JP4149331B2 - Removable information carrying sheet and inkjet printing method - Google Patents

Description

The present invention relates to a releasable information carrying sheet and an inkjet print forming method. More particularly, it comprises an inkjet receiving layer formed in-click inkjet receiving layer formed capable of improving the water resistance of letters and streaked of printing on a sheet of paper or the like by an ink jet printer removability sex information bearing sheet, and to print formation method for performing ink jet printing on the refastenable information bearing for the seat.

  In recent years, a printing method (hereinafter, referred to as an ink jet method) in which a minute amount of ink is ejected in the form of dots onto a substrate surface to form a print or an image has been used in various fields. This ink-jet method is easy to color by using inks corresponding to each color, and the printing cost is low, and further, the resolution can be increased, so that it can be used not only for industrial printers but also for home use. Widely used in simple printers.

However, printing by the ink jet method has the following problems.
(1) For example, when printing on high-quality paper or the like, the ink absorbability decreases and the printed ink tends to remain on the surface of the base material. When continuously printed, the guide roll or the like is contaminated. Then, the previous contaminants may adhere to the surface of the base material to be printed next, and there is a possibility that the printing or the image may be stained.

(2) Inkjet printing may bleed or have poor water resistance. Specifically, if an inkjet-printed bar code or the like is blurred and difficult to read, or if an inkjet-printed postal item is exposed to the rain in the outdoors or accidentally splashed with water, Under the influence of moisture, the printed ink melts, making it difficult to see the printed content or not being visible at all. In addition, there is a problem that hands and clothes are soiled by the dissolved ink.

  As one of the methods for solving the above-mentioned problems relating to printing, a method using a pigment-type inkjet ink having high water resistance has been proposed, and the ink has already been marketed. However, this pigment-type ink has been pointed out as a problem that obstructs stable operation of the head, such as clogging of the head nozzle, which is an ink discharge port of an ink jet printer, and reducing the head life.

  In addition, as another method for solving the above-mentioned problem relating to printing, paper (inkjet compatible paper) or film (inkjet compatible film) in which an ink jet receiving layer is formed when ink jet ink is received have been devised (for example, patents). Reference 1, Patent Document 2, Patent Document 3, Patent Document 4, and Patent Document 5).

Such inkjet-compatible paper and film have the following problems.
(A) Although the ink absorbability is improved by improving the ink jet receiving layer, it is necessary to provide the ink jet receiving layer on the entire surface of the substrate, resulting in an increase in cost.
(B) The cationic resin used in the ink jet receiving layer is not suitable for offset printing because it may dissolve into the H liquid used during offset printing and induce printing stains.
(C) A cationic resin is used in the ink for forming the ink-jet receiving layer for the purpose of insolubilizing the acidic dye in water. However, since the color inks (dyes) used for the printing inks employed by the ink-jet printers of each company are different from each other, the ink for ink-jet receiving layer formation is required to take into consideration compatibility with the ink for printing. That is, a sheet or film on which an ink jet receiving layer optimal for each ink jet printer is formed is required.
JP-A-6-183135 JP-A-6-297830 JP-A-8-72390 Japanese Patent Laid-Open No. 8-291396 JP 2002-67487 A

The present invention has been made in view of the above circumstances, and does not depend on the difference in colorant (dye) constituting the printing ink used by the ink jet printer, has stable ink absorbability, and is ink jet printed information. It is an object of the present invention to provide a releasable information-carrying sheet and an ink-jet print forming method comprising an ink-jet receiving layer formed of an ink-jet receiving layer forming ink that can also have excellent water resistance.

An information-carrying sheet according to the present invention has an ink-jet receiving layer formed using an ink-jet receiving layer forming ink comprising at least a microcapsule containing a water- repellent substance and a hydrophilic solution in which the microcapsule is dispersed. , On one side of a sheet composed of three paper pieces divided by a broken line, arranged on a part or the whole of the paper piece on at least one end side of the three paper pieces ,
On one side of the sheet, an adhesive layer is provided on at least the other end of the three pieces of paper or a central piece of paper,
On the other side of the sheet, a releasable information carrying sheet in which an adhesive layer is provided on a paper piece on at least one end side of the three paper pieces,
The water-repellent substance is an emulsion obtained by adding silicone oil or liquid paraffin to an aqueous solution obtained by dissolving a styrene maleic anhydride copolymer in sodium hydroxide, a fluorine-based oil, or carnauba.
The hydrophilic solution is an unsaturated carboxylic acid or ester thereof; acrylamide, methacrylamide or derivative thereof; allyl compound; maleic acid, maleic anhydride, fumaric acid or ester thereof; styrene; vinyl toluene; divinylbenzene; N-vinylcarbazole. N-vinylpyrrolidone; isobornyl acrylate or methacrylate; norbornyl acrylate or methacrylate; dicyclopentenoxyethyl acrylate or methacrylate; dicyclopentenoxypropyl acrylate or methacrylate; acrylic acid ester of diethylene glycol dicyclopentenyl monoether Or methacrylate; polyoxyethylene or polypropylene glycol dicyclopentenyl monoether acrylic Ester or methacrylic acid ester; dicyclopentenyl cinnamate; dicyclopentenoxyethyl cinnamate; dicyclopentenoxyethyl monofumarate or difumarate; 3,9-bis (1,1-bismethyl-2-oxyethyl)- Spiro [5,5] undecane, 3,9-bis (1,1-bismethyl-2-oxyethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, 3,9-bis (2 -Oxyethyl) -spiro [5,5] undecane, 3,9-bis (2-oxyethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane mono-, diacrylate or mono-, Monomethacrylates of dimethacrylates or ethylene oxide or propylene oxide addition polymers of these spiroglycols Diacrylate, or mono-, dimethacrylate, or methyl ether of said monoacrylate or methacrylate; 1-azabicyclo [2,2,2] -3-octenyl acrylate or methacrylate; bicyclo [2,2,1] -5 Heptene-2,3-dicarboxyl monoallyl ester; dicyclopentadienyl acrylate or methacrylate; dicyclopentadienyloxyethyl acrylate or methacrylate; dihydrodicyclopentadienyl acrylate or methacrylate; epoxy resin acrylic ester; Ring-opening copolymer of glycidyl diacrylate and phthalic anhydride; ester of methacrylic acid dimer and polyol; polyester obtained from acrylic acid, phthalic anhydride and propylene oxide Steal; Unsaturated polyester prepolymer consisting of reaction product of polyethylene glycol, maleic anhydride and glycidyl methacrylate; Reaction product of polyvinyl alcohol and N-methylolacrylamide; After esterifying polyvinyl alcohol with succinic anhydride, Polyvinyl alcohol-based prepolymer to which glycidyl methacrylate is added; Polyamide-based prepolymer comprising a prepolymer obtained by reacting a diallyl ester of pyromellitic dianhydride with p, p'-diaminodiphenyl; ethylene-maleic anhydride Reaction product of acid copolymer and allylamine; reaction product of methyl vinyl ether-maleic anhydride copolymer and 2-hydroxyethyl acrylate or further reacted with glycidyl methacrylate A polyacrylic acid or maleic acid copolymer prepolymer; a urethane prepolymer having a polyoxyalkylene segment and / or a saturated polyester segment linked via a urethane bond, and having acryloyl or methacryloyl groups at both ends; glycol; It is characterized in der Rukoto one or more selected from the group consisting of glycol derivatives.

