forming material by photothermal conversion.

[0002]

2. Related Background Art Hitherto, a recording method or a recording material has been known in which light energy such as a laser beam is focused and irradiated onto a recording material to melt or deform a part of the material, or to scatter, burn or evaporate away. ing. These are dry treatments that do not require treatment liquids such as chemicals, and have the advantage that high-contrast images can be obtained by forming an image only by melting deformation, scattering or evaporation removal of only the light irradiation part. , A resist material, an optical recording material such as an optical disk, and an image forming material that makes itself a visible image. Hereinafter, these image forming methods (methods) are defined as an abrasion method (method), and the image forming process or phenomenon is defined as abrasion.

An image forming method by abrasion is described in, for example, Japanese Patent Application Laid-Open Nos. 59-547 and 59-1047.
No. 5638, No. 62-115153, No. 55-132
No. 536, No. 57-27788, No. 57-10313
7, JP-A 64-56591, JP-A-1-99887
No. 6-40163, Tokuyohei 4-506709,
JP-A-6-43635, JP-A-8-337053, JP-A-9
-15849 and U.S. Pat. No. 4,245,00
No. 3, 5,156,938 and 5,171, 6
No. 50, No. 5,256,506, etc., there are many descriptions.

[0004]

In producing or using the above-mentioned abrasion type image forming material, there are various troubles in any method.
These improvements are desired. One is related to dust adhering during production or use, which may give erroneous information to images, cause defective parts when applying layers, or cause scratches on image forming materials. ing.
Japanese Patent Application Laid-Open No. 9-15849 discloses that an antistatic layer is provided in order to prevent adhesion of dust and poor transport in the process of producing such an image forming material or in abnormal quality. Ordinary organic conductive antistatic agents exhibit good conductivity at room temperature, but generally lose their performance when heated. Photothermal conversion image forming materials are often exposed to high-temperature conditions such as calendering, which will be described later, during the production process, and the deterioration of conductivity is a problem.

[0005] Also, Japanese Patent Application Laid-Open Nos.
JP-A-15849 discloses an abrasion image forming material and method using photothermal conversion, wherein the coloring material of the image forming material is a metal atom-containing particle, which is made of a metal, an alloy, an inorganic metal compound, or the like. Are preferably magnetic powder particles. The magnetic powder particles are acicular, and in order to obtain a good image, it is preferable to perform an orientation treatment.After applying the magnetic powder particle-containing image forming layer coating solution, orienting by applying a magnetic field,
After drying, a high resolution can be imparted by subjecting the image forming layer to calendering. In an image forming layer containing a large amount of metal atom-containing particles, voids are apt to be formed in the image forming layer, which also causes a reduction in the resolving power of the image forming material. When the antistatic layer was provided on the back surface of the image forming material, the back surface of the calender roll was easily cracked, the conductivity was deteriorated by the calender treatment, and the calender was damaged. Further, when the film is wound after being subjected to the calendering treatment, the surfaces on the side opposite to the image forming layer side (hereinafter, also referred to as a back surface) are likely to cause blocking, and it has been a problem to prevent this. For this reason, an attempt has been made to prevent blocking after winding by using an inorganic matting agent such as that usually used in silver halide photographic light-sensitive materials, but the matting agent is crushed during calendering. Rolled or detached,
It is a source of garbage. For this reason, the image forming layer and the back surface may be damaged, and troubles are likely to occur during the production of the image forming material or during transportation in the printer.
The back surface was cracked by the calendering treatment, stuck to the calender roll, damaged the image forming layer side after winding, or damaged the image forming layer and the back surface, and did not serve as a matting agent. As described above, it has been a problem to search for an antistatic agent and a matting agent suitable for the image forming material, and to produce an image forming material free of these troubles.

[0006] It is an object of the present invention to provide a back layer having an outermost layer containing a matting agent which does not break or fall off during calendering on the side of the image forming layer opposite to the image forming layer on the support. Also, due to the calendering process, the conductivity does not deteriorate and the calender roll does not get caught,
Blocking between sheets may occur or be damaged,
An object of the present invention is to provide an image forming material having a back layer that does not crack.

[0007]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and as a result of intensive studies, has been achieved by the following constitution.

(1) The image forming layer on the first support and the second
In the image forming material in which the layer to be transferred on the support is laminated facing the image forming layer, the outermost layer containing the fine fiber particles is provided on the side opposite to the image forming layer on the first support. Characteristic image forming material.

(2) The image forming material according to (1), wherein the fiber fine particles are silk fine particles.

(3) The image forming material as described in (1) or (2), wherein the outermost layer contains a binder having a glass transition point of 50 ° C. or higher.

(4) The image forming material according to (3), wherein the binder is a hydrophilic polyester.

(5) The outermost layer according to any one of claims 1 to 4 and at least one layer of metal oxide fine particles are contained on the first support on the side opposite to the image forming layer side. An image forming material having an antistatic layer.

(6) The method according to (5), wherein the antistatic layer containing the metal oxide fine particles is present adjacent to the first support opposite to the image forming layer. The image forming material as described in the above.

(7) The image forming material according to any one of (1) to (4), wherein the outermost layer is an antistatic layer containing metal oxide fine particles.

(8) The image forming material as described in any one of (5) to (7), wherein the antistatic layer is cured with an epoxy type curing agent.

The present invention will be briefly described in addition to the description of the photothermal conversion type image forming material and the image forming method of the present invention.

The image forming material of the present invention is basically composed of an image forming body having an image forming layer on a first support and a transfer body having a transfer layer on a second support.

The image forming body of the present invention has a backing layer having an image forming layer on one side of a first support and a layer containing an antistatic agent on the other side or an outermost layer containing a matting agent of the present invention. have.

The present invention particularly relates to the improvement of the back layer of an image forming body.

Examples of the first support used for the image forming member include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene butyrate, polycarbonate, polyarylate, vinyl chloride, syndiotactic polystyrene, aromatic polyamide, and polyamid. A film made of a resin such as ether ketone, polysulfone, polyethersulfone, polyimide, and polyetherimide can be given. Among them, polyethylene terephthalate, polyethylene naphthalate, polyethylene butyrate, polycarbonate, syndiotactic polystyrene, aromatic polyamide, polyether ketone, polysulfone, polyethersulfone, polyimide, and a film made of polyetherimide are preferable because they have heat resistance. In particular, a biaxially stretched polyethylene terephthalate (hereinafter sometimes abbreviated as PET) film and a biaxially stretched polyethylene naphthalate (hereinafter sometimes abbreviated as PEN) film have heat resistance, dimensional stability, and transparency. It is preferably used because it is excellent in quality, easy to obtain, and inexpensive. Further, a film obtained by laminating these films or a film formed by mixing two or more kinds of resins can be used as long as it is intended. Further, a filler such as titanium oxide, zinc oxide, barium sulfate, or calcium carbonate may be added as long as the effects of the present invention are not impaired. The thickness of the transparent support is 10 to
It is about 500 μm, preferably 25 to 250 μm.

The image forming layer is basically composed of a coloring material and a binder for holding the coloring material.

As the coloring material used in the present invention, any coloring material can be used as long as it can absorb the light of the wavelength of the exposure light source and has a wide absorption range from the ultraviolet region to the visible and infrared regions. Examples include organic pigments, dyes, metal atom-containing particles, and coloring materials described in JP-A-9-15849.

In the present invention, metal atom-containing particles can be preferably used as a coloring material in terms of sensitivity, resolution, and prevention of stains on exposed portions.

The term “metal atom-containing particles” as used herein is a generic term for particles of a metal such as iron, chromium, manganese, cobalt, nickel, copper, zinc, titanium, silver, aluminum, gold, platinum or a compound of an oxide thereof. is there.

The metal atom-containing particles preferably used in the present invention include a ferromagnetic iron oxide powder, a ferromagnetic metal powder, and a cubic plate-like powder. Among them, a ferromagnetic metal powder is particularly preferably used.

As the ferromagnetic iron oxide, γ-Fe ₂ O ₃ , F
e ₃ O ₄ , or FeO _x (1.3
3 <x <1.50).

Examples of the ferromagnetic metal powder include Fe and Co, Fe-Al, Fe-Al-Ni, and Fe-Al-.
Zn-based, Fe-Al-Co-based, Fe-Al-Ca-based, F
e-Ni system, Fe-Ni-Al system, Fe-Ni-Co
System, Fe-Ni-Zn system, Fe-Ni-Mn system, Fe-
Ni-Si system, Fe-Ni-Si-Al-Mn system, Fe
-Ni-Si-Al-Zn system, Fe-Ni-Si-Al
-Co system, Fe-Al-Si system, Fe-Al-Zn system,
Fe-Co-Ni-P system, Fe-Co-Al-Ca system,
Ferromagnetic metal powders such as metal magnetic powders mainly composed of Ni-Co, Fe, Ni, Co, etc.
Based metal powder is preferred, for example, Co-containing γ-Fe ₂ O ₃ ,
Co-deposited γ-Fe ₂ O ₃ , Co-containing Fe ₃ O ₄ , Co-deposited F
e ₃ O ₄ , Co-containing magnetic FeO _x (4/3 <x <3/2)
Cobalt-containing iron oxide-based magnetic powder such as powder.
Further, from the viewpoint of corrosion resistance and dispersibility, among Fe-based metal powders, Fe-Al-based, Fe-Al-Ca-based, Fe-
Al-Ni system, Fe-Al-Zn system, Fe-Al-Co
System, Fe-Ni-Si-Al-Co system, Fe-Co-A
Fe-Al based ferromagnetic powders such as l-Ca based are preferable, and furthermore, among these, Fe atoms contained in the ferromagnetic powder and Al
Fe: Al = 100: 1 in the content ratio with the atom in atomic ratio.
100: 20 and the ferromagnetic powder ESCA (X
The ratio between the content of Fe atoms and the content of Al atoms present in a surface area of 100 Å or less at an analysis depth by X-ray photoelectron spectroscopy is 30:70 to 7 in terms of atomic ratio.
A ferromagnetic powder having a structure of 0:30 or Fe atom, Ni atom, Al atom, Si atom, and at least one of Co atom and Ca atom, and the content of Fe atom is 90 atom%. As described above, the content of Ni atoms is 1 to
10 atom%, Al atom content is 0.1-5 atom%, S
i atom content is 0.1 to 5 atomic%, Co atom or C
The content of the a-atom (the total amount when both are contained) is 0.
1-13 atomic% and a ferromagnetic powder ESCA (X
(A line photoelectron spectroscopy), the content ratio of Fe atoms, Ni atoms, Al atoms, Si atoms, and Co atoms and / or Ca atoms present in a surface area of 100 or less at an analysis depth of Fe: Ni: Al: Si: (Co and / or Ca) = 100: (4 or less) :( 10-60) :( 10
To 70): those having a structure of (20 to 80) are preferable.

The shape of the ferromagnetic powder is preferably acicular.
The major axis diameter is 0.30 μm or less, preferably 0.20 μm or less. By using such a ferromagnetic powder, the surface property of the image forming layer is improved.

Examples of the hexagonal plate-like powder include hexagonal ferrites such as barium ferrite and strontium ferrite.
i, Co, Zn, In, Mn, Ge, Hb, etc.).
E trans on MAG, Vol. 16, p. 18 (1
982). Among them, examples of barium ferrite magnetic powder include Fe
Has a mean particle size (diagonal height of the plate surface of hexagonal ferrite) of at least part of which is substituted by Co and Zn.
And a plate ratio (a value obtained by dividing a diagonal length of a plate surface of hexagonal ferrite by a plate thickness) is 2.0 to 10.0. Further, the barium ferrite magnetic powder further includes a part of Fe as Ti, In, Mn, C
It may be substituted with a transition metal such as u, Ge, and Sn.

