JP2002254803A - Image forming and recording medium, image forming method, and image recording device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image forming and recording medium, in which a thermal transfer sheet having high image quality and excellent image preservability or the like are employed so as to obtain the print of an photograph or the like image, on the rear surface of which characters or the like can be printed with a low cost ink jet printer or the like in order to realize a technique suitable for post-card-printing such as a small number of sheets of New Year's card and by which a printed matter having a durability more excellent than ever, and an image forming method and an image recording device. SOLUTION: In this image forming and recording medium, at least one image receiving layer including a dye fixing body capable of forming a dye by the reaction with a thermally diffusible dye precursor is provided on one side of a support, on the other side of which an ink jet image receiving layer is provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for obtaining a print of an image such as a photograph using a thermal transfer sheet or the like having high image quality and excellent image storability, and using a low-cost ink-jet printer or the like on the back of the print. It is a technique suitable for postcard printing of a small number of New Year's cards and the like, for example, which can obtain a print such as an image forming medium, an image forming recording medium, an image forming method, and an image for obtaining a printed material having excellent durability compared with the related art It relates to a recording device.

[0002]

2. Description of the Related Art Conventionally, as a technique for forming a color or monochrome image, a thermal transfer sheet provided with a dye layer containing a binder and a dye layer containing a binder, which is capable of diffusing and transferring upon heating, is used as a dye-dyeing binder. A technique is known in which an image is formed by transferring the heat-diffusible dye to the image receiving layer imagewise using a heating means such as a thermal head or a laser, in opposition to an image receiving sheet provided with an image receiving layer containing Have been. In such thermal transfer recording, the heat diffusible dye used in the dye layer plays an important role, but with the conventional heat diffusible dye, the durability of the obtained image (for example, light fastness, weather fastness, Friction resistance, chemical resistance, etc.).

As one of the means for improving the disadvantage, there has been proposed an image forming method using a reactive dye in which an image is formed by reacting a compound in a dye layer with a compound in an image receiving layer by thermal transfer. ing. Here, when the compound contained in the dye layer side is defined as a dye precursor and the compound contained in the image receiving layer is defined as a dye fixing body, for example, Japanese Patent Application Laid-Open No.
No. 3,279,763, U.S. Pat. No. 4,880,769, U.S. Pat. No. 5,534,479 can deprotonate a cationic dye as a dye precursor and protonate the cationic dye as a dye fixer. A method of forming an image by reprotonating a cationic dye by thermal transfer using an organic polymer acid or oligomer acid or the like has been proposed. JP-A-5-221151 proposes a method of forming an image by reacting a dye having a specific structure having a reactive group as a dye precursor and an active hydrogen compound as a dye fixing body by thermal transfer. Have been. Further, JP-A-59-78893,
9-109394, JP-A-60-2398, etc.
A chelatable heat-diffusible dye (hereinafter sometimes referred to as a post-chelating dye) as a dye precursor, and a metal ion-containing compound (hereinafter sometimes referred to as a metal source) as a dye fixing body. A method of forming an image by reacting them by thermal transfer to form a metal chelate dye is disclosed.

An image is formed using such a reactive dye (hereinafter, the dye precursor may be referred to as a dye. In the part according to the present invention, the dye refers to the dye precursor unless otherwise specified). If the reaction rate is higher, the higher the reaction rate, the higher the fixability. Of course, for images formed with these dyes, heat rollers, heat presses, hot air, far infrared rays,
By performing the reheating treatment using a heating means such as a thermal head, the image storability is further improved. For example, as a method for increasing the chelation rate, an image forming method in which an image after the transfer of a post-chelating dye is further subjected to a heat treatment is proposed in Japanese Patent Application Laid-Open No. Hei 4-89292. A method of reheating an image obtained by reacting a dye having a specific structure with an active hydrogen compound has been proposed in JP-A-10-138646. When using a means for heating directly in contact with an image, such as a thermal head, heat roller, or heat press, use a non-transferable resin layer, for example, to destroy the image surface or prevent dye from contaminating the heat source. It is preferable to carry out the reheating treatment via a sheet material provided with a.

As another means for improving storage stability, a protective layer transfer sheet having a heat transferable protective layer is superimposed on the image forming surface of the image receiving sheet, and the sheet is heated using a heating means such as a thermal head or a heat roller. There is known a method of providing a protective layer on an image forming surface by transferring the protective layer. When the protective layer is provided in the form of an image, the friction resistance, chemical resistance, solvent resistance and the like of the image can be improved. Also, an ultraviolet absorber is added to the protective layer to improve the light fastness of the image, or a fluorescent whitening agent is added to the protective layer to prevent forgery or to improve the whiteness of the print. A special function, such as causing the protective layer, can be given to the protective layer. Further, when an image is formed using a reactive dye, reheating treatment is performed simultaneously with the provision of the protective layer, so that further improvement in storage stability can be expected.

In the transfer recording medium for thermal transfer recording including the above-described chelate-type sublimation thermal transfer, the surface opposite to the surface on which an image is to be recorded is improved in mechanical transportability of an image receiving sheet, antistatic, writing property imparting, and the like. For this purpose, a back layer is conventionally provided. The writing layer for imparting writability is a layer provided with writing properties using an aqueous pen, a ballpoint pen, a fountain pen, a pencil or the like, or a layer having printing and printing suitability such as printing ink, ink jet ink, hot melt transfer ink, and toner. In the case where the image receiving sheet is used as a postcard, the writing layer can be provided with adhesiveness of a stamp. The writing layer is mainly composed of a binder resin and an inorganic filler.

In recent years, characters and the like are often printed on the back surface using an inexpensive inkjet printer. In particular, when printing characters on the back side such as postcards or New Year's cards, it is necessary to use an ink jet method that can achieve higher density and consume less material along a smaller printing area than sublimation thermal transfer recording on both sides. Have been. However, in the first place, in the case of inkjet printing, water-based inks are often used in terms of their handleability and the ability to finely control the dot diameter.However, the water-based inks have low volatility and thus easily remain on recording paper after recording.
In particular, the ink tends to bleed in a high density portion where the amount of ink is large. In conventional recording media for thermal transfer recording, the back surface is not particularly suitable for inkjet printing, and when performing inkjet printing with a conventional recording medium, the ink absorption amount is low and the ink amount is large. The overflow of the ink liquid on the surface and the occurrence of bleeding due to the residual solvent as described above not only resulted in an unclear image, but also a low ink holding ability, resulting in low water resistance and weather resistance.

In order to improve weather resistance and water resistance,
There is an ink jet print using a pigment ink as an ink liquid, but there is a problem that surface rubbing is low.

[0009] On the other hand, the art of ink jet recording paper has been known in the art, and its main structure is an image receiving layer containing a hydrophilic binder or a hydrophilic colloid compound in order to enhance ink absorbency and, if necessary, fine particles. The one provided with is used. The main types include a void type in which a void is formed in the ink absorbing layer film to absorb the ink and a swelling type in which the ink is absorbed by the swelling action of the binder in the ink absorbing layer.

As a prior art of the void type, for example, an ink jet recording paper in which a coating material for surface processing is wetted on a low-size base paper described in JP-A-52-53012, and described in JP-A-55-5830. Ink-jet recording paper provided with an ink-absorbing coating layer on the surface of a support, an ink-jet recording paper containing non-colloidal silica powder as a pigment in a wearable layer described in JP-A-56-157, JP-A-57-107878 describes an ink-jet recording sheet using both an inorganic pigment and an organic pigment together, JP-A-58-110287 describes an ink-jet recording sheet having two pore distribution peaks, Ink jet recording paper comprising two upper and lower porous layers described in JP-A-62-111782.
Nos. -68292, 59-123696 and 60
Ink jet recording paper having irregular cracks described in JP-A-1818383
Nos. 61-148092 and 62-14947
JP-A-63-252779, JP-A-1-252, and JP-A-6-252779.
No. 108083, No. 2-136279, No. 3-653
No. 76 and No. 3-27976 and the like, ink jet recording paper containing a pigment having specific physical properties and fine particle silica, JP-A-57-14091, JP-A-57-14091;
0-219083, 60-210984, 61
-20797, 61-188183 and JP-A-5-208.
Nos. 278324, 6-92011, 6-1831
No. 34, No. 7-137431, No. 7-276789, and the like, and an ink jet recording paper containing fine particle silica such as colloidal silica, and
No. 276,671, No. 3-67684, No. 3-2150
No. 82, No. 3-251488, No. 4-67986,
Many ink jet recording papers containing alumina hydrate fine particles described in JP-A-4-263983 and JP-A-5-16517 are known.

In a film having a void structure, it is most effective to increase the coating film thickness in order to achieve a high void volume. However, in this case, there is only a disadvantage that the production cost increases. In addition, since the solid content also increases, curling and brittleness of the film (especially cracking under low humidity and film adhesion to a support) are apt to be greatly reduced.

For this reason, it is preferable to form as many voids as possible by using a minimum amount of solids such as a binder to reduce the overall dry film thickness as much as possible.

A straightforward method for increasing the void volume with respect to the solid content of the binder or the like is to increase the ratio of the inorganic fine particles to the hydrophilic binder, and to use no unnecessary solid content as much as possible. In this case, there is a problem that the fragility of the film is extremely deteriorated.

[0014] When the brittleness of the film is deteriorated, the film is peeled off or cracked at the time of handling or feeding or transporting the ink-jet recording paper, and serious blurring of the image occurs along the cracking. Causes disadvantages.

Conventional techniques of the swelling type include, for example, gelatin, casein, starch, alginic acid, polyvinyl alcohol, various modified polyvinyl alcohols, polyvinyl pyrrolidone, polyethylene oxide, polypropylene oxide, carboxymethyl cellulose, hydroxyethyl cellulose, dextran, pullulan and the like as binders. Many recording papers, films, and the like in which a hydrophilic binder is coated on a support have been conventionally known.

These ink jet recording papers provide a clear image with high gloss and optical density, and have a high ink absorption capacity due to the ink swelling action of the binder of the film with respect to the ink liquid. Although it has the advantage that it can be retained, the ink absorption rate is inferior to inkjet recording paper having a void structure,
In particular, there is a disadvantage that roughness due to repulsion of ink droplets easily occurs in a portion where printing with a large amount of ink is performed.

As the ink used for ink-jet recording, a dye soluble in a solvent having a sharp absorption spectrum, high purity and clear coloration, and having no particles and a clear hue is used. However, a general dye has a problem in that when a molecule is destroyed by a photochemical reaction or the like, the decrease in the number of molecules is directly reflected on the coloring density, so that the weather resistance is poor.

[0018]

SUMMARY OF THE INVENTION An object of the present invention is to provide an image forming / recording system capable of recording an image having both excellent durability and good image quality and an image which can be printed at low cost with good character. Providing a medium, an image forming method and an image recording apparatus, specifically, using a chelate-type sublimation thermal transfer with high image quality and excellent image storability, obtaining an image print such as a photograph, It is a technology suitable for printing postcards such as New Year's cards with a small number of copies that can obtain printing of characters and the like using inkjet printing that is, and a recording medium for obtaining a printed material with excellent durability compared to the conventional An object of the present invention is to provide an image forming apparatus and an image recording method which is optimal for use in the method.

[0019]

The above object of the present invention is achieved by the following constitution. 1. An image having at least one image-receiving layer containing a dye fixing body capable of forming a dye by reacting with a heat-diffusible dye precursor on one surface of a support, and an inkjet image-receiving layer provided on the other surface. Formation recording medium.

2. 2. The image forming recording medium according to claim 1, wherein the ink jet image receiving layer is hardened.

3. 2. The image forming recording medium according to the item 1, wherein the inkjet image receiving layer contains at least a hydrophilic binder, and the hydrophilic binder is hardened.

4. 4. The image forming recording medium according to claim 3, wherein the ink jet image receiving layer contains at least a hydrophilic binder and fine particle powder, and the hydrophilic binder is hardened.

5. One side of the support has at least one image-receiving layer containing a dye fixing body capable of forming a dye by reacting with a heat-diffusible dye precursor, and the other side has a thermoplastic resin as an outermost layer. An image forming recording medium comprising: an ink receiving layer containing particles; and an ink jet image receiving layer having an ink absorbing layer as a second layer adjacent to the ink receiving layer.

6. 6. The image forming recording medium according to claim 5, wherein the ink receiving layer as the outermost layer contains a silicon emulsion or a water-soluble silicon compound.

[7] The image forming recording medium according to any one of the above items 1 to 6, wherein the ink absorbing capacity of the inkjet image receiving layer is 10 ml / m ² or more.

8. A dye layer of a thermal transfer sheet having at least one dye layer containing a heat-diffusible dye precursor on a support, and a dye fixing member capable of forming a dye by reacting with the dye precursor on one of the supports. The dye precursor is transferred to the image receiving layer by superimposing the image receiving sheet having at least one containing image receiving layer so that the image receiving layer side is opposed to the image receiving layer side, and heating imagewise with a thermal head or the like to transfer the dye precursor to the image receiving layer. Forming, and each nozzle based on the image data using an inkjet head or the like that ejects ink for each nozzle based on image data on an inkjet image receiving layer provided on the other surface of the support of the image receiving sheet Forming an image by discharging ink from the image forming apparatus.

9. A dye layer of a thermal transfer sheet having at least one dye layer containing a heat-diffusible dye precursor on a support, and a dye fixing member capable of forming a dye by reacting with the dye precursor on one of the supports. The dye precursor is transferred to the image receiving layer by superimposing the image receiving sheet having at least one containing image receiving layer so that the image receiving layer side is opposed to the image receiving layer side, and heating imagewise with a thermal head or the like to transfer the dye precursor to the image receiving layer. Forming, and each nozzle based on the image data using an inkjet head or the like that ejects ink for each nozzle based on image data on an inkjet image receiving layer provided on the other surface of the support of the image receiving sheet Forming an image by discharging a pigment ink from the image forming apparatus.

10. A dye layer of a thermal transfer sheet having at least one dye layer containing a heat-diffusible dye precursor on a support; and a dye fixing member capable of forming a dye by reacting with the dye precursor on one of the supports. An image receiving sheet having at least one image receiving layer containing at least one image receiving layer is superimposed on the image receiving layer so that the image receiving layer is opposed to the image receiving layer, and the image is heated with a thermal head or the like to transfer the dye precursor to the image receiving layer. Forming, and on the ink-jet image receiving layer provided on the other surface of the support of the image receiving sheet, each of the images based on the image data using an ink jet head or the like that ejects ink for each nozzle based on the image data. An image forming method comprising the steps of forming an image by discharging ink from nozzles, and heating a recording medium after the image formation.

(11) 10. The image forming method according to the item 8 or 9, wherein the inkjet image receiving layer is hardened.

12. The image forming method according to the above item 8 or 9, wherein the inkjet image receiving layer contains at least a hydrophilic binder, and the hydrophilic binder is hardened.

13. The ink-jet image receiving layer according to the above item 8, wherein the ink-jet image-receiving layer contains at least a hydrophilic binder and fine particle powder, and the hydrophilic binder is hardened.
Alternatively, the image forming method according to 9.

14. A dye layer of a thermal transfer sheet having at least one dye layer containing a heat-diffusible dye precursor on a support, and a dye fixing member capable of forming a dye by reacting with the dye precursor on one of the supports. The image is formed by transferring the dye precursor to the image receiving layer by superimposing the image receiving layer of the image receiving sheet having at least one containing image receiving layer so as to face each other and heating imagewise with a thermal head or the like. An ink receiving layer containing thermoplastic resin particles as an outermost layer provided on the other surface of the support of the image receiving sheet, and an ink jet image receiving layer having an ink absorbing layer as a second layer adjacent to the ink receiving layer An image is formed by ejecting ink from each nozzle based on the image data using an inkjet head or the like that ejects ink for each nozzle based on the image data. Image forming method characterized by forming an image from the step of coating the thermoplastic resin particles on the rear the image.

15. The ink receiving layer which is the outermost layer,
15. The image forming method according to the above 14, wherein the image forming method comprises a silicon emulsion or a water-soluble silicon compound.

16. A thermal head in which the thermal element selectively generates heat by printing energy supplied based on image data; a roll-shaped thermal transfer sheet supplied between the thermal head and the recording paper from the supply roll and wound on the take-up roll In a thermal transfer recording apparatus comprising a recording paper, the thermal elements generate heat by the supplied printing energy, and transfer the ink of the thermal transfer sheet to the recording paper to perform recording. And an ink jet head for controlling an ink liquid ejected by a signal supplied based on image data on a side opposite to the recording paper of the thermal head, and performing ink jet recording on the recording paper. An image recording apparatus characterized by the above-mentioned.

17. A thermal head in which the thermal element selectively generates heat by printing energy supplied based on image data; a roll-shaped thermal transfer sheet supplied between the thermal head and the recording paper from the supply roll and wound on the take-up roll A recording element, the thermal element generates heat by the supplied printing energy, the ink of the thermal transfer sheet is transferred to the recording sheet to perform recording, and the thermal head forms image data on the opposite side to the recording sheet. In an image recording apparatus comprising an ink jet head for controlling an ink liquid ejected by a signal supplied based on the recording paper, the ink jet recording can be performed on the recording paper. An image recording device provided with a heat roller.

18. An image recording apparatus, wherein the recording paper according to claim 16 is the image forming recording medium according to claim 1.

