JP2001060007A - Image forming material and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image forming material less liable to stain, having high resolution and causing no minute spot-like image defects in the image forming part. SOLUTION: An image forming sheet obtained by successively laminating at least an image forming layer and a protective layer on a substrate and a sheet to be subjected to transfer obtained by disposing a layer to be subjected to transfer on a substrate are placed opposite to each other to obtain the objective image forming material. This image forming material is irradiated with light having high density energy from the substrate side of the image forming sheet, the bonding force between the image forming layer and the substrate is reduced and the sheet to be subjected to transfer is peeled to perform image formation. At least a binder and filler particles are contained in the layer to be subjected to transfer, and when the coating weight of the layer to be subjected to transfer is represented by A (g/m2) and the average particle diameter and specific gravity of the filler particles are represented by B (μm) and C (g/cm3), respectively, the number E of the filler particles present in 1 mm2 layer to be subjected to transfer satisfies the relation of the expression E>=D =(205,000A-199,000)÷C÷B3 (where A<=B and 1.4D<=E<= 1.7D).

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 and irradiated on a recording material to melt or deform a part of the recording material, or to scatter, burn or evaporate (hereinafter, collectively referred to as ablation). A recording method is known.

[0003] These are dry treatments that do not require treatment liquids such as chemicals, and have the advantage that high contrast can be obtained because only the light irradiation portion is melted, scattered or removed by evaporation. , Optical recording materials such as optical disks, and transparent originals at the time of producing printing plates.

For example, JP-A-8-310124 and JP-A-8-310124
No. 334894, No. 8-337053, No. 8-33
No. 7054, No. 8-337055, No. 9-15849
For example, Japanese Patent Application Laid-Open No. H11-163702 proposes an image forming material using a ferromagnetic powder as a coloring material, and by using these image forming materials, a high-resolution image with less contamination can be obtained.

However, with these image forming materials, minute dot-like image defects may occur in the image forming portion.
The solution had not been fully resolved.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances.
An object of the present invention is to provide an image forming material which has a high resolution with little contamination and which does not cause minute dot-like image defects in an image forming portion.

[0007]

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

(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 on the support are faced to support the image forming sheet. Irradiating high-density energy light from the body side, reducing the bonding force between the support and the image forming layer, in the image forming material for forming an image by peeling the transfer object, at least a binder component to the transfer layer When filler particles are contained and the amount of the transferred layer is A (g / m ² ), the average particle size of the filler particles is B (μm), and the specific gravity of the filler particles is C (g / cm ³ ), An image forming material in which the number E (particles / mm ² ) of filler particles present in 1 mm ² of the transfer layer satisfies the following relationship with the solution D of the following formula 1.

E ≧ D = (205000A-199000) ÷ C ÷ B ³ Formula 1 (2) The image forming material according to (1), wherein A ≦ B in the formula 1.

(3) In the above formula 1, 1.4D ≦ E ≦ 1.7D
(1) The image forming material according to (1).

(4) The image-forming material according to (1), wherein the binder component of the layer to be transferred mainly comprises a polyurethane resin.

(5) The image forming material according to (1), wherein the filler particles of the layer to be transferred are silicone resin particles.

(6) An image forming method using the image forming material according to any one of (1) to (5).

That is, the present inventor defines the relationship between the binder and the filler particles of the layer to be transferred, so that minute dot-like image defects can be formed in the image forming portion while maintaining high sensitivity and high quality image performance. The present inventors have obtained the finding that such a phenomenon does not occur, leading to the present invention.

Hereinafter, the image forming material and the image forming method used in the present invention will be described in detail.

<Image Forming Material> As a form of the image forming material of the present invention, a transferred image having a transfer layer on another support on an exposure sheet having an image forming layer and a protective layer on a support in this order. The structure provided with a sheet is a basic structure, and an intermediate layer may be provided between the first support (the support of the exposure sheet) and the image forming layer. In addition, a back surface treatment layer may be provided on the back surface of each support for the purpose of preventing static electricity or matting the surface.

The transfer sheet basically has a support and a transfer layer.

As a support of the sheet to be transferred, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate, polyacrylate, polyvinyl chloride (PVC)
C), polyethylene (PE), polypropylene, polystyrene, nylon, aromatic polyamide, polyetheretherketone, polysulfone, polyethersulfone,
Each resin film such as polyimide, polyetherimide,
Further, a resin film formed by laminating two or more layers of the above resin can be used.