A method for producing a cubic magnetic powder is, for example, to melt an oxide and a carbonate of each atom necessary for forming a target barium ferrite together with a glass-forming substance such as boric acid. The obtained melt is quenched to form a glass, then the glass is heat-treated at a predetermined temperature to precipitate the desired barium ferrite crystal powder, and finally the glass component is removed by a heat treatment. In addition to the chemical conversion method, there are a coprecipitation-calcination method, a hydrothermal synthesis method, a flux method, an alkoxide method, a plasma jet method and the like. The content of the metal atom-containing particles contained in the image forming layer is about 50 to 99% by weight, preferably 60 to 95% by weight of the components for forming the image forming layer.

The binder for the image forming layer can be used without any particular limitation as long as it can sufficiently hold the above-mentioned coloring material, but the glass transition point (hereinafter sometimes abbreviated as Tg) of 50 ° C. or more is required. Are preferred. As the binder, a polyurethane, a polyester, vinyl chloride resins such as vinyl chloride copolymers are exemplary, these resins are _{-SO 3 M, -OSO 3 M,} -COOM and -
PO (OM ₁ ) ₂ [where M represents a hydrogen atom or an alkali metal, and M ₁ represents a hydrogen atom, an alkali metal or an alkyl group. ] It is preferable to include a repeating unit having at least one type of polar group selected from the above], and by using a resin having such a polar group introduced therein, the dispersibility of the magnetic powder can be improved. Incidentally, the content ratio of this polar group in each resin is about 0.1 to 8.0 mol%, preferably 0.2 to 6.0 mol%.

The binder resin may be used singly or in combination of two or more kinds. When two or more kinds are used in combination, for example, the ratio of at least one kind selected from polyurethane and polyester to the vinyl chloride resin is as follows. , 90:
10 to 10:90, preferably 70:30 to 3
0:70. Examples of the polar group-containing vinyl chloride include, for example, a resin having a hydroxyl group such as vinyl chloride-vinyl alcohol copolymer, ClCH ₂ CH ₂ SO ₃ M, ClCH ₂ CH
₂ OSO ₃ M, ClCH ₂ CO ₂ M, ClCH ₂ P (= O)
It can be synthesized by an addition reaction with a compound having a polar group such as (OM ₁ ) ₂ and a chlorine atom. A polar group-containing vinyl chloride resin is prepared by charging a predetermined amount of a reactive monomer having an unsaturated bond into which a repeating unit containing a polar group is introduced into a reaction vessel such as an autoclave, such as benzoyl peroxide and azobisisobutyronitrile. A general radical polymerization initiator, a redox polymerization initiator, can be obtained by polymerization using a cationic polymerization initiator and the like, as specific examples of the reactive monomer for introducing sulfonic acid or a salt thereof, Examples include unsaturated hydrocarbon sulfonic acids such as vinyl sulfonic acid, allyl sulfonic acid, methacryl sulfonic acid, and p-styrene sulfonic acid, and salts thereof. When a carboxylic acid or a salt thereof is introduced, for example, (meth) acrylic acid or maleic acid is used, and when a phosphoric acid or a salt thereof is introduced, (meth) acryl-2-phosphate may be used.

Further, in order to improve the thermal stability of the binder resin, it is preferable to introduce an epoxy group into the vinyl chloride copolymer. In this case, the content of the repeating unit having an epoxy group in the copolymer is about 1 to 30 mol%, preferably 1 to 20 mol%, and glycidyl acrylate or the like is used as a monomer for introducing an epoxy group. I can do it.

The polyester having a polar group can be synthesized by a dehydration condensation reaction between a polyol and a polybasic acid partially having a polar group. Examples of the polybasic acid having a polar group include 5-sulfoisophthalic acid, -Sulfoisophthalic acid, 4-sulfoisophthalic acid, 3-sulfophthalic acid, 5
-Dialkyl sulfoisophthalate, dialkyl 2-sulfoisophthalate, dialkyl 4-sulfoisophthalate,
Examples thereof include dialkyl 3-sulfophthalates and alkali metal salts thereof. Examples of the polyol include trimethylolpropane, hexanetriol, glycerin, trimethylolethane, neopentyl glycol, pentaerythritol, ethylene glycol, propylene glycol, and 1,3-butane. Examples thereof include diol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, cyclohexanedimethanol and the like.

The polyurethane having a polar group can be synthesized by reacting a polyol with a polyisocyanate. Specifically, the polyurethane is obtained by reacting a polyol with a polybasic acid partially having a polar group as a polyol. It is synthesized by using the obtained polyester polyol as a raw material. Examples of the polyisocyanate include diphenylmethane-4,4'-diisocyanate and 2,4-diisocyanate.
Examples include tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,5-naphthalenediisocyanate, lysine isocyanate methyl ester, and the like. As another method for synthesizing a polyurethane having a polar group, a polyurethane having a hydroxyl group and ClCH ₂ CH ₂ SO ₃ M having a polar group and a chlorine atom, and ClCH ₂ CH ₂ O may be used.
SO ₃ M, ClCH ₂ CO ₂ M, ClCH ₂ P (＝ O) (O
An addition reaction with a compound such as M ₁ ) ₂ is also effective.

As another binder, vinyl chloride
Vinyl chloride resins such as vinyl acetate copolymer, polyolefin resins such as butadiene-acrylonitrile copolymer, polyvinyl acetal resins such as polyvinyl butyral, cellulose resins such as nitrocellulose, and styrene such as styrene-butadiene copolymer. Resin, acrylic resin such as polymethyl methacrylate, polyamide, phenol resin, epoxy resin, phenoxy resin and the like may be used in combination, but when these are used in combination, the content is preferably 50% by weight or less of the total binder. .

The content of the binder in the image forming layer is about 1 to 50% by weight, preferably 5 to 40% by weight in the components for forming the image forming layer.

In the present invention, it is preferable to incorporate a crosslinking agent capable of crosslinking a binder into the composition for forming the image forming layer. For example, a polyisocyanate used for synthesizing a polyurethane can be used. By adding such a cross-linking agent to cross-link and cure the image forming layer, it is possible not only to improve the durability of the formed image but also to eliminate the background stain at the portion where abrasion has occurred.

The amount of these additives is about 0 to 20% by weight, preferably 0 to 15% by weight.

The thickness of the image forming layer is 0.05 to 5.0 μm.
m, preferably in the range of 0.1 to 3.0 μm, particularly preferably 0.1 to 1.0 μm. Within this range, in an image forming method described later, an image can be formed with low-energy, high-energy light irradiation, in other words, with high sensitivity. Further, the image forming layer may be formed as a single layer, or may be constituted by multiple layers having the same or different compositions. When the image forming layer is constituted by multiple layers, the image forming layer near the support may contain a photothermal conversion compound. It is preferable in terms of sensitivity. Further, the image forming layer of the present invention composed of the above composition, when removing the image forming layer of the exposed portion by the image forming method described below, from the viewpoint of resolution, it is preferable that the thickness of the image forming layer is as thin as possible. Although it is preferable to use the high-density energy light efficiently, the spectral absorption wavelength region 35
When the maximum absorption wavelength at 0 to 1200 nm is λmax, the transmission density per 1 μm of film thickness of the image forming layer at least at the maximum absorption wavelength λmax is 3.0 or more, preferably 3.5 or more, more preferably 4.0. That's it,
Further, the transmission density at the wavelength of the high-density energy light needs to be 3.0 or more per 1 μm of the film thickness. Further, a film thickness of 1 μm at the minimum transmittance wavelength λmin in the wavelength region.
The transmittance per m is 0.1% or less, preferably 0.05%
% Or less, further 0.03% or less. The image forming layer may be composed of a single layer or may be composed of multiple layers having different compositions.
In the case of a multilayer structure, it is preferable that a layer nearer to the support contains a larger amount of a coloring material capable of absorbing the wavelength light of the exposure light source. Further, a coloring material capable of absorbing light having a wavelength other than the wavelength of the exposure light source may be added to the layer farther from the support.

The image forming layer may contain additives such as a lubricant, a durability improver, a dispersant, an antistatic agent, a filler, and a filler, as long as the effects of the present invention are not impaired.

Examples of the lubricant include fatty acids, fatty acid esters, fatty acid amides, (modified) silicone oils, (modified) silicone resins, fluororesins, and carbon fluorides. Can be mentioned.

Examples of the dispersant include fatty acids having 12 to 18 carbon atoms such as lauric acid and stearic acid, and amides, alkali metal salts and alkaline earth metal salts thereof; polyalkylene oxide alkyl phosphates, lecithin, trialkyl Polyolefinoxy quaternary ammonium salts; azo compounds having a carboxyl group and a sulfone group; and the like. Examples of the antistatic agent include a cationic surfactant, an anionic surfactant, a nonionic surfactant, Polymer antistatic agents, conductive fine particles, etc.
0 Chemical Products ”, Chemical Daily, p. 875-876 and the like.

As the filler, carbon black, graphite, TiO ₂ , BaSO ₄ , ZnS, MgC
O ₃ , CaCO ₃ , ZnO, CaO, WS ₂ , MoS ₂ , M
gO, SnO ₂ , Al ₂ O ₃ , α-Fe ₂ O ₃ , α-FeO
OH, SiC, CeO ₂ , BN, SiN, MoC, B
Inorganic fillers such as C, WC, titanium carbide, corundum, artificial diamond, garnet, garnet, quartzite, triboli, diatomaceous earth, dolomite, polyethylene resin particles, fluororesin particles, guanamine resin particles, acrylic resin particles, silicon resin particles And organic fillers such as melamine resin particles, which may also serve as a release agent. These inorganic / organic resin particles differ depending on the specific gravity, but are preferably added in an amount of 0.1 to 70% by weight.

The image forming layer comprises, for example, a magnetic powder, a binder and, if necessary, a lubricant, a durability improver, a dispersant, an antistatic agent, a filler, a filler, a crosslinking agent and the like, and a solvent. Kneading, adjusting the high-concentration magnetic paint, then diluting this high-concentration magnetic paint into a magnetic paint for application,
It is formed by coating on a support and drying.

Solvents include alcohols (ethanol, propanol, etc.), cellosolves (methyl cellosolve, ethyl cellosolve), aromatics (toluene, xylene, chlorobenzene, etc.), ketones (acetone, methyl ethyl ketone, etc.), and ester-based solvents. Solvents (such as ethyl acetate and butyl acetate), ethers (such as tetrahydrofuran and dioxane), halogen solvents (such as chloroform and dichlorobenzene), and amide solvents (such as dimethylformamide and N-methylpyrrolidone) can be used. I can do it. The kneading and dispersing of the components of the image forming layer include a two-roll mill, a three-roll mill, a ball mill, a pebble mill, a cobol mill, a tron mill, a sand mill, a sand grinder, a Sqegvari attritor, a high-speed impeller disperser, a high-speed stone mill, and a high-speed impact mill. , Disperser, high-speed mixer, homogenizer, ultrasonic disperser, open kneader, continuous kneader and the like can be used.

The formation of the image forming layer on the support is preferably carried out by, for example, an extrusion-type extrusion coater.

In the present invention, when a magnetic powder is used as a coloring agent, it is preferable to apply a magnetic field after coating and before drying completely to orient the particles. In particular, in order to obtain a high-resolution image, it is preferable to orient the magnetic powder to easily control the cohesive force in the layer. The orientation treatment can be performed, for example, by applying a magnetic field by a horizontal orientation magnet, a vertical orientation magnet, or a non-oriented magnet after application, and then drying by blowing hot air from nozzles arranged above and below, and performing a calendering process. . By such processing, a high-resolution image can be obtained. The magnetic field from a horizontal orientation magnet, a vertical orientation magnet or a non-oriented magnet is 20 to
About 10,000 gauss, calendering conditions are usually about 50 to 140 ° C., and a linear pressure of 50 to 400 kg / c.
m, the conveying speed is 20 to 1000 m / min, and drying is preferably performed at a temperature of about 30 to 120 ° C. for about 0.1 to 10 minutes.