[0037]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The image receiving sheet (image forming recording medium / recording paper) used in the present invention has a structure in which an image receiving layer containing a dye fixing body is provided on one surface of a support. Further, it has a configuration in which an inkjet image receiving layer is provided on the other surface of the support.

First, the thermal transfer sheet used in the present invention will be described. As the support, those used in conventional thermal transfer sheets can be used without any particular limitation.
Specific examples of preferred supports include glassine paper, condenser paper, thin paper such as paraffin paper, polyethylene terephthalate, polyphenylene sulfide, polyether ketone, high heat resistant polyesters such as polyether sulfone, polypropylene, polycarbonate, cellulose acetate, Examples include stretched or unstretched films of plastics such as polyethylene derivatives, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, polyimide, polymethylpentene, and ionomers, and laminates of these materials.

The thickness of the support can be appropriately selected depending on the material so that the strength, heat conductivity, heat resistance and the like are appropriate. Usually, a thickness of about 1 to 100 μm is preferably used. . When the support has poor adhesion to the dye layer formed on the surface, it is preferable to apply a primer treatment or a corona treatment to the surface.

In the present invention, a reactive dye is used as the heat diffusible dye contained in the dye layer provided on one side of the support from the viewpoint of obtaining good image storability.

In the present invention, as described above, the reactive dye is used to form an image by reacting the dye precursor contained in the dye layer side with the dye fixing body contained in the image receiving layer side by thermal transfer. Indicate dyes that cause Specifically, known reactive dyes including those described above can be used, but in the present invention, from the viewpoint of particularly excellent image storability, a combination of a post-chelating dye and a metal source is used. Is preferred.

The post-chelating dye is not particularly limited as long as it can be thermally transferred, and various known compounds can be appropriately selected and used. Specifically, for example, JP-A-59-78893, JP-A-59-109349
Gazette, Japanese Patent Application No. 213303/1990, and 2-24711
9, cyan dye, magenta dye, yellow dye, and the like described in JP-A Nos. 9 and 2-203742 can be used.

The post-chelating dyes preferably used in the present invention include, for example, those represented by the following [I] to [III].

[0044]

Embedded image

In the formula, X represents an atomic group having at least a bidentate chelate-forming group or atom, Y represents an atomic group necessary for forming an aromatic carbocyclic or heterocyclic ring,
R ₁ , R ₂ and R ₃ each represent a hydrogen atom, a halogen atom or a monovalent substituent. n represents 0, 1 or 2.
Y is preferably a group of atoms forming a 5- to 6-membered aromatic carbocyclic or heterocyclic ring, and the ring may further have a substituent.

X is particularly preferably represented by the following general formula [I] -2.

[0047]

Embedded image

In the formula, Z represents an atomic group necessary for forming an aromatic nitrogen-containing heterocyclic ring substituted with a group containing at least one chelatable nitrogen atom.

Specific examples of the above-mentioned aromatic carbocycle and heterocycle include benzene, pyridine, pyrimidine, furan, thiophene, thiazole, imidazole, naphthalene and the like. A carbocyclic ring (such as a benzene ring) or a heterocyclic ring (such as a pyrimidine ring) may form a conjugation ring.

The substituents on the ring include an alkyl group, an aryl group, an acyl group, an amino group, a nitro group, a cyano group,
Examples include an acylamino group, an alkoxyl group, a hydroxyl group, and a halogen atom of an alkoxycarbonyl group, and these groups may be further substituted.

The halogen atom represented by R ₁ , R ₂ and R ₃ is a fluorine atom, a chlorine atom and the like, and the monovalent substituent is an alkyl group, an alkoxyl group, a cyano group and an alkoxycarbonyl group. No.

X is represented by the following general formula [I] -3 or
Those represented by [I] -6 are particularly preferred.

[0053]

Embedded image

In the formula, R ₄ and R ₅ each represent a hydrogen atom, a halogen atom (such as a fluorine atom, a chlorine atom, or a bromine atom) or a monovalent substituent (an alkyl group, an aryl group, an acyl group,
Amino group, nitro group, cyano group, acylamino group, alkoxyl group, hydroxyl group, alkoxycarbonyl group, etc.).

Specific examples of the compounds are described in Japanese Patent Application No. 2000-103.
309, paragraphs [0048] to [0051].

General formula [II] X ₁ -N = N-X ₂ -G In the formula, X ₁ represents an aromatic carbocyclic or heterocyclic ring in which at least one ring is composed of 5 to 7 atoms. Represents a collection of atoms necessary for completion, wherein at least one of the carbon atoms attached to the azo bond is a nitrogen atom or a carbon atom substituted with a chelating group. X ₂ represents an aromatic heterocyclic ring or an aromatic carbocyclic ring in which at least one ring is composed of 5 to 7 atoms, and G represents a chelating group. Representative examples of the above general formula are shown below, but the present invention is not limited thereto.

Specific examples of the compounds are described in JP-A-10-2585.
80, paragraphs [0045] to [0051].

[0058]

Embedded image

In the formula, R ₁ and R ₂ each represent a substituted or unsubstituted alkyl group, and R ₃ represents a substituent. n is 0
Represents an integer of 4, and when n is 2 or more, a plurality of R ₃ may be the same or different. R ₄ represents a linear alkyl group having 2 or more carbon atoms, a cycloalkyl group, a non-tertiary branched alkyl group, an aryl group, an alkoxy group, an aryloxy group or an amino group, and R ₅ and R ₆ each represent a hydrogen atom or Represents a substituent.

In the general formula [III], R ₁ and R ₂
Is a substituted or unsubstituted alkyl group having 2 to 1 carbon atoms.
A linear or branched alkyl group of 0 is preferred, and may be substituted with a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, or the like. Further, R ₁ and R ₂ may combine with each other to form a pyrazoline, piperidine, or morpholine ring.

The substituent represented by R ₃ is not particularly limited as long as it can be substituted on the benzene ring, but is preferably an alkyl group, a cycloalkyl group, an alkoxy group, or an acylamino group. n represents an integer of 0 to 4, preferably 1.

R ₄ represents a linear alkyl group having 2 or more carbon atoms, a cycloalkyl group, a non-tertiary branched alkyl group, an aryl group, an alkoxy group, an aryloxy group or an amino group. Examples of the alkyl group include ethyl, butyl, pentyl, and octyl.
Examples of the branched alkyl group include i-propyl, i-butyl,
Each group such as 2-ethylhexyl is exemplified. In the tertiary alkyl group are excluded from the present invention R _4, but it is apparent in the art, but those carbon adjacent to the pyrazolopyrimidine ring tertiary (t-butyl, t-pentyl, t-octyl, etc.) And the other carbon is tertiary (neo-
Pentyl, neo-hexyl, 2-t-butoxyethyl, etc.) are included in the present invention.

The aryl group, alkoxy group, aryloxy group and amino group represented by R ₄ have the same meanings as the groups represented by R ₅ and R ₆ below.

As R ₄ , among the above substituents, a non-tertiary branched alkyl group, an aryl group having a substituent at the ortho position (o-chlorophenyl, o-tolyl, o-anisyl, 2,6-dichlorophenyl, o- -(2-ethoxyethoxy) phenyl, o-butoxyphenyl, mesityl, etc.) are preferred.

The substituents represented by R ₅ and R ₆ include
Linear or branched alkyl groups (methyl, ethyl, i-propyl, t-butyl, dodecyl, 1-hexylnonyl, etc.), cycloalkyl groups (cyclopropyl, cyclohexyl, bicyclo [2.2.1] heptyl, adamantyl, etc.) ), Alkenyl groups (2-propylene, oleyl, etc.),
Aryl group (phenyl, o-tolyl, o-anisyl, 1
-Naphthyl, 9-anthranyl, etc.), heterocyclic group (2-tetrahydrofuryl, 2-thiophenyl, 4-imidazolyl, 2-pyridyl, etc.), halogen atom (fluorine, chlorine, bromine, etc.), cyano group, nitro group, hydroxyl Group, carbonyl group (alkylcarbonyl group such as acetyl, trifluoroacetyl, pivaloyl, etc., arylcarbonyl group such as benzoyl, pentafluorobenzoyl, 3,5-di-t-butyl-4-hydroxybenzoyl), oxycarbonyl group (methoxy Alkoxycarbonyl groups such as carbonyl, cyclohexyloxycarbonyl, dodecyloxycarbonyl, phenoxycarbonyl, 2,4-di-t
Aryloxycarbonyl groups such as -pentylphenoxycarbonyl, 1-naphthyloxycarbonyl, 2-pyridyloxycarbonyl, 1-phenylpyrazolyl-5-
Heterocyclic oxycarbonyl such as oxycarbonyl, etc.), carbamoyl group (dimethylcarbamoyl, 4- (2,4-
Alkylcarbamoyl groups such as di-t-pentylphenoxy) butylaminocarbonyl, phenylcarbamoyl,
Arylcarbamoyl groups such as 1-naphthylcarbamoyl), alkoxy groups (methoxy, 2-ethoxyethoxy and the like), aryloxy groups (phenoxy, 2,4-di-t)
-Pentylphenoxy, 4- (4-hydroxyphenylsulfonyl) phenoxy and the like), a heterocyclic oxy group (4-pyridyloxy, 2-hexahydropyranyloxy and the like),
Carbonyloxy groups (alkylcarbonyloxy groups such as acetyloxy, trifluoroacetyloxy and pivaloyloxy, aryloxy groups such as benzoyloxy and pentafluorobenzoyloxy), urethane groups (N,
Alkyl urethane groups such as N-dimethyl urethane; aryl urethane groups such as N-phenyl urethane and N- (p-cyanophenyl) urethane; and sulfonyloxy groups (alkyl such as methanesulfonyloxy, trifluoromethanesulfonyloxy, dodecanesulfonyloxy) Arylsulfonyloxy groups such as sulfonyloxy group, benzenesulfonyloxy, and p-toluenesulfonyloxy),
Amino groups (dimethylamino, cyclohexylamino, n
An alkylamino group such as dodecylamino, anilino, p
Arylamino groups such as -t-octylanilino), sulfonylamino groups (alkylsulfonylamino groups such as methanesulfonylamino, heptafluoropropanesulfonylamino and hexadecylsulfonylamino), p-toluenesulfonylamino, pentafluorobenzenesulfonylamino and the like Arylsulfonylamino group), sulfamoylamino group (alkylsulfamoylamino group such as N, N-dimethylsulfamoylamino, arylsulfamoylamino group such as N-phenylsulfamoylamino), acylamino group (Alkylcarbonylamino groups such as acetylamino and myristoylamino, arylcarbonylamino groups such as benzoylamino), ureide groups (alkylureido groups such as N, N-dimethylaminoureide, and N-phenyl) Arylureido groups such as ureido and N- (p-cyanophenyl) ureide; sulfonyl groups (alkylsulfonyl groups such as methanesulfonyl and trifluoromethanesulfonyl; arylsulfonyl groups such as p-toluenesulfonyl); sulfamoyl groups (dimethylsulfayl) Moyl, an alkylsulfamoyl group such as 4- (2,4-di-t-amylphenoxy) butylaminosulfonyl group, an arylsulfamoyl group such as phenylsulfamoyl), an alkylthio group (methylthio group, t-octylthio) ), An arylthio group (such as phenylthio) and a heterocyclic thio group (1-phenyltetrazole-5-thio, 5-methyl-1,3,4-oxadiazole-2-).
Thio, etc.).

Among the above substituents, R5 and R6 are preferably an alkyl group, an aryl group, and an acylamino group. It is also preferred that R5 and R6 form a non-aromatic cyclic structure (eg, cyclopentene, cyclohequine, cycloheptene).

Specific examples of the compounds are described in JP-A-2000-255.
171 paragraphs [0025] to [0034].

The amount of the post-chelating dye used in the present invention is usually 0.1 g to 1 m ^{2 of the} solid content of the dye.
20 g is preferable, and 0.2 g to 5 g is more preferable.

The binder resin used for the dye layer includes water-soluble polymers such as cellulose, polyacrylic acid, polyvinyl alcohol, and polyvinylpyrrolidone, acrylic resin, methacrylic resin, polystyrene, polycarbonate, polysulfone, polyether sulfone, and polyvinyl ether. There are polymers soluble in organic solvents such as butyral, polyvinyl acetal, ethyl cellulose, and nitrocellulose. Among these resins, polyvinyl butyral, polyvinyl acetal or cellulosic resins having excellent storage stability are preferable. When a polymer soluble in an organic solvent is used, one or more of the polymers may be used in the form of a latex dispersion as well as being dissolved in an organic solvent.
The amount of the binder resin used is preferably 0.1 g to 50 g per 1 m ² of the support.

In order to improve the releasability from the image receiving layer, a release agent may be added or a release layer containing the release agent may be provided. As the release agent, a reaction curable silicone, a phosphate ester-based surfactant, a fluorine compound, or the like can be used. The use amount of the release agent is preferably 0.5 to 40% by weight based on the solid content of the layer to be contained. When a release layer is provided, the same binder as that used for the dye layer can be used.

It is also preferable to provide a back layer for imparting heat resistance on the surface of the support opposite to the surface on which the dye layer is provided.

In the thermal transfer recording used in the present invention, a transparent protective layer formed by thermal transfer can be provided on the surface of the recording medium after dye transfer.

The protective layer used in the present invention can be provided on the same surface as the dye layer in a so-called plane-sequential manner (see FIG. 1). When the protective layer alone is used as the protective layer transfer sheet, the same support and back layer as described above can be used.

In the present invention, the heat transferable protective layer is preferably provided on the support with a non-transferable release layer interposed therebetween.

The non-transferable release layer may be provided with or without the above-mentioned primer layer or the like.

The non-transferable release layer ensures that the adhesive force between the support and the non-transferable release layer is always sufficiently higher than the adhesive force between the non-transferable release layer and the heat transferable protective layer. In order to increase the adhesive force between the non-transferable release layer before applying heat and the heat-transferable protective layer to that after applying heat, (1) together with the resin binder, Average particle size is 40n
m or less, or (2) an alkyl vinyl ether / maleic anhydride copolymer, a derivative thereof, or a mixture thereof in a total amount of 20 to 80% by weight.
It is preferable that the content of the ionomer is not less than 20% by weight or (3) the ionomer is not less than 20% by weight.

The non-transferable release layer may contain other additives as necessary.

As the inorganic fine particles, for example, silica fine particles such as anhydrous silica and colloidal silica, and metal oxides such as tin oxide, zinc oxide and zinc antimonate can be used. It is preferable that the particle diameter of the inorganic fine particles be 40 nm or less. If the thickness exceeds 40 nm, the unevenness on the surface of the heat transferable protective layer increases due to the unevenness on the surface of the release layer, and as a result, the transparency of the protective layer is undesirably reduced.

The resin binder mixed with the inorganic fine particles is not particularly limited, and any mixable resin can be used. For example, polyvinyl alcohol resins (PVA) having various degrees of saponification; polyvinyl acetal resins; polyvinyl butyral resins; acrylic resins; polyamide resins; cellulose resins such as cellulose acetate, alkyl cellulose, carboxymethyl cellulose, and hydroxyalkyl cellulose; polyvinyl pyrrolidone Resins.

Mixing ratio of inorganic fine particles to other compounding components mainly composed of resin binder (inorganic fine particles / other compounding components)
Is preferably in the range of 30/70 to 80/20 by weight. If the compounding ratio is less than 30/70, the effect of the inorganic fine particles becomes insufficient, while
If it exceeds 0, the release layer will not be a complete film, and there will be a portion where the support and the protective layer are in direct contact.

Examples of the alkyl vinyl ether / maleic anhydride copolymer or its derivative include those in which the alkyl group of the alkyl vinyl ether moiety is a methyl group or an ethyl group, and those in which the maleic anhydride moiety is partially or completely alcohol (for example, A half ester with methanol, ethanol, propanol, isopropanol, butanol, isobutanol, etc.) can be used.

The release layer may be formed only of an alkyl vinyl ether / maleic anhydride copolymer, a derivative thereof, or a mixture thereof. However, in order to adjust the peeling force between the release layer and the protective layer. Alternatively, another resin or fine particles may be further added. In this case, it is desirable that the release layer contains 20% by weight or more of an alkyl vinyl ether / maleic anhydride copolymer, a derivative thereof, or a mixture thereof. If the content is less than 20% by weight, the effect of the alkyl vinyl ether / maleic anhydride copolymer or a derivative thereof cannot be sufficiently obtained.

The resin or fine particles to be blended with the alkyl vinyl ether / maleic anhydride copolymer or its derivative is not particularly limited as long as it can be mixed and provides high film transparency at the time of film formation. Materials can be used. For example, the aforementioned inorganic fine particles and a resin binder that can be mixed with the inorganic fine particles are preferably used.

As the ionomer, for example, Surlyn A (manufactured by DuPont), Chemipearl S series (manufactured by Mitsui Petrochemical Co., Ltd.) and the like can be used. Further, for example, the above-mentioned inorganic fine particles, a resin binder that can be mixed with the inorganic fine particles, or other resins or fine particles can be further added to the ionomer.

In order to form a non-transferable release layer, a coating solution containing any of the above-mentioned components (1) to (3) in a predetermined mixing ratio is prepared, and the coating solution is applied by a gravure coating method. It is applied on a support by a known technique such as a gravure reverse coating method, and the applied layer is dried. The thickness of the non-transferable release layer is usually about 0.1 to 2 μm in thickness after drying.

