JP2001088442A - Image forming material and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image forming material of good resolution, half-tone dot quality and Dmin characteristics, of constant and stabilized release force of a sheet to be transferred and of sufficiently stabilized high temperature storage properties and productivity and also provide an image forming method using the material. SOLUTION: An image forming material is provided with a constitution in which two sheets, namely an image forming sheet having at least an image forming layer and a protective layer laminated in the above order on a substrate and a sheet to be transferred having a layer to be transferred on a separate substrate, are faced each other, and high density image rays are emitted from the substrate side of the image forming sheet to lower the bonding force between the substrate and the image forming layer, and a body to be transferred is released and simultaneously the image forming layer and the protective layer of a light exposure section are transferred onto the body to be transferred to carry out the formation of an image, and the protective layer and the layer to be transferred contain at least either one of a polyester resin or a polyurethane resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ablation type image forming material and an image forming method using the same.

[0002]

2. Description of the Related Art Conventionally, light energy such as a laser beam is focused to irradiate a recording material to melt, deform, scatter, burn or evaporate a part of the material (hereinafter, these are collectively abbreviated as ablation). A recording method is known. These are dry treatments that do not require treatment liquids such as chemicals, and have the advantage that high contrast can be obtained by melting, deforming, or evaporating and removing only the light irradiation part. It is used for optical recording materials such as, for example, and transparent originals at the time of producing a printing plate. For example, JP-A-8-310124 and JP-A-8-33
No. 4894, No. 8-337053, No. 8-33705
No. 4,8-337055, No. 9-15849, etc., image forming materials using ferromagnetic powders as coloring materials have been proposed. An image with a resolution can be obtained.
JP-A-8-337054 describes an ablation image forming material in which a transfer member and a transfer member are integrated, and discloses a configuration in which a binder resin is coated on the transfer member. Did not mean that a sufficiently stable image could be obtained.

For these image forming materials, the dot quality of an image cannot be said to be sufficiently good, and fog sometimes occurs, and unevenness may occur in a large exposure size sample. . Further, in the image forming material in which the image forming sheet and the transfer sheet having the transfer layer provided on the support face each other, the separation force is different depending on the location of one material, so that the separation can be sufficiently uniform and stable. This has caused a problem of poor conveyance of the image forming material on the image forming apparatus. Further, in the image forming material facing the transfer sheet provided with the transfer layer on the image forming sheet and the support, the performance stability after high-temperature storage is not sufficient, further heating and pressurizing time during image formation, That is, the productivity was not sufficient.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide good resolution, halftone dot quality, and Dmin characteristics, a constant and stable peeling force of a transfer-receiving sheet, and high-temperature storage stability.
An object of the present invention is to provide an image forming material which is sufficiently stable in productivity and an image forming method using the material.

[0005]

The above object of the present invention has been attained by the following constitutions.

[0006] 1. An image forming sheet in which at least an image forming layer and a protective layer are laminated in this order on a support, and a transfer sheet provided with a transfer layer separately on the support face each other, and a high density image is formed from the support side of the image forming sheet. Irradiation with energy light reduces the bonding force between the support and the image forming layer, peels off the transfer-receiving body, and simultaneously transfers the image-forming layer and the protective layer of the exposed portion to the transfer-receiving body to form an image. An image forming material, wherein the protective layer and the transferred layer contain at least one of a polyester resin and a polyurethane resin.

[0007] 2. Wherein the softening point of at least one of the polyester resin and the polyurethane resin contained in the transfer-receiving layer is 60 ° C. or higher.
The image forming material as described in the above.

[0008] 3. The softening point of at least one of the polyester resin and the polyurethane resin contained in the transferred layer is less than 60 ° C., and the content of the resin is 20% to 80% of the total binder resin amount of the transferred layer. 2. The image forming material as described in 1 above, wherein

4. An image forming method using the image forming material according to any one of the above items 1 to 3.

Hereinafter, the present invention will be described in detail.

The image forming material of the present invention comprises an image forming sheet in which at least one image forming layer and a protective layer are laminated on a support in this order, and a transfer sheet having a separate transfer layer provided on the support. And As a support, acrylate, methacrylate, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyarylate, polyvinyl chloride, polyethylene, polypropylene, polystyrene, nylon, aromatic polyamide, polyether ether ketone, Various resin films such as polysulfone, polyethersulfone, polyimide, polyetherimide,
Further, a transparent support such as a laminated resin film obtained by laminating two or more layers of the above resin can be given. In the present invention, the support is capable of transmitting 50% or more of light having an exposure light source wavelength,
A film stretched and heat-set is preferable in terms of dimensional stability, and 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 support is about 10 to 500 μm, preferably 25 to 250 μm.
m.