  The ink jet receiving layer formed with the ink for ink jet receiving layer formation can be selected and provided only in the required portion of the information carrying sheet. That is, it may be provided on one side of a sheet such as a piece of paper, or may be arranged on both sides. Further, the ink jet receiving layer may be disposed only on a part of the paper piece, or may be employed on the entire surface. Therefore, since the installation area and installation location of the ink jet receiving layer can be set on the piece of paper as necessary, it is possible to provide an information carrying sheet in consideration of its use and cost.

  In addition, an ink jet receiving layer formed using such an ink jet receiving layer forming ink can have the ability to stably absorb printing ink when ink jet printing is performed. Then, after the ink jet printing is completed, for example, an external force is applied to the microcapsule to break it, so that the ink jet receiving layer subjected to the ink jet printing can change its property to water repellency. Therefore, it is possible to improve the water resistance of information printed by inkjet.

The sheet such as a piece of paper is suitably used as a postcard or a sealed letter.
Postcards and sealed letters are documents that may encounter, for example, a humid environment during mailing, or may accidentally come into contact with water droplets. If the ink-jet receiving layer having excellent water repellency according to the present invention is applied to, for example, a portion of address writing, information such as an address and address printed by reliable ink absorption is also provided with high water resistance. It is desirable because the information can be protected from accidents at the time of mailing.

The inkjet print forming method according to the present invention includes an inkjet receiving layer formed using an inkjet receiving layer forming ink comprising at least a microcapsule encapsulating a water-repellent substance and a hydrophilic solution in which the microcapsule is dispersed. One side of a sheet composed of three paper pieces divided by a broken line is arranged on a part or the entire surface of at least one end of the three paper pieces, and on one side of the sheet, the three paper pieces Removability in which an adhesive layer is provided on at least the other side of the sheet or a central piece of paper, and an adhesive layer is provided on at least one of the three pieces of paper on the other side of the sheet An information carrying sheet, wherein the water-repellent substance is obtained by dissolving a styrene maleic anhydride copolymer in sodium hydroxide. An emulsion obtained by adding silicone oil or liquid paraffin to an aqueous solution, fluorine oil, or carnauba, and the hydrophilic solution includes an unsaturated carboxylic acid or ester thereof; acrylamide, methacrylamide or derivative thereof; allyl compound; maleic acid , Maleic anhydride, fumaric acid or esters thereof; styrene; vinyl toluene; divinyl benzene; N-vinyl carbazole; N-vinyl pyrrolidone; isobornyl acrylate or methacrylate; norbornyl acrylate or methacrylate; dicyclopentenoxyethyl acrylate Or methacrylate; dicyclopentenoxypropyl acrylate or methacrylate; acrylic acid ester or methacrylate of diethylene glycol dicyclopentenyl monoether Acid esters; acrylic or methacrylic esters of polyoxyethylene or polypropylene glycol dicyclopentenyl monoether; dicyclopentenyl cinnamate; dicyclopentenoxyethyl cinnamate; dicyclopentenoxyethyl monofumarate or difumarate; 3,9-bis (1,1-bismethyl-2-oxyethyl) -spiro [5,5] undecane, 3,9-bis (1,1-bismethyl-2-oxyethyl) -2,4,8,10- Tetraoxaspiro [5,5] undecane, 3,9-bis (2-oxyethyl) -spiro [5,5] undecane, 3,9-bis (2-oxyethyl) -2,4,8,10-tetraoxa Spiro [5,5] undecane mono-, diacrylate or mono-, dimethacact Relate, or mono-, diacrylate, or mono-, dimethacrylate, or methyl ether of the above monoacrylate or methacrylate of ethylene oxide or propylene oxide addition polymer of these spiroglycols; 1-azabicyclo [2,2,2] -3-octenyl acrylate or methacrylate; bicyclo [2,2,1] -5-heptene-2,3-dicarboxyl monoallyl ester; dicyclopentadienyl acrylate or methacrylate; dicyclopentadienyloxyethyl acrylate or Methacrylate; Dihydrodicyclopentadienyl acrylate or methacrylate; Epoxy resin acrylic ester; Ring-opening copolymer of glycidyl diacrylate and phthalic anhydride; Polyester obtained from acrylic acid, phthalic anhydride and propylene oxide; Unsaturated polyester prepolymer consisting of reaction product of polyethylene glycol, maleic anhydride and glycidyl methacrylate; Polyvinyl alcohol Product of N and methylolacrylamide; polyvinyl alcohol prepolymer in which polyvinyl alcohol is esterified with succinic anhydride and glycidyl methacrylate is added; diallyl esterified product of pyromellitic dianhydride, p, p Polyamide-based prepolymer consisting of a prepolymer obtained by reacting '-diaminodiphenyl; reaction product of ethylene-maleic anhydride copolymer and allylamine; methyl vinyl ether-maleic anhydride copolymer Polyacrylic acid or maleic acid copolymer prepolymer obtained by reacting a polymer with 2-hydroxyethyl acrylate or further glycidyl methacrylate; a polyoxyalkylene segment or a saturated polyester segment or both via a urethane bond There was ligated, urethane prepolymer having an acryloyl group or a methacryloyl group at both ends; glycol; using removability information carrying sheet Ru der one or more selected from the group consisting of glycol derivatives, the A print forming method for performing ink jet printing on a releasable information carrying sheet, wherein a printing step for discharging ink on the ink jet receiving layer to perform ink jet printing, and a sheet comprising the three pieces of paper, Tri-fold through the adhesive layer And a pressurizing step of pressurizing the ink jet receiving layer surface to the ink jet receiving layer on which the printing has been performed and pressurizing in a substantially vertical direction against the paper surface on which the three-folded sheets are stacked. And at least.

The inkjet print forming method having such a configuration includes at least a printing process and a pressurizing process.
First, in the printing process, various types of information are inkjet-printed by discharging printing ink onto an ink-jet receiving layer that is disposed on a part or the entire surface of the information-carrying sheet and exhibits hydrophilicity. At that time, consideration is given so that the shape of the microcapsules that are arranged two-dimensionally in the inkjet receiving layer is maintained. As a result, the entire ink-jet receiving layer has a stable ink absorbability, so that good ink-jet printing is performed.

  Next, in the pressurizing step, the surface of the ink jet receiving layer is pressed against the ink jet receiving layer on which the above information is ink jet printed. As a means for carrying out this pressurizing step (hereinafter referred to as pressurizing means), for example, a roller-like or flat-plate-like one or a combination thereof is suitably used. Due to the pressure of the pressurizing means, the microcapsules contained in the ink jet receiving layer are crushed, and the water-repellent substance in the microcapsules diffuses into the hydrophilic ink jet receiving layer. As a result, the properties of the entire inkjet receiving layer change from hydrophilic to water-repellent. Therefore, the printing apparatus according to the present invention realizes ink-jet printing on an information carrying sheet that achieves both good ink-jet printing and excellent water resistance of information printed by ink-jet printing.