The heat transferable protective layer laminated on the support with or without a non-transferable release layer may have a multilayer structure or a single layer structure. In the case of a multi-layer structure, in addition to the main protective layer, which is the main body for imparting various durability to the image, the thermal transfer protective layer is used to enhance the adhesion between the thermal transfer protective layer and the image receiving surface of the print. An adhesive layer disposed on the outermost surface of the layer, an auxiliary protective layer, and a layer for adding a function other than the original function of the protective layer (for example, a forgery prevention layer, a hologram layer, etc.) may be provided. The order of the main protective layer and the other layers is arbitrary, but usually, another layer is arranged between the adhesive layer and the main protective layer so that the main protective layer is the outermost surface of the image receiving surface after transfer. .

The main protective layer, which forms one layer of the heat transferable protective layer having a multilayer structure, or the heat transferable protective layer having a single layer structure, can be formed of various resins conventionally known as resins for forming a protective layer. . As the protective layer forming resin, for example,
Polyester resin, polystyrene resin, acrylic resin,
Examples thereof include a polyurethane resin, an acrylic urethane resin, a resin obtained by modifying each of these resins with silicone, a mixture of these respective resins, an ionizing radiation-curable resin, and an ultraviolet shielding resin.

The protective layer containing the ionizing radiation-curable resin has particularly excellent plasticizer resistance and abrasion resistance. As the ionizing radiation-curable resin, known ones can be used.For example, a radically polymerizable polymer or oligomer is cross-linked and cured by irradiation with ionizing radiation, and a photopolymerization initiator is added as necessary, and an electron beam is irradiated. And those polymerized and cross-linked by ultraviolet rays can be used.

The main purpose of the protective layer containing a UV-blocking resin is to impart light resistance to a print. As the ultraviolet blocking resin, for example, a resin obtained by reacting and bonding a reactive ultraviolet absorber to a thermoplastic resin or the above ionizing radiation curable resin can be used. More specifically, an addition-polymerizable double bond is added to a conventionally known non-reactive organic ultraviolet absorber such as salicylate, benzophenone, benzotriazole, substituted acrylonitrile, nickel chelate, or hindered amine. Examples thereof include those in which reactive groups such as a vinyl group, an acryloyl group, and a methacryloyl group), an alcoholic hydroxyl group, an amino group, a carboxyl group, an epoxy group, and an isocyanate group are introduced.

The main protective layer provided in the heat transferable protective layer having a single-layer structure or the heat transferable protective layer having a multilayer structure as described above depends on the type of the resin for forming the protective layer, but is usually 0.5.
It is formed to a thickness of about 10 to 10 μm.

An adhesive layer may be formed on the outermost surface of the heat transferable protective layer. The adhesive layer may be formed of a resin having good adhesiveness when heated such as an acrylic resin, a vinyl chloride resin, a vinyl acetate resin, a vinyl chloride / vinyl acetate copolymer resin, a polyester resin, and a polyamide resin. it can. Further, in addition to the above-mentioned resin, the above-mentioned ionizing radiation-curable resin, ultraviolet shielding resin and the like may be mixed as necessary. The thickness of the adhesive layer is usually 0.1 to 5 μm.

In order to form the heat transferable protective layer on the non-transferable release layer or on the support, for example, a protective layer coating solution containing a protective layer forming resin, an adhesive layer containing a heat adhesive resin A coating liquid for forming a coating liquid for forming a layer to be added as necessary is prepared in advance, and they are coated in a predetermined order on a non-transferable release layer or a support and dried. Each coating solution may be applied by a conventionally known method. Further, an appropriate primer layer may be provided between the respective layers.

In the thermal transfer recording used in the present invention, the surface of the recording medium on which the dye has been transferred and the surface of the resin layer of the non-transferable resin layer are opposed to each other, and from the side opposite to the non-transferable resin layer. By applying heat, reheating treatment can be performed.

The non-transferable resin layer used in the present invention comprises:
On the same surface as the dye layer, it may be provided in a so-called face-sequential manner (in one face, sequentially). When the non-transferable resin layer is used alone as a sheet, the same support and back layer as described above can be used.

As the binder resin used for the non-transferable resin layer, the same binder resin as used for the dye layer can be used.

In the case where the non-transferable resin layer is provided in the order of the dye layer, the resin layer preferably contains fine particles. This means that when stored in a roll state after application, the dye slightly migrates to the back layer, and when the product is made into a small volume, the dye transferred to the back layer is retransferred to the non-transferable resin layer. This is performed for the purpose of preventing the so-called kickback phenomenon from occurring. When kickback occurs, the dye re-transferred to the resin layer causes the image receiving surface to be colored at the time of printing, which significantly impairs image quality. As the fine particles, in addition to inorganic pigments such as silica, alumina and calcium carbonate, resin fine particles such as acrylic resin, fluorine resin, polyethylene resin and polystyrene resin, or wax particles can be used. The particle size of these fine particles is preferably 0.1 to 50 μm. If it is less than 0.1 μm, the surface of the resin layer has too little unevenness and no effect on kickback, and if it is more than 50 μm, the image surface after printing is roughened, deteriorating the image quality. The preferable addition amount of the fine particles is 1 to 50 with respect to the total solid content of the resin layer.
%, Particularly preferably 5 to 30% by weight.
If it is less than 1%, the surface of the resin layer has too little unevenness and the effect on kickback is small, and if it exceeds 50%, the image surface after printing is roughened and the image quality is impaired.

In the present invention, for the purpose of completing the reaction of the reactive dye at the time of the reheating treatment, a dye fixing body may be contained in the resin layer, or a layer containing the dye fixing body may be provided. . When a layer containing a dye fixing body is provided, the same binder as the binder resin used for the dye layer can be used. When a post-chelating dye is used as the dye precursor, it is preferable to include a metal source as the dye fixing body.

Examples of the metal source include inorganic or organic salts and metal complexes of metal ions, and among them, salts and complexes of organic acids are preferable. As the metal, the I-th of the periodic table
Monovalent and polyvalent metals belonging to Groups VIII to VIII, among which Al, Co, Cr, Cu, Fe, Mg, M
n, Mo, Ni, Sn, Ti and Zn are preferred, and particularly Ni, Cu, Cr, Co and Zn are preferred. Specific examples of the metal source include Ni ²⁺ , Cu ²⁺ , C
Examples thereof include salts of r ²⁺ , Co ²⁺ and Zn ²⁺ with aliphatic salts such as acetic acid and stearic acid, and salts of aromatic carboxylic acids such as benzoic acid and salicylic acid. Further, the complex represented by the following general formula (1) is stable and can be added to the image receiving layer,
It is particularly preferred because it is substantially colorless.

Formula (1) [M (Q1) _X (Q2)
_{Y (Q3) Z] P +} (L -) in _P general formula (1), M a metal ion, preferably N
represents i ²⁺ , Cu ²⁺ , Cr ²⁺ , Co ²⁺ or Zn ²⁺ . Q1, Q2 and Q3 each represent a coordination compound capable of coordinating with the metal ion represented by M, and may be the same or different. These coordination compounds can be selected, for example, from the coordination compounds described in Chelate Science (5) (Nankodo). L ^- represents an organic anion group, and specific examples include tetraphenyl boron anion and alkylbenzene sulfonate anion. X represents 1, 2 or 3, and Y represents 1, 2
Or 0 and Z represents 1 or 0, which is determined by whether the complex represented by the general formula (1) is tetradentate or hexadentate, or Q1, Q2, It is determined by the number of ligands of Q3. P represents 1 or 2. A specific example of this type of metal source is disclosed in U.S. Pat.
7,049, or Japanese Patent Application Laid-Open No.
Compound No. exemplified in JP-A-39423. 1-9
9 and the like.

The amount of the metal source to be added is determined based on the total solid content of the resin layer (including the layer when the layer is provided as a dye fixing body containing layer).
Is preferably from 0.01 to 1% by weight, particularly preferably from 0.05 to 0.5% by weight. If the amount is less than 0.01% by weight, the effect of addition is small, and if it is more than 1% by weight, the above-mentioned kickback is more remarkably generated.

In order to improve the releasability between the image receiving layer and the non-thermal transferable resin layer, a release agent may be added or a release layer may be provided. As the release agent, a reaction curable silicone, a phosphate ester-based surfactant, a fluorine compound, or the like can be used. The use amount of the release agent is preferably 0.5 to 40% by weight based on the solid content of the layer to be contained. When a release layer is provided, the same binder as that used for the dye layer can be used.

At least one layer is provided between the image receiving layer and the support.
An intermediate layer having more than two layers may be provided. The intermediate layer means all layers provided between the image receiving layer and the support, such as an adhesive layer (primer layer), a barrier layer, an ultraviolet absorbing layer, a foaming layer, and an antistatic layer. Either can be used. Furthermore, it is preferable to add a white pigment such as titanium oxide to the intermediate layer in order to hide the glare and unevenness of the support, since the degree of freedom in selecting the support increases. The content of the intermediate layer resin and the white pigment is preferably 30 to 300 parts by weight of the white pigment solid content with respect to 100 parts by weight of the resin solid content.
In order to enhance the concealability, it is more preferable to use 100 to 300 parts by weight.

As the intermediate layer, a layer obtained by curing a thermoplastic resin, a thermosetting resin, or a thermoplastic resin having a functional group by using various additives or other methods can be used. Specifically, polyvinyl alcohol, polyvinylpyrrolidone, polyester, chlorinated polypropylene,
Modified polyolefins, urethane resins, acrylic resins, polycarbonates, ionomers, resins obtained by curing monofunctional and / or polyfunctional hydroxyl-containing prepolymers with isocyanate or the like can be used.

The image receiving layer is composed of a dye fixing body, a binder resin, and various additives such as a release agent, if necessary, on one surface of the support. When a post-chelating dye is used as a dye precursor, a metal source is contained as a dye fixing body. The metal source used in the non-transferable resin layer described above can be used in the same manner. Usually, the addition amount of the metal source is preferably 10 to 60% by weight, more preferably 20 to 50% by weight, based on the solid content of the image receiving layer.

As the binder resin, a known resin can be used, and it is preferable to use a resin to which a dye is easily dyed. Specifically, polyolefin resins such as polypropylene, halogenated resins such as polyvinyl chloride and polyvinylidene chloride, vinyl resins such as polyvinyl acetate and polyacrylate, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, and polystyrene resins Resins, polyamide resins, phenoxy resins, copolymers of olefins such as ethylene and propylene with other vinyl monomers, polyurethane, polycarbonate, acrylic resins, ionomers, simple substances such as cellulose derivatives, or mixtures thereof can be used. Of these, polyester resins and vinyl resins are preferred.

It is preferable to add a release agent to the image receiving layer in order to prevent thermal fusion with the dye layer. As the release agent, a phosphate ester-based plasticizer, a fluorine-based compound, a silicone oil (including a reaction-curable silicone) and the like can be used, and among them, the silicone oil is preferable. Various modified silicones such as dimethyl silicone can be used as the silicone oil.
Specifically, amino-modified silicone, epoxy-modified silicone, alcohol-modified silicone, vinyl-modified silicone, urethane-modified silicone, or the like can be used, and these can be blended or polymerized using various reactions. One or more release agents are used. Further, the amount of the release agent added depends on the amount of the resin for forming the image receiving layer 1.
0.5 to 30 parts by weight per 100 parts by weight is preferred. If the addition amount is not satisfied, problems such as fusion between the thermal transfer sheet and the image receiving layer of the image receiving sheet or reduction in printing sensitivity may occur. Note that these release agents may not be added to the image receiving layer but may be separately provided on the image receiving layer as a release layer.

In the image receiving sheet of the present invention, an ink jet image receiving layer is provided on the surface of the support opposite to the image receiving layer. The ink-jet image receiving layer refers to a dye ink or pigment ink used for ink-jet recording, which is excellent in ink absorption and ink retention.

The specific configuration will be described below. A hydrophilic binder is used in the inkjet image receiving layer of the present invention.

As the hydrophilic binder of the present invention, various conventionally known hydrophilic binders are used, and examples thereof include gelatin, polyvinyl alcohol or cation-modified polyvinyl alcohol, a polymer graft polymer, a protein other than gelatin, a sugar derivative, and a cellulose derivative. A hydrophilic colloid or a gelatin derivative such as a single or copolymerized hydrophilic polymer, polyvinylpyrrolidone (preferably having an average molecular weight of about 200,000 or more), pullulan,
Polyvinyl alcohol or a derivative thereof (preferably having an average molecular weight of about 20,000 or more), polyethylene glycol (preferably having an average molecular weight of at least 100,000), carboxymethylcellulose, hydroxyethylcellulose, dextran, dextrin, polyacrylic acid and salts thereof, agar, κ Carrageenan, λ-carrageenan, ι-carrageenan, xanthen gum, locust bean gum, alginic acid, gum arabic, pullulan, JP-A-7-1958
No. 26 and 7-9957, polyalkylene oxide-based copolymerizable polymers, water-soluble polyvinyl butyral, or vinyl monomers having a carboxyl group or a sulfonic acid group described in JP-A-62-245260, alone or Polymers such as copolymers having these vinyl monomers repeatedly can be mentioned. These hydrophilic binders may be used alone or in combination of two or more.

In the ink jet image receiving layer of the present invention, fine particles are used for the purpose of increasing the ink absorbency.

Examples of the fine particles include inorganic compounds such as silica,
Natural and synthetic organic high molecular compounds such as cellulose esters, polymethyl methacrylate, polystyrene or polydivinylbenzene and copolymers thereof are used.

Examples of the inorganic fine particles used for the above purpose include light calcium carbonate, heavy calcium carbonate, magnesium carbonate, kaolin, clay, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide and zinc hydroxide. , Zinc sulfide, zinc carbonate, hydrotalcite, aluminum silicate, diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, alumina, colloidal alumina, pseudoboehmite, aluminum hydroxide, lithopone, zeolite, hydroxylated Examples include white inorganic pigments such as magnesium, titanium oxide, magnesium sulfate, glass beads, and synthetic mica.

The average particle diameter of the inorganic fine particles can be determined by observing the fine particles themselves or the fine particles that have appeared on the cross section or surface of the void-type ink solvent absorbing layer with an electron microscope and calculating the average particle diameter of 100 arbitrary particles. It is obtained as an average value (number average). Here, the particle diameter of each fine particle is represented by a diameter assuming a circle equal to the projected area.

From the viewpoints of forming a high-density image, recording a clear image, and manufacturing at low cost, inorganic solid fine particles include fine particle silica, colloidal silica, and alumina synthesized by a gas phase method. Alternatively, it is preferable to use inorganic solid fine particles selected from alumina hydrate.

Alumina or alumina hydrate may be crystalline or amorphous, and may have any shape such as irregular particles, spherical particles, and acicular particles.

At present, fine particle silica synthesized by such a gas phase method is commercially available, and various types of commercially available fine particle silica include Aerosil manufactured by Nippon Aerosil Co., Ltd.

In order to obtain the effects of the present invention, the average particle size of the inorganic fine particles is not particularly limited, but is preferably 100 nm or less. The most preferable average particle size for forming the void layer differs depending on the compound. For example, in the case of the above-mentioned fumed silica, the average particle size of the primary particles of the inorganic fine particles dispersed in the state of the primary particles (the particle size in the dispersion state before coating) is 4 to 20.
nm is most preferably used.

The compounds used as the organic fine particles include the following.

The polymer is selected from acrylic resin, vinyl chloride resin, vinyl acetate resin, styrene resin, vinylidene chloride resin, acetal resin, cellulose resin and the like. These resins are preferably used in a state of being dispersed in water or a water-soluble polymer such as gelatin or polyacrylamide to have an average particle size of 0.5 to 20 μm, preferably 1 to 10 μm.

The dispersion of these polymer particles is prepared by dissolving the polymer in an organic solvent and mixing and dispersing the polymer with water or an aqueous gelatin solution with vigorous stirring, or by polymerizing the monomer by emulsion polymerization, precipitation polymerization, or pearl polymerization. The fine particles can be obtained by dispersing the fine particles of the matting agent in water or an aqueous solution of gelatin using a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser, or the like.

[0121] amount with the organic polymer matting agent contained in the ink jet image-receiving layer has a total volume 0.5 g / m @ 2 or more, preferably in the range of ^{0.8g / m 2 ~10g / m 2} , more preferably 1g / ranges m2~5g / ^{m 2.}

Further, as the ink absorbing layer, besides using the above-mentioned inorganic fine particles, for example, JP-A-59-148583
No. 55-51583, No. 58-72495, etc., a liquid mixture with various hydrophilic resins and silica,
A urethane resin emulsion containing an alkylene oxide or a polycarbonate described in JP-A-9-150574 and JP-A-10-181189 can also be used.

Further, in addition to forming an ink absorbing layer using the inorganic fine particles, a polyurethane resin emulsion was used in combination with a water-soluble epoxy compound and / or acetoacetylated polyvinyl alcohol, and further used together with an epichlorohydrin polyamide resin. The ink absorbing layer may be formed using a coating liquid.