In the present invention, it is also preferable to carry out a calendering treatment in order to make the surface properties of the image forming layer smooth or uniform and to impart a lubricating property. Further, in the image forming layer of the present invention, when the content of the metal atom-containing particles is large, voids are easily generated in the image forming layer, and in such a case, such as a calendar process or a press process. It is preferable to reduce the gap by applying pressure, whereby the residual ratio of the portion where the exposed portion has been transferred to the layer to be transferred when image exposure is performed with high-density energy light can be reduced. Therefore, the calendar process is one of the important processes in the present invention. In order to reduce the residual ratio of the transferred image, it is preferable to perform the pressure treatment so that the porosity of the image forming layer is 30% or less, preferably 20% or less. The porosity can be measured by a mercury intrusion method using a porosimeter. The conditions for such a calendar process are:
For example, after the image forming layer is dried, the image forming material is guided to a super calender, and usually at about 50 to 140 ° C., at a linear pressure of 10 to 1000 kg / cm and a line speed of 1 to 10
It can be performed under conditions such as 00 m / min. Drying is preferably performed at a temperature of about 30 to 120 ° C. for about 0.1 to 10 minutes.

Next, the back layer of the image forming body of the present invention will be described.

An image forming body in which a constituent layer such as an image forming layer is provided on one side of the first support and a back layer such as an antistatic layer or an outermost layer is provided on the other side is formed by adhering to a transfer receiving body. Before being made into a material, it is subjected to a calendering process and then once wound up. When the image forming body is calendered, pressure is applied when the layer on the side of the image forming layer and the backing layer come into contact with an alternate calender cylinder. By applying a calendar, the surface on either side becomes smooth, so that it may stick to a calendar roll, block when rolled up, or when sheets are stacked, resulting in cuts. To prevent this blocking, a normal inorganic matting agent, for example, silica particles, was added, but as described above, the matting agent during calendering was crushed, desorbed, and the back surface and the image forming layer were damaged. The present inventors have intensively searched and examined matting agents and antistatic agents for problems such as scratches, dust adhesion, deterioration of antistatic performance, cracks, etc. As a result, they found excellent matting agents and antistatic agents and backed them up. The problem was solved by using it for the layer.

The present inventors, even when calendered, deform at that time, but after being calendered, they are restored to their original state, so that they do not crush and have excellent adhesion to the binder, so that they do not fall off or crush. An excellent matting agent for fine fiber particles was found. By using these fiber fine particles in the outermost layer, it is possible to prevent the occurrence of cracks on the calender roll due to the calendering process, provide excellent slipperiness, and produce a very outstanding effect of not damaging the back surface as well as the image forming layer. I understand.

The fibers in the fine fiber particles of the present invention include, in addition to the fibers, fibrous substances in the form of fibers. As the fiber used for the fiber fine particles of the present invention, almost any fiber such as natural fiber, semi-synthetic fiber, regenerated fiber or synthetic fiber can be used, and in addition, fibrous substances of outer hair and leather of animals are also included. . Fibers generally referred to as natural fibers include plant fibers and animal fibers, and plant fibers include any natural fibers obtained from wood fibers, stem stem fibers, vein fibers, bast fibers, seed fibers, and the like. Cellulose fibers can be used. For example, cotton, linter, hemp, mulberry,
Kozo, Mitsumata, etc. can be mentioned. Regenerated fibers from natural fibers include rayon fiber, cupra fiber (trade name of Asahi Kasei Corporation), Tencel or Dexel fiber (trade name of Coatles), and semi-synthetic fibers such as cellulose acylate and cellulose ether. Fibers and the like can be mentioned, as cellulose acylate fibers, cellulose triacetate, cellulose diacetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose cellulose benzoate,
Examples of fibers made from cellulose acetate benzoate or the like and cellulose ether fibers include cellulose acetate propionate and cellulose ether fiber made from cellulose phenyl ether, cellulose benzyl ether and the like. Examples of the synthetic fiber include vinylon, nylon, polyester fiber having a hydrophilic group, polyimide or polyamide having a hydrophilic group, and polyacryl fiber having a hydrophilic group. Animal fibers include silk and silk (fibroin) fibers from silkworms and wild silkworms (eg, cocoon, tussah or Eri silkworm), wool, cashmere hair fibers, camel hair fibers, and goat hair fibers. And fibers from animal hair, such as alpaca hair fibers, and fibrous substances forming animal skin. Examples of the fibers mentioned here are not limited to these.

Of these, particularly preferred fibers are silk and silk fibers, and more preferably, silk from silkworms having a pure white luster. Silk fiber (fibroin) has a specific triangular cross-sectional shape, and the fiber itself has a very high affinity for gelatin, and it can be easily fixed in a gelatin binder moderately, it is white, water-absorbing and It is most preferably used because it has excellent moisture release properties and is easily obtained as silk powder (silk powder). Of course, other silks are also preferably used.

As for other animal fibers, the hair fibers of the above-mentioned animals such as wool are used as fibers after degreasing or decoloring. Further, a fibrous substance forming a skin, that is, a collagen fiber is also preferably used. Collagen fiber is a precursor of gelatin for the binder used in the present invention and has an excellent affinity for gelatin. Cattle, pigs,
Herbivore animals such as sheep, horse camels and deer are preferred.

Triangular, square, polygonal, star-shaped, irregular shapes and hollow fibers can be obtained from synthetic fibers, semi-synthetic fibers or regenerated fibers by modifying the cross-sectional shape of the nozzle of the spinning die. Fibers which are said to have a good hand when formed into yarn or woven fabric are preferred in the present invention. Further, the surface of the fiber can be made scaly like wool, and such a fiber is preferable because it is easily fixed in a binder.

The fiber fine particles of the present invention have a moisture absorption of 20 ° C.
3.0% to 20% at 5% RH, or 20 ° C, 95% R
H is preferably 8 to 40%, and a moisture absorption similar to that of the binder is preferred because it is easily compatible with the binder and hardly desorbs. Note that the hygroscopicity in the present invention is the same as that of a normal sample. From the weight A of the sample in the atmosphere and the dry weight B of the sample, the hygroscopicity (%) = {(AB) / B} × 100 expressed.

The fiber fine particles of the present invention are produced as follows. First, when there is fat contained in the fiber, degreasing is performed with an alkali or another degreasing agent, and when coloring is extreme, bleaching is performed with a bleaching agent or the like. It is also important to take out the fiber, and the way to take out the fiber depends on the fiber source.

For example, in the case of silk, in the same manner as in a method of taking out raw silk from a normal cocoon, the cocoon is boiled to find a clue of one cocoon and taken out. Fibroin (fiber) is taken out by dissolving and removing sericin while boiling in hot soapy water, since it consists of fiber and sericin wrapping it.

For other animal fibers, the skin may be subjected to lime treatment or acid treatment to separate collagen fibers, or the treated skin may be used as it is. The hair protein is made of keratin, has a fibrous shape, and can be used as it is. The hair is as thin and soft as possible,
Although the white hair can be used by pulverizing it as it is, it is preferable to perform bleaching with a bleaching agent and degreasing with an alkali or the like as described above.

For natural fibers other than cotton and linter, the raw material is immersed in water or hot water, and the skin is separated and taken out while tapping, and if necessary, bleached or the resin content contained in the bark is treated with water for a long time. Exposure or removal.

The fine particles of the silk fiber of the present invention will be described. The fine particles of the silk of the present invention are disclosed in JP-A-8-113714.
The method can be performed by the method described in Japanese Patent Application Laid-Open Publication No. HEI 10-76, pp. A first crushing means for crushing silk fibroin into coarse powder by dry mechanical crushing means, a second crushing means for crushing silk fibroin coarse powder to fine powder by dry mechanical crushing means, and a fine powder of silk fibroin. With an average particle size of 10 μm by dry mechanical grinding means.
Pulverization is performed through the following pulverization step of pulverization into ultrafine powder. The average particle size of the coarse powder is about 100 μm. As the mechanical pulverizing means used in the coarse powder step, any means can be used as long as it can be pulverized, but a rotary mill is preferred. As the second mechanical pulverizing means, a ball mill is preferable, and as the third mechanical means, a jet mill is preferable. It is preferable to make the particles finer in this manner as a means for forming fine particles. In addition, a vibrating mill, a planetary mill, a sand mill, a colloid mill, or the like may be used according to each means. The number of steps of these means is not limited to three, but may be any number. It is preferable to perform the β treatment after any of the mechanical pulverizing means, but it may be performed twice or more. It is said that fibroin generally has a β structure as a secondary structure, but by increasing the proportion of the β structure, fibroin powder can be converted to an organic solvent such as methanol, ethanol, or acetone. By dipping, the β structure can be effectively increased. By performing this process, 70%
As described above, crystallization can be increased, and dispersibility can be improved. As a result, properties such as moisture absorption, moisture release, antistatic performance, and moisture permeability specific to silk are obtained.

The fine powderization of the fiber of the present invention can be carried out in the same manner as the above-mentioned fine powdering of silk (except for β-forming).

The average particle size of the fiber fine particles of the present invention is 20 μm.
Below, it is preferably 0.4 to 10 μm. The particle size can be controlled by adjusting the above three stages by the time and strength, and by adjusting the number of stages, and these three stages of pulverizing means may be properly used.

The amount of the fiber fine particles of the present invention is from 1 to 200.
0 mg / m ² is preferred.

As the binder forming the outermost layer containing the fine fiber particles, any ordinary binder can be used without limitation as long as the effects of the present invention are not impaired.
C. or higher, especially 55.degree. C. or higher is preferred. Tg is 50
By using a binder above ℃ for the outermost layer,
The sticking to the calender roll due to the calendering treatment is less likely to occur, and cracks are less likely to occur.
In particular, these effects are remarkably improved by combining with fiber fine particles as a matting agent. The type of binder in the outermost layer may be selected according to the type of binder used in the layer below.

In the present invention, if a binder having a Tg of 50 ° C. or higher is contained as a mixture, either in the form of a copolymer or in the form of a copolymer, the binder hardly sticks to the metal roll (cylinder) of the calender during calendering. Calendar processing can be performed. In addition, Tg is obtained by DSC measurement.

As the binder for the outermost layer, the following resins having excellent layer forming properties are preferably used. For example, melamine resin, phenol resin, acrylic resin, urethane resin, alkyd resin, epoxy resin, polyacetal,
Examples thereof include polyarylate, polyimide, polyester, and polyolefin. One or more of these resins selected as appropriate can be used in combination. Among these, acrylic resins, polyolefin resins, polyester resins, carbonate resins, urethane resins, epoxy resins, and polyvinyl chloride resins can also be preferably used. Also rosin,
Natural products such as shellac and derivatives thereof can also be used. Acrylic resins and polyolefin resins are obtained, for example, by polymerizing monomers selected in any combination from styrene, styrene derivatives, alkyl acrylates, alkyl methacrylates, olefin derivatives, halogenated ethylene derivatives, vinyl ester derivatives, acrylonitrile, and the like. Styrene derivative, alkyl acrylate, alkyl methacrylate,
It is preferably contained at 0 mol%. Especially 50 mol%
The above is preferred.

The outermost layer of the present invention can be formed by applying these resins as a coating solution in the form of a latex. Specific examples of these resins will be shown.