The thickness of the support is about 6 to 100 μm, preferably 10 to 50 μm.

The transferred layer contains a binder resin and filler particles as basic constituents.

The binder resin may be any of those having adhesiveness at normal temperature or those exhibiting adhesiveness by applying heat or pressure, and examples thereof include resins having a low softening point.

Examples of the resin having a low softening point include polystyrene resin, polyester resin, polyolefin resin, polyvinyl ether resin, acrylic resin, ionomer resin, cellulose resin, epoxy resin, vinyl chloride resin, urethane resin. Resins.

In the binder, an adhesiveness-imparting agent, a thermal solvent, a wax and the like can be appropriately selected and added as long as the effects of the present invention are not impaired.

Examples of the adhesion-imparting agent include unmodified or modified products such as rosin, hydrogenated rosin, rosin maleic acid, polymerized rosin and rosin phenol, terpenes, petroleum resins and modified products thereof. As a hot solvent,
A known compound which is solid at ordinary temperature and liquefies or softens reversibly upon heating can be appropriately selected and used. 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.

The filler particles include carbon black, graphite, TiO ₂ , BaSO ₄ , ZnS, Mg
CO ₃ , CaCO ₃ , ZnO, CaO, WS ₂ , MoS ₂ ,
MgO, SnO ₂ , Al ₂ O ₃ , α-Fe ₂ O ₃ , α-Fe
OOH, SiC, CeO ₂ , BN, SiN, MoC, B
Inorganic fillers such as C, WC, titanium carbide, corundum, artificial diamond, feldspar, garnet, quartzite, triboli, diatomaceous earth, dolomite, polyethylene resin particles, fluorine resin particles, guanamine resin particles, acrylic resin particles, silicon resin particles, Organic fillers such as melamine resin particles can be used.

The filler particles preferably have a narrow particle size distribution and a uniform particle size. Specifically, Toshiba Silicone Co., Ltd .: Silicone resin fine particles (product name: Tospearl), Soken Chemical Co., Ltd .: Crosslinked acrylic fine powder MR series, Crosslinked polystyrene fine powder SGP series, Acrylic ultrafine powder M
P series: manufactured by Fuji Silysia Chemical Ltd. (product name: Silo Hobik).

The particle size of the filler particles can be determined as an average particle size using a laser diffraction / scattering type particle size distribution analyzer LA-920 (manufactured by HORIBA, Ltd.).
0 μm, preferably about 0.3 to 10 μm.

In the present invention, the amount of filler particles added is
The weight of the transfer-receiving layer is A (g / m ² ), the average particle size of the filler particles is B (μm), and the specific gravity of the filler particles is C (g / cm 2).
³ ), the number E (particles / mm ² ) of the filler particles present in 1 mm ² of the transfer-receiving layer satisfies the relationship of Expression 1, and more preferably within the range of 1 to 2 times D. It is. 1
The number E of the filler particles present in mm ² is represented as “60000 × A × F ÷ C ÷ π × B ^-3 ” when the solid content ratio of the filler particles in the transfer layer coating liquid is F (% by weight). Can be calculated.

The thickness of the layer to be transferred is not more than the average particle size of the filler particles, more preferably 50 to 80% of the average particle size of the filler particles.

As a solvent for coating the layer to be transferred, a solvent capable of dissolving or dispersing the binder resin and dispersing the filler particles can be appropriately selected and used. Examples of the solvent include water, alcohols (ethanol, propanol, etc.), and cellosolve. (E.g., methyl cellosolve, ethyl cellosolve), aromatics (e.g., toluene, xylene, chlorobenzene), ketones (e.g., acetone, methyl ethyl ketone), ester solvents (e.g., ethyl acetate, butyl acetate), ethers (e.g., tetrahydrofuran, dioxane) And the like, halogen-based solvents (such as chloroform and dichlorobenzene), and amide-based solvents (such as dimethylformamide and N-methylpyrrolidone).

Next, the image forming sheet will be described.

As a support for the image forming sheet, PE
T, each resin film such as polybutylene terephthalate, PEN, polycarbonate, polyacrylate, PVC, PE, polypropylene, polystyrene, nylon, aromatic polyamide, polyetheretherketone, polysulfone, polyethersulfone, polyimide, polyetherimide, and the like. Examples thereof include a transparent support such as a resin film obtained by laminating two or more layers of the resin.