The polyurethane resin emulsion in this case is preferably a polyurethane resin emulsion having a polycarbonate chain, a polycarbonate chain and a polyester chain and having a particle size of 3.0 μm, and the polyurethane resin of the polyurethane resin emulsion has a polycarbonate polyol, a polycarbonate polyol and a polyester polyol. The polyurethane resin obtained by reacting a polyol with an aliphatic isocyanate compound has a sulfonic acid group in the molecule, and further has an epichlorohydrin polyamide resin and a water-soluble epoxy compound and / or acetoacetylated vinyl alcohol. More preferred.

It is presumed that weak agglomeration of cations and anions is formed in the ink absorbing layer using the polyurethane resin, and accordingly, voids having an ink solvent absorbing ability are formed, so that an image can be formed.

The ink-jet image receiving layer of the present invention is hardened with a hydrophilic binder in order to increase the ink absorption without deteriorating the fragility.

The hardener is generally a compound having a group capable of reacting with the hydrophilic binder or a compound which promotes a reaction between different groups of the hydrophilic binder. It is appropriately selected and used depending on the situation.

Specific examples of the hardener include epoxy hardeners (diglycidyl ethyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-diglycidyl cyclohexane, N , N-diglycidyl 4-glycidyloxyaniline, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, etc., aldehyde hardeners (formaldehyde, glyoxal, etc.), active halogen hardeners (2,4-dichloro-4-hydroxy) -1,3,5-s-triazine, etc.), active vinyl compounds (1,3,5-trisacryloyl-hexahydro-)
s-triazine, bisvinylsulfonylmethyl ether, etc.), boric acid and its salts, borax, aluminum alum, or vinyl sulfone hardener, chlorotriazine hardener, polymer hardener, carboxyl group active hardener The agents can be used alone or in combination.

The amount of the above hardener varies depending on the kind of the hydrophilic binder, the kind of the hardener, the kind of the inorganic fine particles, the ratio to the hydrophilic binder, and the like. Is 5-10
0 mg.

The above-mentioned hardener may be added to the coating solution for forming the image receiving layer and / or to the coating solution for forming another layer adjacent to the image receiving layer when the coating solution for forming the image receiving layer is applied. Alternatively, a coating solution for forming the image receiving layer is applied to a support on which a coating solution containing a hardening agent is applied in advance, or a coating solution containing no hardening agent for forming an image receiving layer. The hardening agent can be supplied to the image receiving layer by, for example, overcoating the hardening agent solution after coating and drying. However, from the viewpoint of manufacturing efficiency and preventing cracks during formation of the image receiving layer, the image receiving layer is preferably used. It is preferable to add a hardening agent to the coating solution for forming the toner or the coating solution for the layer adjacent thereto to supply the hardening agent at the same time as forming the image receiving layer.

In a particularly preferred embodiment in which the image receiving layer is formed of ultrafine silica and polyvinyl alcohol, a hardening agent is added in advance to the coating solution for forming the image receiving layer, and the solution is kept for a predetermined time (preferably 10 minutes). When the composition is applied and dried after elapse of the above (especially preferably 30 minutes or more), a higher porosity can be achieved without deteriorating the brittleness of the film.

In the ink jet recording paper of the present invention, when the image receiving layer further contains a polyol having at least two hydroxyl groups in the molecule and a molecular weight of 300 or less, the image receiving layer is further improved in the brittleness of the film. Can be obtained.

Examples of such polyols include ethylene glycol, diethylene glycol, polyethylene glycol having an average molecular weight of 300 or less, glycerin,
Butanediol, butanetriol, triethanolamine and the like can be mentioned.

The use amount of the above polyols is preferably 0.01 to 2 g, more preferably 0.05 to 1 g per 1 g of the hydrophilic binder.

Various additives other than those described above can be added to the image receiving layer of the present invention and other layers provided as necessary.

For example, polystyrene, polyacrylates, polymethacrylates, polyacrylamides, polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, or copolymers thereof,
Organic latex fine particles such as urea resin or melamine resin, oil droplet fine particles such as liquid paraffin, dioctyl phthalate, tricresyl phosphate, and silicone oil; various surfactants such as anions, cations, and nonions; Nos. 57-87988 and 6
An ultraviolet absorber described in JP-A-2-261476;
Nos. -74192, 57-87989, 60-72
No. 785, No. 61-146591, JP-A-1-950
Nos. 91 and 3-13376; and JP-A-59-42993 and JP-A-59-5268.
No. 9, 62-80069, 61-242871
Brighteners, sulfuric acid, phosphoric acid, citric acid, sodium hydroxide, potassium hydroxide, potassium carbonate, etc., pH adjusting agents, defoamers, preservatives, etc. Various known additives such as a thickener, an antistatic agent, and a matting agent can be contained.

In order to prevent the growth of fungi and bacteria which adversely affect the photographic performance and image storability, Japanese Patent Application Laid-Open No.
Preservatives or antifungal agents as described in JP 157646 can be added.

In any of the constituent layers on the ink recording surface side of the present invention, a polycationic polymer electrolyte disclosed in JP-A-56-89992 and a JP-A-57-36692 are used as a water-proofing agent for images.
No. basic latex polymer, Tokiko 4-15744
No., JP-A-61-58788 and 62-174184.
Described in JP-A-61-47290
One or more of the alkali metal weak acid salts described in the above item can be used.

In the ink jet image receiving layer of the present invention,
In particular, in the case where voids are formed in the film, various conventionally known methods are used as a forming method.

In order to form voids in the film, for example,
(1) a method in which a uniform coating solution containing two or more polymers is coated on a support and these polymers are phase-separated from each other in a drying process to form voids; (2) solid fine particles and hydrophilic or A method in which a coating solution containing a hydrophobic binder is applied on a support, and after drying, the ink jet recording paper is immersed in a solution containing water or a suitable organic solvent to dissolve solid fine particles to form voids; 3) a method of applying a coating solution containing a compound having a property of foaming at the time of film formation and then foaming the compound in a drying process to form voids in the film; (4) a method of forming porous solid fine particles and a hydrophilic binder. A method in which a coating solution is applied onto a support to form voids in and between porous fine particles, and (5) a volume approximately equal to or more than that of the hydrophilic binder (preferably 1.0 times or more). With Forming a void between solid fine particles by applying a coating solution containing fine particles and / or oil droplets of fine particles and a hydrophilic binder onto a support, (6) a coating solution of inorganic solid fine particles used in the present invention. There is known a method of forming a void by forming a secondary particle or a three-dimensional structure by soft agglomeration during preparation or film formation.

In the ink jet recording paper of the present invention, high glossiness, high porosity to dry film thickness, and
From the viewpoint of the stability during storage of the void structure and the like, among the above, the void forming method by the method of forming soft aggregation (6) is preferable.

The method of forming a void structure in a film by forming soft agglomeration is preferably a method in which primary ultrafine particles dispersed in an aqueous solution containing a hydrophilic binder have a contact point relatively restricted. Are formed through a state of aggregating with each other.

A particularly preferable hydrophilic binder for forming voids is polyvinyl alcohol or cation-modified polyvinyl alcohol.

Such a soft agglomerate structure has a state in which an aggregate formed in a linear or branched form is dispersed in an aqueous solution, or these aggregates are further aggregated to form a three-dimensional network structure in an aqueous solution. Is included.

In any case, a fine void structure can be formed in the formed film by applying and drying the aqueous solution on the support.

The size of the fine voids in the film thus obtained is approximately several times larger than the size of the primary particles, and is characterized by the fine size of the voids. is there.

As a method for forming such a soft aggregation structure, for example, primary particles are hardly aggregated with each other, and the aggregation of particles is accelerated in an aqueous solution containing a hydrophilic binder that can be stably present. It is formed by a method in which a slight amount of a hydrophilic polymer is added to form a slight aggregation, or in an aqueous solution having a water-soluble binder capable of weakly binding to the surface of the primary particles.

In the present invention, in particular, the latter method is advantageous in that the amount of voids is relatively easily controlled and easily formed, that the amount of voids can be increased as compared with the amount of fine particles used, and that the method of coating Is preferable because a film having higher glossiness can be obtained.

In the case where the void is formed by the latter method, 1
It is preferable to use primary particles having a particle diameter of approximately 0.003 to 0.05 μm because higher glossiness can be obtained. Particularly preferred primary particles are 0.004 μm
~ 0.02 µm.

The polyvinyl alcohol preferably used in the present invention preferably has an average degree of polymerization of from 300 to 4,000, and is particularly preferable because the film having an average molecular weight of 1,000 or more has good brittleness.
The saponification degree of polyvinyl alcohol is 70 to 100.
%, Particularly preferably 80 to 100%. Further, the cation-modified polyvinyl alcohol is obtained by saponifying a copolymer of an ethylenically unsaturated monomer having a cationic group and vinyl acetate.

Examples of the ethylenically unsaturated monomer having a cationic group include trimethyl- (2-acrylamido-2,2-dimethylethyl) ammonium chloride and trimethyl- (3-acrylamido-3,3-dimethylpropyl). Ammonium chloride, N-vinylimidazole, N-vinyl-2-methylimidazole, N
-(3-dimethylaminopropyl) methacrylamide,
Examples thereof include hydroxylethyltrimethylammonium chloride, trimethyl-(-methacrylamidopropyl) ammonium chloride, and N- (1,1-dimethyl-3-dimethylaminopropyl) acrylamide.

The proportion of the cation-modified group-containing monomer in the cation-modified polyvinyl alcohol is from 0.1 to 10 mol%, preferably from 0.2 to 5 mol%, based on vinyl acetate.

The polymerization degree of the cation-modified polyvinyl alcohol is usually 500 to 4000, preferably 1000 to 40.
00 is preferred.

The degree of saponification of the cation-modified polyvinyl alcohol is usually 60 to 100 mol%, preferably 70 to 100 mol%.
~ 99 mol%.

Particularly preferred in the present invention is a case where fine silica particles are used as primary particles and polyvinyl alcohol or modified polyvinyl alcohol is used as a hydrophilic binder. In this case, the silanol group on the surface of the fine particle silica and the hydroxyl group of vinyl alcohol form a weak hydrogen bond, and a soft aggregate is formed.

The primary particle silica preferably has an average particle size of not more than 0.02 μm, and more preferably has a mean particle size of 0.015 to 0.015 μm.
Most preferably, the thickness is 0.006 μm. Further, it is preferable that the secondary particles to which these are connected have a thickness of about 0.02 to 0.2 μm, preferably about 0.03 to 0.1 μm.

As such fine particle silica, fine particle silica synthesized by a synthesis method called a gas phase method is preferably used.

In the present invention, a particularly preferred hydrophilic binder for forming a soft aggregation structure is polyvinyl alcohol.

The ratio between the hydrophilic binder and the inorganic solid fine particles is approximately from 1:15 to 1: 1 by mass, preferably from 1:10 to 1: 2.

An example of a method for forming a film containing a soft agglomerate using polyvinyl alcohol and fine-particle silica will be described below.

A silica fine particle dispersion (generally 5 to 15%) was gradually added to a polyvinyl alcohol aqueous solution (generally 3 to 15%) maintained at a pH of 6 to 8 and a temperature of about 40 ° C. with vigorous stirring. After the addition is completed, the mixture is dispersed with an ultrasonic dispersing machine or a high-speed homogenizer. In this case, if necessary, it is convenient to use various surfactants and water-miscible organic solvents such as methanol, acetone and ethyl acetate in preparing a uniform coating solution.

Then, after adding various additives, the viscosity is adjusted to a value required for coating, and the film is coated on a support by a known method and dried to obtain a film having the above-mentioned voids.

In order to obtain a high porosity without deteriorating the brittleness of the film, the ink jet recording paper of the present invention needs to have the above-mentioned hydrophilic binder hardened.

The hardening agent particularly preferred when the void layer is formed is at least one selected from boric acid and salts thereof and / or epoxy hardening agents.

Most preferred are hardeners selected from boric acid and its salts. In the present invention, the boric acid or a salt thereof refers to an oxyacid having a boron atom as a central atom and a salt thereof, and specifically, orthoboric acid, diboric acid, metaboric acid, tetraboric acid, pentaboric acid, and octanoic acid And their salts.

The amount of the hardener used varies depending on the type of the hydrophilic binder, the type of the hardener, the type of the inorganic fine particles, the ratio to the hydrophilic binder, and the like. Is 5-10
0 mg.

The above-mentioned hardener may be added to the coating liquid for forming the void layer and / or to the coating liquid for forming another layer adjacent to the void layer when the coating liquid for forming the void layer is applied. Alternatively, on a support on which a coating solution containing a hardener has been applied in advance, a coating solution for forming the void layer may be applied, or a hardener-free coating solution for forming a void layer may be further applied. The hardener can be supplied to the void layer by overcoating the hardener solution after coating and drying, but preferably from the viewpoint of manufacturing efficiency and preventing cracking during formation of the void layer, the void layer is preferably used. It is preferable to add a hardening agent to a coating solution for forming a layer or a coating solution for a layer adjacent thereto to supply a hardening agent at the same time as forming a void layer.

In a particularly preferred embodiment in which the void layer is formed of ultrafine silica and polyvinyl alcohol, a hardening agent is added in advance to the coating solution for forming the void layer, and a predetermined time (preferably 10 minutes) is used. When the composition is applied and dried after elapse of the above (especially preferably 30 minutes or more), a higher porosity can be achieved without deteriorating the brittleness of the film.

In the ink jet recording paper of the present invention, when the void layer further contains at least two hydroxyl groups in the molecule and a polyol having a molecular weight of 300 or less, the void layer is further improved in the brittleness of the film. Can be obtained.

Examples of such polyols include ethylene glycol, diethylene glycol, polyethylene glycol having an average molecular weight of 300 or less, glycerin,
Butanediol, butanetriol, triethanolamine and the like can be mentioned.

The amount of the polyols to be used is preferably from 0.01 to 2 g, more preferably from 0.05 to 1 g, per 1 g of the hydrophilic binder.

The ink jet recording paper of the present invention has a maximum ink amount of 20 ml per 1 m ^{2 of the} ink jet recording paper.
/ M ² or more, the effect of the present invention is particularly remarkable in an ink jet recording method.

The void volume of the ink jet recording paper of the present invention is 90% or more of the maximum ink volume to be printed, especially 95%.
% Or more. The dry thickness of the ink receiving layer constituting the void layer is preferably set to approximately 50 μm or less so as not to deteriorate physical properties of the film such as cracks.

On the other hand, it is preferable that the ratio of the void volume to the volume of the entire void layer is approximately 70% by volume or less from the viewpoint of the physical strength and fragility of the film.

In the ink jet recording paper of the present invention, an amount in the range of 20 to 30 ml / m ² is appropriate as the void volume satisfying the above conditions.

The above-mentioned void layer may be composed of two or more layers. In this case, the configuration of these void layers may be different as long as it is within the range described above.

In order to improve weather resistance and abrasion resistance, the ink-jet image-receiving layer of the present invention comprises, as an outermost layer, an ink-receiving layer containing thermoplastic resin particles and a second layer adjacent to the ink-receiving layer. Those having an ink absorbing layer can be used.

The ink-receiving layer provided as the outermost layer adjacent to the ink-absorbing layer forms a film by dissolving or melting the thermoplastic resin particles by applying a solvent or heating after image formation. It is.

As the ink absorbing layer, the structure of the above-described ink image receiving layer can be used. Examples of the composition of the fine-grained thermoplastic resin used in the ink receiving layer include, for example, polymonovinylidene aromatics such as polystyrene, polymethylstyrene, polymethoxystyrene, and polychlorostyrene, polyvinyl chloride, polyvinyl-cyclohexane, polyethylene, and polypropylene. Polyolefins and polyhaloolefins such as polyvinyl acetate, polyvinylidene chloride, etc., esters of α, β-ethylenically unsaturated acids such as polymethacrylate, polychloroacrylate, polymethyl methacrylate, polyester, polyacrylic acid, polycarbonate, etc. , Polyacrylonitrile, polyamide, polyether and the like and copolymers thereof.

The finely divided thermoplastic resin is preferably made by emulsion polymerization of one or more vinyl monomers, so-called plastic pigment on a slurry, its dried product, and plastic on a solid are pulverized by various means. It can be obtained as fine powder or powder molded into fine particles.

The particle size of these thermoplastic resin particles is as follows:
If the thickness is less than 0.05 μm, separation of the dye and pigment particles in the ink from the ink solvent will be slow, and the ink absorption speed will decrease. On the other hand, if it exceeds 10 μm, it is not preferable from the viewpoint of the coating strength of the recording medium after coating and drying on the support. Therefore, the preferred particle size of the thermoplastic resin particles is 0.05 to
It is 10 μm, more preferably 0.1 to 5 μm.

Further, as a criterion for selecting the thermoplastic resin particles, a glass transition point (Tg) can be mentioned.

When the Tg is lower than the coating / drying temperature, for example, the coating / drying temperature during the production of the recording medium is already higher than the Tg,
The voids due to the thermoplastic fine particles through which the ink solvent permeates disappear.

If the Tg is higher than the temperature at which the support is denatured by heat, a fixing operation at a high temperature is required to form a melted film after inkjet recording with the pigment ink. Heat stability and the like become problems. The preferred Tg of the thermoplastic resin particles is 50 to 150 ° C.
It is.

Further, after the image is formed, it is necessary to suppress the deterioration of the image quality of the recorded image due to its storage over time as much as possible. When pigment ink is used, there is no need to worry about the density decrease and discoloration in a relatively short period of time unlike dye ink, but from the viewpoint of suppressing yellowing (decomposition) of unprinted areas due to UV light. It is necessary to select thermoplastic resin particles from the above.