The image forming layer is used for improving image durability.
More preferably, it is composed of a color material layer (hereinafter, the image forming layer is also referred to as a color material layer). The coloring material layer has a basic structure of a coloring material and a binder resin for holding the coloring material. The colorant used in the present invention is a colorant capable of absorbing the wavelength light of the exposure light source.For example, carbon black is preferably used since it is a colorant having a wide absorption from the ultraviolet region to the visible and infrared regions. it can. In addition, inorganic or organic pigments and dyes are used, and are composed of a single-color, two-color, or three-color pigment compound. As inorganic pigments, titanium dioxide, carbon black, zinc oxide,
Prussian blue, cadmium sulfide, iron oxide and chromates of lead, zinc, barium and calcium. Examples of the organic pigment include azo-based, thioindigo-based, anthraquinone-based, anthranthrone-based, and triphenedioxazine-based pigments, vat dye pigments, phthalocyanine pigments (copper phthalocyanine and derivatives thereof), and quinacridone pigments. Also, as organic dyes,
Acid dyes, direct dyes, disperse dyes and the like can be mentioned. When the wavelength of the exposure light source is near infrared, as a near infrared light absorber, cyanine, polymethine, azurenium, squarium, thiopyrylium, naphthoquinone, organic compounds such as anthraquinone dyes, phthalocyanine,
An azo-based or thioamide-based organometallic complex is preferably used. Specifically, JP-A-63-139191, 6
4-33547, JP-A-1-160683, 1-
No. 280750, No. 1-293342, No. 2-207
No. 4, No. 3-26593, No. 3-30991, No. 3
-34891, 3-36093 and 3-3609
No. 4, No. 3-36095, No. 3-42281, No. 3
And compounds described in JP-A-97589 and JP-A-3-103476. Metal atom-containing particles can be preferably used as a coloring agent that further exerts the effects of the present invention.
When metal atom-containing particles are used as the colorant in the colorant layer of the image forming material of the present invention, the effects become more remarkable in improving the sensitivity, resolution, and transmission density of the exposed portion. The term “metal atom-containing particles” is a general term for compounds such as metals such as iron, chromium, manganese, cobalt, nickel, copper, zinc, titanium, silver, aluminum, gold and platinum or oxides thereof. The metal atom-containing particles preferably used in the present invention include ferromagnetic iron oxide powder, ferromagnetic metal powder, cubic plate-like powder and the like, and among them, ferromagnetic metal powder can be suitably used. Γ-Fe ₂ O ₃ , Fe
₃ O ₄ FeO _x (1.33 or these intermediate iron oxide, <
x <1.50).
Examples of ferromagnetic metal powders include Fe and Co, Fe-A
1 system, Fe-Al-Ni system, Fe-Al-Zn system, Fe
-Al-Co system, Fe-Al-Ca system, Fe-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-N
i-P system, Fe-Co-Al-Ca system, Ni-Co system,
Ferromagnetic metal powders such as metal magnetic powders mainly composed of Fe, Ni, Co, etc., are preferred. Among them, Fe-based metal powders are preferable. For example, Co-containing γ-Fe ₂ O ₃ , Co-coated γ-F
Cobalt-containing iron oxide-based magnetic powders such as e ₂ O ₃ , Co-containing Fe ₃ O ₄ , Co-coated Fe ₃ O ₄ , and Co-containing magnetic FeO _x (4/3 <x <3/2) 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-based, F
e-Al-Zn system, Fe-Al-Co system, Fe-Ni-
F of Si-Al-Co type, Fe-Co-Al-Ca type, etc.
An e-Al-based ferromagnetic powder is preferable. In this, the content ratio of Fe atoms and Al atoms contained in the ferromagnetic powder is Fe: Al = 100: 1 to 100: 20 in atomic ratio. And the content ratio of Fe atoms and Al atoms present in a surface area of 100 ° or less at an analysis depth of ESCA (X-ray photoelectron spectroscopy) of the ferromagnetic powder is Fe: A in atomic ratio.
having a structure in which 1 = 30: 70 to 70:30,
Alternatively, the ferromagnetic powder contains Fe atoms, Ni atoms, Al atoms, and Si atoms, and at least one of Co atoms and Ca atoms, and has a Fe atom content of 90 atomic% or more and a Ni atom content of 1 to 1. 10 atomic%, the content of Al atoms is 0.1%.
1 to 5 atomic%, the content of Si atoms is 0.1 to 5 atomic%,
The content of Co atoms or Ca atoms (the total amount when both are contained) is 0.1 to 13 atomic%, and the analysis depth of the ferromagnetic powder by ESCA (X-ray photoelectron spectroscopy) is 100 ° or less. The content ratio of Fe atom, Ni atom, Al atom, Si atom, and Co atom and / or Ca atom existing in the surface area is Fe: Ni: Al: Si: (C
o and / or Ca) = 100: (4 or less) :( 10-6
0): (10 to 70): (20 to 80) are preferable. The shape of the ferromagnetic powder has a major axis diameter of 0.30 μm or less, preferably 0.20 μm or less. According to such a ferromagnetic powder, the surface property of the coloring material layer is improved. Examples of the hexagonal plate-like powder include hexagonal ferrites such as barium ferrite and strontium ferrite, and a part of the iron element is replaced with another atom (Ti, C
o, Zn, In, Mn, Ge, Hb, etc.).
ran on MAG, p18, 16 (1982). Among these, as an example of the barium ferrite magnetic powder, an average particle diameter (a diagonal height of the plate surface of hexagonal ferrite) in which at least a part of Fe is replaced by Co and Zn is 400 to 900 °.
And the plate ratio (value obtained by dividing the length of the diagonal line of the plate surface of the hexagonal ferrite by the plate thickness) is 2.0 to 10.0.
In the barium ferrite magnetic powder, a part of Fe may be further substituted by a transition metal such as Ti, In, Mn, Cu, Ge, or Sn. A method for producing a cubic magnetic powder is obtained, for example, by melting oxides and carbonates of each atom necessary to form a target barium ferrite together with a glass-forming substance such as boric acid. A glass is formed by quenching the melt to form a glass, and then heat-treating the glass at a predetermined temperature to precipitate the desired barium ferrite crystal powder, and finally removing the glass component by a heat treatment. Other examples include a coprecipitation-calcination method, a hydrothermal synthesis method, a flux method, an alkoxide method, and a plasma jet method. The content of the metal atom-containing particles contained in the color material layer is about 50 to 99% by weight, preferably 60 to 95% by weight of the color material layer forming component.

As the binder resin used in the image forming layer, there is no particular problem as long as it can sufficiently retain the colorant capable of absorbing the wavelength light of the exposure light source and the particles containing metal atoms. As the binder resin, a polyurethane, a polyester, vinyl chloride resins such as vinyl chloride copolymers are exemplary, these resins are -SO ₃ M, -OS
O 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 the dispersibility of the magnetic powder can be improved by using a resin into which such a polar group is introduced.
Incidentally, the content ratio of this polar group in each resin is 0.1 to 8.0.
Mol%, preferably about 0.2 to 6.0 mol%.

The binder resin may be used alone or in combination of two or more kinds. When two or more kinds are used in combination, for example, the ratio of polyurethane and / or polyester to vinyl chloride resin is 90:10. 10:90, preferably 70:30 to 30:70.

Examples of polar group-containing vinyl chloride include, for example,
Vinyl chloride - a resin having a vinyl alcohol copolymer _{hydroxyl, Cl-CH 2 CH 2 SO} 3 M, Cl-CH 2 CH
_{2 OSO 3 M, Cl-CH} 2 CO 2 M, Cl-CH 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.

One example is shown below.

-CH ₂ C (OH) H- + Cl-CH ₂
CH ₂ SO ₃ Na → —CH ₂ C (OCH ₂ CH ₂ SO ₃ N
a) H-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, and adding benzoyl peroxide, azobisisobutyl General radical polymerization initiators such as butyronitrile, and redox polymerization initiators,
It can be obtained by polymerization using a cationic polymerization initiator or the like. Specific examples of the reactive monomer for introducing sulfonic acid or a salt thereof include vinyl sulfonic acid, allyl sulfonic acid, methacryl sulfonic acid, p- Examples include unsaturated hydrocarbon sulfonic acids such as 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. be able to.

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, and cyclohexanedimethanol.

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, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,5-naphthalene diisocyanate, and lysine isocyanate methyl ester. As the other synthetic methods of the polyurethane having a polar _{group, Cl-CH 2 CH 2 SO} 3 M with polyurethane and polar group and a chlorine atom with a hydroxyl group, Cl-CH ₂ CH
_{2 OSO 3 M, Cl-CH} 2 C0 2 M, Cl-CH 2 P (=
An addition reaction with a compound such as O) (OM ₁ ) ₂ is also effective.

Other binder resins include vinyl chloride resins such as vinyl chloride-vinyl acetate copolymer, polyolefin resins such as butadiene-acrylonitrile copolymer, polyvinyl acetal resins such as polyvinyl butyral, and celluloses such as nitrocellulose. Resin, styrene resin such as styrene-butadiene copolymer, acrylic resin such as polymethyl methacrylate, polyamide,
A phenol resin, an epoxy resin, a phenoxy resin, or the like may be used in combination, but when these are used in combination, the content is preferably 20% by weight or less of the total binder resin.

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

The coloring material layer may contain additives such as a durability improver, a dispersant, an antistatic agent, a filler and a curing agent as long as the effects of the present invention are not impaired. Examples of the durability improver include polyisocyanate.

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 cationic surfactants, anionic surfactants, nonionic surfactants, Polymer antistatic agents, conductive fine particles, etc.
0 Chemical Products ”, Chemical Daily, p. And the compounds described in 875-876 and the like.

As fillers, 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. In addition, examples of the filler include inorganic fine particles and organic resin particles, and these may also serve as a release agent. Examples of the inorganic fine particles include silica gel, calcium carbonate, titanium oxide, acid clay, activated clay, and alumina.Examples of the organic fine particles include fluororesin particles, guanamine resin particles, and the like.
Resin particles such as acrylic resin particles and silicon resin particles can be used.

The curing agent can be used without any particular limitation as long as it can cure the colorant layer. Examples of such a curing agent include those used when synthesizing the polyurethane in the binder resin described above. And polyisocyanates. By adding such a curing agent to cure the color material layer, it is possible not only to improve the durability of the formed image but also to eliminate the background stain on the portion where ablation has occurred. Moreover,
In order to improve the durability against solvents,
Even if an organic solvent is used when applying the protective layer, the protective layer can be laminated without damaging the image forming layer. As a result, it is possible to produce an image forming material having higher durability than the protective layer made of a water-soluble or water-dispersible resin. The amount of these additives is about 0 to 20% by weight, preferably 0 to 15% by weight.