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Further, an aqueous polyester can be preferably used as a binder for forming the outermost layer of the present invention. Here, the aqueous polyester refers to a polyester dissolved or dispersed in water. Examples of such aqueous polyesters include, for example, U.S. Pat. Nos. 4,252,885, 4,241,169, 4,394,442, EP 29,620, 78,559, and Water-based polyesters described in JP-A-54-43017 and Research Disclosure 18928 can be exemplified.

The aqueous polyester used in the outermost layer of the present invention will be further described. Examples of the aqueous polyester include a substantially linear polymer obtained by a polycondensation reaction between a polybasic acid or an ester-forming derivative thereof and a polyol or an ester-forming derivative thereof.

As a basic skeleton of the polyester, polybasic acid components include, for example, terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, 2,6-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid , Adipic acid, sebacic acid, trimellitic acid, pyromellitic acid and dimer acid can be used, together with these components unsaturated polybasic acids such as maleic acid, fumaric acid, itaconic acid and p-hydroxybenzoic acid, p- Hydroxycarboxylic acids such as (β-hydroxyethoxy) benzoic acid can be used in small proportions.

Among the above, as the polybasic acid component, those having terephthalic acid and isophthalic acid as the main dicarboxylic acid components are preferable, and the ratio of terephthalic acid and isophthalic acid to be used is preferably 30/70 to 70/70 in molar ratio. 3
A value of 0 is particularly preferred in view of coatability on a polyester support and solubility in water. Further, it is preferable that the terephthalic acid component and the isophthalic acid component are contained in an amount of 50 to 80 mol% based on the total dicarboxylic acid components.

In order to impart water solubility to the polyester, a component having a hydrophilic group, for example, a component having a sulfonate, a diethylene glycol component, a polyalkylene ether glycol component, a polyether dicarboxylic acid component, and the like are commonly used in the polyester. It is an effective means to introduce as a polymerization component. In particular, it is preferable to use a dicarboxylic acid having a sulfonic acid salt as the component having a hydrophilic group.

The dicarboxylic acid having a sulfonic acid salt is particularly preferably a dicarboxylic acid having an alkali metal sulfonic acid group, for example, 4-sulfoisophthalic acid and 5-sulfonic acid.
Examples thereof include alkali metal salts such as sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, and 5- (4-sulfophenoxy) isophthalic acid.
-Sulfoisophthalic acid sodium salt is particularly preferred. These dicarboxylic acids having a sulfonic acid salt are preferably used in the range of 5 to 15 mol%, particularly in the range of 6 to 10 mol% based on the total dicarboxylic acid component from the viewpoint of water solubility and water resistance.

For a water-soluble polyester using terephthalic acid and isophthalic acid as main dicarboxylic acid components, it is preferable to use an alicyclic dicarboxylic acid as a copolymerization component. Examples of these alicyclic dicarboxylic acids include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid,
4,4'-bicyclohexyldicarboxylic acid can be mentioned.

Further, in water-soluble polyesters using terephthalic acid and isophthalic acid as main dicarboxylic acid components, other dicarboxylic acids other than those described above can be used as copolymer components. As these dicarboxylic acids, for example,
Aromatic dicarboxylic acids and linear aliphatic dicarboxylic acids are exemplified. The aromatic dicarboxylic acid is preferably used within a range of 30 mol% or less of the total dicarboxylic acid component. Examples of the aromatic dicarboxylic acid component include phthalic acid, 2,5-dimethylterephthalic acid, 2,6-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, and biphenyldicarboxylic acid. Further, the linear aliphatic dicarboxylic acid is preferably used within a range of 15 mol% or less of all dicarboxylic acid components. Examples of these linear aliphatic dicarboxylic acid components include adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid.

Examples of the polyol component include ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, dipropylene glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, xylylene glycol, Methylol propane, poly (ethylene oxide) glycol, and poly (tetramethylene oxide) glycol can be used.

As the glycol component of the water-soluble polyester, ethylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, diethylene glycol, triethylene glycol and polyethylene glycol are preferred.

When the water-soluble polyester is one using terephthalic acid and isophthalic acid as the main dicarboxylic acid components, use a water-soluble polyester having ethylene glycol of 50 mol% or more of the total glycol component as the glycol component. Is preferable from the viewpoint of mechanical properties and adhesion to the polyester support.

The water-soluble polyester can be synthesized using dicarboxylic acid or its ester-forming derivative and glycol or its ester-forming derivative as starting materials. Various methods can be used for the synthesis.For example, a precondensate of a dicarboxylic acid and a glycol is formed by a transesterification method or a direct esterification method, and is obtained by a known polyester production method of melt-polymerizing this. I can do it.

More specifically, for example, a transesterification reaction is carried out between an ester of a dicarboxylic acid, for example, a dimethyl ester of a dicarboxylic acid, and a glycol, and methanol is distilled off. A method of performing polycondensation, performing an esterification reaction of dicarboxylic acid and glycol, distilling off generated water, gradually reducing the pressure, and performing a polycondensation under high vacuum, a method of performing polycondensation with an ester of dicarboxylic acid and glycol. Perform a transesterification reaction, and further,
After the esterification reaction is performed by adding a dicarboxylic acid, a method of performing polycondensation under a high vacuum may be used.

As the transesterification catalyst and polycondensation catalyst, known catalysts can be used. Transesterification catalysts include manganese acetate, calcium acetate, zinc acetate and the like, and polycondensation catalysts include antimony trioxide and germanium oxide. , Dibutyltin oxide, titanium tetrabutoxide and the like can be used. However, various conditions such as a polymerization method and a catalyst are not limited to the above examples.

Here, specific examples of the aqueous polyester copolymer will be described, but the present invention is not limited thereto.

[Aqueous polyester copolymer dispersion (A)
Preparation] 34.02 parts by weight of dimethyl terephthalate, 25.52 parts by weight of dimethyl isophthalate, 12.97 parts by weight of dimethyl 5-sulfoisophthalate sodium salt, 47.85 parts by weight of ethylene glycol, 1,4-cyclohexanedimethanol 18.95 parts by weight, calcium acetate-water salt 0.065 parts by weight, and manganese acetate tetrahydrate 0.022 parts by weight were subjected to transesterification while distilling off methanol at 170 to 220 ° C. under a nitrogen stream. , 0.04 part by weight of trimethyl phosphate, 0.04 part by weight of antimony trioxide as a polycondensation catalyst and 15.08 parts by weight of 1,4-cyclohexanedicarboxylic acid were added at a reaction temperature of 220 to 235 ° C. Water was distilled off and esterification was performed. Thereafter, the pressure inside the reaction system was further reduced and the temperature was increased over about 1 hour, and finally polycondensation was performed at 280 ° C. and 1 mmHg or less for about 1 hour to produce an aqueous polyester copolymer. The mixture was stirred and dispersed in pure water at 95 ° C. for 17 hours to obtain an aqueous polyester copolymer dispersion (A) (solid content: 1
2%). The polyester copolymer of this dispersion is referred to as an aqueous polyester copolymer (A).

[Aqueous polyester copolymer dispersion (B)
Preparation of acid components] naphthalenedicarboxylic acid 40% by weight, isophthalic acid 33% by weight, sulfoisophthalic acid 7
Aqueous polyester copolymer was prepared according to a standard method using 100% by weight of ethylene glycol as a diol component, 10% by weight of cyclohexanedicarboxylic acid, and 10% by weight of acrylic acid as a diol component, and the obtained copolymer was purified with 95 ° C pure water. 17
The mixture was stirred and dispersed over time to obtain an aqueous polyester copolymer dispersion (B) (solid content: 12%). The polyester copolymer of this dispersion is referred to as an aqueous polyester copolymer (B).

[Aqueous polyester copolymer dispersion (C)
Preparation of an aqueous polyester copolymer according to a standard method using 93% by weight of naphthalenedicarboxylic acid, 7% by weight of sulfoisophthalic acid as an acid component, and 100% by weight of ethylene glycol as a diol component. The mixture was stirred and dispersed in pure water at 95 ° C. for 17 hours to obtain an aqueous polyester copolymer dispersion (C) (solid content: 12%).
The polyester copolymer of this dispersion is referred to as an aqueous polyester copolymer (C).

As the binder of the outermost layer of the present invention, FPY6762, MPS7762, manufactured by Eastman Chemical Co., Ltd.
WD3652, WTL6342, WNT9519, WM
S5113, WD SIZE, WNT, WHS (all are trade names) and the like can be used.

Further, as a preferable binder used in the outermost layer of the present invention, a polyester modified with a vinyl monomer can be mentioned.

[0096] The term "modified" as used herein means a dispersion of a vinyl monomer in an aqueous solution of a water-soluble polyester, and the dispersion is obtained, for example, by dissolving a water-soluble polyester in hot water. It can be obtained by dispersing a vinyl monomer in an aqueous solution of a water-soluble polyester and subjecting it to emulsion polymerization or suspension polymerization. The polymerization is preferably by emulsion polymerization.

For the modification of the vinyl monomer, a polymerization initiator is used, and examples thereof include ammonium persulfate, potassium persulfate, sodium persulfate, and benzoyl peroxide. Of these, ammonium persulfate is preferred.

The polymerization can be carried out without using a surfactant, but it is also possible to use a surfactant as an emulsifier for the purpose of improving polymerization stability. In this case, a general nonionic or anionic surfactant can be used.

As the vinyl monomer used for the modification, an acrylic monomer such as CH ₂ ＣC (R) COO
R in R 'is a hydrogen atom or a methyl group, R' is a hydrogen atom,
Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-
Ethylhexyl group, cyclohexyl group, phenyl group, benzyl group, phenylethyl group, 2-hydroxyethyl group, 2-hydroxypropyl acrylate, 2-hydroxypropyl group, N, N-diethylaminoethyl group, glycidyl group, alkali metal, ammonium group Etc .; CH ₂
R in C (R) CON (R ', R ") is a hydrogen atom or a methyl group; R' and R" are hydrogen atoms, together or separately;
Methyl group, ethyl group, propyl group, butyl group, cyclohexyl group, methylol group, dimethylol group, methoxymethyl group, phenyl, benzyl group, phenethyl group and the like; and monomers other than acrylic monomers include, for example, allyl glycidyl ether Monomers containing sulfonic acid groups or salts thereof, such as styrene sulfonic acid, vinyl sulfonic acid and salts thereof (sodium salt, potassium salt, ammonium salt, etc.);
Monomers containing carboxyl groups or salts thereof such as crotonic acid, itaconic acid, maleic acid, fumaric acid and salts thereof (sodium salt, potassium salt, ammonium salt, etc.); acid anhydrides such as maleic anhydride and itaconic anhydride A monomer containing: vinyl isocyanate; allyl isocyanate; styrene; vinyl trisalkoxysilane;
Alkyl maleic acid monoester; alkyl fumaric acid monoester; acrylonitrile; methacrylonitrile; alkyl itaconic acid monoester; vinylidene chloride; vinyl acetate; The amount of the vinyl monomer used is preferably such that (water-soluble polyester) / (vinyl monomer) is in a weight ratio of 99/1 to 5/95, and 97/3 to 50/50. More preferably, it is in the range of 95/5 to 80/20.

Specific examples of the modified aqueous polyester copolymer will be described, but the present invention is not limited thereto.

[Preparation of Modified Aqueous Polyester Copolymer Dispersion (D)] 30 g of styrene, 30 g of butyl methacrylate, 20 g of glycidyl methacrylate, 20 g of acrylamide and 20 g of ammonium persulfate were added to 3300 g of the aqueous polyester copolymer dispersion (A). 0 g was added and reacted at 80 ° C. for 5 hours, cooled to room temperature, the solid content was adjusted to 12% by weight, and this modified aqueous polyester copolymer dispersion (D) was prepared. The modified polyester copolymer of this dispersion is referred to as a modified aqueous polyester copolymer (D).