In the ink receiving layer and the ink absorbing layer of the ink jet recording medium of the present invention, the total amount of voids (void volume) is preferably 20 ml or more per 1 m ² of recording paper.

In the case where the void volume is less than 20 ml / m ² , if the ink amount at the time of printing is 1 ml / m ² or less, the ink absorbency is good, but if the ink amount exceeds 40 ml / m ² , the ink becomes It is not completely absorbed and tends to cause problems such as deterioration of image quality and slow drying property.

The upper limit of the void volume is not particularly limited, but it is necessary that the thickness of the void-type ink absorbing layer is usually 50 μm or less so as not to deteriorate the physical properties of the film such as cracks. , The void volume is 40 ml / m
It is difficult to make more than ² .

In the present invention, the void volume is determined according to J.I. TAPP
I pulp test method No. When measured by the liquid absorption test method (Bristow method) of 51-87 paper or paperboard, it is represented by the liquid transfer amount (ml / m ² ) at an absorption time of 2 seconds. In the above measurement method, pure water (ion-exchanged water) is used for the measurement, but a water-soluble dye of less than 2% may be contained in order to easily determine the measurement area.

The application of the ink receiving layer and the ink absorbing layer
A coating solution dissolved or dispersed in a solvent such as water or an organic solvent on a support, coated by a normal method such as a bar coater, a gravure printing method, a screen printing method, a reverse roll coating method using a gravure plate, It can be formed by drying.

The drying after the application needs to be performed at a temperature lower than the melting point of the thermoplastic resin particles used in the ink receiving layer. If the ink is dried at a temperature equal to or higher than the melting point, fusion and coating of the ink receiving layer will proceed, and the ink absorbency will be reduced.

In the present invention, a step of dissolving or melting the thermoplastic resin particles of the outermost layer by an appropriate means to form a film and change the film into a transparent layer is required. As a method of forming a film on the outermost layer, there is a method of dissolving the thermoplastic resin particles by applying a solvent, or a method of forming a molten film by applying heat.

At the time of heating, a substance for lowering the melting point of the thermoplastic resin particles, for example, a plasticizer can be applied in advance.

A method in which a solvent or a plasticizer is directly applied by a coating apparatus, applied by spraying, or immersed in a bath, a method of blending it as an emulsion when forming a coating layer, or a method specially provided during or after inkjet recording A method in which a solvent or plasticizer is ejected from a nozzle that has been applied to the ink receiving layer, and microcapsules containing the solvent or plasticizer are contained in the ink receiving layer in advance, and after ink jet recording, microcapsules are applied by appropriate means such as pressure. A method of breaking the capsule and releasing the solvent and plasticizer of the contents.Furthermore, another sheet coated with the microcapsules is pressed against the coated surface to break the microphone and the capsule, and the contents are received with ink. There is a method of transferring to a layer.

Further, an ultraviolet absorber as usually used,
Antioxidants, release agents, light stabilizers, etc. are contained in the ink receiving layer or added together with a solvent or a plasticizer to prevent deterioration of the formed thermoplastic resin film and further improve weather resistance. Desirable to improve.

The ink receiving layer provided as the outermost layer of the present invention preferably contains a silicone emulsion or a water-soluble silicon compound in addition to the thermoplastic resin particles. Examples of the compound include a dimethylsiloxane compound in which the functional group of siloxane is methyl and the release agent is a general dimethylsiloxane compound, and a vinyl group, a hydrogen group, a mercapto group, a methacryl group, an acryl group, an amino group, and a phenyl group as a substituent of the compound. And the like.

The content of the thermoplastic resin particles 1
It is preferably less than 1% by weight with respect to 00. When the addition amount is 1% or more, the releasability is improved, but color unevenness presumably caused by non-uniformity of fixing by heating and pressurization occurs, which is not preferable.

Further, a compound for the purpose of improving the mechanical transportability of the image-receiving sheet, preventing static charge, imparting writability, and adhering to stamps may be contained. In order to obtain an antistatic function, a layer made of a conductive resin such as an acrylic resin or a conductive filler is further added to a fatty acid ester, a sulfate ester, a phosphate ester, an amide, a quaternary ammonium salt, a betaine,
A layer to which an antistatic agent such as amino acids and ethylene oxide additions may be added may be formed.

The amount of the antistatic agent varies depending on the layer to which the antistatic agent is added and the type of the antistatic agent. In any case, the surface electric resistance of the image receiving sheet is 10 ¹³ ohm / cm ² or less. Is preferred. If it is larger than 10 ¹³ ohm / cm ² , the image receiving sheets stick together due to electrostatic contact and cause a paper feeding trouble. Quantitatively 0.0
A use amount of 1 to 3.0 g / m ² is preferred. When the amount of the antistatic agent used is less than 0.01 g / m ² , the antistatic effect is insufficient, while when it exceeds 3.0 g / m ² , the amount is too uneconomical, Problems may occur.

For the purpose of improving transportability, addition of nylon resin particles or higher fatty acid salts is also effective. As the nylon resin particles, for example, nylon 1
2, particles of nylon 6 and the like. These nylon resin particles may be used alone or in combination of two or more.

As higher fatty acid salts, for example, calcium stearate, magnesium stearate, barium stearate, zinc stearate and the like can be used.

The image receiving sheet of the present invention may be provided with a writing layer, and the means for forming the writing layer may be a conventionally known printing coating means. The thickness of the writing layer is 0.5 to 20 g / m when dry.
^{About 2} . The writing layer may be provided on the entire surface of the image receiving sheet or may be formed partially.

It is preferable that the support of the image receiving sheet has a role of holding the image receiving layer and has a mechanical strength that does not hinder handling even in an overheated state because heat is applied during thermal transfer.

The material of such a support is not particularly limited, and examples thereof include condenser paper, glassine paper, parchment paper, or high-size paper, synthetic paper (polyolefin-based, polystyrene-based), high-quality paper, art paper, and the like. Coated paper,
Cast coated paper, wallpaper, backing paper, synthetic resin or emulsion impregnated paper, synthetic rubber latex impregnated paper, synthetic resin internal paper, board paper, cellulose fiber paper, or polyester, polyacrylate, polycarbonate, polyurethane, polyimide, polyetherimide , Cellulose derivatives, polyethylene, ethylene-vinyl acetate copolymer,
Polypropylene, polystyrene, acrylic, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl butyral, nylon, polyetheretherketone, polysulfone, polyethersulfone, tetrafluoroethylene, perfluoroalkylvinylether, polyvinylfluoride, tetrafluoroethylene・ Ethylene, tetrafluoroethylene / hexafluoropropylene, polychlorotrifluoroethylene, polyvinylidene fluoride, etc., and a white opaque film formed by adding a white pigment or a filler to these synthetic resins or A foamed sheet can also be used, and is not particularly limited.

Further, a laminate formed by any combination of the above supports can also be used. As an example of a typical laminate, there is a synthetic paper of cellulose fiber paper and synthetic paper or a synthetic paper of cellulose synthetic paper and plastic film. The thickness of these supports may be arbitrary, and is usually about 10 to 300 μm.

In order to have higher printing sensitivity and to obtain high image quality without density unevenness or white spots, it is preferable to have a layer having fine voids. As the layer having fine voids, a plastic film or synthetic paper having fine voids inside can be used. Further, a layer having fine voids can be formed on various supports by various coating methods. As a plastic film or synthetic paper having fine voids, a polyolefin, particularly polypropylene, is mainly used, and an inorganic pigment and / or a polymer incompatible with polypropylene is blended therewith, and these are used as a void (void) forming initiator. A plastic film or synthetic paper obtained by stretching and forming a mixture of the above is preferred. When these are mainly composed of polyester, etc., the viscoelastic or thermal properties thereof, the cushioning properties, and the heat insulation properties are inferior to those mainly composed of polypropylene, so that the printing sensitivity is inferior. Density unevenness is also likely to occur.

In consideration of these points, the elastic modulus at 20 ° C. of the plastic film and the synthetic paper is 5 × 10 ⁸
Pa to 1 × 10 ¹⁰ Pa is preferable. Further, since these plastic films and synthetic papers are usually formed by biaxial stretching, they shrink by heating. When these are left at 110 ° C. for 60 seconds, the shrinkage is 0.5 to 2.5%. The above-mentioned plastic film or synthetic paper may be a single layer including layers having fine voids, or may have a multi-layer structure. In the case of a multi-layer structure, all the constituent layers may contain fine voids, or a layer having no fine voids may be contained. If necessary, a white pigment may be mixed into the plastic film or synthetic paper as a concealing agent.
Further, in order to increase whiteness, an additive such as a fluorescent whitening agent may be contained. The layer having fine voids is 30 to 80 μm
Is preferred.

As the layer having fine voids, a layer having fine voids can be formed on a support by a coating method. As plastic resin to be used, polyester, urethane resin, polycarbonate,
Known resins such as acrylic resin, polyvinyl chloride, polyvinyl acetate and the like can be used alone or by blending plural resins. As the support, various types of paper, synthetic paper, nonwoven fabric, plastic film, and the like described above can be used.

If necessary, a surface of the support opposite to the side on which the image receiving layer is provided may be coated with polyvinyl alcohol, polyvinylidene chloride, polyethylene, polypropylene, modified polyolefin, polyethylene terephthalate, for the purpose of curling prevention. A layer of resin such as polycarbonate or synthetic paper can be provided. As a bonding method,
For example, known lamination methods such as dry lamination, non-solvent (hot melt) lamination, and EC lamination can be used, and preferred methods are dry lamination and non-solvent lamination. Examples of an adhesive suitable for the non-solvent lamination method include Takenate 720L manufactured by Takeda Pharmaceutical Co., Ltd., and examples of an adhesive suitable for dry lamination include Takelac manufactured by Takeda Pharmaceutical Co., Ltd. A969 / Takenate A-5 (3/1), Polysol PSA SE-140, manufactured by Showa Polymer Co., Ltd.
0, vinylol PSA AV-6200 series and the like. The amount of these adhesives, from about 1-8 g / ^{m 2} on a solids, and preferably from 2 to 6 g / ^{m 2.}

In the case of laminating a plastic film and synthetic paper as described above, or between them, or between various kinds of paper and a plastic film or synthetic paper, the lamination can be performed with an adhesive layer.

For the purpose of increasing the adhesive strength between the support and the thermal transfer image-receiving layer and the ink-jet image-receiving layer, it is preferable to subject the surface of the support to various primer treatments or corona discharge treatment.

The above-mentioned thermal transfer image-receiving layer, ink-jet image-receiving layer, ink-receiving layer and ink-absorbing layer are formed on a support by coating a coating solution dissolved or dispersed in a solvent such as water or an organic solvent with a bar coater, a gravure printing method. , Screen printing method, roll coating method, reverse roll coating method using gravure plate, air knife coating method,
It can be formed by coating by a usual method such as a spray coating method, a curtain coating method, an extrusion coating method and the like, followed by drying. The barrier layer, the intermediate layer, and the back layer are also formed by the same method as in the case of the image receiving layer. In addition, the image receiving layer is formed not only by coating the coating solution directly on the support as described above and drying it, but also by forming the image receiving layer on another support in advance, The image receiving layer may be formed by transfer. In addition, two or more layers can be applied simultaneously, and in particular, all the layers can be applied at one time, and simultaneous application can be performed.

The thickness of the image receiving layer is the thickness after coating and drying.
It is preferably about 0.1 to 10 μm.

The image receiving sheet used in the present invention may be supplied to the printer in sheet form or in a roll form. The single-sheet supply refers to, for example, a form in which an image receiving sheet is cut into a fixed size, about 50 sheets are put into a cassette as one set, and mounted on a printer for use. or,
The roll form is a form in which an image receiving sheet is supplied to the printer in that form, cut into a desired size after printing, and used. In particular, the latter is preferable because troubles in the transport system such as defective paper feeding and defective discharge such as insertion of two sheets can be solved, and the capacity for printing can be increased.

When supplying the image receiving sheet in a roll form,
In particular, when using the postcard specification as described above, or when using a label or a sticker-type image receiving sheet, cut off the design mark such as a postal code frame formed on the back side or the half cut position of the seal. A detection mark can be provided on the back surface side for alignment.

Next, an example of the thermal transfer recording method of the present invention will be described. An embodiment in the case where the transparent protective layer or the non-transferable resin layer is supplied in the order of the dye layer of the thermal transfer sheet 1 will be described with reference to the drawings. FIG. 1 is a view showing a thermal transfer sheet according to one embodiment of the present invention. In FIG. 1, yellow (Y), magenta (M),
A cyan (C) dye layer 2 and, in some cases, a transparent protective layer or a non-transferable resin layer 4 are provided face-to-face.

In FIG. 1, gaps are provided between the respective layers. However, gaps may not be provided as appropriate according to the control method of the thermal transfer recording apparatus. In addition, in order to perform cueing of each layer with high accuracy, it is preferable to provide a detection mark on the thermal transfer sheet 1, and the method of providing the detection mark is not particularly limited. In this example, the dye layer and the transparent protective layer or the non-transferable resin layer 4 are provided on the same plane of the support, but it goes without saying that each may be provided on a separate support. In addition, as for the definition of the dye layer, when a reactive dye is used, the dye itself contained in the dye layer is a compound before the reaction, and strictly speaking, it cannot be said that the dye is Y, M, or C dye. ,
Y, M, and C images are similarly expressed for the sake of convenience in terms of layers for finally forming the images.

As a thermal transfer recording apparatus used in the present invention, for example, an apparatus as shown in FIG. 2 can be used. 2 (A), 2 (B) and 2 (C), 10 is a thermal transfer sheet supply roll, 15 is a thermal transfer sheet, 11 is a take-up roll for winding up the used thermal transfer sheet 15, 12
Denotes a thermal head, 13 denotes a platen roller, and 14 denotes an image receiving sheet inserted between the thermal head 12 and the platen roller 13.

In FIG. 2, 16 is an image receiving sheet supply roll, 17 is an ink jet head, and 18 is a heat roller.

In the thermal transfer printer of the present invention, it is preferable that glossy and matte tone controls can be selected in the same printer, since a print having desired surface properties can be obtained with one model. The selection method is not particularly limited. For example, the control data corresponding to the glossy tone and the matte tone of the present invention is held in the thermal transfer recording apparatus, the selected control data is read out by a simple operation of the operator, and the control unit is controlled according to the data. Alternatively, when a personal computer is connected to the printer, the control data may be stored in the personal computer, and the selected control data may be sent to the printer by a simple operation of the operator. When heating with a heat roller, apply a material that alters the surface, for example, a release sheet that gives gloss, a sheet with unevenness for matting, to the surface of the image receiving layer after image recording. By heating from the back surface of the sheet with a heat roller, it is possible to obtain a recording medium having a different surface.

The ink jet head used in the image forming method of the present invention may be of an on-demand type or a continuous type. The discharge method includes an electro-mechanical conversion method (for example, a single-cavity type, a double-cavity type, a bender type, a piston type, a shared mode type, a shared wall type, etc.), and an electro-thermal conversion method (for example, thermal inkjet). , A bubble jet (registered trademark) type, an electrostatic suction method (for example, an electric field control type, a slit jet type, etc.), a discharge method (for example, a spark jet type, etc.), and the like. However, any discharge method may be used.

In the present invention, a recording medium obtained by thermal transfer recording and ink jet recording is subjected to a heating step after image formation.

Heating after image formation is performed for the purpose of fixing the transferred dye in the image receiving layer for thermal transfer recording.
For ink jet recording, the purpose is to quickly volatilize the solvent of the ejected ink from the ink image receiving layer, or an ink receiving layer composed of thermoplastic resin particles as the outermost layer, and an ink absorbing layer as a second layer adjacent to the ink receiving layer. When the side on which the inkjet image receiving layer is provided is heated, the heating is performed for the purpose of forming a film of the thermoplastic resin particles.

Examples of the heating method include a method using a thermal head used for thermal transfer recording, a method using a heat roller, a method using a heating heater or a hot air heater, a method using electron beam radiation or infrared radiation [(FIG. C)
reference].

The heating of the recording medium can be performed from both the front and back surfaces of the recording medium or from one surface. The heating is performed on one surface or on both surfaces simultaneously, one side is shifted or simultaneously performed.

In the present invention, a preferable heating method is a method using a thermal head or a method using a heat roller.

In particular, in the present invention, when the ink-receiving layer comprising thermoplastic resin particles as the outermost layer and the ink-jet image-receiving layer having the ink-absorbing layer as the second layer adjacent to the ink-receiving layer are heated, Since it is preferable to apply pressure together with heating for the purpose of forming a film of the thermoplastic resin particles, it is preferable to use a method using a heat roller.

The heating and pressurizing method using a heat roller which is preferably used in the present invention is a method for heating an ink jet recording medium on which an image is recorded with a pigment ink containing a dispersant between a metal cylinder having a built-in heat source and a silicone rubber roller. It is a method of passing.

The heat roller preferably used in the present invention has a metal cylinder and a silicone rubber roller. Among them, the metal cylinder may use a general material such as iron or aluminum, and may be coated with a tetrafluoroethylene or a polytetrafluoroethylene-perfluoroalkylvinyl ether copolymer or the like for the purpose of increasing heat durability. Then, in order to enhance the smoothness after fixing, it may be mirror-finished. The metal cylinder preferably has a built-in heat source, and this heat source has a linear heater and is preferably heated to 50 to 150 ° C.