The thickness of the color material layer is about 0.05 to 5.0 μm, preferably 0.1 to 3.0 μm. or,
The color material layer may be composed of a single layer or may be composed of multiple layers having different compositions.However, when the color material layer is composed of multiple layers, a color material capable of absorbing the wavelength light of the exposure light source is provided in a layer close to the support. Is preferably contained more. Further, a colorant 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 coloring material layer includes, for example, a coloring agent, a binder resin, and if necessary, a durability improver, a dispersant, an antistatic agent,
A coating material is prepared by kneading a filler, a filler, a curing agent and the like with a solvent, and then the coating material is diluted, applied on a support and dried to form a coating.

As the solvent, alcohols (ethanol, propanol, etc.), cellosolves (methyl cellosolve, ethyl cellosolve), aromatics (toluene, xylene, chlorobenzene, etc.), ketones (acetone, methyl ethyl ketone, etc.), ester-based Use of 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. Further, for kneading and dispersing the components of the image forming layer, 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,
Sqegvari Attritor, High Speed Impeller Disperser, High Speed Stone Mill, High Speed Impact Mill, Disper,
A high-speed mixer, a homogenizer, an ultrasonic disperser, an open kneader, a continuous kneader, or the like can be used.

The formation of the color material layer on the support is performed, for example, by applying and drying with an extrusion-type extrusion coater. If necessary, the magnetic powder may be subjected to a calendering treatment in order to make the orientation thereof uniform or to make the surface properties of the image forming layer uniform. In particular, in order to obtain a high-resolution image, it is preferable to orient the magnetic powder because the cohesive force in the layer can be easily controlled.

When a protective layer is provided on the color material layer, the coating and drying may be repeated for each layer, or may be performed by applying a multilayer coating by a wet-on-wet method and drying. In that case, it can be applied by a combination of a reverse roll, a gravure roll, an air doctor coater, a blade coater, an air knife coater, a squeeze coater, an impregnating coater, a bar coater, a transfer roll coater, a kiss coater, a cast coater or a spray coater and an extrusion coater. it can.

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 the present invention, the effect of the present invention can be more remarkably exerted by calendering the surface of the color material layer. The calendering treatment in the present invention means that after a color material layer is laminated on a support, it usually has a diameter of 1 mm.
By applying a temperature and pressure between the nip roller having a high smoothness of 100 cm to 100 cm and a heatable roller facing the nip roller, the application of the color material layer coating liquid, the drying process of the color material layer, etc. It refers to a step of reducing the voids and increasing the density of the color material layer itself. Conditions for the calendering treatment include a linear pressure of 2 to 100 kg / cm, preferably 5 to 50 kg / c, in order to reduce the porosity of the color material layer.
Preferably, the treatment is performed with a nip thickness of m. The heating temperature is usually 40 ° C to 200 ° C, preferably 50 ° C.
Although the heating temperature is from 120 ° C. to 120 ° C., the optimum heating temperature varies depending on the transport speed. Therefore, usually, the maximum instantaneous temperature at which the color material layer rises during the calendering process is set from about 30 ° C. to about 100 ° C. When the linear pressure and the heating temperature of the calendering treatment are lower than the above ranges, the effects aimed at by the present invention are small. Is not preferred. The calendering treatment is preferably performed immediately after the coloring material layer is applied irrespective of the presence or absence of the curing treatment of the coloring material layer. However, if necessary, the calendering treatment may be performed after coating and laminating the protective layer.

In the present invention, an intermediate layer having a sensitivity adjusting function may be provided between the support and the image forming layer. For the intermediate layer, a specific binder resin may be used in a certain film thickness. The kind of the binder used for the intermediate layer is not particularly limited, and the binders and the like listed for the color material layer can be used as appropriate.

The protective layer can greatly affect the image performance and productivity of the image forming material of the present invention. The thickness of the protective layer is usually 0.03 μm or more and 1.0 μm or less, preferably 0.05 μm or more and 0.5 μm or less. One form of the protective layer of the present invention is mainly composed of a resin binder and fine particles.

In the present invention, if the binder resin for the protective layer contains at least one of a polyester resin and a polyurethane resin, the image performance, high-temperature storage property, and further, the transport speed (productivity) can be significantly improved. I found it. Further, as a binder resin that can be used in combination with the resin, a vinyl chloride resin such as a vinyl chloride copolymer, a vinyl chloride resin such as a vinyl chloride-vinyl acetate copolymer, and a polyolefin resin such as a butadiene-acrylonitrile copolymer. Resins, polyvinyl acetal resins such as polyvinyl butyral, cellulose resins such as nitrocellulose,
Styrene resin such as styrene-butadiene copolymer, acrylic resin such as polymethyl methacrylate, polyamide, phenol resin, epoxy resin, phenoxy resin,
Polyvinyl butyral, polyvinyl acetoacetal,
Examples include acetal resins such as polyvinyl formal, and water-soluble resins such as polyvinyl alcohol and gelatin.

The binder resin contained in the protective layer may be any one of the polyester resin and the polyurethane resin.
Species may be used alone or in combination of two or more. The content of the binder resin in the protective layer is 10% in the protective layer component.
９９99.5% by weight, preferably 40-98% by weight. It is also preferable to add a curing agent such as polyisocyanate in order to increase the durability of the protective layer. As the binder selected when curing the protective layer, it is preferable to use a resin having in its molecule a functional group capable of undergoing a crosslinking reaction with a curing agent. Specifically, when an isocyanate-based curing agent is used as a curing agent, a phenoxy resin, an epoxy resin, a cellulose resin, an acetal resin, an acrylic resin, a urethane resin, a vinyl chloride resin, a polyester resin, or the like is used. Is preferred.

The fine particles used in the protective layer preferably have a smaller particle size than the fine particles used in the image forming layer. 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. For example, the fine particles added to the protective layer preferably have an average particle diameter r smaller than twice the film thickness L of the image forming layer. Further, the average particle size r of the fine particles used in the protective layer is preferably 0.3 μm or more and 20 μm or less, more preferably 0.8 μm or more and 4.5 μm or less. The amount of fine particles present in the protective layer per unit area, the so-called attached amount, is 5%.
mg / m ² or more and 150 mg / m ² or less, preferably 10 mg / m ² or more and 100 mg / m ² or less. When the surface of the fine particles used in the present invention has a polymerizable functional group, the adhesion between the protective layer and the fine particles is improved when the protective layer is cured, so that the image durability is further improved. Specific examples include FX-GSZ-07 manufactured by Nippon Shokubai Co., Ltd. Other forms of the protective layer of the present invention are mainly composed of a resin binder, contain additives such as fine particles as needed, and have a smoother value of 23 on the surface facing the transfer object.
The temperature is 5 mmHg or more and 200 mmHg or less at 55 ° C. and 55% RH. More preferably 23 ° C./55
% RH is 15 mmHg or more and 100 mmHg or less.