The pressure applied by the pressurizing unit to the ink jet receiving layer is 0.1 MPa (approximately 1 kgf / cm ² ) to 100 MPa, preferably 1 MPa to 50 MPa, more preferably ² MPa to 20 MPa. When the pressure is smaller than 0.1 MPa, microcapsules that remain without being crushed are generated, so that the entire area of the inkjet receiving layer is not water-repellent and a hydrophilic portion may be locally generated. . On the other hand, a pressure exceeding 100 MPa is not good because the paper piece is easily damaged.

  In addition, the information-carrying sheet including the ink jet receiving layer formed from the ink jet receiving layer forming ink does not depend on the difference in the colorant (dye) constituting the printing ink used by the ink jet printer, and is stable. Ink absorbency. By applying pressure treatment after printing, the information printed by inkjet can be provided with excellent water resistance. Therefore, the present invention provides an information carrying sheet having both stable ink absorbability and excellent water resistance.

  Furthermore, since the ink jet print forming method according to the present invention includes a printing means for performing ink jet printing and a pressurizing step for pressurizing the ink jet receiving layer surface on which the ink jet printing has been performed, the microcapsules in the ink jet receiving layer are reliably destroyed. It is possible to change the properties of the ink jet receiving layer from hydrophilic to water-repellent. Therefore, the ink jet print forming method according to the present invention realizes stable ink jet printing on the information carrying sheet described above and excellent water resistance of the information carrying sheet.

Hereinafter, the present invention will be described in detail based on embodiments.
FIG. 1 is a schematic cross-sectional view showing an ink-jet receiving layer forming ink according to the present invention. The enlarged cross section of the microcapsule 1 contained in the hydrophilic solution 4 in a state of being dispersed individually is shown, and the microcapsule 1 maintains its shape. The microcapsule 1 includes a water repellent material 2 and a capsule wall material 3 that encloses the water repellent material 2. As a method for producing the microcapsule 1, a conventionally used method such as an in situ method, an interfacial polymerization method, a coacervation method, or an orifice method can be used. Considering a decrease in coating solution suitability due to excessive addition amount, the proportion of the microcapsule 1 in the vehicle (hydrophilic solution) 4 is appropriately 1 to 30% by mass, preferably 3 to 20% by mass, Preferably, 5-15 mass% is good.

  As the water-repellent substance 2, an emulsion obtained by adding silicone oil or liquid paraffin to an aqueous solution obtained by dissolving a styrene maleic anhydride copolymer in sodium hydroxide, an melamine-formalin initial weight is used as the capsule wall material 3. Condensates are preferably used, but are not limited thereto. The water-repellent substance 2 other than the emulsion is not particularly limited as long as it has a liquid water-repellent property at room temperature. However, for example, fluorine-based oil and carnauba can be preferably used because they are easily available and inexpensive. As the capsule wall material 3, gelatin, polyamide, polyurethane, polyester, polyurea, polysulfonamide, polysulfonate, polyurea, or the like may be used as the capsule wall material.

  FIG. 2 is a perspective view showing an example of the information carrying sheet according to the present invention, and shows a case where the sheet is composed of one sheet. The information carrying sheet 10 is provided with an ink jet receiving layer 12 made of an ink jet receiving layer forming ink according to the present invention on one side of a paper piece 11, and an ink jet printing 13 is applied on the ink jet receiving layer 12. Show.

The method of forming the ink jet receiving layer 12 differs depending on whether the hydrophilic solution 4 constituting the ink for forming the ink jet receiving layer is an ultraviolet curable type or a penetrating dry type.
When the vehicle (hydrophilic solution) 4 is an ultraviolet curable type, the obtained ink for ink-jet receiving layer is applied to a predetermined region of the information carrying sheet 10 by dry offset printing using a resin relief plate, and then ultraviolet rays are applied. The ink jet receiving layer 12 is formed by irradiation and curing and drying.
On the other hand, when the vehicle (hydrophilic solution) 4 is a permeation dry type, the obtained ink for ink-jet receiving layer is applied to a predetermined region of the information carrying sheet 10 by dry offset printing using a resin relief plate. Then, the inkjet receiving layer 12 is formed by drying.

  The ultraviolet curable photocuring component can be arbitrarily selected from known photopolymerizable monomers and / or photopolymerizable oligomers. Examples of such photopolymerizable monomers include unsaturated carboxylic acids such as acrylic acid and methacrylic acid or esters thereof such as alkyl-, cycloalkyl-, halogenated alkyl-, alkoxyalkyl-, hydroxyalkyl-, aminoalkyl- Tetrahydrofurfuryl-, allyl-, glycidyl-, benzyl-, phenoxy-acrylate and methacrylate, alkylene glycol, polyoxyalkylene glycol mono- or diacrylate and methacrylate, trimethylolpropane triacrylate and methacrylate, pentaerythritol tetraacrylate and Methacrylate, acrylamide, methacrylamide or derivatives thereof, for example acrylics mono- or di-substituted with alkyl or hydroxyalkyl groups Allyl compounds such as allyl alcohol, allyl isocyanate, diallyl phthalate, triallyl isocyanurate, maleic acid, maleic anhydride, etc., and methacrylamide, diacetone acrylamide and methacrylamide, N, N'-alkylenebisacrylamide and methacrylamide Other unsaturated compounds such as styrene, vinyltoluene, divinylbenzene, N-vinylcarbazole, N-vinylpyrrolidone, and the like, fumaric acid or esters thereof, such as alkyl, halogenated alkyl, alkoxyalkyl mono- or dimaleate and fumarate Used.

Further, in the case of applications where curing shrinkage is an obstacle, for example, isobornyl acrylate or methacrylate, norbornyl acrylate or methacrylate, dicyclopentenoxyethyl acrylate or methacrylate, dicyclopentenoxypropyl acrylate or methacrylate, Dicyclopentenyl cinnamate, dicyclopentenoxyethyl cinnamate, such as acrylic ester or methacrylic ester of diethylene glycol dicyclopentenyl monoether, acrylic ester or methacrylic ester of polyoxyethylene or polypropylene glycol dicyclopentenyl monoether 3,9-bis (1,1-bismethyl-2-oxyethyl), such as dicyclopentenoxyethyl monofumarate or difumarate ) -Spiro [5,5] undecane, 3,9-bis (1,1-bismethyl-2-oxyethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, 3,9-bis Mono-, diacrylates such as (2-oxyethyl) -spiro [5,5] undecane, 3,9-bis (2-oxyethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane or Mono-, dimethacrylate, or mono-, diacrylate, or mono-, dimethacrylate of these spiroglycol or ethylene oxide or propylene oxide addition polymers, or methyl ether of the monoacrylate or methacrylate, 1-azabicyclo [2 , 2,2] -3-octenyl acrylate or methacrylate, bicyclo [2,2,1] -5 Use photopolymerizable monomers such as heptene-2,3-dicarboxyl monoallyl ester such as dicyclopentadienyl acrylate or methacrylate, dicyclopentadienyloxyethyl acrylate or methacrylate, dihydrodicyclopentadienyl acrylate or methacrylate be able to.
These photopolymerizable monomers may be used alone or in combination of two or more.