The type of the modified aqueous polyester copolymer and the type of the vinyl monomer to be modified can be changed in any manner and can be used without any limitation as long as the object of the present invention can be achieved.

The polymer or copolymer used for the image forming layer can be used for the outermost layer.

The thickness of the outermost layer is preferably in the range of 0.01 to 10 μm, particularly preferably in the range of 0.1 to 3 μm.

It is preferable that the back layer of the image forming material of the present invention has the outermost layer and at least one layer has an antistatic layer containing a conductive antistatic agent of fine metal oxide particles.
This antistatic layer may be present in any of the back layers, but is preferably a layer adjacent to the support or an outermost layer. The former is preferable for preventing adhesion of foreign substances such as dust in the manufacturing stage, and the latter is preferable in that it is easy to prevent static electricity in the manufacturing stage as well as in the use stage. In the present invention, there is a heating treatment and a pressure treatment such as a calendering treatment, and an antistatic agent that does not deteriorate the conductivity even under these conditions is required, but the metal oxide fine particles used in the present invention are as described above. As strong as heat,
It has been found that deterioration of conductivity due to heat is small.

The antistatic agent of the metal oxide fine particles used in the present invention is a conductive metal oxide fine particle, for example, an unstable metal such as an oxygen-deficient oxide, a metal-rich oxide, a metal-deficient oxide, or an oxygen-rich oxide. Metal oxide particles that easily form a specific compound can be used. Among them, the most preferable compounds for the present invention are metal oxide fine particles which can be produced in various manners by using various methods. As the metal oxide fine particles, crystalline metal oxide particles are generally used, for example, ZnO, Ti
O ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , Mg
O, B ₂ O, MoO ₃ and their composite oxides can be mentioned, and among them, ZnO, TiO ₂ and SnO ₂ are particularly preferable. Examples of the composite oxide include Al and In for ZnO, and Nb and TiO2 for TiO ₂ .
For SnO ₂ such as Ta, those containing 0.01 to 30 mol% of different elements of Sb and Nb halogen elements are preferable,
In particular, those containing 0.1 to 10 mol% are preferable. It is preferable to use a compound having oxygen vacancies in the crystal and a small amount of a different kind of atom serving as a so-called donor to the metal oxide because conductivity is improved. Details of the method for producing such conductive metal oxide fine particles are described in, for example,
No. 143430. However, such crystalline fine particles have high conductivity, but it is necessary to consider the particle diameter and the ratio of particles / binder to light scattering, etc., and there is deterioration of haze, and it is difficult to disperse. It is more preferable to use an inorganic colloid existing in a colloidal form in water. The term "inorganic colloid" as used herein is defined in the Kyoritsu Shuppan Co., Ltd. Chemical Dictionary, and contains 10 ⁵ to 10 ⁹ atoms per particle. Depending on the element, it can be obtained as a metal colloid, an oxide colloid, or a hydroxide colloid. As the metal colloid, gold, palladium, platinum, silver, sulfur and the like are preferably used. As the metal oxide colloid, metal hydroxide colloid, carbonate colloid and sulfate colloid, Z
n, Mg, Si, Ca, Al, Sr, Ba, Zr, T
Colloids of metal oxides such as i, Mn, Fe, Co, Ni, Sn, In, Mo and V, metal hydroxide colloids, carbonate colloids and sulfate colloids are preferably used in the present invention. Particularly, ZnO, TiO ₂ and SnO ₂ are preferable,
Further, SnO ₂ is particularly preferred. Further, as an example of doping with different atoms, for ZnO, Al, In, etc.
Nb, Ta, etc. for iO ₂ , S for SnO ₂
b, Nb, a halogen element and the like. The average particle size of the inorganic colloid particles is preferably from 0.001 to 1 μm from the viewpoint of dispersion stability.

The metal oxide colloid used in the present invention,
In particular, with respect to a method for producing a colloidal SnO ₂ sol composed of stannic oxide, a method of dispersing SnO ₂ ultrafine particles in an appropriate solvent or a method of dispersing a tin compound soluble in a solvent in a solvent is employed. Any method may be used.

Regarding the method for producing ultrafine particles of SnO ₂ , temperature conditions are particularly important, and a method involving a high-temperature heat treatment is not preferable because it causes a phenomenon in which primary particles grow and the crystallinity increases. If it is necessary to do so, it should be done at 300 ° C. or lower, preferably 200 ° C. or lower, more preferably 150 ° C. However, 25 ° C-1
Heating to 50 ° C. is a means that is suitably selected when dispersion in the binder is considered.

Further, with the recent advance in powder manufacturing technology, a method of spraying a compound manufactured by a wet method into an electric furnace and a method of high-temperature pyrolysis of an organometallic compound have been developed for manufacturing ultrafine particles. However, redispersion of ultrafine particles produced by such a method in a solvent involves considerable difficulty and is not economically preferable, and when applied to a silver halide photographic light-sensitive material such as generation of aggregated particles. Can cause serious defects. For this reason, the method of redispersing in a solvent after the production process of isolating only the metal oxide fine particles is not employed when used as a photographic antistatic agent. However, the binder and SnO ₂
When the compatibility of the sol with the solvent is poor, the solvent needs to be replaced. In such a case, an appropriate amount of another compound having good compatibility or dispersion stability with the solvent of the SnO ₂ sol is added, and SnO _{2 is} added. The SnO ₂ ultrafine particles and the compound added in an appropriate amount from the sol are dried and separated by heating at 300 ° C. or less, preferably 200 ° C., more preferably 150 ° C. or less, and then redispersed in another solvent.

A method for producing a Sn compound soluble in a solvent from a decomposition reaction in the solvent will be described below.
Examples of the tin compound soluble in a solvent include a compound containing an oxo anion such as K ₂ SnO ₃ .3H ₂ O, a water-soluble halide such as SnCl ₄ , R ′ ₂ SnR ₂ , R ₃ SnR ₂ , R _Three
A compound having the structure of SnX, R ₂ SnX ₂ (where R and R ′ represent an alkyl group), for example, (CH ₃ ) ₃
SnCl. (Pyridine), (C ₄ H ₉ ) ₂ Sn (O ₂ CC ₂
H _{5) 2,} such as an organometallic _{compound, Sn (SO 4) 2 ·} 2H 2 O
And the like. As a method for producing a SnO ₂ sol using a Sn compound soluble in these solvents, a physical method such as heating and pressurization, a chemical method such as oxidation, reduction, hydrolysis, or the like, after dissolving in a solvent, or There is a method of producing a SnO ₂ sol after passing through an intermediate. To describe a method for manufacturing a SnO ₂ sol described in Japanese Patent Publication 35-6616 discloses as an example, the SnCl ₄ 100
Dissolve in twice the volume of distilled water to form a precipitate of stannic hydroxide as an intermediate. Ammonia water is added to the stannic hydroxide to make it slightly alkaline and dissolved. Then, the mixture is heated until the smell of ammonia disappears, whereby a colloidal SnO ₂ sol is obtained. In this example, water was used as the solvent, but methanol, ethanol, alcohol solvents such as isopropanol, tetrahydrofuran, dioxane, ether solvents such as diethyl ether, hexane, aliphatic organic solvents such as heptane, benzene, pyridine and the like. Various solvents such as aromatic organic solvents can be used depending on the Sn compound, and the present invention is not particularly limited with respect to the solvent.
Preferably, solvents such as water and alcohols are selected. In a method for producing from a decomposition reaction of a Sn compound soluble in a solvent in a solvent, Sn which is soluble in the solvent during the process is used.
It is also possible to add a compound containing an element other than. For example, addition of a fluorine-containing compound that is soluble in a solvent or addition of a metal compound that can take a trivalent or pentavalent coordination number that is soluble in a solvent. The fluorine-containing compound soluble in the solvent may be either ionic fluoride or covalent fluoride. For example, HF or metal fluorides such as KHF ₂ , SbF ₃ , MoF ₆ , N
Compounds that generate fluoro complex anions such as H ₄ MnF ₃ and NH ₄ BiF ₄ , inorganic molecular fluorides such as BrF ₃ , SF ₄ and SF ₆ , CF ₃ I, CF ₃ COOH, P (CF ₃ ) ₃ And the like, but when the solvent is water, like the combination of CaF ₂ and sulfuric acid,
Combinations of fluorine containing compounds and non-volatile acids can also be used. A metal compound that can take a trivalent or pentavalent coordination number that is soluble in a solvent is a group III element such as Al, Ga, In, or Tl, or a V compound such as P, As, Sb, or Bi.
Group elements, Nb capable of taking a trivalent or pentavalent coordination number,
A group of compounds containing transition metals such as V, Ti, Cr, Mo, Fe, Co, and Ni.

As the binder for the antistatic layer of the present invention, gelatin as used in ordinary silver halide photographic materials can be preferably used. As gelatin,
Gelatin produced by calcination of alkali-treated gelatin, acid-treated gelatin, enzyme-treated gelatin, or the like of ossein, pigskin, calfskin or the like can be used. Derivative gelatin obtained by modifying the functional group of gelatin with a reactive compound, such as phthalated gelatin, acetyl gelatin methyl ester gelatin, propyl ester gelatin, and the like can also be used. Examples of the water-soluble polymer that can be mixed with gelatin or used alone include, for example, hydroxyethyl cellulose, sodium carboxymethyl cellulose, cellulose derivatives such as cellulose sulfate, starch derivatives, polyvinyl alcohol, poly-N-vinyl pyrrolidone, poly Acrylamide or a derivative thereof, and a partial hydrolyzate, polyvinyl acetate, polyacrylonitrile, polyacrylic acid and sodium salt, polyvinyl imidazole,
Sodium alginate, dextrin, dextran,
Cyclodextrin, chitantan gum, carrageenan,
Pectin, glycogen and the like can be mentioned.

The same binder as the image forming layer or the outermost layer can be used. Of these binders, a latex-like vinyl copolymer and an aqueous polyester copolymer are preferable.

Copolymers of styrene and other monomers, copolymers of butadiene and other monomers, copolymers of acrylamide and other monomers, acrylonitrile and other monomers Copolymer of alkyl (meth) acrylate and other monomer, copolymer of hydroxyalkyl (meth) acrylate and other monomer, glycidyl (meth)
Copolymer of acrylate and other monomer, copolymer of vinyl acetate and other monomer, copolymer of vinyl chloride and other monomer, vinylidene chloride and other monomer Emulsion polymers such as copolymers, carbonates, polyesters,
Epoxy resins and resins such as organic semiconductors such as polypyrrole can also be used. These binders can be used as a mixture of two or more kinds. Of these, from the viewpoint of ease of handling during production and performance of products, particularly, copolymers of acrylamide and other monomers, acrylonitrile and other copolymers, and alkyl (meth) acrylate and other Copolymers with monomers, copolymers with hydroxyalkyl (meth) acrylate and other monomers, copolymers with glycidyl (meth) acrylate and other monomers, vinyl acetate and other monomers Emulsion polymers, such as copolymers with monomers, copolymers with vinyl chloride and other monomers, copolymers with vinylidene chloride and other monomers, and carbonate-based and polyester-based resins are preferred.

When the antistatic layer of the present invention is adjacent to the first support, a compound which swells or dissolves the first support may be used in order to make the antistatic layer adhere well to the support. You may make it contain. Compounds that swell or dissolve the first support include, for example, resorcinol, chlorresorcinol, methylresorcinol, o-cresol,
m-cresol, p-cresol, phenol, o-chlorophenol, p-chlorophenol, dichlorophenol, trichlorophenol, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluorochloroacetic acid, chloral hydrate and the like. Can be preferably used, but resorcinol and p-chlorophenol are particularly preferred. The amount of the compound that swells the first support is suitably from 0.01 to 5.0 g / m ² , and preferably from 0.05 to 1.0 g / m ² , as a coating amount.