The protective layer preferably contains at least one additive (lubricant) among waxes, silicon compounds and fluorine compounds. Specific examples of the wax include solid waxes such as beeswax, candelilla wax, paraffin wax, ester wax, montan wax, carnauba wax, amide wax, polyethylene wax, and microcrystalline wax. Specific examples of silicon-based compounds (including wax-like compounds) include straight silicone oils such as dimethyl silicone oil, methylphenyl silicone oil, and methyl hydrogen silicone oil, olefin-modified silicone oil, polyether-modified silicone oil, and epoxy. Modified silicone oil, epoxy / polyether-modified silicone oil, alcohol-modified silicone oil, fluorine-modified silicone oil, amino-modified silicone oil, phenol-modified silicone oil, mercapto-modified silicone oil, carboxy-modified silicone oil, higher fatty acid-modified silicone oil, carnauba-modified Radical-reactive silicone oils such as silicone oil, amide-modified silicone oil, (meth) acrylic-modified silicone oil, silicon diol, and silicon Terminal reactive silicone oil diamine, a halogen group, an alkoxy group, and an ester group, an amide group, an organic modified silicone oil modified with an imide group. Examples of the fluorine-based compound include polytetrafluoroethylene, tetrafluoroethylene copolymer (eg, alkyl vinyl ether, ethylene, etc.), polyvinylidene fluoride,
Fluoroalkyl methacrylate, fluorocarbon resin such as fluororubber, perfluoropolyether oil, fluoroalcohol, fluorocarboxylic acid, perfluoroalkylcarboxylate, perfluoroalkyl quaternary ammonium salt,
Examples include low molecular weight fluorine compounds such as perfluoroalkyl betaine, perfluoroalkyl ethylene oxide (adduct), and perfluoroalkyl oligomer. The amount of each of these materials is preferably 0.1 to 30% by weight, more preferably 0.5 to 20% by weight of the solid content in the protective layer. When multiple additions are made, the value is a multiple of this.

The image-forming material of the present invention reduces the bonding strength between the support of the irradiated portion and the image-forming layer by exposure to high-density energy light, and peels off the transfer-receiving sheet adhered to the protective layer. The image forming layer and the protective layer are separated from the support, and as a result, the image forming layer and the protective layer in the irradiated portion are transferred to and removed from the transfer layer of the transfer sheet.

As the support for the transfer sheet, the same support as that used for the image forming material can be used, and the image forming layer of the high-density energy light irradiated portion can be received on the support. A suitable image receiving layer.

That is, examples of the support for the transfer-receiving sheet include synthetic paper (for example, synthetic paper containing polypropylene as a main component). Specifically, each grade of Yupo (trade name, manufactured by Oji Yuka Kabushiki Kaisha, Ltd.) or Peachcoat (trade name, manufactured by Nisshinbo Co., Ltd.), or Dianal W-900E (Diafoil Hoechst Co., Ltd.) can be preferably used. When a substrate made of a synthetic resin is used as the support of the sheet to be transferred, it is preferable that these substrates are stretched into a sheet or a film and heat-set from the viewpoint of dimensional stability. Even those having no microvoids or those having microvoids can be appropriately selected according to the application. Specifically, W-400 and T-100E manufactured by Diafoil Hoechst Co., Ltd.
And the like can be preferably used.

The base paper used as the support of the sheet to be transferred of the present invention is preferably pulp paper made from natural pulp, synthetic pulp, or a mixture thereof. Natural pulp paper is preferred. The paper is formed using a fourdrinier paper machine or the like, and is preferably subjected to a calendering process 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 resin layer containing a pigment for improving smoothness can also be suitably used. Specific base papers include high-quality paper, art paper, coated paper, matte paper, impregnated paper, paperboard, and the like. The paper may have a Bekk smoothness of 50 to provide smoothness when a laminating layer of polypropylene and polyolefin containing white fine particles described later is provided.
The time is preferably at least 100 seconds, more preferably at least 100 seconds.
It is preferable to have a smoothness of seconds or more. The thickness of the paper is not particularly limited, but is preferably 30 to 800 μm,
50 to 500 μm is more preferable. The base paper contains additives such as a sizing agent, a fixing agent, a paper strength enhancer, a filler, an antistatic agent, a dye, a pigment, a fluorescent whitening agent, an antioxidant, and a lubricant as necessary. It may be.

As the base material used as a support of the transfer-receiving sheet, a material having high transparency is preferable when transparency is required such as a transparent original such as an OHP or a seal used for sticking to glass or the like. In the case of a reflection image, in order to enhance the sharpness of the formed image, a white pigment such as titanium oxide, zinc oxide, silica, barium sulfate, magnesium carbonate, calcium carbonate, talc, clay is added to the layer constituting the substrate. Etc. may be added. The thickness of the substrate is usually 20 to 1,000 μm, preferably 50 to 5 μm.
00 μm, and is appropriately selected from such a range. Since the sheet to be transferred becomes unnecessary after image formation, it is preferable that its thickness is as thin as possible from the viewpoint of reducing waste materials. However, if the thickness is too small, there is a fear that the transferred body may be broken when the transferred body is peeled off from the image forming layer, and there is a concern that the transferability of the transferred body after peeling is difficult, so the thickness of the support is usually It is about 6 to 100 μm, preferably 12 to 50 μm.

The transfer sheet has at least one layer of a support, and the surface roughness Ra of the support is 0.1 mm on both sides.
It is preferably from 05 to 0.4 μm. As a method of adjusting the surface roughness of the transferred body to the above range, the surface of the support itself is roughened, or by laminating a resin binder layer containing inorganic or organic fine particles on the support, or the like. Can be achieved. Surface roughness is Ra value 0.05
Specific examples of the support having a range of from 0.4 to 0.4 include W-400 manufactured by Diafoil Hoechst Co., Ltd. (Ra value = 0.1).
6), E150 (Ra value = 0.25), E130 (Ra
Value = 0.34). Means for adjusting the surface roughness of the support include bubbles in the support,
A method of adding inorganic or organic fine particles to roughen the surface is general. If the Ra value does not exceed 0.04 μm, the desired sensitivity of the present invention cannot be obtained, and if it exceeds 0.4 μm, the desired resolution cannot be obtained. .

The transfer sheet has a transfer layer on the support, and the binder resin used for the transfer layer is mainly a thermoplastic resin. The feature of the present invention is that the binder resin used for the transferred layer contains at least one of a polyester resin and a polyurethane resin, and more preferably at least one of the polyester resin and the polyurethane resin of the transferred layer. One of the resins has a softening point of 60 ° C. or more, or the softening point of the resin is less than 60 ° C., and the content of the resin is 20% to 80% of the total binder resin used in the transferred layer.
%. It has been found that by satisfying these conditions, the image-forming material of the present invention can sufficiently satisfy the points of image performance, peeling stability, high-temperature storage property, and transport speed (productivity).

Examples of the urethane resin include a resin having a urethane bond (—NHCOO—) in a molecule, specifically, a polyurethane resin Nipporan for adhesives manufactured by Nippon Polyurethane Industry Co., Ltd.

Examples of the resin other than the polyester resin or the polyurethane resin which can be used in the transfer layer include ethylene-ethyl acrylate copolymer resin (EE).
A), acrylic resins such as ethylene-acrylic acid copolymer resin (EAA), and other modified acrylic resins. Specifically, EVAFLEX manufactured by DuPont-Mitsui Polychemicals Co., Ltd.
-EEA and Nipol LX series manufactured by Zeon Corporation. As the styrene copolymer elastomer, polystyrene block (S) and polybutadiene (B), polyisoprene (I), polyethylene / butylene (EB), polyethylene / propylene (EP) block copolymerized SBS, SIS, SEBS, SEP
S or the like can be preferably used. Specific examples include Califlex TR, Clayton D and Clayton G manufactured by Shell Japan Co., Ltd., Septon manufactured by Kuraray Co., Ltd., and Hibler and Tuftec H and M series manufactured by Asahi Kasei Corporation.