The transparent support is provided with a light of an exposure light source wavelength of 50.
% Or more, and a film-stretched and heat-set support is preferable from the viewpoint of dimensional stability. Titanium oxide, zinc oxide, barium sulfate, calcium carbonate, etc. are used as long as the effects of the present invention are not impaired. A filler may be added. The thickness of the transparent support is about 10 to 500 μm, preferably 25 to 250 μm.

The image forming layer basically comprises a magnetic material and a binder resin for holding the magnetic material.

Examples of the magnetic material include a ferromagnetic iron oxide powder, a ferromagnetic metal powder, a cubic plate-like powder, a hexagonal plate-like powder and the like. Among them, a ferromagnetic metal powder can be preferably used.

As the ferromagnetic iron oxide, γ-Fe ₂ O ₃ , F
e ₃ O ₄ , or FeOx (1.33) with these intermediate iron oxides
<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 FeOx (4/3 <x <3/2)
Cobalt-containing iron oxide-based magnetic powder such as powder.
Also, from the viewpoint of corrosion resistance and dispersibility, among the Fe-based metal powders, Fe-Al-based, Fe-Al-Ca-based, Fe-A
l-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
Having a structure in which the content ratio between Fe atoms and Al atoms existing in a surface area of 100 ° or less at an analysis depth by line photoelectron spectroscopy is Fe: Al = 30: 70 to 70:30 in atomic ratio. Alternatively, at least one of Fe atom, Ni atom, Al atom, Si atom, and Co atom and Ca atom is contained in the ferromagnetic powder, the content of Fe atom is 90 atom% or more, and the content of Ni atom is 1 to 1. 10 atom%, Al atom content is 0.1 to 5 atom%, Si atom content is 0.1 to 5 atom%, Co atom or Ca atom content (when both are contained, the total amount) Is 0.1 to 13 atomic%, and Fe, Ni, Al, and Si atoms present in a surface area of 100 ° or less at an analysis depth of the ferromagnetic powder by ESCA (X-ray photoelectron spectroscopy), With Co and / or Ca atoms Fe content ratio in atomic ratio: N
i: Al: Si: (Co and / or Ca) = 100:
(4 or less): (10-60): (10-70): (20
To 80) are preferred.

The shape of the ferromagnetic powder is such that the major axis diameter is 0.3.
0 μm or less, preferably 0.20 μm or less. According to such a ferromagnetic powder, the surface property of the colorant 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.).
trans on MAG, p. 18, 16 (1982)
Can be mentioned. Among these, examples of the barium ferrite magnetic powder include an average particle size in which at least a part of Fe is replaced by Co and Zn (diagonal height of the plate surface of hexagonal ferrite) 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, for example, to melt an oxide or 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. Other than 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 amount 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, based on all components of the image forming layer.

The binder resin can be used without any particular limitation as long as it can sufficiently retain the colorant capable of absorbing the wavelength light of the exposure light source and the metal atom-containing powder. Examples of such a binder resin, a polyurethane, a polyester, vinyl chloride resins such as vinyl chloride copolymers are exemplary, these resins are -SO ₃ M, -OS
A repeating unit having at least one polar group selected from O ₃ M, —COOM and —PO (OM ₁ ) ₂ (M represents a hydrogen atom or an alkali metal, and M ₁ represents a hydrogen atom, an alkali metal or an alkyl group); The resin preferably contains a unit, and by using such a resin having 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 it is 0.2 to 6.0 mol%. The binder resin may be used alone or in combination of two or more.

Examples of the polar group-containing vinyl chloride include a resin having a hydroxyl group, such as a vinyl chloride-vinyl alcohol copolymer, and ClCH ₂ CH ₂ SO ₃ M, ClCH ₂ CH ₂ O.
SO ₃ M, ClCH ₂ CO ₂ M, ClCH ₂ P (＝ O) (OM ₁ ) ₂
Can be synthesized by an addition reaction with a compound having a polar group and a chlorine atom. Here, M represents a hydrogen atom or an alkali metal, and M ₁ represents a hydrogen atom, an alkali metal or an alkyl group.

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 examples of a monomer for introducing an epoxy group include glycidyl acrylate. 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, and specifically, 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. Esters and the like can be mentioned. 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 (M, M ₁
As described above).

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.

The content of the magnetic material in the image forming layer is 60 to 99% by weight based on the total solids of the image forming layer.

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

Examples of the lubricant include fatty acids, fatty acid esters, fatty acid amides, (modified) silicone oils, (modified) silicone resins, fluororesins, and carbon fluorides. The durability improvers include polyisocyanate. And the like.