In the heat roller, a pressure is applied between the metal cylinder and the silicon rubber roller to deform the silicon rubber roller to form a so-called nip. The nip width is 1 to 20 mm, preferably 1.5 to 7 mm.

The pressure is 9.8 × 10 ⁴ to linear pressure.
The pressure is preferably 4.9 × 10 ⁶ Pa, and if it is less than 9.8 × 10 ⁴ Pa, the pigment ink is not sufficiently pushed into the thermoplastic resin particle layer by heating and pressing, and the linear pressure is 4.9 × 10 ⁶ Pa.
When the value exceeds a, the pigment ink can be sufficiently pushed in, but the smoothness and glossiness are reduced.

In the present invention, either thermal transfer recording or ink jet recording may be performed first (see FIGS. 2A and 2B).

In the present invention, dye-based and pigment-based inks are used as inks used for ink-jet recording. Since the address of a post card, which is cited as a main application of the present invention, is often composed of characters, it is preferable to use a pigment ink in view of its ink concealing properties, bleeding resistance, and weather resistance.

As the dye ink, those composed of known direct dyes, acidic dyes, basic dyes, reactive dyes, water-soluble dyes such as food dyes, liquid media and additives can be used.

Examples of the solvent for the aqueous ink include water and various water-soluble organic solvents, for example, alcohols such as methyl alcohol, isopropyl alcohol, n-butyl alcohol, tert-butyl alcohol and isobutyl alcohol; dimethylformamide, dimethylacetamide and the like. Amides; ketones or ketone alcohols such as acetone and diacetone alcohol; ethers such as tetrahydrofuran and dioxane; polyalkylene glycols such as polyethylene glycol and polypropylene glycol; ethylene glycol, propylene glycol, butylene glycol, triethylene glycol; 1,2,6
Polyhydric alcohols such as hexanetriol, thiodiglycol, hexylene glycol, diethylene glycol, glycerin and triethanolamine; polyhydric alcohols such as ethylene glycol methyl ether, diethylene glycol methyl (or ethyl) ether and triethylene glycol monobutyl ether; And lower alkyl ethers.

Among many of these water-soluble organic solvents,
Preferred are polyhydric alcohols such as diethylene glycol, triethanolamine and glycerin, and lower alkyl ethers of polyhydric alcohols such as triethylene glycol monobutyl ether.

Other additives for the aqueous ink include, for example, a pH adjuster, a metal sequestering agent, a fungicide, a viscosity adjuster,
Examples include a surface tension adjuster, a wetting agent, a surfactant, and a rust inhibitor.

The aqueous ink liquid is usually 25 to 50 dyn / cm, preferably 30 to 40 dy at 20 ° C. in order to improve the wettability on the ink jet recording paper.
It preferably has a surface tension in the range of n / cm.

Examples of the pigment ink include a dispersed pigment ink containing a dispersant, and a self-dispersible pigment ink containing no dispersant. Among them, the dispersant-containing pigment ink can be preferably used because the abrasion resistance is improved by heating and / or pressure after recording.

The pigment ink of the present invention preferably contains a surfactant in order to improve the dispersion stability. Examples of the surfactant preferably contained in the pigment ink of the present invention include anionic surfactants such as dialkyl sulfosuccinates, alkyl naphthalene sulfonates, and fatty acid salts, polyoxyethylene alkyl ethers, and polyoxyethylene alkyl allyl. Examples include nonionic surfactants such as ethers, acetylene glycols, and polyoxyethylene / polyoxypropylene block copolymers, and cationic surfactants such as alkylamine salts and quaternary ammonium salts. In particular, an anionic surfactant and a nonionic surfactant can be more preferably used.

As the pigment ink of the present invention, conventionally known organic and inorganic pigments can be used. For example, azo pigments such as azo lakes, insoluble azo pigments, condensed azo pigments, chelated azo pigments, phthalocyanine pigments, perylene pigments, perylene pigments, anthraquinone pigments, quinacridone pigments, dioxane pigments, thioindigo pigments, isoindolinone pigments, quinophthaloni pigments and the like. Dye lakes such as cyclic pigments, basic dye lakes, and acid dye lakes; organic pigments such as nitro pigments, nitroso pigments, aniline black, and daylight fluorescent pigments; and inorganic pigments such as carbon black.

Specific examples of the organic pigment are shown below. Pigments for magenta or red include C.I. I. Pigment Red 2, C.I. I. Pigment Red 3, C.I. I. Pigment Red 5, C.I. I. Pigment Red 6, C.I.
I. Pigment Red 7, C.I. I. Pigment Red 1
5, C.I. I. Pigment Red 16, C.I. I. Pigment Red 48: 1, C.I. I. Pigment Red 53:
1, C.I. I. Pigment Red 57: 1, C.I. I. Pigment Red 122, C.I. I. Pigment Red 12
3, C.I. I. Pigment Red 139, C.I. I. Pigment red 144, C.I. I. Pigment Red 149,
C. I. Pigment Red 166, C.I. I. Pigment Red 177, C.I. I. Pigment Red 178, C.I.
I. Pigment Red 222 and the like.

Examples of orange or yellow pigments include C.I. I. Pigment Orange 31, C.I. I. Pigment Orange 43, C.I. I. Pigment Yellow 12,
C. I. Pigment Yellow 13, C.I. I. Pigment Yellow 14, C.I. I. Pigment Yellow 15, C.I.
I. Pigment Yellow 17, C.I. I. Pigment Yellow 93, C.I. I. Pigment Yellow 94, C.I. I.
Pigment Yellow 138 and the like.

The pigments for green or cyan include:
C. I. Pigment Blue 15, C.I. I. Pigment Blue 15: 2, C.I. I. Pigment Blue 15: 3,
C. I. Pigment Blue 16, C.I. I. Pigment Blue 60, C.I. I. Pigment Green 7 and the like.

The present invention is characterized by containing a dispersant in a pigment ink. However, in order to use a pigment as a coloring material for ink jet recording, it is necessary to realize a high degree of dispersion stability. Also, the demand for sharper hues has become apparent. This generally requires that the pigment particles be dispersed at a finer level. However, the finer the particle, the stronger the cohesion and the more difficult it is to maintain dispersion and its stability. For this reason, in the preparation of the pigment ink, it is important to select a dispersant for appropriately dispersing and maintaining the pigment.

Examples of the dispersant of the present invention include higher fatty acid salts, alkyl sulfates, alkyl ester sulfates, alkyl sulfonates, sulfosuccinates, naphthalene sulfonates, alkyl phosphates, polyoxyalkylene alkyl ether phosphates. Acid salt, polyoxyalkylene alkyl phenyl ether, polyoxyethylene polyoxypropylene glycol, glycerin ester, sorbitan ester, polyoxyethylene fatty acid amide, surfactant such as amine oxide, or styrene, styrene derivative, vinyl naphthalene derivative, acrylic acid , Acrylic acid derivatives, maleic acid, maleic acid derivatives, itaconic acid, itaconic acid derivatives, fumaric acid, block copolymers having two or more monomers selected from fumaric acid derivatives,
Examples include random copolymers and salts thereof.

As a method for dispersing the pigment ink, various methods such as a ball mill, a sand mill, an attritor, a roll mill, an agitator, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, a pearl mill, a wet jet mill, and a paint shaker can be used.

It is also preferable to use a centrifugal separator or a filter for the purpose of removing coarse particle components of the pigment ink dispersion of the present invention.

The average particle size of the pigment dispersion used in the ink of the present invention is preferably from 10 nm to 200 nm,
10 nm to 100 nm is more preferable, and 10 nm to 50 n
m is more preferred. The average particle size of the pigment dispersion is 200 n
When m exceeds m, gloss deteriorates in an image recorded on a glossy medium, and remarkable deterioration in transparency occurs in an image recorded on a transparency medium. When the average particle size of the pigment dispersion is less than 10 nm, the stability of the pigment dispersion is likely to be deteriorated, and the storage stability of the ink is likely to be deteriorated.

The particle size of the pigment ink dispersion can be determined by a commercially available particle size measuring device using a light scattering method, an electrophoresis method, a laser Doppler method or the like. It is also possible to obtain a particle image with a transmission electron microscope on at least 100 particles or more and perform a statistical process on the image using image analysis software such as Image-Pro (manufactured by Media Cybernetics). It is.

The pigment ink of the present invention may contain a latex. As used herein, latex refers to polymer particles dispersed in a medium. Examples of polymer types include, for example, styrene-butadiene copolymer, polystyrene, acrylonitrile-butadiene copolymer,
Polyacrylic acid esters, polyurethanes, silicone-acrylic copolymers, acrylic-modified fluororesins, and the like are mentioned, and among them, polyacrylic acid esters, polyurethanes, and silicon-acrylic copolymers are preferable.

As an emulsifier used in the production of latex, a low molecular weight surfactant is generally used. Among them, a high molecular weight surfactant (for example, a solubilizing group is graft-bonded to a polymer) Type or a block polymer type in which a portion having a solubilizing group and an insoluble portion are linked) as an emulsifier, or by directly bonding a solubilizing group to a central polymer of a latex without using an emulsifier. Some latex is also dispersed. The latex using a high-molecular-weight surfactant as the emulsifier and the latex not using the emulsifier are called soap-free latex. The latex preferably used in the present invention is not limited to the type and form of the emulsifier, but it is more preferable to use a soap-free latex having excellent storage stability of the pigment ink.

In addition, recently, besides the latex in which the polymer in the central portion is uniform, there is also a core-shell type latex having a different composition between the central portion and the outer edge of the polymer particles, and this type of latex is also preferably used. be able to.

The average particle size of the latex preferably used in the present invention is preferably 150 nm or less, more preferably 50 nm or less.

The average particle size of the latex can be easily measured using a commercially available measuring device using a light scattering method or a laser Doppler method.

The added amount of the solid content of the latex is 0.1% by mass to 10% by mass with respect to the total mass of the pigment ink.
It is particularly preferred that the content is 3% by mass to 5% by mass.

If the addition amount is less than 0.1% by mass, it is difficult to exert a sufficient effect on the water resistance.
If the ratio exceeds the above range, problems occur in terms of the storability of the pigment ink, such as an increase in the viscosity of the pigment ink and an increase in the dispersed particle diameter of the pigment ink over time.

In the present invention, an electric conductivity regulator can be used, and examples thereof include inorganic salts such as potassium chloride, ammonium chloride, sodium sulfate, sodium nitrate and sodium chloride, and aqueous amines such as triethanolamine. .

The pigment ink of the present invention further comprises a preservative,
A fungicide, a viscosity modifier and the like may be contained as necessary.

[0260]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a specific example will be described. In the following description, “parts” or “%” is based on weight unless otherwise specified.

<Preparation of Thermal Transfer Sheet> 6 μm thick PE
T film (K-20, manufactured by Diafoil Hoechst Co., Ltd.)
3E-6F), a 0.5 μm thick primer layer made of a urethane resin is provided on one side, and a 1 μm thick silicone resin layer is provided on the other side (back side) as a heat-resistant lubricating layer. Support.

<Preparation of Thermal Transfer Sheet 1> For Thermal Transfer Sheet
On a support, yellow (Y) and magenta having the following composition
(M), cyan (C) in order from each dye layer and the support
From a three-layer laminate consisting of a release layer, a transferable transparent protective layer, and an adhesive layer.
A thermal transfer sheet 2 having a transparent protective layer formed
Created. Release layer is applied by gravure coating method after drying
0.4 g / m²So that the transferable transparent protective layer is
By gravure coating method, the coated amount after drying is 2.0 g / m ²
So that the adhesive layer is a gravure coat method
1.0 g / m coating amount ²It was formed to become.

(Y Dye Layer Coating Solution) Post-Chelating Dye Exemplary Compound (Y-1) 1.0 part Polyvinyl butyral (KY-24, manufactured by Denki Kagaku Kogyo Co., Ltd.) 5.5 parts Urethane-modified silicone resin ( Dialomer SP-2105 manufactured by Dainichi Seika Co., Ltd.) 1.5 parts Methyl ethyl ketone 80.0 parts Butyl acetate 10.0 parts

(M Dye Layer Coating Solution) Post-Chelating Dye Exemplary Compound (M-1) 1.0 part Polyvinyl butyral (KY-24, manufactured by Denki Kagaku Kogyo Co., Ltd.) 5.5 parts Urethane-modified silicone resin ( Dialomer SP-2105 manufactured by Dainichi Seika Co., Ltd.) 1.5 parts Methyl ethyl ketone 80.0 parts Butyl acetate 10.0 parts

(C Dye Layer Coating Solution) Post-Chelating Dye Exemplary Compound (C-1) 1.0 part Polyvinyl butyral (KY-24, manufactured by Denki Kagaku Kogyo Co., Ltd.) 5.5 parts Urethane-modified silicone resin ( Dialomer SP-2105 manufactured by Dainichi Seika Co., Ltd.) 1.5 parts Methyl ethyl ketone 80.0 parts Butyl acetate 10.0 parts

[0266]

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(Coating liquid for release layer) Inorganic fine particles (colloidal silica, manufactured by Nissan Chemical Co., Ltd.) 10.0 parts Polyvinyl alcohol (manufactured by Nippon Synthetic Chemical Co., Ltd.) 8.0 parts Water 50.0 parts Ethanol 40.0 parts

(Coating Liquid for Transferable Transparent Protective Layer) Vinyl chloride / vinyl acetate copolymer (# 1000A, manufactured by Denki Kagaku Kogyo Co., Ltd.) 15.0 parts Copolymer with reactive UV absorber Resin (UVA635L, manufactured by BASF Japan Ltd.) 20.0 parts Methyl ethyl ketone 50.0 parts Toluene 50.0 parts

(Coating Solution for Adhesive Layer) Vinyl chloride / vinyl acetate copolymer (# 1000A, manufactured by Denki Kagaku Kogyo KK) 20.0 parts Micro silica 1.0 part Methyl ethyl ketone 40.0 parts Toluene 40.0 Department

<Preparation of Thermal Transfer Sheet 2> A yellow (Y), magenta (M), and cyan (C) dye layers of the above composition used in the thermal transfer sheet 1 are formed on a support for the thermal transfer sheet in the order of surface. Thus, a heat transfer sheet 2 was prepared. The release layer is a gravure coat method, and the coated amount after drying is 0.4 g /
m ² , the transferable transparent protective layer is gravure coated by a gravure coating method so that the coated amount after drying is 2.0 g / m ² .
The adhesive layer is a gravure coat method, and the coating amount after drying is 1.0
g / m ² .

<Preparation of Image Receiving Sheet> (Support) As a porous PET sheet A, the following first, second and third layers were simultaneously extruded at 300 ° C. from an extruder, and three layers were formed on a stainless steel belt. After forming a sheet, the sheet was cooled and solidified. 115
The film was stretched three times in the transport direction while being transported by a roll heated to ° C. Subsequently, the film was stretched three times in the direction perpendicular to the transport direction while holding both ends of the film with clips. Then 200 ° C
And then cooled to room temperature.
A film-like porous PET sheet A having a layer of 35 μm, a third layer of 8 μm, and a specific gravity of 0.7 was produced.

(Composition of Porous PET Sheet A) Composition of First Layer and Third Layer PET Composition of Second Layer PET 90 parts PET-PTMG (PET and PTMG (polytetramethylene glycol having a molecular weight of 4000) during the polymerization of PET) 1 part Syndiotactic styrene (Zarek S10 manufactured by Idemitsu Petrochemical Co., Ltd.) 6 parts

Both sides of the PET sheet produced as described above were subjected to corona discharge treatment. Next, a basis weight of 130 g / m ² ,
Porous PET sheet A on one side of high quality paper of 110μm thickness
Is bonded through a laminator at 140 ° C. using Polysol PSA SE-1400 (manufactured by Showa Polymer Co., Ltd.) as an adhesive, and the other surface is extruded by an extrusion coating method.
Density containing 9.5% by weight of anatase type titanium oxide
92 low-density polyethylene was applied by a melt extrusion coating method to a thickness of 40 μm to prepare a support 1 for an image receiving sheet.

<Preparation of Image Receiving Sheet 1> An undercoat layer having the following composition was applied to the surface of the porous PET sheet of the image receiving sheet support 1, and dried at 120 ° C. for 1 minute. Then, on top of that,
An image receiving layer having the following composition was applied so that the coating amount at the time of drying was 2.5 g / m ² and dried at 130 ° C. for 2 minutes.
The sheet was slit to a width of 52 mm to obtain a roll-shaped image receiving sheet 1.

(Coating liquid for forming undercoat) Acrylic emulsion (Nippon Carbide Co., Ltd., Nicazole A-08) 35% aqueous solution 5.7 parts Pure water 94.0 parts

(Composition of Coating Solution for Image Receiving Layer) Vinyl chloride / vinyl acetate copolymer resin (# 1000GK, manufactured by Denki Kagaku KK) 42.0 parts Metal source (MS-1) 18.0 parts Epoxy-modified silicone ( Shin-Etsu Chemical Co., Ltd., KF-393) 0.7 parts Amino-modified silicone (Shin-Etsu Chemical Co., Ltd., KS-343) 0.3 parts Methyl ethyl ketone 20.0 parts Toluene 20.0 parts MS-1: Ni ²⁺ [C ₇ H ₁₅ COC (COOCH ₃ ) = C (CH ₃ ) O-] ₃

<Preparation of Image Receiving Sheet 2> On the image receiving sheet 1, a back coating liquid having the following composition was applied to the opposite side of the undercoat layer and the image receiving layer so as to have a dry film thickness of 4.5 g / m ^2. Then, a back layer was formed and slit to a width of 152 mm to obtain a roll-shaped image receiving sheet 2.