The solvent for applying the coating solution for the antistatic layer is preferably selected from those suitable for the kind of the binder used.

It is preferable that a hardener is added to the antistatic layer of the present invention and the outermost layer to cure the layer. As the hardening agent, any hardening agent capable of hardening by reacting with a binder can be used without any limitation. Examples of such hardening agents include aldehyde-based hardening agents and aziridine-based hardening agents (for example, PB Report, 19921, U.S. Pat. Nos. 2,950,197, 2,964,404, 2,983,611 and 3,271,175, and JP-B-46-175.
40898 and JP-A-50-91315), isoxazoles (for example, those described in U.S. Pat. No. 3,331,609), and epoxy-based (for example, U.S. Pat. No. 3,047,394,
German Patent 1,085,663 and British Patent 1,0
Nos. 33,518 and JP-B-48-3549.
5, JP-A-9-311400, and JP-A-9-281650
Publication), vinyl sulfones (for example, P
B report 19,920, West German patent 1,100,94
No. 2, No. 2,337,412, No. 2,545,7
No. 22, No. 2,635,518, No. 2,742,
No. 308, No. 2,749,260 and British Patent No. 1,251,091;
Nos. 3563 and 48-110996, and U.S. Pat. Nos. 3,539,644 and 3,491,911.
Acryloyl series (for example, JP-B-53-778 and U.S. Pat. No. 3,643).
0,720), carbodiimide-based (for example, U.S. Pat. Nos. 2,938,892, 4,
Nos. 043,818 and 4,061,499), triazines (for example, West German Patent Nos. 2,410,973, 2,553,915 and U.S. Pat. , 325, 287, and further, those described in JP-A-51-2722), oxazoline-based compounds (for example, those described in JP-A-5-295275), and high molecular type (for example, UK) Patent No. 822,061
Nos. 3,623,878 and 3,39.
6,029 and 3,226,234, JP-B-47-18578, JP-B-47-18579 and JP-B-47-48896), isocyanates, polyamide- Epichlorohydrin resins (for example, those described in JP-A-51-3619), compounds having a reactive halogen, and other hardening agents of maleimide type, acetylene type, methanesulfonic acid ester type and N-methylol type. I can do it. A hardener that can be preferably used for these antistatic layers is an epoxy hardener. Specific examples are shown below, but are not limited thereto.

[0117]

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[0118]

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[0119]

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[0120]

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By hardening the binder of the antistatic layer using the metal oxide fine particles of the present invention using an epoxy hardener, it is possible to further prevent the deterioration of the conductivity after the calendering treatment, and to obtain an excellent effect. Can be demonstrated.

The resistance value of the antistatic layer in the present invention is 1
It is preferably in the range of 0 ¹ to 10 ¹⁰ Ω · cm, and can be easily adjusted by adjusting the volume content of the metal oxide fine particles in the antistatic layer or the thickness of the antistatic layer. The ratio of the metal oxide fine particles to the binder is 30 to 90% by volume content, more preferably 50 to 8%.
0%, and the amount of the metal oxide fine particles used is 0.05 to
5.0 g / m ^2, preferably from 0.1 to 2.0 g / m ^2.

The method for providing the constituent layers of the image forming layer and the back layer is not particularly limited, and any method can be selected from known methods. The coating and drying may be repeated for each layer, but it is also preferable that the coating and drying are performed in a multi-layered manner by a wet-on-wet method. In that case, reverse roll, gravure roll, air doctor coater, blade coater, air knife coater, squeeze coater, impregnation coater, bar coater, transfer roll coater, kiss coater, cast coater or spray coater or the like can be applied by a combination with an extrusion coater. I can do it.

In the multi-layer coating in the wet-on-wet system, the upper layer is coated while the lower layer is kept wet, so that the adhesion between the upper and lower layers is improved. In particular, it is preferable to perform simultaneous multi-layer coating with the back layer coating solution.

In coating, known coating aids such as saponin and dodecylbenzene sulfonic acid, a hardener, a heat ray cutting agent and the like can be appropriately added to the coating liquid as required.

In order to improve the adhesiveness between the first support and the antistatic layer of the present invention, before providing an undercoat layer between the first support and the antistatic layer, the surface of the support may be corona-coated. It is preferable to perform discharge treatment, glow discharge treatment, UV irradiation treatment, flame treatment, or the like. An undercoat layer may be provided without treatment or after these treatments. The presence of the antistatic layer adjacent to the first support of the present invention means that these treatments or the subbing layer provide the adhesion of the antistatic layer. It does not disturb the will of neighbors.

The number of constituent layers of the back layer of the image forming material of the present invention may be any number as long as the effects of the present invention are not impaired. However, from the viewpoint of productivity and cost, 1 to 3 layers are preferable, and 2 layers are particularly preferable. Layers are preferred. It may also serve as the antistatic layer and the outermost layer,
It may have two or more antistatic layers. In the case of three layers, an intermediate layer having another special function may be provided. The thickness of the back layer is 0.05 to 10 μm, preferably 0.1 to 5 μm.
μm.

Next, a method of forming an image on the transfer object and the image forming material will be described.

The method of forming an image according to the present invention will be briefly described. The image forming layer of the image forming material is exposed to high-density energy light in an imagewise manner, and the first portion of the exposed portion of the image forming layer is exposed.
The method is to reduce the adhesive force of the image forming body and the transfer-receiving member, thereby forming a transfer image on the transfer-receiving layer. Here, the transfer object is mainly composed of the second support and the transfer layer.

[0130] The transfer object has a number of forms, and mainly includes one having a second support and a transfer layer, one having a second support, a transfer layer and an adhesive layer, and heat sealability. There is a substrate having a support, etc., and a back layer of the object to be transferred on the side opposite to the transfer side, for example, a substrate having antistatic performance.

Since the present invention is outside the improvement of the present invention, it will be briefly described. These contents are described in JP-A-8-3.
Reference can be made to the description of Japanese Patent No. 37053 or No. 9-15849.

As the second support of the object to be transferred of the photothermographic material of the present invention, a sheet or a film stretched and heat-set is preferable from the viewpoint of dimensional stability. Alternatively, even those having microvoids can be appropriately selected according to the application. A support having a surface roughness (Ra) in the range of 0.1 to 0.5 is preferred. In addition to those similar to the support used for the above-mentioned image forming body, synthetic paper (for example, synthetic paper containing polypropylene as a main component) can also be used. Also,
Other supports include pulp paper made from natural pulp, synthetic pulp, or mixtures thereof. The paper is preferably formed by using a fourdrinier and the like, and subjected to calendering using a machine calender, a super calender, a heat calender or the like after the paper making for the purpose of improving smoothness. In the present invention, a base paper coated with a pigment-containing resin layer for improving smoothness can also be suitably used. Specific base papers include high quality paper,
Examples include art paper, coated paper, matte paper, impregnated paper, paperboard, and the like.

As the binder for the layer to be transferred, a polymer having a softening point of 50 to 120 ° C. is preferably used. 50
When the temperature is below ℃, when the image forming material before image formation is stored under a high temperature condition, the adhesion between the image forming body and the transfer receiving body is liable to change, and the image forming material is displaced, peeled off, and has poor stability.
When the softening point exceeds 120 ° C., it becomes difficult to bond the image forming body and the transfer-receiving body during production. As the resin binder used for the transfer-receiving layer, urethane resin, acrylic resin, and styrene copolymer elastomer are preferably used. Styrene copolymerized elastomer has polystyrene block (S) and polybutadiene (B), polyisoprene (I), poly (ethylene-co-
(Butylene) (EB), poly (ethylene-co-propylene) (EP), block copolymerized SBS, SIS,
SEBS, SEPS and the like can be mentioned. Further, other resins can be mixed as long as the effects of the present invention are not impaired. The transferred layer may contain fine particles, and some of the fine particles may protrude from the surface of the transferred layer, and the surface roughness (Ra) may be 0.1 to 0.5. preferable. Ra mentioned here is JIS B 060
It shall be obtained by the measuring method according to 1. Examples of the fine particles include silica, titanium oxide, aluminum oxide, zinc oxide, magnesium oxide, metal oxides such as aluminum borate, calcium carbonate, magnesium carbonate,
Metal salts such as barium sulfate, magnesium sulfate, aluminum hydroxide, magnesium hydroxide, boron nitride, kaolin, clay, talc, zinc white, lead white, ziglite,
Quartz, diatomaceous earth, perlite, bentonite, mica,
Examples include inorganic fine particles such as synthetic mica, organic fine particles such as melamine resin particles, guanamine resin particles, styrene-acrylic copolymer resin particles, silicone resin particles, and fluororesin particles. Among the fine particles, hollow white resin fine particles are preferable in order to increase the transfer density, and examples thereof include crosslinked styrene-acrylic hollow resin particles. When such fine particles are added, the content is usually 0.1 to
Preferably it is in the range of 50% by weight, in particular 1-30% by weight. The average particle size of the white fine particles is usually 0.01 to
It is 20 μm, preferably 0.02 to 5 μm.

The coverage of the layer to be transferred is preferably 10 to 30 g / m ² .

The transfer layer may contain additives such as an antistatic agent, a heat stabilizer, an antioxidant, an ultraviolet absorber, a light stabilizer, and a fluorescent whitening agent. The amount of the additive in the composition for forming a transferred layer is 30% by weight or less, particularly 20% by weight.
It is preferable to set the following.

The thickness of the transferred object is about 10 to 100 μm including the support, and the thickness of the transferred layer is 0.1 to 100 μm.
It is preferably about 40 μm.

The adhesive layer may be any of those which have adhesiveness at room temperature themselves and those which exhibit adhesiveness by applying heat or pressure. Examples thereof include a resin having a low softening point, an adhesion-imparting agent, and a hot-melt agent. Can be formed by appropriately selecting.

Examples of the resin having a low softening point include ethylene copolymers such as ethylene-vinyl acetate and ethylene-ethyl acrylate; polystyrene resins such as styrene-butadiene, styrene-isoprene and styrene-ethylene-butylene; polyester resins; Polyolefin resins such as polyethylene and polypropylene; polyvinyl ether resins; acrylic resins such as polybutyl methacrylate;
Ionomer resins; cellulosic resins; epoxy resins; vinyl chloride resins such as vinyl chloride-vinyl acetate copolymers, and the like. Examples of the adhesion-imparting agent include rosin, hydrogenated rosin, rosin maleic acid, polymerized rosin and Unmodified or modified products such as rosin phenol, terpenes, petroleum resins and modified products thereof, and the like.

Examples of the hot-melt agent include compounds which are solid at ordinary temperature and which reversibly liquefy or soften when heated.
Specifically, terpineol, menthol, acetamide, benzamide, coumarin, benzyl cinnamate, diphenyl ether, crown ether, camphor, p-
Monomolecular compounds such as methyl acetophenone, vanillin, dimethoxybenzaldehyde, p-benzylbifevir, stilbene, margaric acid, eicosanol, cetyl palmitate, stearamide, behenylamine, beeswax, candelilla wax, paraffin wax, ester wax, Examples thereof include waxes such as montan wax, carnauba wax, amide wax, polyethylene wax, and microcrystalline wax; ester gum; rosin derivatives such as rosin maleic resin and rosin phenol resin. Phenoxy resin, phenol resin, ketone resin, epoxy resin, diallyl phthalate resin, terpene hydrocarbon resin, cyclopentadiene resin, polyolefin resin, which can be melted by heat,
Polycaprolactone resin, polyethylene glycol,
Polymer compounds represented by polyolefin oxides such as polypropylene glycol can also be used, and may be used by mixing with the above waxes.