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, In addition to polymer antistatic agents, conductive fine particles, etc., "112
90 Chemical Products ", Kagaku Kogyo Nippo, pp. 875-876, and the like.

As the filler, those used for the above-mentioned layer to be transferred can be appropriately selected and used.

As a coloring agent for forming an image, the above-described magnetic material may also serve as a coloring agent, or a filler may also serve as a coloring agent.

As the curing agent, any one can be used without particular limitation as long as it can cure the image forming layer. Such a curing agent may be used, for example, when synthesizing the polyurethane in the binder resin described above. The polyisocyanate used can be mentioned. By adding such a curing agent to cure the image forming layer, it is possible not only to increase the durability of the formed image, but also to remove the background stain at the portion where ablation has occurred.

The amount of these additives is about 0 to 20% by weight, preferably 0 to 15% by weight, based on the total solids of the image forming layer.

The thickness of the image forming layer is 0.05 to 5.0 μm
Degree, preferably in the range of 0.1 to 3.0 μm.
Further, the image forming layer may be composed of a single layer or a multilayer having different compositions, but when composed of multiple layers, the wavelength light of the exposure light source can be absorbed in a layer closer to the support. It is preferable to contain more coloring agents. Further, a colorant capable of absorbing wavelength light other than the wavelength light of the exposure light source may be added to the layer farther from the support.

The image forming layer is formed by kneading, for example, a magnetic powder, a binder resin, and if necessary, additives such as a lubricant, a durability improver, a dispersant, an antistatic agent, a filler, a filler, a curing agent and a solvent. Then, a high-concentration magnetic paint is prepared, and then the high-concentration magnetic paint is diluted to obtain a coating magnetic coating, which is applied to a support and dried to form a coating.

As the solvent, any solvent may be used without departing from the spirit of the present invention. Alcohols (ethanol, propanol, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, etc.), aromatics (toluene, xylene,
Chlorobenzene, etc.), ketones (acetone, methyl ethyl ketone, etc.), ester solvents (ethyl acetate, butyl acetate, etc.), ethers (tetrahydrofuran, dioxane, etc.), halogen solvents (chloroform, dichlorobenzene, etc.), amide solvents (Eg dimethylformamide,
N-methylpyrrolidone) can be used.
Further, for kneading and dispersing the components of the image forming layer, a two-roll mill,
3-roll mill, ball mill, pebble mill, kobol mill, tron mill, sand mill, sand grinder, S
qegvari attritor, high-speed impeller dispersion machine,
A high-speed stone mill, high-speed impact mill, disper, 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 carried out, for example, by coating and drying with an extrusion type extrusion coater. If necessary, align the orientation of the magnetic powder,
In order to make the surface properties of the image forming layer uniform or to lower the porosity and increase the strength of the coating film, it is preferable to carry out a heat and pressure treatment. As the heating / pressing process, for example, a calendar process is performed. The calendering can be performed, for example, by guiding the support having the dried image forming layer to a super calendering apparatus, and performing calendering here.

The calendering conditions are preferably from 60 to 120 ° C., more preferably from 70 to 110 ° C. The pressure is preferably 100 to 500 kg / cm as a linear pressure, and more preferably 200 to 400 kg / cm.

When layers other than the image forming layer are provided, the coating and drying may be repeated for each layer, but the coating and drying may be performed in a wet-on-wet manner and dried. 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 impregnation 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 method, the upper layer is coated while the lower layer is kept wet, so that the adhesion between the upper and lower layers is improved.

It is preferable to provide a protective layer on the image forming layer.

For the protective layer, a binder resin is used. The binder resin can be used without any particular limitation as long as it can sufficiently hold the additive and the filler. As such a binder resin, polyurethane, polyester, vinyl chloride resin such as vinyl chloride copolymer,
Vinyl chloride resin such as vinyl chloride-vinyl acetate copolymer, polyolefin resin such as butadiene-acrylonitrile copolymer, polyvinyl acetal resin such as polyvinyl butyral, cellulose resin such as nitrocellulose, styrene-butadiene copolymer Styrene resins such as styrene resins, acrylic resins such as polymethyl methacrylate, polyamides, phenol resins, epoxy resins, phenoxy resins, acetal resins such as polyvinyl butyral, polyvinyl acetoacetal, and polyvinyl formal, and water-soluble resins such as polyvinyl alcohol and gelatin. Etc.