Examples of the photopolymerizable oligomer include acrylic ester of epoxy resin such as diglycidyl ether diacrylate of bisphenol A, reaction product of epoxy resin, acrylic acid and methyltetrahydrophthalic anhydride, epoxy resin and 2-hydroxyethyl acrylate. Reaction products of epoxy resins, epoxy resin prepolymers such as reaction products of diglycidyl ether of epoxy resin and diallylamine, ring-opening copolymerization ester of glycidyl diacrylate and phthalic anhydride, methacrylic acid dimer and polyol Unsaturated polyester-based prepolymers such as polyesters obtained from acrylic acid, phthalic anhydride and propylene oxide, reaction products of polyethylene glycol, maleic anhydride and glycidyl methacrylate, and polyvinyl Reaction product of rucol and N-methylol acrylamide, polyvinyl alcohol prepolymer such as polyvinyl alcohol esterified with succinic anhydride and glycidyl methacrylate added, dialmyl ester of pyromellitic dianhydride A polyamide-based prepolymer such as a prepolymer obtained by reacting a compound with p, p'-diaminodiphenyl, a reaction product of an ethylene-maleic anhydride copolymer and allylamine, a methyl vinyl ether-maleic anhydride copolymer. Polyacrylic acid or maleic acid copolymer prepolymer such as a reaction product of a polymer and 2-hydroxyethyl acrylate or a product obtained by further reacting this with glycidyl methacrylate, and other polyoxyalkylene series via a urethane bond. Instruments or saturated linked polyester segment or both, and the like urethane prepolymer having an acryloyl group or a methacryloyl group at both ends.
These photopolymerizable oligomers suitably have a weight average molecular weight in the range of about 2000 to 30000.

The photopolymerization initiator used in the present invention may be a conventionally known photopolymerization initiator such as 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [ 4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-methyl-1-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1-bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide-bis (2 , 4,6-trimethylbenzoyl) -phenylphosphine oxide.
These photopolymerization initiators may be used alone or in combination of two or more. The content is usually preferably selected in the range of 5 to 15 parts by mass per 100 parts by mass of the acrylic photocurable component.

  Examples of the osmotic dry hydrophilic solvent 4 include glycol (glycerin, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol) and glycol derivatives (ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate), and mixtures of two or more thereof Can be mentioned.

  When performing ink jet printing on the ink jet receiving layer 12 provided on the information carrying sheet 10, for example, commercially available ink jet printers from various companies may be used. Printing inks used in individual inkjet printers have very different characteristics. However, according to the present invention, the microcapsules contained in the ink jet receiving layer 12 are destroyed by applying pressure in the substantially vertical direction to the ink jet receiving layer 12 after the ink jet printing 13 is performed. The water repellent material 2 that is an inclusion diffuses into the ink jet receiving layer 12. As a result, the ink-jet receiving layer 12 that has been shown to be hydrophilic before the microcapsules are broken becomes hydrophilic to water-repellent. Therefore, the ink jet receiving layer 12 of the information carrying sheet 10 can have excellent water resistance while keeping the information printed by ink jet printing.

3 to 6 are views showing other examples of the information carrying sheet according to the present invention. FIG. 3 is a cross-sectional view after an ink jet receiving layer and ink jet printing are provided thereon, and FIG. 4 is a perspective view of FIG. FIG. 5 is a cross-sectional view showing a tri-folded state, and FIG. 6 is a perspective view of FIG.
The information carrying sheet 20 shown in FIGS. 3 and 4 is composed of paper pieces 21A, 21B, and 21C divided into three by broken lines 24 and 25, and the ink for ink-jet receiving layer according to the present invention is formed on one side of the paper piece 21A. The inkjet receiving layer 22 produced in (1) is provided, and the inkjet printing 23 is applied on the inkjet receiving layer 22. Reference numeral 22 denotes an ink jet receiving layer before being pressurized. By making the broken line 24 into a mountain fold and the broken line 25 into a valley fold, a state of being folded in three as shown in FIG. 5 is obtained.

  The information carrying sheet 20 shown in FIGS. 5 and 6 shows a state in which the paper pieces 21A, 21B, and 21C are folded in three via the peelable adhesive layers 26 and 27. FIG. When the paper pieces 21A, 21B, and 21C are bonded to each other by the adhesive layers 26 and 27, it is necessary to apply pressure in a direction substantially perpendicular to the stacked paper surfaces. Using this pressure, the microcapsules (not shown) contained in the ink jet receiving layer 22 are simultaneously crushed, and the water-repellent substance in the microcapsules is diffused into the hydrophilic ink jet receiving layer, so that the ink jet receiving layer is obtained. You may change 22 'whole from hydrophilicity to water repellency. Reference numeral 22 'denotes the ink jet receiving layer after being pressurized.

FIG. 7 is a flowchart showing an ink jet print forming method according to the present invention.
In FIG. 7, the printing process, which is the first process, is a process of printing fixed information such as ruled lines and entry fields on the information carrying sheet in advance. The ink jet receiving layer forming step, which is the second step, is to form an ink jet receiving layer which is disposed on a part or the entire surface of the information carrying sheet and exhibits hydrophilicity, using the ink for ink jet receiving layer formation according to the present invention. It is a process. As described above, the printing process, which is the third process, is arranged on a part or the entire surface of the information carrying sheet, and by ejecting the printing ink onto the hydrophilic ink-jet receiving layer, various information is inkjetted. This is a printing process. The pressurizing process as the fourth process is a process of pressurizing the ink jet receiving layer surface on which the information printed by the ink jet in the printing process is placed.

  In particular, the ink jet print forming method according to the present invention includes a pressurizing step for performing good ink jet printing in the printing step and then pressurizing the ink jet receiving layer surface on which the ink jet printing has been performed. Can be reliably destroyed, and the properties of the ink jet receiving layer can be changed from hydrophilic to water-repellent, providing an information carrying sheet that has both good ink jet printing and excellent water resistance of information printed by ink jet printing. Contribute to.

  Hereinafter, the present invention will be described more specifically, but the present invention is not limited to these examples.

<Preparation of water-repellent substance-containing microcapsule dispersion A>
In the water-repellent substance-containing microcapsule dispersion A, silicone oil was used as the water-repellent substance 2 that is an inclusion of microcapsules.
A styrene maleic anhydride copolymer [trade name: Scrispset-520 (manufactured by Monsanto)] was dissolved together with a small amount of sodium hydroxide, and this was dissolved in 200 parts by mass of an aqueous solution prepared to 5% by mass and pH 4.5. 200 parts by mass of oil [trade name: SH200 (manufactured by Toray Dow Corning Silicone)] was emulsified and dispersed to obtain an emulsion having an average particle diameter of 2 to 4 μm. Next, 60 parts by mass of melamine-formalin initial polycondensate <trade name: Sumirez Resin 513 (manufactured by Sumitomo Chemical Co., Ltd.)> Is added to this emulsion, and the system temperature is stirred at 75 ° C. for 2 hours to enclose the water-repellent substance. A microcapsule dispersion A was obtained.