Further, fine particles may be added to the transfer sheet of the present invention, if necessary, for the purpose of improving storage stability. Examples of the inorganic fine particles include metal oxides such as silica, titanium oxide, aluminum oxide, zinc oxide, magnesium oxide, and aluminum borate, calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum hydroxide, magnesium hydroxide, and nitride. Metal salts such as boron,
Examples include kaolin, clay, talc, zinc white, lead white, siegrite, quartz, diatomaceous earth, perlite, bentonite, mica, synthetic mica and the like. Examples of the organic fine particles include melamine resin particles, guanamine resin particles, styrene-acryl copolymer resin particles, silicone resin particles, and fluororesin particles. Among the white fine particles, hollow resin fine particles are preferable in order to increase the transfer sensitivity or transfer density, and examples of the hollow fine particles include crosslinked styrene-acrylic hollow resin particles. These fine particles may be used in combination of two or more as necessary. When these are added to the transferred sheet binder, the maximum particle size is smaller than the transferred sheet binder film thickness or larger than the transferred sheet binder film thickness mainly from the viewpoint of resolution, halftone dot quality, and storage stability over time. When a filler is added, it is necessary that the maximum particle size be within 180% of the film thickness in order to balance the total performance.

It is preferable to add a wax to the transfer-receiving sheet of the present invention in order to obtain uniform image performance without fluctuation over time. Those having a particle size and a melting point, such as a wax, have been found to vary various properties by controlling the particle size and the melting point. The wax mentioned here can be used without any particular limitation as long as it has a particle size and a melting point. Specifically, beeswax, candelilla wax,
Solid waxes such as paraffin wax, ester wax, montan wax, carnauba wax, amide wax, polyethylene wax, microcrystalline wax and the like.

<Image Forming Method> In a preferred image forming method of the present invention, an image forming sheet having an image forming layer and a protective layer on a support in this order is exposed to high-density energy light to support an irradiated portion. After the bonding force between the body and the image forming layer is reduced, the image forming layer and the protective layer in the irradiated area are removed by the transfer sheet to form an image. In the present invention, an image can be formed by the following method from the configuration of the image forming material described above.

An image forming material in which a sheet to be transferred is previously laminated on the protective layer is used. After lowering the bonding force between the support and the image forming layer by exposing the image forming material to the image forming layer with high-density energy light, the image forming layer in the irradiated portion is separated by separating the transfer target and the support. And the protective layer can be transferred to the transfer target.

As a method of previously laminating the transfer-receiving sheet on the protective layer, the transfer-receiving sheet is obtained by dispersing or dissolving a tacky resin in water or a solvent at room temperature or by heating and coating and drying. Can be As a method of laminating the transfer-receiving sheet on the image protective layer, the transfer can be performed by bringing a pair of facing bonding rollers into close contact with each other while applying pressure. When the transfer-receiving sheet has adhesiveness by heating, it is preferable to secure the adhesion by heating immediately before the laminating roller, during laminating, or after laminating.

The peeling force required to peel off the protective layer of the image forming material and the sheet to be transferred is JIS.
In the 180 degree peeling method of C 2107 (JIS Z 0237), the thickness is preferably 5 gf / cm or more and 50 gf / cm or less.

The exposure direction of the light energy is preferably from the side of the support, and furthermore, the image forming layer in the image-exposed portion is not broken, and only the adhesive strength between the support and the image forming layer is reduced. It is preferable to adjust the exposure intensity so as to eliminate the problem, since the image-exposed portion can be uniformly transferred to the transfer-receiving sheet side.
In short, a) the components of the image forming material are not substantially changed by the image exposure, the bonding force between the support and the image forming layer is reduced, and b) the transfer target sheet and the image forming sheet are separated. By transferring and removing the image forming layer and the protective layer of the irradiating section to the transfer-receiving sheet, c) image formation is performed.

In this image forming method, the thickness of the sheet to be transferred is preferably 5 μm to 300 μm,
Further, the thickness is preferably from 10 μm to 150 μm.

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, and excimer laser; semiconductor lasers such as InGaP laser and AlGaAs laser can be used.

[0058]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto. In the following, “parts” means “parts by weight as active ingredients” unless otherwise specified.

Example 1 Preparation of Image Forming Sheet The following image forming layer forming compositions were separately kneaded and dispersed using a Henschel mixer and a sand mill.
Liquid, two liquids and polyisocyanate compound [Nippon Polyurethane Industry Co., Ltd., Coronate HX; active ingredient 100
%] In a weight ratio of 100: 2.39: 0.37,
The mixture was stirred with a dissolver to prepare a coating solution for the image forming layer.
The prepared coating solution for the image forming layer is ultrasonically dispersed, and then applied on a transparent polyethylene terephthalate film (Lumirror T60, manufactured by Toray Industries, Inc.) having a 100 μm-thick surface subjected to corona discharge treatment by extrusion coating using an extrusion method. Dry, then use a heat roll, temperature 100 ℃,
A calendering process was performed at a linear pressure of 150 kg / cm and a conveying speed of 60 m / sec, and the film was aged at 60 ° C. for 120 hours to form an image forming layer having a thickness of 1.33 μm.

<Coating solution for image forming layer> Ferromagnetic metal powder [MAP T1650SB, manufactured by Kanto Denka Kogyo Co., Ltd.] 100 parts Polyurethane resin [Byron UR4122, manufactured by Toyobo Co., Ltd.] 8.3 parts Polyester resin [Toyo Spinon Co., Ltd., Byron 280] 4.2 parts Phenoxy resin [Phenoxy Associates, Phenoxy resin PKHH] 2.5 parts Phosphate ester [Toho Chemical Industry Co., Ltd., Phosphanol RE610] 3.0 parts Methyl ethyl ketone 105.0 parts Toluene 105.0 parts Cyclohexanone 90.0 parts Next, a protective layer 1 coating solution having the following composition was prepared using a sand mill, and was coated on the image forming layer by a reverse bar coater and dried. Thereafter, aging was further performed at 60 ° C. for 72 hours to form a protective layer having a thickness of 0.25 μm.

<Coating Solution for Protective Layer 1> UCAR phenoxy resin PKHH (manufactured by Union Carbide) 0.59 parts Elitel UE-3690 (manufactured by Unitika) 0.59 parts Urethane resin [manufactured by Nippon Polyurethane Industry Co., Ltd.] , Nipporan 3109] 0.79 parts Coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd.) 0.77 parts Polyethylene wax CE-155 (manufactured by Koyo Chemical Co., Ltd.) 0.06 parts Silica [manufactured by Fuji Silysia Chemical Ltd.] , Silo Hobic 200] 0.06 parts Stearic acid 0.06 parts Lumina [Sumitomo Chemical Co., Ltd., high-purity alumina HIT60G] 0.06 parts Toluene 29.1 parts Cyclohexanone 67.9 parts This protective layer is a protective layer. Let it be 1.

Preparation of Transferred Sheet Next, a coating liquid for the transferred layer 1 having the following composition was applied in an amount of 1.6 g /
A transfer sheet having a transfer layer 1 coated at m ² was prepared.

<Coating Liquid for Transferred Layer 1> Urethane resin [Nipporan 3109, manufactured by Nippon Polyurethane Industry Co., Ltd.] 4.90 parts Silicone resin particles [Tospearl 120, manufactured by Toshiba Silicone Co., Ltd.] 0.10 parts Toluene 42 .75 parts Methyl ethyl ketone 42.75 parts Cyclohexanone 9.50 parts This transfer sheet is referred to as transfer sheet 1.