(Backside Layer Coating Solution) Polyvinyl Butyral (manufactured by Denki Kagaku Kogyo Co., Ltd., # 3000-1) 6.0 parts Nylon filler (manufactured by Shinto Paint Co., Ltd., MW-330) 1.0 part Silica 12.0 parts Chelating agent (Matsumoto Pharmaceutical Co., Ltd., Olgatex TC-750) 1.0 part Toluene / IPA 80.0 parts

<Preparation of Image Receiving Sheet 3> On the image receiving sheet 1, a back coating liquid having the following composition was applied to the opposite side of the undercoat layer and the image receiving layer so as to have a dry film thickness of 4.5 g / m ^2. Then, a back layer was formed and slit to a width of 152 mm to obtain a roll-shaped image receiving sheet 2.

(Coating Solution for Back Layer) Polyvinyl butyral (# 3000-1 manufactured by Denki Kagaku Kogyo KK) 20.0 parts Toluene / IPA 80.0 parts

<Preparation of Image Receiving Sheet 4> In the image receiving sheet 1, on the side opposite to the side where the undercoat layer and the image receiving layer were coated, an ink jet image receiving coating liquid having the following composition was dried to have a dry film thickness of 4.5 g / m ^2. To form an inkjet image receiving layer, and slit to a width of 152 mm to obtain a roll-shaped image receiving sheet 4.

(Coating solution for inkjet image receiving layer) Gelatin 14.5 parts Gelatin hardener (H-1) 0.5 parts Silica matting agent (average particle size 4 μm) 5.0 parts Water 80.0 parts

<Preparation of Image Receiving Sheet 5> In the image receiving sheet 1, on the side opposite to the side where the undercoat layer and the image receiving layer were applied, an ink jet image receiving coating liquid having the following composition was dried to have a dry film thickness of 4.5 g / m ^2. To form an inkjet image receiving layer, and slit to a width of 152 mm to obtain a roll-shaped image receiving sheet 5.

(Ink-jet image receiving layer coating liquid) Gelatin 13.0 parts Gelatin hardener (H-1) 0.5 part Organic polymer matting agent (polymethyl methacrylate particle average particle diameter 5 μm) 5.0 parts G i- Decyl phthalate 1.5 parts Water 80.0 parts

<Preparation of Image Receiving Sheet 6> On the image receiving sheet 1, an ink jet image receiving coating liquid having the following composition was applied to the opposite side of the undercoat layer and the image receiving layer after corona discharge so that the wet film thickness was 150 μm. And dried with air at 20 to 40 ° C. to form an inkjet image receiving layer.
The sheet was slit to a width of m to obtain a roll-shaped image receiving sheet 6.

(Inkjet image receiving layer coating liquid) 160 g of ultrafine silica powder having an average particle diameter of about 0.07 μm and having an anionic surface was added to 1000 ml of pure water, and dispersed with a high-speed homogenizer. Next, this aqueous silica dispersion (I)
5% of which average polymerization degree is 1700 and saponification degree is 90%
Polyvinyl alcohol aqueous solution (II) (Surfactant-1
(Containing 0.3% by weight) was gradually added, and dispersed by a high-speed homogenizer for 30 minutes to obtain a translucent coating solution.

<Preparation of Image Receiving Sheet 7> On the image receiving sheet 1, the opposite side where the undercoat layer and the image receiving layer were applied was subjected to corona discharge, and thereafter an inkjet image receiving coating liquid having the following composition was applied so as to have a wet film thickness of 150 μm. And dried with air at 20 to 40 ° C. to form an inkjet image receiving layer.
The sheet was slit to a width of m to obtain a roll-shaped image receiving sheet 7.

(Ink-jet image-receiving layer coating liquid) 160 g of ultrafine silica powder having an average particle size of about 0.07 μm and having an anionic surface was added to 1000 ml of pure water, and dispersed by a high-speed homogenizer. Next, this aqueous silica dispersion (I)
5% of which average polymerization degree is 1700 and saponification degree is 90%
Polyvinyl alcohol aqueous solution (II) (Surfactant-1
(Containing 0.3% by weight). Further, 60 ml of a 2% by weight aqueous solution of sodium tetraborate was added as a hardener and dispersed with a high-speed homogenizer for 30 minutes to obtain a translucent coating solution.

<Preparation of Image Receiving Sheet 8> On the image receiving sheet 1, the opposite side where the undercoat layer and the image receiving layer were applied was subjected to corona discharge, and thereafter an inkjet image receiving coating liquid having the following composition was applied so as to have a wet film thickness of 150 μm. And dried with air at 20 to 40 ° C. to form an inkjet image receiving layer.
The sheet was slit to a width of m to obtain a roll-shaped image receiving sheet 8.

(Ink-jet image receiving layer coating solution) 160 g of ultrafine silica powder having an average particle diameter of about 0.07 μm and having an anionic surface was added to 1000 ml of pure water, and dispersed with a high-speed homogenizer. Next, this aqueous silica dispersion (I)
5% of which average polymerization degree is 1700 and saponification degree is 90%
Polyvinyl alcohol aqueous solution (II) (Surfactant-1
(Containing 0.3% by weight). Further, 60 ml of an aqueous solution of ethylene glycol glycidyl ether by weight was added as a hardener, and the mixture was dispersed with a high-speed homogenizer for 30 minutes to obtain a translucent coating solution.

<Preparation of Image Receiving Sheet 9> In the image receiving sheet 1, on the side opposite to the side where the undercoat layer and the image receiving layer were applied, three layers of an ink jet image receiving coating liquid having the following composition were applied at 40 ° C. after corona discharge. Using a three-layer slide hopper, a first layer (wet film thickness of 40 μm), a second layer (wet film thickness of 110 μm), and a third layer (wet film thickness of 30 μm) are applied in this order from the support side. 60 in the wind (relative humidity 15%)
50 seconds at 45 ° C (25% relative humidity) for 60 seconds
C. in an air (25% relative humidity) for 60 seconds.
The sample was wound up by adjusting the humidity for 2 minutes in an atmosphere at ２５25 ° C. and a relative humidity of 40 to 60%, and then slit into a width of 152 mm to obtain a roll-shaped image receiving sheet 9.

(Coating Solution for Inkjet Image Receiving Layer) Next, a coating solution having the following composition was prepared for the ink absorbing layer on the front side. "Preparation of titanium oxide dispersion-1" having an average particle size of 0.25 µm
20 kg of titanium oxide (W-10, manufactured by Ishihara Sangyo)
150 g of sodium tripolyphosphate of H = 7.5, polyvinyl alcohol (manufactured by Kuraray Co., Ltd .: PVA23)
5) 500 g, 150 of the cationic polymer (P-1)
g and Sannobuco's antifoaming agent SN381, 10
g, and dispersed in a high-pressure homogenizer (manufactured by Sanwa Kogyo Co., Ltd.).
To obtain a uniform titanium oxide dispersion liquid-1.

[0293]

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[Preparation of Silica Dispersion-1] 125 kg of fumed silica (QS-20, manufactured by Tokuyama Corporation) having an average primary particle size of about 0.014 μm was added to a jet stream manufactured by Mitamura Riken Kogyo Co., Ltd.・ Inductor mixer TD
Using S, the mixture was suction-dispersed at room temperature in 600 L of pure water adjusted to pH = 2.5 with nitric acid, and then the total amount was made up to 660 L with pure water.

[Preparation of Silica Dispersion-2] 1.29 kg of cationic polymer (P-1) and 4.2 parts of ethanol
Aqueous solution containing 1.5 L of L, n-propanol (pH
= 2.3) To 15 L, 66.0 L of silica dispersion-1 was added with stirring, and then 6.0 L of an aqueous solution containing 260 g of boric acid and 230 g of borax was added, and the above-mentioned antifoaming agent SN381 was added. Was added.

This mixture was mixed with a high-speed homomixer for 1 hour.
The mixture was dispersed at 2,000 rpm, and the whole amount was adjusted to 90 L with pure water to prepare a silica dispersion liquid-2.

[Preparation of Emulsified Dispersion-1] Oil-soluble optical brightener UVITEX-OB, 40, manufactured by Ciba-Geigy, Inc.
0 g and the following antioxidant AO-1 (6000 g) were dissolved by heating in 3000 g of diisodecyl phthalate and 12 L of ethyl acetate, and this was dissolved in 3500 g of acid-treated gelatin, cationic polymer (P-1), 50% aqueous solution of saponin 4000
The mixture was added to and mixed with 35 L of an aqueous solution containing 50 ml of water, emulsified and dispersed by a high-pressure homogenizer manufactured by Sanwa Kogyo Co., Ltd., and ethyl acetate was removed under reduced pressure.

[Preparation of Matting Agent Dispersion-1] Methacrylate monodispersed matting agent MX manufactured by Soken Kagaku Co., Ltd.
156 g of -1500 (average particle diameter 15 μm)
A235 was added to 7 L of pure water containing 3 g, and dispersed by a high-speed homogenizer to finish the whole amount to 7.8 L.

"Preparation of Coating Solution" Coating solutions for the first, second and third layers were prepared in the following procedure. Coating solution for first layer: 40 in 560 ml of silica dispersion-2
While stirring at ℃, the following additives were sequentially mixed.

-10% aqueous solution of polyvinyl alcohol (Kuraray Industries, Ltd .: PVA203): 6 ml-5% aqueous solution of polyvinyl alcohol (Kuraray Industries, Ltd .: PVA235): 170 ml-Polyvinyl alcohol (Kuraray Industries, Ltd .: PVA245) 5% aqueous solution: 120 ml Emulsion dispersion-1: 22 ml Titanium oxide dispersion-1: 40 ml Latex emulsion manufactured by Dai-ichi Kogyo Co., Ltd. AE-803: 24 ml The total amount is made up to 1000 ml with pure water.

Coating solution for second layer: 65 of silica dispersion liquid-2
The following additives were sequentially mixed with 0 ml while stirring at 40 ° C. (1) Polyvinyl alcohol (Kuraray Industries, Ltd .: 10% aqueous solution of PVA203) (2) Polyvinyl alcohol (Kuraray Industries, Ltd .: PVA235) 5% aqueous solution: (3) Polyvinyl alcohol (Kuraray Industries, Ltd .: PVA245) 5% aqueous solution of): 120 ml (4) Emulsified dispersion-1: 30 ml (5) Parafix EP (produced by Ohara Palladium Co., Ltd.) 16 ml (6) The total amount is made up to 1000 ml with pure water.

Coating liquid for third layer: 65 of silica dispersion liquid-2
The following additives were sequentially mixed with 0 ml while stirring at 40 ° C. (1) 10% aqueous solution of polyvinyl alcohol (Kuraray Industries, Ltd .: PVA203): 0.6 ml (2) 5% aqueous solution of polyvinyl alcohol (Kuraray Industries, Ltd .: PVA235): 270 ml (3) Silicon dispersion (Toray) -Dow Corning Silicone Co., Ltd.-BY-22-839): 3.5 ml (4) Saponin 50% aqueous solution: 4 ml (5) Matting agent dispersion liquid-1: 10 ml (6) Surfactant 1 (6%) Solution): 4 ml (7) Make up to 1000 ml with pure water.

<Preparation of Image Receiving Sheet 10> In the image receiving sheet 1, on the side opposite to the side where the undercoat layer and the image receiving layer were applied, three layers of the ink absorbing layer coating liquid having the following composition were applied after corona discharge.
The coating liquid was applied to the first layer (wet film thickness 50 μm) and the second layer (wet film thickness 1) from the support side at 40 ° C. using a three-layer slide hopper.
00 μm), the third layer (wet film thickness 50 μm) in this order, and a wind of 25 ° C. (relative humidity 15%) for 60 seconds, a wind of 45 ° C. (relative humidity 25%) for 60 seconds, 50 ° C.
Dried in the wind (relative humidity 25%) for 60 seconds
The sample is wound up by adjusting the humidity for 2 minutes in an atmosphere of 25 ° C. and a relative humidity of 40 to 60%, and then a coating liquid of an ink receiving layer having the following composition is applied using a wire bar to a dry film thickness of 5 μm. Then, it was dried at 50 ° C. for 30 minutes, and then slit into a width of 152 mm to obtain a roll-shaped image receiving sheet 10.

(Coating Liquid for Ink Absorbing Layer) In the following examples, (%) indicates mass% unless otherwise specified. Example 1 (Preparation of Recording Medium A) <Preparation of Titanium Oxide Dispersion-1> Average particle size 0.25 μm
20 kg of titanium oxide (Ishihara Sangyo: W-10)
150 g of 7.5 sodium tripolyphosphate, 500 g of polyvinyl alcohol (Kuraray Co., Ltd .: PVA235, average polymerization degree 3500), cationic polymer (P-
1) 150 g and Sannobuco Co., Ltd. Antifoamer SN38
1 was added to 90 liters of an aqueous solution containing 10 g, and the mixture was dispersed with a high-pressure homogenizer (manufactured by Sanwa Kogyo Co., Ltd.), and the whole was finished to 100 liters to obtain a uniform titanium oxide dispersion liquid-1.

[0305]

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<Preparation of Silica Dispersion-1> 125 kg of fumed silica (Aerosil Kogyo Co., Ltd .: A300) having an average primary particle size of 0.007 μm was jet-streamed by Mitamura Riken Kogyo Co., Ltd. Adjusted to pH = 2.5 with nitric acid using Ducter Mixer TDS 6
After suction-dispersed in 20 liters of pure water at room temperature, the total amount was made up to 694 liters with pure water. Electron micrographs of particles obtained by diluting this dispersion were taken, and it was confirmed that most of the particles had an average particle size of 0.01 μm or less and were dispersed to primary particles (most particles were 85 to 85 μm). 90% of particles).

<Preparation of Silica Dispersion-2> A solution containing 1.41 kg of the cationic polymer (P-2) and 4.2 liters of ethanol (pH = 2.3) was added to 18 liters of a solution at a temperature of 25 to 30 ° C. In the range, silica dispersion-1 of 69.
4 liters were added over 20 minutes with stirring, and then an aqueous solution containing 260 g of boric acid and 230 g of borax (pH
= 7.3) 7.0 liters were added over about 10 minutes, and 1 g of the antifoaming agent SN381 was added. The mixed solution was subjected to 24.5 MPa with a high pressure homogenizer manufactured by Sanwa Kogyo Co., Ltd.
, And the whole amount was made up to 97 liters with pure water to prepare an almost transparent silica dispersion liquid-2.

[0308]

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<Preparation of Fluorescent Whitening Agent Dispersion-1> Oil-soluble fluorescent whitening agent UIVITEX-O manufactured by Ciba-Geigy, Inc.
B, 400 g was dissolved in 9000 g of diisodecyl phthalate and 12 liters of ethyl acetate under heating, and this was dissolved in an aqueous solution 65 containing 3500 g of acid-treated gelatin, cationic polymer (P-2) and 6000 ml of a 50% aqueous solution of saponin.
Liter and mixed with a high-pressure homogenizer manufactured by Sanwa Kogyo Co., Ltd. to 24.5 Mpa (250 kgf / cm ² ).
The emulsion was emulsified and dispersed three times under the pressure described above, and ethyl acetate was removed under reduced pressure. PH of this dispersion
Was about 5.3.

<Preparation of Coating Solution> Coating solutions for the first layer, the second layer and the third layer were prepared in the following procedure. First Layer Coating Liquid The following additives were sequentially mixed with 600 ml of the silica dispersion liquid 1 at 40 ° C. while stirring.

A 7% aqueous solution of polyvinyl alcohol (manufactured by Kuraray Industries, Ltd .: PVA235 (average degree of polymerization: 3500)) 194.6 ml Fluorescent brightener dispersion liquid-1 25 ml Titanium oxide dispersion liquid-1 33 ml Manufactured by Daiichi Kogyo Co., Ltd. : Latex emulsion AE-803 18ml Make up to 1000ml with pure water. The coating solution pH was 4.4.

The following additives were sequentially mixed with 650 ml of the silica dispersion liquid 2 at 40 ° C. while stirring.

201.6 ml of a 7% solution of polyvinyl alcohol (manufactured by Kuraray Co., Ltd .: PVA235 (average degree of polymerization: 3500)) 201.6 ml Fluorescent brightener dispersion liquid-1 35 m The total amount is made up to 1000 ml with pure water. The coating solution pH was 4.4.

Third Layer Coating Liquid The following additives were sequentially mixed with 650 ml of the silica dispersion liquid 2 at 40 ° C. while stirring.

71.6% aqueous solution of polyvinyl alcohol (manufactured by Kuraray Industries: PVA235 (average degree of polymerization: 3500)) 201.6 ml Silicon dispersion (BY-22-839 manufactured by Dow Corning Toray Silicone Co., Ltd.) 15 ml Saponin 50 % Aqueous solution 4ml Make up to 1000ml with pure water. The pH of the coating solution was 4.5.

(Ink receiving layer coating liquid) Next, a coating liquid for a thermoplastic resin layer was prepared according to the following formulation.