<Preparation of water-repellent substance-containing microcapsule dispersion B>
In the water-repellent substance-containing microcapsule dispersion B, liquid paraffin was used as the water-repellent substance 2 that is an inclusion of microcapsules.
Styrene maleic anhydride copolymer [trade name: Scripset-520 (manufactured by Monsanto)] was dissolved together with a small amount of sodium hydroxide, and this was flown into 200 parts by mass of an aqueous solution prepared to 5% by mass and pH 4.5. 200 parts by mass of paraffin [trade name: Daphne Oil CP (Idemitsu Kosan Co., Ltd.)] was emulsified and dispersed to obtain an emulsion having an average particle size of 2 to 4 μm. Next, 60 parts by mass of melamine-formalin initial polycondensate <trade name: Sumirez Resin 513 (manufactured by Sumitomo Chemical Co., Ltd.)> Is added to this emulsion, and the system temperature is stirred at 75 ° C. for 2 hours to enclose the water-repellent substance. A microcapsule dispersion B was obtained.

(Example 1)
In this example, the water-repellent substance-encapsulating microcapsule dispersion A was used and irradiated with ultraviolet rays to be cured and dried to form an ink jet print receiving layer.
(A1) In a planetary mixer (model: PLM-2 / Inoue Seisakusho) with a tank capacity of 2 liters equipped with a hot air blower, 200 parts by mass (in terms of solid content) of 50 wt% microcapsule dispersion A and UV curing 200 parts by mass of a type varnish (trade name: Silver Varnish / T & K TOKA) is added and mixed.
(A2) The sufficiently mixed liquid was heated to 45 ° C. and warm air (exit temperature 50 ° C.) was sent while stirring to diffuse the evaporated water vapor to the outside.
(A3) Water was removed while maintaining this state for 4 hours, and the water content was reduced to 1% by mass or less.

(A4) To 15 parts by mass of the resulting mixture, 40 parts by mass of trimethylolpropane triacrylate <trade name: V # 295 (manufactured by Osaka Organic Chemical Co., Ltd.)> And propoxylated glyceryl triacrylate <trade name: SR-9020 ( Nippon Kayaku Co., Ltd.)> 27 parts by mass, and 7 parts by mass of a photopolymerization initiator <trade name: VICURE 55 (manufactured by Akzo Nobel)> are mixed therewith.
(A5) In this mixed solution, aluminum oxide fine particles <trade name: aluminum oxide C (manufactured by Nippon Aerosil Co., Ltd.)> 4 parts by mass and fine powder titanium oxide <trade name: R-780 (manufactured by Ishihara Sangyo Co., Ltd.)> 7 parts by mass Knead.
(A6) To this mixture, 0.1 part by mass of methylhydroquinone (stabilizer) was added as an additive and kneaded using a three-roll mill to obtain a water-repellent microcapsule-containing inkjet receiving layer forming ink.

(A7) Predetermined portions of the exposed surface of the base paper sheet of the POSTEX-III (trade name: Toppan Forms re-peelable information carrying sheet, POSTEX is a registered trademark) by offset printing of the obtained ink with resin relief printing (Address printing part) was subjected to dry offset printing so as to have a coating amount of 2 g / m ² , irradiated with 350 mJ / cm ² of ultraviolet rays and cured and dried to form an ink jet print receiving layer.
(A9) Address printing was performed on the obtained ink jet print receiving layer using a black ink (model number: # 1040) with an ink jet printer (trade name: Scitex 6240 type).

(A10) After drying, an information carrying sheet according to this example was obtained by applying pressure (pressure bonding) so that the peeled adhesive strength was 8 N / m between the overlapping surfaces.
(A11) In this pressure bonding step, the microcapsules encapsulating the water-repellent substance in the inkjet print receiving layer are destroyed, and the inclusions diffuse into the inkjet print receiving layer, so that the entire inkjet print receiving layer becomes water repellent. As a result, the printed character / image area becomes water resistant. The following evaluation of water resistance was performed on the obtained ink jet printing / image area by the following method. The evaluation results are shown in Table 1.

The water resistance evaluation in this example is to determine the ink state of the print location visually by the following criteria after the print location is immersed in water (hydrostatic) for 30 seconds.
A: No print flow or bleeding occurred.
○ mark: Almost no printing flow or bleeding occurs.
Δ mark: If you look closely, bleeding can be visually recognized, but it is in a range where there is no practical problem.
X mark: Printing flows and it cannot be used practically.

(Example 2)
The same operation as in Example 1 was carried out except that the water-repellent substance-encapsulating microcapsule dispersion A used in Example 1 was changed to 25 parts by mass and propoxylated glyceryl triacrylate was changed to 17 parts by mass. A supporting sheet was obtained. The obtained ink jet printing / line drawing part was evaluated for water resistance in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Example 3)
The same operation as in Example 1 was carried out except that the water-repellent substance-containing microcapsule dispersion A used in Example 1 was 10 parts by mass and propoxylated glyceryl triacrylate was 32 parts by mass. A supporting sheet was obtained. The obtained ink jet printing / line drawing part was evaluated for water resistance in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 4
The information carrying sheet according to this example was obtained by performing the same operation as in Example 1 except that the water-repellent substance-encapsulating microcapsule dispersion A used in Example 1 was changed to the water-repellent substance-encapsulating microcapsule dispersion B. . The obtained ink jet printing / line drawing part was evaluated for water resistance in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Example 5)
In this example, the water-repellent substance-encapsulating microcapsule dispersion B was used, irradiated with ultraviolet rays, and cured and dried to form an inkjet print receiving layer.
(B1) In a planetary mixer (model: PLM-2 / Inoue Seisakusho) with a tank capacity of 2 liters equipped with a warm air blower, 200 parts by mass (in terms of solid content) of 50 wt% microcapsule dispersion B and UV curing 200 parts by mass of a type varnish (trade name: Silver Varnish / T & K TOKA) is added and mixed.
(B2) The sufficiently mixed liquid was heated to 45 ° C., and warm air (outlet temperature 50 ° C.) was sent while stirring to diffuse the evaporated water vapor to the outside.
(B3) Water was removed while maintaining this state for 4 hours, and the water content was reduced to 1% by mass or less.

(B4) To 15 parts by mass of the obtained mixture, trimethylolpropane triacrylate <trade name: V # 295 (manufactured by Osaka Organic Chemical Co., Ltd.)> 43 parts by mass and ethoxylated trimethylolpropane triacrylate <trade name: SR-9035 (Nippon Kayaku Co., Ltd.)> 22 parts by mass, and 8 parts by mass of a photopolymerization initiator <trade name: VICURE55 (manufactured by Akzo Nobel)> are mixed therewith.
(B5) In this mixed solution, 6 parts by mass of synthetic hydrophilic silica fine particles <trade name: NIPSIL E220 (manufactured by Nippon Silica Kogyo Co., Ltd.) and fine particulate silica <trade name: SYLOSPHERE C-1504 (manufactured by Fuji Silysia Chemical)> 6 mass And kneading the part.
(B6) Further, 0.1 part by mass of methyl hydroquinone (stabilizer) is added as an additive.