Preparation of Integrated Image Forming Material 1 The protective layer 1 and the transfer-receiving layer 1 are faced to each other, and heated and pressed [roll temperature: 60 ° C., pressure 1.1 kg / cm ² , peeling of the transfer-receiving sheet] The transfer speed is adjusted so that the peeling force at the time becomes 5 g / cm], and an integrated image forming material on which the transfer-receiving sheet is bonded is obtained. This is referred to as an integrated image forming material 1.

Preparation of Integrated Image Forming Material 2 An integrated image forming material 2 was prepared in the same manner except that the coating solution for the protective layer 1 of the integrated image forming material 1 was changed to the following coating solution for the protective layer 2. Produced.

<Coating solution for protective layer 2> UCAR phenoxy resin PKHH (manufactured by Union Carbide Co.) 0.59 parts Elitel UE-3690 (manufactured by Unitika Ltd.) 0.59 parts Urethane resin [manufactured by Nippon Polyurethane Industry Co., Ltd.] , Nipporan 5120] 0.79 parts Coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd.) 0.77 parts Polyethylene wax CE-155 (manufactured by Koyo Chemical Co., Ltd.) 0.06 parts Silica [manufactured by Fuji Silysia Chemical Ltd.] , Silo Hovic 200] 0.06 parts Stearic acid 0.06 parts Alumina [manufactured by Sumitomo Chemical Co., Ltd., high-purity alumina HIT60G] 0.06 parts Toluene 29.1 parts Cyclohexanone 67.9 parts-Integrated image forming material Preparation of 3 Same as above except that the coating solution for the protective layer 1 of the integrated image forming material 1 was changed to the following coating solution for the protective layer 3 Thus, an integrated image forming material 3 was produced.

<Protective Layer 3 Coating Solution> UCAR phenoxy resin PKHH (manufactured by Union Carbide Co.) 1.18 parts Urethane resin [manufactured by Nippon Polyurethane Industry Co., Ltd., Nipporan 5120] 0.79 parts Coronate HX (Nippon Polyurethane Industry Co., Ltd.) 0.77 parts Polyethylene wax CE-155 (manufactured by Koyo Chemical Co., Ltd.) 0.06 parts Silica [manufactured by Fuji Silysia Chemical Ltd., Silo Hobic 200] 0.06 parts Stearic acid 0.06 Part Alumina [manufactured by Sumitomo Chemical Co., Ltd., high-purity alumina HIT60G] 0.06 part Toluene 29.1 parts Cyclohexanone 67.9 parts ・ Preparation of integrated image forming material 4 Protective layer 1 coating of integrated image forming material 1 In the same manner as above, except that the coating solution was changed to the following coating solution for the protective layer 4 and the coating solution for the layer to be transferred 1 was changed to the coating solution for the layer to be transferred 2 The material 4 was prepared.

<Coating solution for protective layer 4> UCAR phenoxy resin PKHH (manufactured by Union Carbide) 0.99 parts Byron RV-200 (manufactured by Toyobo Co., Ltd.) 0.99 parts Coronate HX (Nippon Polyurethane Industry Co., Ltd.) 0.77 parts Polyethylene wax CE-155 (manufactured by Koyo Chemical Co., Ltd.) 0.06 parts Silica [manufactured by Fuji Silysia Chemical Ltd., Silo Hobic 200] 0.06 parts Stearic acid 0.06 parts alumina [High-purity alumina HIT60G, manufactured by Sumitomo Chemical Co., Ltd.] 0.06 parts Toluene 29.1 parts Cyclohexanone 67.9 parts <Coating liquid for transfer-receiving layer 2> (1.8 g / m ^{2 in} weight) Byron RV-200 (Manufactured by Toyobo Co., Ltd.) 4.90 parts Silicone resin particles [Tospearl 120, manufactured by Toshiba Silicone Co., Ltd.] 0.10 parts Toluene 42.75 parts 42.75 parts of tyl ethyl ketone 9.50 parts of cyclohexanone ・ Preparation of integrated image forming material 5 Same as above except that coating liquid for protective layer 4 of integrated image forming material 4 was changed to coating liquid for protective layer 5 shown below. Thus, an integrated image forming material 5 was produced.

<Coating solution for protective layer 5> UCAR phenoxy resin PKHH (manufactured by Union Carbide) 0.39 parts Byron RV-200 (manufactured by Toyobo Co., Ltd.) 1.58 parts Coronate HX (Nippon Polyurethane Industry Co., Ltd.) 0.77 parts Polyethylene wax CE-155 (manufactured by Koyo Chemical Co., Ltd.) 0.06 parts Silica [manufactured by Fuji Silysia Chemical Ltd., Silo Hobic 200] 0.06 parts Stearic acid 0.06 parts alumina [High-purity alumina HIT60G, manufactured by Sumitomo Chemical Co., Ltd.] 0.06 parts Toluene 29.1 parts Cyclohexanone 67.9 parts Production of integrated image forming material 6 Coating solution for protective layer 1 of integrated image forming material 1 Was changed to the following coating solution for the protective layer 6, thereby producing an integrated image forming material 6.

<Coating solution for protective layer 6> Byron RV-200 (manufactured by Toyobo Co., Ltd.) 1.98 parts Coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd.) 0.77 parts Polyethylene wax CE-155 (Koyo) 0.06 parts Silica [Silohobic 200 manufactured by Fuji Silysia Chemical Ltd.] 0.06 parts Stearic acid 0.06 parts Alumina [High purity alumina HIT60G manufactured by Sumitomo Chemical Co., Ltd.] 0 0.06 parts Toluene 29.1 parts Cyclohexanone 67.9 parts ・ Preparation of integrated image forming material 7 All except that the coating liquid for protective layer 1 of the integrated image forming material 1 was changed to the following coating liquid for protective layer 7 Similarly, an integrated image forming material 7 was produced.

<Coating Liquid for Protective Layer 7> Urethane resin [Nipporan 3109, manufactured by Nippon Polyurethane Industry Co., Ltd.] 1.98 parts Coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd.) 0.77 parts Polyethylene wax CE-155 ( 0.06 parts Silica [Silohobic 200 manufactured by Fuji Silysia Chemical Ltd.] 0.06 parts Stearic acid 0.06 parts Alumina [High purity alumina HIT60G manufactured by Sumitomo Chemical Co., Ltd.] 0.06 parts Toluene 29.1 parts Cyclohexanone 67.9 parts Production of integrated image forming material 8 The coating liquid for the protective layer 1 of the integrated image forming material 1 is transferred to the coating liquid for the following protective layer 8 An integrated image forming material 8 was prepared in the same manner except that the coating liquid for layer 1 was changed to the coating liquid for layer 3 to be transferred.

<Coating solution for protective layer 8> UCAR phenoxy resin PKHH (manufactured by Union Carbide) 0.99 parts Urethane resin [manufactured by Dainippon Ink and Chemicals, Inc., Pandex T5201] 0.99 parts Coronate HX (Japan) Polyurethane Industry Co., Ltd.) 0.77 parts Polyethylene wax CE-155 (Koyo Chemical Co., Ltd.) 0.06 parts Silica [Fuji Silysia Chemical Ltd., Silo Hobic 200] 0.06 parts Stearic acid 0.06 parts Alumina [High-purity alumina HIT60G, manufactured by Sumitomo Chemical Co., Ltd.] 0.06 parts Toluene 29.1 parts Cyclohexanone 67.9 parts <Coating solution for layer 3 to be transferred> (1.8 g / m ²⁾ 4.) Pesresin S-110G (manufactured by Takamatsu Yushi Co., Ltd.) 4.90 parts Silicone resin particles [Tospearl 120 manufactured by Toshiba Silicone Co., Ltd.] 0 10 parts Toluene 42.75 parts Methyl ethyl ketone 42.75 parts Cyclohexanone 9.50 parts ・ Preparation of integrated image forming material 9 Change the coating liquid of protective layer 1 of integrated image forming material 1 to the following protective layer 9 coating liquid. In this manner, an integrated image forming material 9 was produced in the same manner as described above.