The binder resin may be used alone or in combination of two or more. The content of the binder resin in the protective layer is about 10 to 99.5% by weight, preferably 40 to 98% by weight of the total solids of the image protective layer.

When the protective layer is cured, it is preferable to use a resin having a functional group capable of undergoing a cross-linking reaction with a curing agent in the molecule as a selected binder. Specifically, when an isocyanate-based curing agent is used as the curing agent, a phenoxy-based resin, an epoxy-based resin, a cellulose-based resin, an acetal-based resin, an acrylic resin, a urethane-based resin, a vinyl chloride-based resin, a polyester-based resin, or the like is used. Preferably, it is used.

In order to increase the durability of the protective layer, it is preferable to add a curing agent such as polyisocyanate.
As a binder selected when curing the protective layer,
It is preferable to use a resin having a functional group capable of undergoing a cross-linking reaction with a curing agent in the molecule. Specifically, when an isocyanate-based curing agent is used as the 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 It is preferable to use

In the protective layer, wax, silicon compound and fluorine compound, as long as the effects of the present invention are not impaired,
Additives (lubricants) such as fatty acid compounds and abrasives can be appropriately selected and contained.

Specific compounds as wax include beeswax,
Solid waxes such as candelilla wax, paraffin wax, ester wax, montan wax, carnauba wax, amide wax, polyethylene wax, microcrystalline wax and the like.

Specific examples of the silicon-based compound (including a wax-like compound) include straight silicone oils such as dimethyl silicone oil, methylphenyl silicone oil, and methyl hydrogen silicone oil; olefin-modified silicone oil, and polyether-modified silicone. Oil, 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,
Radical reactive silicone oil such as higher fatty acid modified silicone oil, carnauba modified silicone oil, amide modified silicone oil, (meth) acrylic modified silicone oil; terminal reactive silicone oil such as silicon diol or silicon diamine; halogen group, alkoxy group And an organically modified silicone oil modified with an ester group, an amide group, an imide group or the like.

Examples of the fluorine compound include polytetrafluoroethylene, tetrafluoroethylene copolymer (alkyl vinyl ether, ethylene, etc.), polyvinylidene fluoride, fluoroalkyl methacrylate,
Fluorinated resins such as fluorine rubber, perfluoropolyether oil, fluorine alcohol, fluorine carboxylic acid, perfluoroalkyl carboxylate, perfluoroalkyl quaternary ammonium salt, perfluoroalkyl betaine, perfluoroalkyl ethylene oxide (adduct) And low molecular weight fluorine compounds such as perfluoroalkyl oligomers.

The amount of each of these materials is preferably from 0.1 to 30% by weight, more preferably from 0.5 to 20% by weight of the total solids in the protective layer. When multiple additions are made, the value is a multiple of this.

The fatty acid may be a monobasic acid or a dibasic acid, and preferably has 6 to 30 carbon atoms, and preferably has 1 to 30 carbon atoms.
The range of 2 to 22 is more preferable. Specifically, stearic acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid,
Linolenic acid, oleic acid, elaidic acid, behenic acid, malonic acid, succinic acid, maleic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, 1,1,
2-dodecanedicarboxylic acid, octanedicarboxylic acid and the like can be mentioned. Fatty acid esters include oleyl oleate, i-butyl stearate, dioleyl alate, butyl stearate, butyl palmitate, butoxyethyl stearate, butoxyethyl palmitate, butyl myristate, octyl myristate, octyl palmitate, pentyl Stearate, pentyl palmitate, i-butyl oleate, stearyl stearate, lauryl oleate, octyl oleate, i-butyl oleate, ethyl oleate, i-tridecyl oleate, 2-ethylhexyl stearate, 2-ethylhexyl palmitate, i- Propyl palmitate, i-propyl myristate, butyl laurate, cetyl-2-ethylhexarate, dioleyl adipate, diethyl adipate, di-i-butyl adipate, di- i- Deshiruajipeto, oleyl stearate, 2-ethylhexyl myristate, i- pentyl myristate, i- pentyl stearate, diethylene - mono - ether palmitate, diethylene - mono - ether palmitate and the like.