The thickness of the layer to be transferred is preferably about 0.1 to 100 μm, more preferably 0.5 to 50 μm.
The thickness of the adhesive layer is preferably about 0.1 to 40 μm, and more preferably 0.3 to 30 μm.

Next, a method for producing an image forming material will be described.

The image-forming layer of the image-forming body and the transfer-receiving layer or the adhesive layer of the transfer-receiving body can be tightly attached to each other by pressure or heat and pressure. For pressure or heat and pressure treatment, any material can be used without particular limitation as long as it has excellent adhesiveness and can be subjected to pressure or heat and pressure treatment without introducing bubbles, etc. In the case where the heating and pressurizing treatment is performed on a stamper or a stamper, a thermal head, a heat roll, a hot stamp or the like can be used. The pressure when using a pressure roll is usually 0.1 to 20 kg / cm, preferably 0.5 kg / cm.
-10 kg / cm, and the transport speed is usually 0.1 kg / cm.
1 to 200 mm / sec, preferably 0.5 to 100 mm / sec
And the pressure when using a stamper is usually 0.05 to 10 kg / cm ² , preferably 0.5 to 5 kg / cm ² .
kg / cm ² , and the pressurizing time is usually 0.1 to 50
Seconds, preferably 0.5 to 20 seconds. Further, the thermal head can be used as it is under the conditions used for ordinary melt transfer, sublimation transfer and the like. The heating temperature when using a heat roll is usually in the range of 60 to 200 ° C, preferably 80 to 180 ° C, and the pressure is usually 0.1 to
20 kg / cm, preferably 0.5 to 10 kg / cm, and the transfer speed is usually 0.1 to 200 mm / cm.
Second, preferably 0.5 to 100 mm / sec.
The heating temperature when using a hot stamp is usually 60 to
The temperature is in the range of 200 ° C., preferably 80 to 150 ° C., the pressure is usually 0.05 to 10 kg / cm ² , preferably 0.5 to 5 kg / cm ² , and the heating time is usually 0.
It is 1 to 50 seconds, preferably 0.5 to 20 seconds.

Next, an image forming method will be described.

As described above, according to the image forming method of the image forming material of the present invention in which the image forming body and the transfer receiving body are laminated, the image forming body is exposed to high-density energy light from the back layer side of the image forming body. Ablation is caused in the portion, the bonding strength of the image portion between the support and the image forming layer is reduced, and the image (formed layer) of the exposed portion is transferred to the transferred member by separating the transferred member from the image formed member. That is, an image forming body having an image remaining after being transferred onto the layer is used. However, the peeled side may be used.

The imagewise exposure is performed in order to obtain a high resolution.
Electromagnetic wave whose energy application area can be narrowed down, especially wavelength 1
UV to 1 nm to 1 mm, visible light, infrared light is preferable,
Examples of light sources to which such light energy can be applied include lasers, light-emitting diodes, xenon flash lamps, halogen lamps, carbon arc lamps, metal halide lamps, tungsten lamps, quartz mercury lamps, high-pressure mercury lamps, and the like. The energy applied at this time depends on the type of the image forming material, the exposure distance,
By adjusting the time and intensity, it can be selected as appropriate.

In the case where the above energy is subjected to collective exposure,
A mask material in which a negative pattern of a desired exposure image is formed of a light-shielding material may be overlaid and exposed, or an image controlled by a computer may be scanned.

When an array type light source such as a light emitting diode array is used, or when a light source such as a halogen lamp, a metal halide lamp, or a tungsten lamp is controlled to be exposed by an optical shutter material such as a liquid crystal or PLZT, an image signal is used. It is possible to carry out the corresponding digital exposure. In this case, direct writing can be performed without using a mask material. However, in this method, a new optical shutter material is required in addition to the light source. Therefore, in the case of digital exposure, it is preferable to use a laser as the light source.

When laser light is used as a light source,
It is possible to form a latent image by scanning light according to image data by squeezing light into a beam, and furthermore, by using a laser as a light source, it is easy to narrow the exposure area to a very small size, and it is possible to form a high-resolution image Formation is possible.

As a laser light source used in the present invention, generally known ruby lasers, YAG
Solid lasers such as lasers and glass lasers;
Gas lasers such as Ne laser, Ar ion laser, Kr ion laser, CO ₂ laser, CO laser, He-Cd laser, N ₂ laser, excimer laser, InGaP laser, AlGaAs laser, Ga
AsP laser, InGaAs laser, InAsP laser, CdSnP ₂ laser, a semiconductor laser such as GaSb laser, other chemical laser, can be exemplified dye laser or the like, in order to cause the efficient abrasion Among these, wavelength 600 ~ 1200
Using a laser in the near infrared region from visible light of nm
This is preferable in terms of sensitivity because light energy can be efficiently converted to heat energy.

The exposure direction of the high-density light energy is preferably from the side of the support opposite to the image forming layer of the image forming body. It is also preferable to apply pressure like a nip roll before peeling to facilitate transfer.

Examples of the method for peeling the transfer object include a peeling plate, a method for fixing the peeling angle using a peeling roll, and a manual peeling method for peeling off the transfer material and the image forming material without fixing them by hand.
Various peeling methods can be used as long as they do not affect image formation.

The preparation of the image forming material and the image formation can be performed with reference to the above description. In the following examples, the preparation of the image forming material from the image forming body and the transfer receiving body and the image forming method are described. Is omitted.

[0153]

EXAMPLES The present invention will be described below in more detail with reference to Examples, but it should not be construed that the invention is limited thereto.

[Evaluation Method] <Mat Agent Peeling (Detachment) Test> A 100 μm transparent polyethylene terephthalate film (hereinafter abbreviated as PET film) was stacked on a sample cut out from each image-formed body with the back layer facing upward. Further, a 100 gf / cm ² load was applied, the PET film was peeled off at a rate of 10 cm / min, and the number of samples before and after peeling on the back layer side was counted by observation with an optical microscope, and evaluated according to the following ranks.

A: No desorption of the matting agent is observed at all. B: Desorption of the matting agent is less than 5%. C: Desorption of the matting agent is 5% or more and less than 20%. D: Desorption of the matting agent is 20%. Not less than 60% E: Detachment of the matting agent is 60% or more.

<Friction Coefficient Before and After Calender> Samples were sampled before and after calendering the image forming body at 120 ° C. and 150 kgf / cm ² , and each sample was placed on a horizontal table with the back layer side facing up. It was brought into contact with the transparent PET film surface and given a vertical load (P) of 100 gf. By tilting the table, the static sliding friction coefficient was obtained from the friction angle that started sliding.

<Substitution Test for Adhesion to Calender Roll> A sample was sampled before and after calendering the image formed body at 1200 ° C. and 1500 kgf / cm ^2.
× 10 cm, and overlaid on a 180 μm PET film so that the back layer faces each other.
A calender roll (industrial chrome-plated ultra-mirror finish) was heated and pressurized at a linear pressure of 300 kgf / cm ² at a speed of 1 m / min. The PET film and one end of the sample were peeled off and evaluated according to the following rank.

A: Smoothly peeled so that no load was felt at all. B: Peeling was not felt but the sound was peeled off while sound was not felt. C: Peeling was heavy and peeled while the sound of peeling was continuous. D: Peeling. The outermost layer or the antistatic layer was partially transferred to the PET film. E: The antistatic layer or the outermost layer was completely transferred to the PET film.

<Cracks> Cracks of the antistatic layer of the samples used for the calender substitution test of the image formed body were observed and evaluated.

A: No cracks at all B: Not visible, but slightly cracked when viewed with a 100-fold loupe C: Not visible, but quite cracked when viewed with a 100-fold loupe D: Cracks can be visually confirmed.

<Surface resistivity before and after calender> A sample of the image formed body was sampled before and after the calender, and measured at 23 ° C. and 20% RH using a Teraohmmeter model VE-30 manufactured by Kawaguchi Electric Co., Ltd. It was expressed by.

[Preparation of Support] As a support for the image forming body, a 100 μm PET support was prepared by performing corona discharge at an intensity of 25 W / m ² · min.

[Resin used and its Tg] (BP-1) butyl acrylate / styrene / glycidyl acrylate (weight ratio 40/20/20) copolymer latex liquid (solids 30% by weight) (Tg: 35 ° C.) and styrene / Glycidyl acrylate (60/40) copolymer latex liquid (solid content 30% by weight) (Tg: 75 ° C).

(BP-2) Styrene / glycidyl acrylate (60/40) copolymer latex liquid (solid content 30
(% By weight) (Tg: 75 ° C.) (BP-3) butyl acrylate / t-butyl acrylate / styrene / 2-hydroxyethyl acrylate (10/35/30/25) copolymer latex liquid (solids 30% by weight) ( Tg:) (BP-4) Aqueous polyester copolymer (A) (T
g: 55 ° C) (BP-5) Modified aqueous polyester copolymer (D)
(Tg: 55 ° C.) (BP-6) Aqueous polyester copolymer (B) (T
g: 85 ° C) (BP-7) Aqueous polyester copolymer (C) (T
g: 105 ° C.) [Preparation of antistatic layer coating solution] <Preparation of conductive metal oxide (A-1)> A mixed solution of 65 g of stannic chloride hydrate in water and ethanol (1: 1) 200
Dissolved in 0 ml. Then, the mixture was boiled, and the formed coprecipitate was taken out by decantation, and the precipitate was washed with distilled water many times. Silver nitrate was dropped into the washed solution of the precipitate, and after confirming that there was no chloride ion, 1000 ml of distilled water was added to the decanted precipitate, and the total amount was 20 ml.
00 ml. Further, 40 ml of 30% aqueous ammonia was added thereto and heated in a water bath to obtain a colloidal gel dispersion. This colloidal gel dispersion is concentrated to 10% by weight.
(Solid content), which is referred to as A-1.

<Preparation of Conductive Metal Oxide (A-2)> 65 g of stannic chloride hydrate and 1.0 g of antimony trichloride were dissolved in 2000 ml of a water / ethanol mixed solution. Then, the mixture was boiled, and the formed coprecipitate was taken out by decantation, and the precipitate was washed with distilled water many times.
Silver nitrate was added dropwise to the washed solution of the precipitate, and after confirming that there was no chloride ion, 1000 ml of distilled water was added to the decanted precipitate to make the total amount 2000 ml. Further, 40 ml of 30% aqueous ammonia was added thereto and heated in a water bath to obtain a colloidal gel dispersion. The colloidal gel dispersion was concentrated to a solid content of 10% by weight. This is A
-2.

<Preparation of Conductive Metal Oxide (Preparation of A-3)> 65 g of stannic chloride hydrate and 1.5 g of antimony trichloride were dissolved in 1000 g of ethanol, and a 1N aqueous sodium hydroxide solution having a pH of 3 was added. The co-precipitate of colloidal stannic oxide and antimony oxide was obtained, and the obtained co-precipitate was left at 50 ° C. for 24 hours to obtain a red-brown colloidal precipitate. Water was added to the precipitate to remove excess ions, and the precipitate was washed with water by centrifugation.This operation was repeated three times to remove excess ions.Colloidal precipitate 1 from which excess ions were removed
To 100 g, 50 g of barium sulfate having an average particle diameter of 0.3 μm and 1000 g of water were added to obtain a mixture. 9
The powder was sprayed into a firing furnace heated to 00 ° C. to obtain a bluish powder mixture of stannic oxide and barium sulfate having an average particle diameter of 0.1 μm. The powder mixture was dispersed in water to obtain a dispersion having a solid content of 10% by weight. This is designated as A-3.