(B7) This was kneaded using a three-roll mill to obtain a water-repellent microcapsule-containing inkjet receiving layer forming ink.
(B8) Predetermined portions of the exposed surface of the base paper sheet of POSTEX-III (trade name: Toppan Forms removable information-carrying sheet, POSTEX is a registered trademark) by offset printing with the resin relief printing of the obtained ink (Address printing part) was subjected to dry offset printing so as to have a coating amount of 2 g / m ² , irradiated with 350 mJ / cm ² of ultraviolet rays and cured and dried to form an ink jet print receiving layer.
(B9) Address printing was performed on the obtained ink jet printing receiving layer using a black ink (model number: # 1040) with an ink jet printer (trade name: Scitex 6240 type).

(B10) After drying, the information-carrying sheet according to the present invention was obtained by applying pressure (pressure bonding) so that the peel-off adhesive strength was 8 N / m between the overlapping surfaces.
(B11) In this pressure bonding step, the microcapsules encapsulating the water-repellent substance in the inkjet print receiving layer are destroyed, and the inclusions diffuse into the inkjet print receiving layer, so that the entire inkjet print receiving layer becomes water repellent. As a result, the printed character / image area becomes water resistant. The same ink-jet printing / image area as in Example 1 was evaluated for water resistance. The evaluation results are shown in Table 1.

(Example 6)
The same procedure as in Example 5 was carried out except that the water-repellent substance-encapsulating microcapsule dispersion B used in Example 5 was 20 parts by mass and trimethylolpropane triacrylate was 38 parts by mass. A sheet was obtained. The obtained ink jet printing / line drawing part was evaluated for water resistance in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Example 7)
The same procedure as in Example 5 was carried out except that 10 parts by mass of the water-repellent substance-encapsulating microcapsule dispersion B used in Example 5 and 48 parts by mass of trimethylolpropane triacrylate were used. A sheet was obtained. The obtained ink jet printing / line drawing part was evaluated for water resistance in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Example 8)
The same procedure as in Example 5 was performed except that the water-repellent substance-encapsulating microcapsule dispersion liquid B used in Example 5 was changed to a water-repellent substance-encapsulating microcapsule dispersion liquid A, whereby an information carrying sheet according to this example was obtained. . The obtained ink jet printing / line drawing part was evaluated for water resistance in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Comparative Example 1)
The ink jet print receiving layer according to the present invention is not provided, and POSTEX-III (trade name: Removable information carrying sheet manufactured by Toppan Forms Co., Ltd., POSTEX is a registered trademark) is directly subjected to ink jet printing on a substrate sheet. An information carrying sheet was obtained. The obtained information carrying sheet was evaluated for water resistance in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Comparative Example 2)
An information carrying sheet according to this example was obtained in the same manner as in Example 1 except that the water-repellent substance-encapsulating microcapsule dispersion A used in Example 1 was not used. The obtained information carrying sheet was evaluated for water resistance in the same manner as in Example 1. The evaluation results are shown in Table 1.

  From Table 1, the information-carrying sheet having an inkjet print receiving layer formed by using the water-repellent-substance-encapsulating microcapsule dispersion A or B according to the present invention and being cured and dried by irradiating with ultraviolet rays has a print flow and bleeding. Since it hardly occurred, it was confirmed to have sufficient water resistance during actual use.

Example 9
In this example, the water-repellent substance-encapsulating microcapsule dispersion A was used for osmotic drying to form an inkjet print receiving layer.
(C1) In a planetary mixer (model: PLM-2 / Inoue Seisakusho) with a tank capacity of 2 liters equipped with a warm air blower, 200 parts by mass (in terms of solid content) of 50 wt% microcapsule dispersion A and diethylene glycol 200 Part by mass was added and mixed.
(C2) The sufficiently mixed liquid was heated to 45 ° C., and warm air (exit temperature 50 ° C.) was sent while stirring to diffuse the evaporated water vapor to the outside.
(C3) Water was removed while maintaining this state for 4 hours, and the water content was reduced to 1% by mass or less.

(C4) In 15 parts by mass of the resulting mixture, 10% by mass of rosin-modified maleic acid <trade name: Tespol (manufactured by Hitachi Chemical Co., Ltd.)> Is dissolved in advance and 75 parts by mass of propylene glycol solution is added to fine powder silica <product Name: SYLOSPHERE C-1504 (Fuji Silysia Chemical Co., Ltd.)> 7 parts by mass and hydrophobic fine powder silica <Product name: Nipsil SS-15 (Nippon Silica Kogyo Co., Ltd.)> 3 parts by mass were kneaded.
(C5) This mixture was kneaded using a three-roll mill to obtain an ink jet receiving layer forming ink.
(C6) Predetermined portions of the exposed surface of the base paper sheet of the POSTEX-III (trade name: Toppan Forms re-peelable information carrying sheet, POSTEX is a registered trademark) by offset printing with the resin relief printing on the obtained ink (Address printing part) was subjected to dry offset printing so as to have a coating amount of 2 g / m ² and osmotically dried to form an ink jet printing receiving layer.

(C7) Address printing was performed on the obtained ink jet printing receiving layer using a black ink (model number: # 1040) with an ink jet printer (trade name: Scitex 6240 type).
(C8) After drying, the information-carrying sheet according to this example was obtained by applying pressure (pressure bonding) so that the overlapping surfaces had a separation force of 20 gf with a width of 25 mm.
(C9) In this pressure bonding step, the microcapsules encapsulating the water-repellent substance in the inkjet print receiving layer are destroyed, and the inclusions diffuse into the inkjet print receiving layer, so that the entire inkjet print receiving layer becomes water repellent. As a result, the printed character / image area becomes water resistant. The same ink-jet printing / image area as in Example 1 was evaluated for water resistance. The evaluation results are shown in Table 2.

(Example 10)
The same procedure as in Example 9 except that the water-repellent substance-encapsulating microcapsule dispersion A used in Example 9 was 25 parts by mass, 10% by mass of rosin-modified maleic acid was dissolved in advance, and the propylene glycol solution was 65 parts by mass. The operation was performed to obtain an information carrying sheet according to this example. The obtained ink jet printing / line drawing part was evaluated for water resistance in the same manner as in Example 1. The evaluation results are shown in Table 2.

(Example 11)
The same as in Example 9 except that the water-repellent substance-encapsulating microcapsule dispersion A used in Example 9 was 10 parts by mass, 10% by mass of rosin-modified maleic acid was dissolved in advance, and the propylene glycol solution was 80 parts by mass. The operation was performed to obtain an information carrying sheet according to this example. The obtained ink jet printing / line drawing part was evaluated for water resistance in the same manner as in Example 1. The evaluation results are shown in Table 2.

(Example 12)
The information carrying sheet according to this example was obtained by performing the same operation as in Example 1 except that the water-repellent substance-encapsulating microcapsule dispersion A used in Example 9 was changed to the water-repellent substance-encapsulating microcapsule dispersion B. . The obtained ink jet printing / line drawing part was evaluated for water resistance in the same manner as in Example 1. The evaluation results are shown in Table 2.