The abrasive is preferably present as primary particles in the protective layer. For kneading / dispersing, a two-roll mill, a three-roll mill, a ball mill, a pebble mill, a cobol mill,
Tron mill, sand mill, sand grinder, Sqe
A gvari attritor, a high-speed impeller disperser, a high-speed stone mill, a high-speed impact mill, a disper, a high-speed mixer, a homogenizer, an ultrasonic disperser, an open kneader, a continuous kneader, and the like can be appropriately selected and used. As the abrasive, inorganic oxides, inorganic nitrides, and inorganic carbides that are stable to the coating solvent and have high hardness of the fine particles themselves and are widely used as the abrasive are preferable. The average particle size of the abrasive is preferably 0.01 to 1 μm, more preferably 0.05 to 0.5 μm.

The protective layer preferably contains a matting agent in order to improve the adhesion of fingerprints by sebum and the ease of handling after image formation.

As the matting agent, 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
C, WC, titanium carbide, corundum, artificial diamond, pearlite, garnet, quartzite, triboli, diatomaceous earth, inorganic fillers such as dolomite, polyethylene resin particles, fluorine resin particles, guanamine resin particles, acrylic resin particles, silicone resin particles, melamine Organic fillers such as resin particles can be used.

Further, examples of the matting agent include inorganic fine particles and organic resin particles, and these may also serve as a releasing 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 fluorine compound particles, guanamine resin particles, acrylic resin particles, and silicon compound particles. Resin particles can be used.
These inorganic / organic resin particles vary depending on the specific gravity, but it is preferable to add 0.1 to 70% by weight of the total solids of the protective layer.

The matting agent preferably has a narrow particle size distribution and a uniform particle size. Specifically, Toshiba Silicone Co., Ltd .: Silicone resin fine particles (product name: Tospearl), Soken Chemical Co., Ltd .: Crosslinked acrylic fine powder MR series, Crosslinked polystyrene fine powder SGP series, Acrylic ultrafine powder M
P series, manufactured by Fuji Silysia Chemical Ltd. (product name: Silo Hobik) and the like. The average particle size of the matting agent is preferably from 0.3 to 20 μm, more preferably from 0.8 to 20 μm.
It is 4.5 μm.

When the surface of the matting agent has a polymerizable functional group, the adhesion between the image forming layer and the fine particles is improved when the image forming layer is cured, so that the image durability is further improved.

The thickness of the protective layer is preferably from 0.03 to 1.0 μm, more preferably from 0.05 to 0.8 μm, and particularly preferably from 0.1 to 0.4 μm.

In order to apply a coating solution in which the prepared protective layer forming component is dissolved and / or dispersed, an extrusion type extrusion coater, reverse roll coater, gravure roll coater, air doctor coater, blade coater, air knife, etc. Various known coater stations such as a coater, a squeeze coater, an impregnated coater, a bar coater, a transfer roll coater, a kiss coater, a cast coater, and a spray coater can be appropriately selected and used. Among these coaters, the coating of the protective layer is not particularly limited as long as the image forming layer is not damaged, but when the thickness of the protective layer is small,
Among the above-described coater stations, those suitable for thin layer coating are preferable, and an extrusion-type extrusion coater, gravure roll coater, bar coater, or the like can be used. Incidentally, among these, gravure roll coater, such as a bar coater, when using a coating method that comes into contact with the image forming layer, the rotation direction of the gravure roll or bar with respect to the transport direction may be forward or reverse, or,
In the case of forward rotation, a constant speed or a peripheral speed difference may be provided. Further, when using a contacting coating method, after applying an image forming layer described later, performing a smoothing process such as a calendar process, or after applying the image forming layer, cured and heat cured. It is preferably used.

As a method of laminating the image forming sheet and the transfer-receiving layer sheet, the image-protecting layer face and the transfer-receiving layer face each other, and are heated and heated using a heat roll or a hot stamp.
It can be bonded by applying pressure. As a condition for the heating and pressure treatment, when using a heat roll,
The heating temperature is usually from room temperature to 180 ° C, preferably from 30 to 180 ° C.
160 ° C., and the linear pressure is usually 0.1 to 20 kg.
/ Cm, preferably 0.5 to 10 kg / cm, and the transport speed is usually 1 to 1000 mm / sec, preferably 5 to 1000 kg / cm.
500 mm / sec. When using a hot stamp, the heating temperature is from room temperature to 180 ° C, preferably from 30 to 15 ° C.
0 ° C. and pressure is usually 0.05 to 10 kg / c
m ² , preferably 0.5 to 5 kg / cm ^2.
The pressurization time is usually 0.1 to 50 seconds, preferably 0.5 to
20 seconds.