<Coating Liquid for Protective Layer 9> Urethane resin [Pandex T5201 manufactured by Dainippon Ink and Chemicals, Inc.] 1.98 parts Coronate HX (Nippon Polyurethane Industry Co., Ltd.) 0.77 parts Polyethylene wax CE -155 (manufactured by Koyo Chemical Co., Ltd.) 0.06 parts Silica [manufactured by Fuji Silysia Chemical Ltd., Silo Hobic 200] 0.06 parts Stearic acid 0.06 part Alumina [manufactured by Sumitomo Chemical Co., Ltd. Purity alumina HIT60G] 0.06 parts Toluene 29.1 parts Cyclohexanone 67.9 parts ・ Preparation of integrated image forming material 10 (for comparison) The protective layer 1 coating solution of the integrated image forming material 1 is coated with the following protective layer 10 An integrated image forming material 10 was prepared in the same manner except that the coating liquid was changed.

<Coating Solution for Protective Layer 10> UCAR phenoxy resin PKHH (manufactured by Union Carbide Co.) 1.98 parts Coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd.) 0.77 parts Polyethylene wax CE-155 (Koyo Chemical Co., Ltd.) Co., Ltd.) 0.06 parts Silica [Silohobic 200, manufactured by Fuji Silysia Chemical Ltd.] 0.06 parts Stearic acid 0.06 parts Alumina [Sumitomo Chemical Co., Ltd., high-purity alumina HIT60G] 0.06 Part Toluene 29.1 parts Cyclohexanone 67.9 parts ・ Preparation of integrated image forming material 11 (for comparison) Coating liquid for protective layer 1 of integrated image forming material 1 is transferred to coating liquid for protective layer 10 An integrated image forming material 11 was produced in the same manner except that the coating liquid for the layer 1 was changed to the coating liquid for the layer to be transferred 2.

Preparation of Integrated Image Forming Material 12 (Comparative) The same procedure was repeated except that the coating liquid for the transfer layer 1 of the integrated image forming material 1 was changed to the coating solution for the transfer layer 4 described below. A body type image forming material 12 was produced.

<Coating Solution for Transferred Layer 4> (Coating Weight 1.2 g / m ² ) Clayton D-1117 (manufactured by Shell Japan Co., Ltd.) 4.90 parts Silicone resin particles [manufactured by Toshiba Silicone Co., Ltd., Tospearl 120] 0.10 parts Toluene 42.75 parts Methyl ethyl ketone 42.75 parts Cyclohexanone 9.50 parts The following evaluations were performed on the integrated image forming materials 1 to 12 described above.

The image was evaluated using a semiconductor laser (LT090MD manufactured by Sharp Corporation, dominant wavelength: 830 nm), focusing on the surface of the image forming layer, and exposing energy 360 mj (illuminance 9583, rotation number 295 r) from the support side of the image forming layer.
pm) is image-exposed by scanning exposure to reduce the bonding force between the image forming layer and the support of the laser-irradiated portion imagewise, and then the image forming layer (image forming layer and protective layer) is transferred from the transfer sheet. An image was formed by peeling.

Resolution: 508 × 610 mm image size was exposed by a test pattern, and the following visual observation was performed with a 100 × loupe.

◎: A fine line of 10 μm can be formed ○: A fine line of 20 μm can be formed △: A fine line of 40 μm can be formed ×: A fine line of 40 μm cannot be formed

Dot quality (Dot Quality = D)
Q): A sample having been subjected to 50% halftone dot exposure of a 508 × 610 mm image size was visually observed using a 100 × loupe as follows.

5: No roughening 4: Very slight roughness but no problem 3: Gas roughing but no real harm 2: Frequent roughening and real harmful occurrence 1: Very rough and very harmful

Dmin: evaluation screen ruling 70 L /
cm, halftone dot round, 0% at screen angle 45 °
The halftone dot image is formed, and the transmission density of the halftone dot image formed on the image is determined by using a densitometer [X-rite: X-
And the evaluation was averaged.

Conveying speed evaluation: Heating and pressurizing treatment [Roll temperature: 60 ° C., Conveying speed m / min of each sample subjected to pressure of 1.1 kg / cm ² [Peel force when peeling off transfer-receiving sheet is 5 g / cm. The transport speed was adjusted so that A higher transport speed is more suitable for productivity.

Measurement of lateral peel force: Each sample was previously heated and pressurized to a size of 1 × 10 cm and a peel force of 5 g / cm.
After adjusting the transfer speed so that
In each width direction when a 00 × 10 cm size sample is passed, 100 points of 1 × 10 cm size, JIS C 21
07 (JIS Z 0237) 180 degree peeling method, peeling force was evaluated, and the maximum value, minimum value, and average value of the peeling force (g / cm) at that time were measured.

Evaluation of 50% screen unevenness: 508 × 610 mm
The sample subjected to halftone exposure of 50% of the image size was evaluated for the presence or absence of unevenness by visual observation.

5: No unevenness at all 4: Very slight unevenness but no problem 3: Unevenness but no real harm 2: Frequent unevenness sometimes causes real harmfulness 1: Extremely large unevenness and real harmfulness Yes.

Tables 1 and 2 show the evaluation results.

[0088]

[Table 1]

[0089]

[Table 2]

PKHH: phenoxy resin UE-3690: polyester resin N3109: urethane resin N5120: urethane resin RV-200: polyester resin T5201: urethane resin S-110G: polyester resin D-1117: styrene -Isoprene copolymer As is clear from Tables 1 and 2, when the binder resin used for the protective layer and the layer to be transferred contains at least one of a polyester resin and a polyurethane resin, the performance of each property is improved. It can be seen that the most stable sample was obtained.

Example 2 An integrated image forming material was produced in the same manner as in Example 1 except for the protective layer and the transfer-receiving layer shown below.

Preparation of Integrated Image Forming Material 13 An integrated image forming material was prepared in the same manner except that the coating liquid for the layer to be transferred 1 of the integrated image forming material 1 was changed to the coating liquid for the layer to be transferred 5 shown below. 13 was produced.

<Coating Liquid for Transferred Layer 5> (Coating Weight 1.6 g / m ² ) Urethane resin [Nipporan 5120, manufactured by Nippon Polyurethane Industry Co., Ltd.] 4.90 parts Silicone resin particles [manufactured by Toshiba Silicone Co., Ltd.] , Tospearl 120] 0.10 parts Toluene 42.75 parts Methyl ethyl ketone 42.75 parts Cyclohexanone 9.50 parts ・ Preparation of integrated image forming material 14 The coating liquid for the transfer layer 1 of the integrated image forming material 1 was coated as follows. An integrated image forming material 14 was prepared in the same manner except that the coating liquid for the transfer layer 6 was changed.

<Coating solution for transfer-receiving layer 6> (coating amount: 1.6 g / m ² ) Urethane resin (Nipporan 5193, manufactured by Nippon Polyurethane Industry Co., Ltd.) 4.90 parts Silicone resin particles (manufactured by Toshiba Silicone Co., Ltd.) , Tospearl 120] 0.10 parts Toluene 42.75 parts Methyl ethyl ketone 42.75 parts Cyclohexanone 9.50 parts-Preparation of integrated image forming material 15 An integrated image forming material 15 was prepared in the same manner except that the transfer layer 7 was changed to a coating liquid.