(Example 13)
In this example, the water-repellent substance-encapsulating microcapsule dispersion B was used and permeated and dried to form an ink jet print receiving layer.
(D1) In a planetary mixer (model: PLM-2 / Inoue Seisakusho) with a tank capacity of 2 liters equipped with a warm air blower, 200 parts by mass (in terms of solid content) of 50 wt% microcapsule dispersion B, and diethylene glycol 200 Part by mass was added and mixed.
(D2) The sufficiently mixed liquid was heated to 45 ° C., and warm air (outlet temperature 50 ° C.) was sent while stirring to diffuse the evaporated water vapor to the outside.
(D3) Water was removed while maintaining this state for 4 hours, and the water content was reduced to 1% by mass or less.

(D4) In 15 parts by mass of the obtained mixture, 10% by mass of rosin-modified maleic acid <trade name: Tespol (manufactured by Hitachi Chemical Co., Ltd.)> Is dissolved in advance, and in 75 parts by mass of propylene glycol solution, fine powder silica <product Name: SYLOSPHERE C-1504 (manufactured by Fuji Silysia)> 7 parts by mass and hydrophobic fine powder silica <trade name: Nipsil SS-15 (manufactured by Nippon Silica Kogyo)> 3 parts by mass were kneaded.
(D5) This mixture was kneaded using a three-roll mill to obtain an ink jet receiving layer forming ink.
(D6) Predetermined portions of the exposed surface of the base paper sheet of the POSTEX-III (trade name: Toppan Forms removable information carrying sheet, POSTEX is a registered trademark) by offset printing with the resin relief printing Dry offset printing was performed on the (address printing portion) so that the coating amount was 2 g / m ² to form an ink jet printing receiving layer.

(D7) Address printing was performed on the obtained ink jet print receiving layer using a black ink (model number: # 1040) with an ink jet printer (trade name: Scitex 6240 type).
(D8) After drying, the information-carrying sheet according to this example was obtained by applying pressure (pressure bonding) so that the overlapping surfaces had a separation force of 20 gf with a width of 25 mm.
(D9) In this pressure bonding step, the microcapsules enclosing the water-repellent substance in the inkjet print receiving layer are destroyed, and the inclusions diffuse into the inkjet print receiving layer, so that the entire inkjet print receiving layer becomes water repellent. As a result, the printed character / image area becomes water resistant. The same ink-jet printing / image area as in Example 1 was evaluated for water resistance. The evaluation results are shown in Table 2.

(Example 14)
The same as in Example 13, except that the water-repellent substance-encapsulating microcapsule dispersion B used in Example 13 was 20 parts by mass, and 7.5% by mass of rosin-modified maleic acid was dissolved in advance to make the diethylene glycol solution 67 parts by mass. The information carrying sheet according to this example was obtained. The obtained ink jet printing / line drawing part was evaluated for water resistance in the same manner as in Example 1. The evaluation results are shown in Table 2.

(Example 15)
Except that the water-repellent substance-encapsulating microcapsule dispersion B used in Example 13 was 10 parts by mass, 7.5% by mass of rosin-modified maleic acid was dissolved in advance and 77 parts by mass of diethylene glycol solution was used. The information carrying sheet according to this example was obtained. The obtained ink jet printing / line drawing part was evaluated for water resistance in the same manner as in Example 1. The evaluation results are shown in Table 2.

(Example 16)
The information carrying sheet according to this example was obtained by performing the same operation as in Example 13 except that the water repellent substance-encapsulated microcapsule dispersion B used in Example 13 was changed to the water-repellent substance-encapsulated microcapsule dispersion A. . The obtained ink jet printing / line drawing part was evaluated for water resistance in the same manner as in Example 1. The evaluation results are shown in Table 2.

(Comparative Example 3)
The ink jet print receiving layer according to the present invention is not provided, and POSTEX-III (trade name: Removable information carrying sheet manufactured by Toppan Forms Co., Ltd., POSTEX is a registered trademark) is directly subjected to ink jet printing on a substrate sheet. An information carrying sheet was obtained. The obtained information carrying sheet was evaluated for water resistance in the same manner as in Example 1. The evaluation results are shown in Table 2.

(Comparative Example 4)
An information carrying sheet according to this example was obtained in the same manner as in Example 9 except that the water-repellent substance-encapsulating microcapsule dispersion A used in Example 9 was not used. The obtained information carrying sheet was evaluated for water resistance in the same manner as in Example 1. The evaluation results are shown in Table 2.

  From Table 2, the information-carrying sheet having the ink-jet print receiving layer formed by osmotic drying using the water-repellent substance-encapsulating microcapsule dispersion A or B according to the present invention hardly generates a print flow or bleeding. It was confirmed that the product has sufficient water resistance during actual use.

  According to the present invention, there are provided an ink for ink-jet receiving layer, an information-carrying sheet, and an ink-jet print forming method that have stable ink absorptivity and that can provide ink-printed information with excellent water resistance. can do. The information-carrying sheet of the present invention is suitable for postcards, sealed letters, posters posted outdoors, etc., which may encounter a humid environment during transportation, or may accidentally come into contact with water droplets. Used for.

It is typical sectional drawing which shows the ink for inkjet receiving layer formation which concerns on this invention. It is a perspective view showing an example of a sheet for information carrying concerning the present invention. It is a figure which shows another example of the information carrying sheet which concerns on this invention, and is sectional drawing after providing an inkjet receiving layer and inkjet printing on it. FIG. 4 is a perspective view of the information carrying sheet shown in FIG. 3. It is sectional drawing which shows the state which folded the information carrying sheet shown in FIG. 3 into three. FIG. 6 is a perspective view of the information carrying sheet shown in FIG. 5. It is a flowchart which shows the inkjet printing formation method which concerns on this invention.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 Microcapsule, 2 Water repellent material, 3 Capsule wall material, 4 Hydrophilic solution (vehicle), 10 Information carrying sheet, 11 Paper piece, 12 Inkjet receiving layer, 13 Inkjet printing, 20 Information carrying sheet, 21A, 21B, 21C Paper piece, 22 Ink-jet receiving layer, 23 Ink-jet printing, 24, 25 Polyline, 26, 27 Adhesive layer.

Claims (2)