[Preparation of Fiber Fine Particles] <Preparation of Silk Fiber Fine Particles> First, sericin was completely removed from the cocoon while immersing it in warm water or warm water containing enzymes, and then the raw silk was taken out. 2-3 on the mill
The fiber was cut into a size of about 1 cm to obtain short fiber silk fibroin. Next, the cut silk fibroin was fed into a rotary blade mill [Orient hard type pulverizer VM- manufactured by Orient Co., Ltd.].
32 (trade name)], the mixture was pulverized into a coarse silk fibroin powder having an average particle size of about 100 μm, and the coarse silk fibroin powder was put into a fluidized drier and dried at 100 ° C. Next, using a ball mill (manufactured by Kondo Kagaku Seisakusho), the silk fibroin coarse powder was sufficiently pulverized into a fine silk fibroin powder having an average particle diameter of about 20 μm. The ball mill pulverization is completed with an average particle size of about 20 μm. Then, after transferring the silk fibroin fine powder taken out of the ball mill to a cylindrical tank, methanol is poured into the tank, and the mixture is stirred at room temperature to perform a β-treatment to increase the degree of crystallinity. The fine silk fibroin powder was taken out of the tank and the fine silk fibroin powder was dried. Further, the fine powder of silk fibroin was pulverized using a jet mill (single track jet mill (trade name) manufactured by Seishin Enterprise Co., Ltd.) to obtain fine silk fiber particles having an average particle size of 5 to 6 μm.

<Preparation of Fiber Fine Particles from Leather> A lump of chrome-tanned cowhide leather (shaving leather) is unraveled to a size of about 10 mm in width and 12 cm in length using a crusher, and then crushed. And coarsely pulverized to a particle size of 10 mm or less. This is put into a vacuum dryer, and dried until the water content becomes 20 to 30% by weight. Then, the dried and coarsely ground leather is put into a degreasing machine, defatted sufficiently while adding n-hexane, filtered, and degreased. A powder was obtained. The residual oil content was 0.5% by weight or less. Next, 2 kg / cm at 130 ° C.
² G steam was applied until the solvent odor disappeared. Water was added to the degreasing machine, stirred, filtered, and dehydrated. This washing process is 5
Repeated times to remove impurities. Next, the mixture was transferred to a steam steamer and steamed at 130 ° C. with 2 kg / cm ² G steam while stirring. This coarsely pulverized powder was dried at 90 ° C. and further sufficiently dried with a vacuum drier to obtain a dry coarsely pulverized powder having a water content of 1% by weight or less. Next, this powder was finely pulverized at 1700 rpm using a Fine Victory Mill (trade name) manufactured by Hosokawa Micron Corporation, and classified with a cyclone.
A fine leather powder having an average particle size of 30 μm was obtained. Further, this fine powder was treated with the jet mill at an air pressure of 8 kg / min and 10 m ³ / min to obtain fine leather fiber particles having an average particle diameter of 6 μm or less.

<Preparation of Fiber Fine Particles from Recycled Fibers> Preparation of fine particles of tencel or dexel fibers (hereinafter referred to as tencel fibers) of regenerated fibers is described as an example. After cutting a long fiber Tencel (manufactured by Coatles) (trade name) with a cutter blade mill to about 2 to 3 mm, average it with a rotary blade mill (Orient Co., Ltd., Orient hard type pulverizer VM-32). After coarsely pulverized to a particle size of about 90 μm, it was placed in a fluidized drier and dried sufficiently at 100 ° C. Next, the coarse powder was pulverized by a ceramic ball mill to obtain a fine powder having an average particle diameter of 20 μm, and further pulverized by a jet mill to obtain fine Tencel fiber particles having an average particle diameter of 4 μm.

Example 1 << Preparation of Antistatic Layer Coating Solution >> 45 g of a mixture of BP-1 (solid content of 30% by weight) and BP-2 (solid content of 30% by weight) of 80% by weight and 20% by weight, respectively Fine particles A-1 (metal oxide fine particles / a mixture of BP-1 and BP-2) A 2% by weight aqueous solution having a volume ratio of 30 (C-1) 36 g H-21 0.2 g Finished to 1 liter with water.

<< Aqueous polyester copolymer dispersion BP-
Preparation of 4> Aqueous polyester copolymer dispersion (BP-4) was prepared by stirring and dissolving 500 g of aqueous polyester copolymer (A) in 3400 g of hot water at 95 ° C. for 3 hours.

<< Preparation of Coating Solution for Outer Layer >> 250 g of BP-4 Matting agent (type and amount added / mg / m ² described in Table 1) 36 g of 2% by weight aqueous solution of (C-1) Finished to 1 liter with water.

The symbols of the matting agents in Table 1 are S: silk fine particles, H: leather fiber fine particles, T: tencel regenerated fiber fine particles, and Cy: silica particle thyricia 50 (Fuji Silysia Co., Ltd.) as a comparative matting agent. )), Ts: Tosnomar 105 (manufactured by Toshiba Silicone Co., Ltd.).

[0174]

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<< Preparation of Image Formed Body >> As the back layer, the above-mentioned antistatic layer coating solution and the outermost layer coating solution were subjected to corona discharge treatment on a PET support at the same time by multilayer coating using an extruder coating machine. 0.2 μm and 0.3 μm
And applied at 123 ° C. for 2 minutes.

Next, an image forming layer was coated on the surface opposite to the back layer as follows.

The following composition was kneaded and dispersed by using a kneader and a sand mill to prepare a coating solution for an image forming layer containing particles containing metal atoms, and was applied on a support by an extrusion coating machine. During the drying, a magnetic field orientation treatment was performed, followed by a calender treatment and further curing at 60 ° C. for 72 hours.

Was carried out.

<< Preparation of Image Forming Layer Coating Solution >> Fe—Al ferromagnetic metal powder F [e: Al atomic ratio = 100: 4 (entire), 50:50 (surface), average major axis diameter: 014 μm, Hc: 1760 Oe, σs: 120 emu / g, BET: 53 m ² / g] 100 parts Potassium sulfonate group-containing vinyl chloride resin (manufactured by Zeon Corporation: MR-110) 10 parts Sodium sulfonate-containing polyurethane resin (Toyobo Co., Ltd.) 10 parts α-alumina (average particle size: 0.15 μm) 8 parts Stearic acid 1 part Butyl stearate 1 part Polyisocyanate compound (manufactured by Nippon Polyurethane Industry Co., Ltd.) 5 parts Cyclohexanone 100 parts Methyl ethyl ketone 100 parts Toluene 100 parts << calendering >> linear pressure 150kg / cm, roll temperature 100 ℃, Perform calender treatment at the emission speed 10 m / min, to form an image forming layer having a thickness of 1.3 .mu.m. Film thickness 1 at 830 nm of the formed image forming layer
The transmission concentration and light transmittance per μm, and the volume% and weight% of the metal atom-containing particles are 4.1, 0.008%, respectively.
50% and 74%.

The samples were evaluated for the matting agent peeling test and the coefficient of friction before and after the calender. Table 1 shows the results
Shown in

[0181]

[Table 1]

(Results) The fiber fine particles of the present invention hardly peeled off the matting agent and did not deteriorate in the friction coefficient before and after the calender.

Example 2 The antistatic agent of the antistatic layer was A-1, the binder of the outermost layer was C-1, 2, 5, 6, 7 as shown in Table 2, and the matting agent was fine silk particles. The procedure was performed in the same manner as in Example 1 except that the addition amount was 6 mg / m ² . As a comparative example,
A sample was prepared in which the silk fine particles were changed from the above formulation to silica Cy. The image forming layer was produced in the same manner as in Example 1. The evaluation was performed for a calender substitution test and for cracks. Table 2 shows the results.

[0184]

[Table 2]

(Results) In the present invention to which the silk fine particles were added, the combination of the binder having a Tg of 50 ° C. or more gave good results of the calender roll adhesion test and the crack resistance, and even if the Tg was 50 ° C. or less. While good results were obtained, it was found that when silica was used for the matting agent, adhesion to the calender roll was easy to occur even if the Tg of the binder resin was high, and cracking was also likely to occur.

Example 3 << Preparation of Coating Solution for Antistatic Layer >> 45 g of a mixture of BP-1 (solid content of 30% by weight) and BP-2 (solid content of 30% by weight) of 80% by weight and 20% by weight, respectively Fine particles (types and ratios shown in Table 3) 36 g of a 2% by weight aqueous solution of (C-1) Hardener (types and addition amounts shown in Table 3) Finished to 1 liter with water.

The HBU of the hardener is an abbreviation of 1,6-hexamethylenebisethyleneurea.

<< Preparation of Comparative Antistatic Layer Liquid >> A mixture of BP-1 (solid content of 30% by weight) and BP-2 (solid content of 30% by weight) of 80% by weight and 20% by weight, respectively, 45 g of poly (styrene sulfonic acid) (Sodium-co-styrene) (weight ratio 60:40) (The compound is a polymer antistatic agent other than metal oxide fine particles) Volume ratio 30 (C-1) 2% by weight aqueous solution 36 g H-21 0.2 g with water Finish to 1 liter.

<< Preparation of Outer Layer Coating Solution >> Resin (type and Tg shown in Table 3) 45 g S (matting agent) Added to be 6 mg / m ² (C-1) 2% by weight aqueous solution 36 g 1 liter of water Finish.

<< Preparation of Image Forming Body >> An image forming layer was formed in the same manner as in Example 1 to prepare an image forming body. The above samples were evaluated for changes in conductivity before and after the calender. Table 3 shows the results.

[0191]

[Table 3]

(Results) It was confirmed that the conductivity of the antistatic layer cured by using an epoxy compound as a hardening agent together with the metal oxide fine particles did not deteriorate even after the calendering treatment. In the case of a hardener other than epoxy, a slight deterioration was recognized, but the width was slight. On the other hand, in the sample without the hardener,
Deterioration was noticeable.

[0193]

The photothermal conversion image forming material of the abrasion method can solve various troubles caused by calendering by using the fiber fine particle matting agent, the metal oxide fine particles and the epoxy hardening agent of the present invention. An image forming material can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B41M 5/26 B (72) Inventor Ikuo Kurachi In-house Konica Co., Ltd. 1 Sakuracho, Hino City, Tokyo (72) Inventor Masataka Takimoto 1st Konica Corporation, Sakuracho, Hino-shi, Tokyo In-house (72) Inventor Yasunori Wada 1st Konica Corporation, Sakuracho, Hino-shi, Tokyo In-house F-term (reference) 2H025 AB20 AC01 AC08 DA20 DA38 DA40 FA03 FA24 2H096 AA00 AA30 BA16 BA20 CA20 EA02 EA04 GA50 2H111 AA01 AA16 AA26 AA35 AB01 BA03 BA08 BA12 BA32 BA53 BA55 BA68 BA71 BA76 CA03 HA05 HA14 HA23 HA35

Claims (8)

[Claims] 1. An image forming material in which an image forming layer on a first support and a layer to be transferred on a second support are laminated facing each other, wherein the image forming layer on the first support is provided. An image forming material having an outermost layer containing fiber fine particles on the side opposite to the side. 2. The image forming material according to claim 1, wherein the fiber fine particles are silk fine particles. 3. The image forming material according to claim 1, wherein the outermost layer contains a binder having a glass transition point of 50 ° C. or higher. 4. The image forming material according to claim 3, wherein the binder is a hydrophilic polyester. 5. The outermost layer and at least one layer of metal oxide fine particles according to claim 1 on the side opposite to the image forming layer side on the first support. An image forming material having an antistatic layer. 6. The image forming apparatus according to claim 5, wherein the antistatic layer containing the metal oxide fine particles is present adjacent to the first support opposite to the image forming layer. Image forming material. 7. The image forming material according to claim 1, wherein the outermost layer is an antistatic layer containing metal oxide fine particles. 8. The image forming material according to claim 5, wherein the antistatic layer is cured with an epoxy curing agent.