AT-2000 (styrene-acrylic acid copolymer latex (Tg: 80 ° C., MFT: 85 ° C., manufactured by Showa Polymer Co., Ltd.)) 50% AS-7180 3% Water 47%

A coating liquid for a thermoplastic resin layer was applied to the recording medium having only the solvent absorbing layer using a wire bar so as to have a dry film thickness of 5 μm, and dried at 50 ° C. for 30 minutes. A was prepared.

<Preparation of Ink for Inkjet> <Preparation of Dye Ink> I. Direct Black 199 (dye) 2.0% by weight Diethylene glycol (wetting agent) 5.0% by weight Glycerin (wetting agent) 10% by weight Triethylene glycol mono-n-butyl ether (penetrating agent) 8.0% by weight potassium hydroxide ( pH adjuster) 0.2 wt% pure water balance

<Preparation of Pigment Ink> (Preparation of Black Pigment Dispersion) Hostfine Black T (manufactured by Clariant Co., Ltd., average particle size: 50 nm) 167 g Latex 4 (Superflex 460, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 78 0.9 g Ethylene glycol 200 g Triethylene glycol monomethyl ether 120 g Olfin GXL (Nissin Chemical Co., Ltd.) 4 g Proxel GXL (Zeneca) 2 g Finish the above to 1000 g with ion-exchanged water and pass twice through a 1 μm Millipore filter twice. Thus, a pigment ink was prepared.

(Embodiments 1-1 to 1-6) A resistor having a square shape (length in the main scanning direction: 80 μm × length in the sub-scanning direction: 120 μm)
m), a thermal head of 300 dpi line head;
The image receiving sheets 4-1 are mounted on an apparatus A equipped with a piezo-type head having a nozzle particle diameter of 20 μm, a driving frequency of 12 kHz, a nozzle number of 128 per color, and a nozzle density of 180 dpi of the same color.
Superposing a dye layer of the image receiving layer portion and the thermal transfer thermal transfer sheet 1 of 0 and set, while pressed against the thermal head and the platen roll, yellow sequentially increase in applied energy range 5~80mJ / mm ^2, magenta, cyan The neutral (the above three color superimposed) step pattern, the transparent protective layer is then heated at a feed rate of 10 msec / line at a feed length of 85 μm per line from the back side of the dye layer to transfer the dye onto the image receiving layer. Was. Subsequently, an image was formed by discharging 20 ml / m ^{2 of a} black dye ink from the piezo type head on the opposite side of the side on which the thermal transfer recording was performed, using the same transport flow.

(Comparative Examples 1-1 to 1-3) The same procedure as in Example 1 was carried out except that the number of image receiving sheets was changed to 1 to 3.

(Embodiment 2) A resistor having a square shape (length in the main scanning direction × 80 μm in the sub-scanning direction), 300
An image receiving apparatus B equipped with a thermal head of a dpi line head and a platen roller capable of changing the surface temperature, and a piezo type head having a nozzle particle diameter of 20 μm, a driving frequency of 12 kHz, a number of nozzles of 128 per color, and a nozzle density of 180 dpi of the same color. The thermal transfer image-receiving layer portion of the sheet 9 and the dye layer portion of the thermal transfer sheet 1 are set so as to overlap each other. First, 20 ml / m ^{2 of} black dye ink is ejected from a piezo-type head on the surface opposite to the thermal transfer image-receiving layer, and the image is formed. while heating contact with the platen roll to the opposite surface and the ink jet recorded side thermal head and the surface temperature was adjusted to 90 ° C. by the transport stream, yellow sequentially increase in applied energy range 5~80mJ / mm ^2, magenta , Cyan, neutral (the above three color superimposition) step pattern, and then a transparent protective layer, At a feed speed of 10 msec / line, the feed length per line was 85 μm, and the image was formed by heating the dye layer from the back side to transfer the dye onto the image receiving layer.

Example 3 In Example 1, an image was formed using 9 as an image receiving sheet and using black pigment ink for ink jet recording.

(Comparative Example 2) In Example 1, an image was formed by using 2 as an image receiving sheet and using black pigment ink for ink jet recording.

(Embodiment 4) The resistor shape is square (main running)
80 μm in scanning direction × 120 μm in sub-scanning direction), 300
Thermal head of dpi line head and nozzle particle size 2
0 μm, drive frequency 12 kHz, number of nozzles per color 1
28. Piezo type head with the same color nozzle density of 180 dpi
The image receiving sheet on the downstream side in the transport direction of both heads
C equipped with two heat rollers provided as follows:
Thermal transfer image receiving layer portion of image receiving sheet 9 and dye of thermal transfer sheet 1
Lay the layers on top of each other and set them first.
20m black pigment ink from piezo type head
l / m²After forming the discharged image, the ink jet
Thermal head and surface temperature on the side opposite to the side where
Is heated and pressed with a platen roll adjusted to 90 ° C.
Et al., 5-80 mJ / mm ²In the applied energy range of
Increasing yellow, magenta, cyan, neutral
(The above three colors overlap) Step pattern, then transparent protection
Layer is fed at 10msec / line per line
The feed length is 85 μm, and heating from the back side of the dye layer
The dye was transferred onto the image receiving layer to form an image.

Subsequently, the image receiving sheet was conveyed between the heat rollers of which the surface temperature on the thermal transfer image receiving layer side was adjusted to 160 ° C. and the surface temperature on the ink jet image receiving layer side was adjusted to 90 ° C. in the same conveying flow.

Example 5 An image was formed using the image receiving sheet 10 in Example 1-1.

Example 6 An image was formed using the image receiving sheet 10 and the thermal transfer sheet 2 in Example 1-1.

Example 7 In Example 4, an image was formed using the image receiving sheet 10.

Example 8 In Example 4, an image was formed using the image receiving sheet 10 and the thermal transfer sheet 2.

Example 9 In Example 2, an image was formed using the image receiving sheet 10.

[0333]

[Table 1]

From the results shown in Table 1-1, in the image receiving sheets 4 to 9 using the hydrophilic binder as the image receiving layer for ink jet, especially the image receiving sheets 4, 5, and 7 containing the hardener and the fine particle powder were used. , 8, and 9 have excellent effects in printability by ink jet recording and image storability on both sides as compared with Comparative Examples.

From the results shown in Table 1-2, even when the pigment ink is used in the ink-jet image receiving sheets 3 and 4, the effects of the ink-jet recording and the image preservability on both sides are superior to those of the comparative examples. Is obtained.

From the results shown in Tables 1-3, by using the apparatus B or C for performing a heat treatment after printing on the ink-jet image-receiving sheet 10, the suitability for printing by ink-jet recording and the preservation of images on both sides can be compared to the comparative example. An excellent effect on the properties is obtained.

Ink absorption ink jet printer (Epson PM-750C)
After printing each color of yellow (Y), magenta (M), and cyan (C) using, a commercially available high-quality paper was brought into close contact with the printed image, and the degree of transfer of the ink to the high-quality paper was evaluated.

◎: No transfer at 30 seconds of print ○: Slight transfer at 30 seconds of print, no transfer at 1 minute △: Slight transfer at 1 minute of print, but no problem in practical use ×: 2 minutes of print But transfer is seen, there is a problem in practical use

Image bleeding Ink jet printer (Epson PM-750C)
Was used to print each color of yellow (Y), magenta (M), and cyan (C), and the degree of bleeding of the printed image was visually evaluated.

◎: no bleeding is observed. 良好: almost no bleeding is good.…: Bleeding is present but there is no problem in practical use.…: Bleeding is observed in a large amount, outside the practical upper limit.

Image density Ink jet printer (Epson PM-750C)
Was solid printed with black ink, and the image density was measured.

◎: Maximum density of 2.0 or more…: Maximum density of 1.7 to less than 2.0 Δ: Maximum density of 1.5 to less than 1.7 ×: Maximum density of less than 1.5

Film forming property The film forming property of the film surface before printing was judged according to the following criteria.

◎: No cracking, no peeling of the film even when strongly rubbing the surface with a finger at 23 ° C., 80% RH ○: No cracking, a slight film rubbing with a finger at 23 ° C., 80% RH The film may be peeled off, but the film will not peel off under normal handling. △: The surface is slightly cracked, but the film does not peel off when transported by the inkjet printer. ×: The film is easily transported by the inkjet printer. Peels off or the film spontaneously peels off after coating and drying

<Image Preservation> Using the devices shown in FIG.
Thermal transfer and inkjet recording were performed, and the following image storability was evaluated using black patch portions on both surfaces of each image sample.

Weather Resistance A portion of each image near the black patch density of 1.0 was measured with a xenon fade meter (WEL-6X, manufactured by Suga Test Instruments Co., Ltd.).
-HC-Ec, the sample surface illuminance 70,000 lux) after the exposure for 14 days and from the Visual concentration before the exposure,
The residual ratio of the concentration was determined. X-Rite3 for concentration measurement
This was performed with a status A reference filter using 10TR (manufactured by X-Rite). The higher the residual ratio, the better the weather resistance. The evaluation was performed in the following four stages.

A: 85 to 100% B: 70 to less than 85% C: 55 to less than 70% X: Less than 55% The residual ratio is preferably 70% or more.

Water Resistance The portion of each image near the black patch density of 1.0 was immersed in water at 23 ° C., pulled up after 10 minutes, and the density remaining ratio was determined from the Visual density before and after immersion. The concentration was measured with a status A reference filter using X-Rite310TR (manufactured by X-Rite).
The higher the residual ratio, the better the water resistance. The evaluation was performed in the following four stages.

A: 85 to 100% B: 70 to less than 85% C: 55 to less than 70% X: Less than 55% The residual ratio is preferably 70% or more.

Moisture resistance The portion near the black patch density of 1.0 of each image was treated at 60 ° C.
V before and after standing for one month under% RH conditions
The residual concentration was determined from the actual concentration. The concentration was measured with a status A reference filter using X-Rite310TR (manufactured by X-Rite). The higher the residual ratio, the better the moisture resistance. The evaluation was performed in the following four stages.

A: 85 to 100% B: 70 to less than 85% C: 55 to less than 70% X: Less than 55% The residual ratio is preferably 70% or more.

Abrasion Resistance For each image, the printed portion was rubbed five times with a plastic eraser, and the degree of density reduction was classified as follows.

◎: No discoloration at all…: Slight discoloration is observed, but not disturbing as an image △: Discoloration can be confirmed, image is degraded ×: Discoloration is large, and the effect on the image is large

[0354]

According to the present invention, a print of an image such as a photograph is obtained by using a chelate-type sublimation thermal transfer having high image quality and excellent image storability, and a character is formed by using an inexpensive inkjet print on the back surface. It is a technique suitable for postcard printing of a small number of New Year's cards and the like, for example, which enables printing of a small number of copies, a recording medium and an image forming method for obtaining a printed material having excellent durability compared with the conventional method, and its implementation And an optimum image recording apparatus can be provided.

[Brief description of the drawings]

FIG. 1 is an explanatory plan view showing one embodiment of a thermal transfer sheet used in the present invention.

FIG. 2 is an explanatory plan view showing three embodiments of the image recording apparatus according to the present invention.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Hiroshi Watanabe 1 Sakuracho, Hino-shi, Tokyo Konica Corporation F term (reference) 2C056 EA30 FC01 HA45 HA46 2H086 BA05 BA14 BA15 BA24 BA32 BA34 BA35 BA41 BA47 2H111 CA03 CA05 CA25 CA33 CA41

Claims (18)

[Claims] 1. A support having at least one image-receiving layer containing a dye fixing body capable of forming a dye by reacting with a heat-diffusible dye precursor on one surface, and an ink-jet image-receiving layer on the other surface. An image forming recording medium provided with a layer. 2. The image forming recording medium according to claim 1, wherein said ink jet image receiving layer is hardened. 3. The image forming recording medium according to claim 1, wherein said ink jet image receiving layer contains at least a hydrophilic binder, and said hydrophilic binder is hardened. 4. The image forming recording medium according to claim 3, wherein said ink jet image receiving layer contains at least a hydrophilic binder and fine particle powder, and said hydrophilic binder is hardened. 5. A support having at least one image-receiving layer containing a dye fixing body capable of forming a dye by reacting with a heat-diffusible dye precursor on one surface, An image forming recording medium comprising an ink receiving layer containing thermoplastic resin particles as an outer layer, and an ink jet image receiving layer having an ink absorbing layer as a second layer adjacent to the ink receiving layer. 6. The image forming recording medium according to claim 5, wherein the ink receiving layer as the outermost layer contains a silicone emulsion or a water-soluble silicone compound. 7. The image forming recording medium according to claim 1, wherein the ink absorbing capacity of the ink jet image receiving layer is 10 ml / m ² or more. 8. A dye layer of a thermal transfer sheet having at least one dye layer containing a heat-diffusible dye precursor on a support, and a dye formed on one of the supports by reacting with the dye precursor. The dye precursor is superimposed on the image receiving layer by superimposing the image receiving sheet having at least one image receiving layer containing the obtained dye-fixed body so as to face the image receiving layer side and heating imagewise with a thermal head or the like. Forming an image by transferring the image, and forming the image on an inkjet image receiving layer provided on the other surface of the support of the image receiving sheet by using an inkjet head or the like that discharges ink for each nozzle based on image data. An image forming method, comprising a step of forming an image by discharging ink from each nozzle based on data. 9. A dye layer of a thermal transfer sheet having at least one dye layer containing a heat-diffusible dye precursor on a support, and a dye formed by reacting the dye precursor on one of the supports. The dye precursor is superimposed on the image receiving layer by superimposing the image receiving sheet having at least one image receiving layer containing the obtained dye-fixed body so as to face the image receiving layer side and heating imagewise with a thermal head or the like. Forming an image by transferring the image, and forming the image on an inkjet image receiving layer provided on the other surface of the support of the image receiving sheet by using an inkjet head or the like that discharges ink for each nozzle based on image data. An image forming method comprising: forming an image by discharging pigment ink from each nozzle based on data. 10. A dye layer of a thermal transfer sheet having at least one dye layer containing a heat-diffusible dye precursor on a support, and forming a dye on one of the supports by reacting with the dye precursor. An image receiving sheet having at least one image receiving layer containing a dye fixing body is superposed on the image receiving layer so as to face the image receiving layer, and is heated imagewise with a thermal head or the like, whereby the dye precursor is added to the image receiving layer. Transferring the image to form an image, on the inkjet image receiving layer provided on the other surface of the support of the image receiving sheet, using an inkjet head or the like that ejects ink for each nozzle based on image data. An image forming method comprising the steps of forming an image by discharging ink from each nozzle based on image data, and heating a recording medium after the image formation. 11. The image forming method according to claim 8, wherein said ink jet image receiving layer is hardened. 12. The image forming method according to claim 8, wherein the ink jet image receiving layer contains at least a hydrophilic binder, and the hydrophilic binder is hardened. 13. The image forming method according to claim 8, wherein the ink jet image receiving layer contains at least a hydrophilic binder and fine particle powder, and the hydrophilic binder is hardened. 14. A dye layer of a thermal transfer sheet having at least one dye layer containing a heat-diffusible dye precursor on a support, and forming a dye on one of the supports by reacting with the dye precursor. At least one image-receiving layer containing the obtained dye-fixed body.
By superimposing the image receiving layer of the image receiving sheet having a layer so as to face, and heating imagewise with a thermal head or the like,
Transferring the dye precursor to an image receiving layer to form an image, and an ink receiving layer containing thermoplastic resin particles as an outermost layer provided on the other surface of the support of the image receiving sheet; On an inkjet image receiving layer having an ink absorbing layer as a second layer adjacent to the image, an image is formed by ejecting ink from each nozzle based on the image data using an inkjet head or the like that ejects ink for each nozzle based on image data. Forming an image, and then forming an image from a step of forming a thermoplastic resin particle on the image. 15. The image forming method according to claim 14, wherein the ink receiving layer as the outermost layer contains a silicone emulsion or a water-soluble silicone compound. 16. A thermal head in which the thermal element selectively generates heat by printing energy supplied based on image data, and is supplied between a thermal head and a recording sheet from a supply side roll and wound on a take-up side roll. In a thermal transfer recording apparatus that includes a roll-shaped thermal transfer sheet and a recording paper, and a thermal element generates heat by the supplied printing energy, and transfers the ink of the thermal transfer sheet to the recording paper to perform recording, An ink jet head for controlling ink liquid ejected by a signal supplied based on image data on the opposite side of the thermal head to the recording paper, and performing ink jet recording on the recording paper. An image recording apparatus characterized in that the image recording apparatus is configured to perform the operation. 17. A thermal head in which the thermal element selectively generates heat by printing energy supplied based on image data, and is supplied between a thermal head and a recording sheet from a supply side roll and wound on a winding side roll. The thermal element generates heat by the supplied printing energy, the ink of the thermal transfer sheet is transferred to the recording paper to perform recording, and the thermal head is opposite to the recording paper. In the image recording apparatus which is provided with an ink jet head for controlling an ink liquid ejected by a signal supplied based on image data on the side thereof and which can perform ink jet recording on the recording paper, a recording paper is provided downstream of the thermal head and the ink jet head. An image recording apparatus characterized in that heat rollers are provided on both front and back sides of the image recording apparatus. 18. An image recording apparatus, wherein the recording paper according to claim 16 is the image forming recording medium according to any one of claims 1 to 7.