In the image forming material of the present invention, other layers may be provided in addition to the transparent support, the intermediate layer, the image forming layer, the protective layer, and the release sheet. For the purpose of preventing blocking or the like, a backing layer is provided on the surface of the transparent support opposite to the image forming layer and / or the surface of the release sheet opposite to the image forming layer, and a protective layer is provided between the image forming layer and the protective layer. In order to prevent the penetration of the coating solvent,
A filler layer may be provided.

<Image Forming Method> The image forming material of the present invention is obtained by irradiating light from the transparent support side imagewise.
An image can be formed on the transparent support by causing ablation in the exposed portion and then peeling off the release sheet. In addition, any light source can be used without particular limitation as long as it can generate ablation.
By using laser light, it is possible to perform scanning exposure in accordance with image data by squeezing into a beam shape, and further, by using a laser as a light source, it is easy to narrow the exposure area to a very small size and to achieve high resolution. It is preferably used because image formation is possible.

The image exposure with a laser beam can be used without any particular limitation as long as it is a light source which ablates at the interface between the transparent support and the image forming layer. Electromagnetic waves whose application area can be narrowed down, in particular, ultraviolet light, visible light, and infrared light having a wavelength of 1 nm to 1 mm are preferable. As such a laser light source, generally known solid lasers such as a ruby laser, a YAG laser and a glass laser; He-Ne
Laser, Ar ion laser, Kr ion laser,
CO ₂ laser, CO laser, He-Cd laser,
Gas lasers such as N ₂ lasers and excimer lasers;
InGaP laser, AlGaAs laser, GaAs
P lasers, InGaAs lasers, InAsP lasers, semiconductor lasers such as CdSnP ₂ lasers, GaSb lasers; chemical lasers, dye lasers, and the like. Among them, a wavelength of 600 nm is required for efficient ablation. It is preferable to use a laser having a wavelength of up to 1200 nm in terms of sensitivity since light energy can be converted into heat energy.

In the case of the scanning exposure, either the outer surface scanning or the inner surface scanning may be performed depending on the power of the laser light source or the like. The exposure method may be any method as long as it causes ablation at the interface between the body or the intermediate layer and the image forming layer. However, from the viewpoint of energy efficiency, the exposure is preferably performed from the transparent support side.

The ablation referred to here means that the image forming layer and the protective layer are completely scattered due to a physical or chemical change, a part of the image forming layer and the protective layer are destroyed, and / or
Or a phenomenon in which only the image forming layer is scattered or broken, or a physical or chemical change occurs only near the interface between the image forming layer and the transparent support or the intermediate layer. In addition, as a method of peeling the exposed image forming material, a peeling plate, a peeling angle fixing method using a peeling roll, a hand peeling method of peeling off the peeling sheet and the image forming material without fixing the image by hand, and the like, affect the image formation. , Various peeling methods can be used.

[0088]

Example 1 Hereinafter, the present invention will be described 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.

(Preparation of Image Forming Material Samples) The following image forming layer compositions were separately kneaded and dispersed using a Henschel mixer and a sand mill, and then the obtained one-part, two-part and polyisocyanate compounds (Japan) Made by polyurethane industry:
Coronate HX, 100% active ingredient) by weight
0: 2.39: 0.37, and stirred with a dissolver to prepare an image forming layer coating solution.

The prepared coating solution was dispersed in an ultrasonic wave, and then extruded by extrusion extrusion coating, and a 100 μm-thick transparent PET film having a corona discharge treatment on one side (manufactured by Toray:
L60), and then calendered using a heat roll at a temperature of 100 ° C., a linear pressure of 150 kg / cm, and a conveyance speed of 60 m / sec.
For 120 hours to form an image forming layer having a thickness of 1.33 μm.

<Image forming layer composition> Ferromagnetic metal powder (manufactured by Kanto Denka Kogyo KK: MAP T1650SB) 100 parts Polyurethane resin (manufactured by Toyobo Co., Ltd .: Byron UR4122) 8.3 parts Polyester resin (manufactured by Toyobo Co., Ltd .: Byron) 280) 4.2 parts Phenoxy resin (Phenoxy Associates: Phenoxy resin PKHH) 2.5 parts Phosphate ester (Toho Chemical Industries, Ltd .: Phosanol RE610) 3.0 parts Methyl ethyl ketone 105.0 parts Toluene 105.0 parts Cyclohexanone 90 Next, a protective layer 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, and then aged at 60 ° C. for 72 hours to obtain a thickness. A 0.25 μm protective layer was formed.

<Protective layer coating liquid> UCAR phenoxy resin PKHH (manufactured by Union Carbide) 0.99 parts Elitel UE-3690 (manufactured by Unitika) 0.99 parts Coronate HX (manufactured by Nippon Polyurethane Industry) 0.77 parts Polyethylene wax CE-155 (Koyo Chemical Co., Ltd.) 0.06 parts Silica (Fuji Silysia Chemical Co., Ltd .: Silo Hobic 200) 0.06 parts Stearic acid 0.06 parts Alumina (Sumitomo Chemical Co., Ltd .: high purity alumina HIT60G) 0.06 parts Toluene 29.1 parts Cyclohexanone 67.9 parts Then, the protective layer surface of the above-mentioned image forming sheet and the coating liquids for transfer-receiving layers 1 to 20 shown in Table 1 were applied on the support in the amounts specified respectively. The transfer-receiving layer surface of the transfer-receiving sheet coated on the substrate is heated and pressed (roll temperature: 60 ° C., pressure: 1.1 k
g / cm ² , the peeling force when peeling off the transfer-receiving sheet is 5 g
/ Cm), and integrated image forming material samples 1 to 20 in which the transfer sheet was bonded to the image forming sheet were produced.

<Composition of the layer to be transferred: as shown in Table 1> Urethane resin (Nipporan 3109, manufactured by Nippon Polyurethane Industry Co., Ltd.) Shown Toluene 42.75 parts Methyl ethyl ketone 42.75 parts Cyclohexanone 9.50 parts

[0094]

[Table 1]

Using the image forming material sample prepared as described above, the focal point was adjusted to the interface between the transparent support of the image forming material and the image forming layer, and the EV laser proofer was used by using postscript data (PS data). After exposing at (Konica Corporation: 425 rotations, power 100%), an image was obtained by peeling. The resolution, D _min (dirt of the exposed portion), and scratch resistance of each image were evaluated as follows.

<< Black Pot >> A 0% halftone dot image is formed at a screen ruling of 175 lines, a halftone dot square, and a screen angle of 45 °, and the formed halftone dot image is 10 cm × 10 cm.
Was inspected with a 40-fold loupe, and the number of black pots was evaluated on a 4-point scale.

：: None ○: 1 to 10 △: 11 to 100 ×: 101 or more << Resolution >> An image is formed using a vertical stripe pattern in the main scanning direction of a 2000 DPI drum as PS data, and the formed vertical stripes The pattern was arbitrarily extracted in the main scanning direction at 30 points, observed with a loupe in the sub-scanning direction, and the difference in width between the exposed and unexposed portions was measured.

A: Average of difference in width between exposed portion / unexposed portion is less than 1 μm O: Average of difference in width between exposed portion / unexposed portion is less than 1 to 2 μm Δ: width of exposed portion / unexposed portion The average of the difference is less than 2 to 4 μm. ×: The average difference in width between the exposed part and the unexposed part is 4 μm or more.

[0099]

[Table 2]

As shown in Table 2, when the number of filler particles per 1 mm ² is larger than that of the formula 1, it can be seen that the number of black spots is less than 10.

[0101]

By using the ablation type image forming material of the present invention, an image having excellent resolution and little black spots was obtained.

Claims (6)

[Claims] 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 layer to be transferred on the support are opposed to each other. Irradiating high-density energy light from the, to reduce the bonding force between the support and the image forming layer, in the image forming material to form an image by peeling the transfer object, at least the binder component and filler in the transfer layer A (g / m ² ), the average particle size of the filler particles is B (μm), and the specific gravity of the filler particles is C.
(G / cm ³ ), wherein the number E (particles / mm ² ) of filler particles present in 1 mm ² of the transfer-receiving layer satisfies the following relationship with the solution D of the following formula (1). . E ≧ D = (205000A-199000) ÷ C ÷ B ³ Formula 1 2. The image forming material according to claim 1, wherein A ≦ B in the formula (1). 3. The image forming material according to claim 1, wherein 1.4D ≦ E ≦ 1.7D in the formula (1). 4. The image forming material according to claim 1, wherein the binder component of the layer to be transferred contains a polyurethane resin as a main component. 5. The image forming material according to claim 1, wherein the filler particles of the layer to be transferred are silicone resin particles. 6. An image forming method using the image forming material according to claim 1.