An ink jet receiving layer formed using an ink for forming an ink jet receiving layer comprising at least a microcapsule enclosing a water-repellent substance and a hydrophilic solution in which the microcapsule is dispersed is composed of three pieces of paper divided by broken lines. in becomes one of one side of the sheet, disposed on part or entire surface of at least one end of the paper out of the three pieces of paper,
On one side of the sheet, an adhesive layer is provided on at least the other end of the three pieces of paper or a central piece of paper,
On the other side of the sheet, a releasable information carrying sheet in which an adhesive layer is provided on a paper piece on at least one end side of the three paper pieces,
The water-repellent substance is an emulsion obtained by adding silicone oil or liquid paraffin to an aqueous solution obtained by dissolving a styrene maleic anhydride copolymer in sodium hydroxide, a fluorine-based oil, or carnauba.
The hydrophilic solution is an unsaturated carboxylic acid or ester thereof; acrylamide, methacrylamide or derivative thereof; allyl compound; maleic acid, maleic anhydride, fumaric acid or ester thereof; styrene; vinyl toluene; divinylbenzene; N-vinylcarbazole. N-vinylpyrrolidone; isobornyl acrylate or methacrylate; norbornyl acrylate or methacrylate; dicyclopentenoxyethyl acrylate or methacrylate; dicyclopentenoxypropyl acrylate or methacrylate; acrylic acid ester of diethylene glycol dicyclopentenyl monoether Or methacrylate; polyoxyethylene or polypropylene glycol dicyclopentenyl monoether acrylic Ester or methacrylic acid ester; dicyclopentenyl cinnamate; dicyclopentenoxyethyl cinnamate; dicyclopentenoxyethyl monofumarate or difumarate; 3,9-bis (1,1-bismethyl-2-oxyethyl)- Spiro [5,5] undecane, 3,9-bis (1,1-bismethyl-2-oxyethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, 3,9-bis (2 -Oxyethyl) -spiro [5,5] undecane, 3,9-bis (2-oxyethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane mono-, diacrylate or mono-, Monomethacrylates of dimethacrylates or ethylene oxide or propylene oxide addition polymers of these spiroglycols Diacrylate, or mono-, dimethacrylate, or methyl ether of said monoacrylate or methacrylate; 1-azabicyclo [2,2,2] -3-octenyl acrylate or methacrylate; bicyclo [2,2,1] -5 Heptene-2,3-dicarboxyl monoallyl ester; dicyclopentadienyl acrylate or methacrylate; dicyclopentadienyloxyethyl acrylate or methacrylate; dihydrodicyclopentadienyl acrylate or methacrylate; epoxy resin acrylic ester; Ring-opening copolymer of glycidyl diacrylate and phthalic anhydride; ester of methacrylic acid dimer and polyol; polyester obtained from acrylic acid, phthalic anhydride and propylene oxide Steal; Unsaturated polyester prepolymer consisting of reaction product of polyethylene glycol, maleic anhydride and glycidyl methacrylate; Reaction product of polyvinyl alcohol and N-methylolacrylamide; After esterifying polyvinyl alcohol with succinic anhydride, Polyvinyl alcohol-based prepolymer to which glycidyl methacrylate is added; Polyamide-based prepolymer comprising a prepolymer obtained by reacting a diallyl ester of pyromellitic dianhydride with p, p'-diaminodiphenyl; ethylene-maleic anhydride Reaction product of acid copolymer and allylamine; reaction product of methyl vinyl ether-maleic anhydride copolymer and 2-hydroxyethyl acrylate or further reacted with glycidyl methacrylate A polyacrylic acid or maleic acid copolymer prepolymer; a urethane prepolymer having a polyoxyalkylene segment and / or a saturated polyester segment linked via a urethane bond, and having acryloyl or methacryloyl groups at both ends; glycol; refastenable information carrying sheet to one or more der wherein Rukoto is selected from the group of glycol derivatives. An ink jet receiving layer formed using an ink for ink jet receiving layer formation comprising at least a microcapsule enclosing a water-repellent substance and a hydrophilic solution in which the microcapsule is dispersed is composed of three pieces of paper divided by broken lines. On one side of the sheet, the sheet is disposed on a part or the entire surface of at least one end of the three sheets, and on one side of the sheet, on at least the other end of the three sheets, A releasable information carrying sheet, wherein an adhesive layer is provided on a central piece of paper, and an adhesive layer is provided on at least one end of the three pieces of paper on the other side of the sheet. Aqueous substances can be prepared by adding silicone oil or fluidized solution to an aqueous solution prepared by dissolving styrene maleic anhydride copolymer in sodium hydroxide. An emulsion obtained by adding fins, a fluorine-based oil or carnauba, and the hydrophilic solution includes an unsaturated carboxylic acid or an ester thereof; acrylamide, methacrylamide or a derivative thereof; an allyl compound; maleic acid, maleic anhydride, fumaric acid Or esters thereof; styrene; vinyl toluene; divinyl benzene; N-vinyl carbazole; N-vinyl pyrrolidone; isobornyl acrylate or methacrylate; norbornyl acrylate or methacrylate; dicyclopentenoxyethyl acrylate or methacrylate; Xylpropyl acrylate or methacrylate; acrylic acid or methacrylic acid ester of diethylene glycol dicyclopentenyl monoether; Acrylic ester or methacrylic ester of propylene glycol dicyclopentenyl monoether; dicyclopentenyl cinnamate; dicyclopentenoxyethyl cinnamate; dicyclopentenoxyethyl monofumarate or difumarate; 3,9-bis (1 , 1-bismethyl-2-oxyethyl) -spiro [5,5] undecane, 3,9-bis (1,1-bismethyl-2-oxyethyl) -2,4,8,10-tetraoxaspiro [5,5 ] Undecane, 3,9-bis (2-oxyethyl) -spiro [5,5] undecane, 3,9-bis (2-oxyethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane Mono-, diacrylate or mono-, dimethacrylate, or spiroglycols thereof A mono-, diacrylate, or mono-, dimethacrylate, or methyl ether of the monoacrylate or methacrylate; 1-azabicyclo [2,2,2] -3-octenyl acrylate or Methacrylate; Bicyclo [2,2,1] -5-heptene-2,3-dicarboxyl monoallyl ester; Dicyclopentadienyl acrylate or methacrylate; Dicyclopentadienyloxyethyl acrylate or methacrylate; Dihydrodicyclopentadi An acrylate or methacrylate; an acrylic ester of an epoxy resin; a ring-opening copolymer of glycidyl diacrylate and phthalic anhydride; an ester of a methacrylic acid dimer and a polyol; Polyester obtained from crylic acid, phthalic anhydride and propylene oxide; Unsaturated polyester prepolymer consisting of reaction product of polyethylene glycol, maleic anhydride and glycidyl methacrylate; Reaction product of polyvinyl alcohol and N-methylolacrylamide; Polyvinyl alcohol-based prepolymer obtained by esterifying polyvinyl alcohol with succinic anhydride and then adding glycidyl methacrylate; prepolymer obtained by reacting diallyl esterified product of pyromellitic dianhydride with p, p'-diaminodiphenyl A polyamide-based prepolymer comprising a polymer; a reaction product of an ethylene-maleic anhydride copolymer and allylamine; a methyl vinyl ether-maleic anhydride copolymer and 2-hydroxyethyl acrylate; Polyacrylic acid or maleic acid copolymer prepolymer obtained by reacting the reaction product or glycidyl methacrylate with the reaction product; a polyoxyalkylene segment and / or a saturated polyester segment are connected via a urethane bond, and an acryloyl group at both ends or urethane prepolymer having a methacryloyl group; glycol; using removability information carrying sheet Ru der one or more selected from the group consisting of glycol derivatives, to the removability information bearing for sheet A printing method for performing inkjet printing,
A printing step of ejecting printing ink on the inkjet receiving layer and performing inkjet printing;
A stacking step in which the sheet made of the three pieces of paper is folded in three through the adhesive layer;
A pressure step of pressing the surface of the ink jet receiving layer on the ink jet receiving layer on which the printing has been performed and pressing the surface of the tri-folded sheet in a direction substantially perpendicular to the stacked paper surface; A method for forming an ink-jet print, comprising:

Images