<Coating Liquid for Transferred Layer 7> (1.6 g / m ² ) Urethane resin [Nipporan 5138, manufactured by Nippon Polyurethane Industry Co., Ltd.] 4.90 parts Silicone resin particles [manufactured by Toshiba Silicone Co., Ltd.] , Tospearl 120] 0.10 parts Toluene 42.75 parts Methyl ethyl ketone 42.75 parts Cyclohexanone 9.50 parts ・ Preparation of integrated image forming material 16
An integrated image forming material 16 was prepared in the same manner except that the coating liquid for the layer to be transferred 1 was changed to the coating liquid for the layer to be transferred 8 described below.

<Coating liquid for transfer-receiving layer 8> (1.8 g / m ^{2 in} weight) Byron RV-500 (manufactured by Toyobo Co., Ltd.) 4.90 parts Silicone resin particles [manufactured by Toshiba Silicone Co., Ltd., Tospearl 120] 0.10 parts Toluene 42.75 parts Methyl ethyl ketone 42.75 parts Cyclohexanone 9.50 parts Preparation of integrated image forming material 17 Protective layer 1 of the integrated image forming material 1 is applied to the protective layer 7
An integrated image forming material 17 was prepared in the same manner except that the coating liquid for the layer to be transferred 1 was changed to the coating liquid for the layer to be transferred 9 described below.

<Coating Solution for Transferred Layer 9> (1.8 g / m ² ) Pesresin S-111S (manufactured by Takamatsu Oil & Fats Co., Ltd.) 4.90 parts Silicone resin particles [Tospearl manufactured by Toshiba Silicone Co., Ltd. 120] 0.10 parts Toluene 42.75 parts Methyl ethyl ketone 42.75 parts Cyclohexanone 9.50 parts After the above-mentioned integrated image forming materials 13 to 17 were subjected to heat and pressure treatment, and then left in an oven at 55 ° C. for 3 days. Dot quality (Dot Quality = D) as in the first embodiment.
Q), Dmin, lateral peel force, and 50% screen unevenness were evaluated to evaluate environmental stability. For comparison, an integrated image forming material 10 was used. Tables 3 and 4 show the evaluation results.

[0098]

[Table 3]

[0099]

[Table 4]

N5193: urethane resin N5138: urethane resin RV-500: polyester resin S-111S: polyester resin As is clear from Tables 3 and 4, polyester resin or polyurethane resin used for the layer to be transferred is used. Softening point is 6
It can be seen that when the temperature is 0 ° C. or higher, the image forming material has excellent environmental stability.

Example 3 Preparation of Integrated Image Forming Materials 18 to 24 Same as above except that the coating liquid for the layer to be transferred 1 of the integrated image forming material 2 was changed to the following coating liquid for the layers to be transferred 10 to 16 Thus, integrated image forming materials 18 to 24 were produced.

<Coating liquids for transfer layers 10 to 16> (coating amount: 1.6 g / m ² ) Binder (Nipporan 3109 (softening point: 45 ° C.) [manufactured by Nippon Polyurethane Industry Co., Ltd.]) and Nipporan 5120 (softening point: 100 ° C) The ratio of [Nippon Polyurethane Industry Co., Ltd.] was changed as shown in Table 5.) 4.90 parts Silicone resin particles [Tospearl 120, Toshiba Silicone Co., Ltd.] 0.10 parts Toluene 42.75 parts Methyl ethyl ketone 42.75 parts Cyclohexanone 9.50 parts ・ Preparation of integrated image forming materials 25 to 31 The coating liquid for the layer to be transferred 1 of the integrated image forming material 3 was changed to the following coating liquid for the layers to be transferred 17 to 23 Except for the above, integrated image forming materials 25 to 31 were prepared in the same manner.

<Coating Liquids for Transfer Layers 17 to 23> (1.8 g / m ² ) Binder (Nipporan 2304 of urethane resin (softening point: 55 ° C.) [Nippon Polyurethane Industry Co., Ltd.]) and Nipporan 5138 (Softening point 80 ° C.) The ratio of [Nippon Polyurethane Industry Co., Ltd.] was changed as shown in Table 5. 4.90 parts Silicone resin particles [Tospearl 120, manufactured by Toshiba Silicone Co., Ltd.] 0.10 parts Toluene 42.75 parts Methyl ethyl ketone 42.75 parts Cyclohexanone 9.50 parts ・ Preparation of integrated image forming materials 32-38 Coat the coating layer 1 coating solution of the integrated image forming material 5 with the following transferred layers 24-30 Except for changing to the working liquid, the same procedure was carried out to produce integrated image forming materials 32-38.

<Coating Solution for Transferred Layers 24 to 30> (1.8 g / m ² ) Binder (Pesthresin S-250 of polyester resin (softening point 40 ° C.) [manufactured by Takamatsu Yushi Co., Ltd.]) and Pesresin S -90G (softening point 65 ° C) [Takamatsu Oil & Fat Co., Ltd.] ratio was changed as shown in Table 5.) 4.90 parts Silicone resin particles [Tospearl 120, manufactured by Toshiba Silicone Co., Ltd.] 0.10 parts Toluene 42.75 parts Methyl ethyl ketone 42.75 parts Cyclohexanone 9.50 parts The above-mentioned integrated image forming materials 18 to 38 were evaluated for the conveying speed in the same manner as in Example 1, and after and after the heat and pressure treatment in the same manner as in Example 2. Further, the dot quality (Dot Quality = D) of the integrated image forming material left in an oven at 55 ° C. for 3 days.
Q), Dmin, lateral peel force, and 50% screen unevenness were evaluated to evaluate environmental stability. Tables 5 and 6 show the evaluation results.

[0105]

[Table 5]

[0106]

[Table 6]

As is clear from Tables 5 and 6, the softening point of the polyester resin or polyurethane resin used in the layer to be transferred is less than 60 ° C. and 20% of the total amount of the binder resin used in the layer to be transferred. It can be seen that when the content is in the range of from 80% to 80%, the image forming material is excellent in productivity and environmental stability.

[0108]

As described above, an image forming sheet in which at least an image forming layer and a protective layer are laminated in this order on a support as shown in the examples, and a transfer sheet having a transfer layer provided on the support When high-density energy light is irradiated on the image forming material facing the image forming layer, the protective layer and the transfer-receiving layer contain at least one of a polyester resin and a polyurethane resin, so that the image forming layer and the protective layer of the exposed portion are exposed. Is transferred to the transfer sheet satisfactorily, and an image forming material having good dry treatment can be provided.

Claims (4)

[Claims] An image forming sheet in which at least an image forming layer and a protective layer are laminated in this order on a support and a transfer sheet provided with a transfer layer separately on the support face each other to form an image forming sheet. By irradiating high-density energy light from the support side, the bonding force between the support and the image forming layer is reduced, the transfer target is peeled off, and at the same time, the image forming layer and the protective layer of the exposed part are transferred to the transfer target. An image forming material for forming an image, wherein the protective layer and the transferred layer contain at least one of a polyester resin and a polyurethane resin. 2. The softening point of at least one of a polyester resin and a polyurethane resin contained in the transfer-receiving layer is 60 ° C. or higher.
The image forming material as described in the above. 3. The softening point of at least one of the polyester resin and the polyurethane resin contained in the transferred layer is less than 60 ° C., and the content of the resin is less than the total binder resin amount of the transferred layer. 2. The image forming material according to claim 1, wherein the content is in the range of 20% to 80%. 4. An image forming method using the image forming material according to claim 1. Description: