JP5997621B2 - INKJET RECORDING SHEET, PRINTED MATERIAL, AND METHOD FOR PRODUCING PRINTED MATERIAL - Google Patents

Description

  The present invention relates to an inkjet recording sheet, a printed material, and a method for producing the printed material.

  An ink jet system that ejects an ink composition as droplets from an ink ejection port is small and inexpensive, and is used in many printers because it can form an image without contact with a recording medium. Among these inkjet methods, the piezo inkjet method that ejects ink using deformation of a piezoelectric element and the thermal inkjet method that ejects droplets of an ink composition using the boiling phenomenon of the ink composition due to thermal energy are high resolution. It has a feature that it is excellent in high-speed printability.

  Recently, not only photo printing and document printing for home use or office use, but also commercial printing equipment and industrial printing equipment using an ink jet printer have been developed. In particular, the demand for wide format ink jet printers that perform UV irradiation immediately after ink landing, which is suitable for printing large format advertisements to be attached to walls such as show windows, station passages, and buildings, is growing rapidly. Such advertisements are required to maintain the initial color density over a long period of time.

In general, a radiation curable ink that is cured by radiation such as ultraviolet rays is used as an ink used in a wide format ink jet printer. The ink includes a non-aqueous ink containing an organic solvent and a solventless ink containing no organic solvent. Since the organic solvent dissolves the resin that forms the ink receiving layer on the recording sheet, the ink easily permeates and the ink adhesion is easily obtained.
However, a process for volatilizing the organic solvent is required, and use of a solvent-free radiation curable ink is required because of problems in the working environment in which the organic solvent (VOC) is handled. Solvent-free radiation curable inks do not dissolve the ink receiving layer, so that the ink is less likely to penetrate. Furthermore, the improvement of the adhesiveness between a radiation curable ink and a recording medium is calculated | required.

  For example, Patent Document 1 proposes a method for improving adhesion to UV curable ink with a recording layer made of at least one resin selected from polyester, polyurethane, acrylic, and polyester urethane resin. Patent Document 2 proposes a method of forming an ink receiving layer made of water-based polyurethane, a porous pigment, and magnesium chloride to improve printability for a wide format ink jet printer and pigment (UV) ink. Patent Document 3 proposes a method in which an ink receiving layer formed of a urethane / acrylic blend or a blend of two or more urethanes is formed to improve the printability for non-aqueous inks containing organic solvents. Has been.

Japanese Patent Laid-Open No. 2001-232738 JP 2002-111942 A JP 2010-47015 A

  However, Patent Document 1 has a problem that a wide format ink jet printer cannot obtain excellent adhesiveness and has insufficient adhesiveness over time after printing. In addition, when the present inventors examined a method of forming an ink receiving layer using the epoxy compound described in Patent Document 2 or the melamine compound described in Patent Document 3 as a cross-linking agent, the ink immediately after printing was examined. It was found that adhesion and ink adhesion after aging were not good.

  The present invention has been made to solve the above problems, and exhibits excellent ink adhesion, and particularly when printed with a wide format ink jet printer using a solvent-free radiation curable ink, immediately after printing. It is an object of the present invention to provide an inkjet recording sheet, a printed matter, and a method for producing the printed matter, which have good ink adhesion and good ink adhesion after aging.

  As a result of earnest studies to solve the above problems, the present inventors have determined that the ink receiving layer in the inkjet recording sheet is at least one selected from polyester resins, polyurethane resins, and acrylic resins. Incorporation of the above resin and at least one of a cross-linking agent of an oxazoline-based compound and a carbodiimide-based compound, it has been found that ink adhesion is improved by a mechanism that improves ink penetration. It came to complete.

Specifically, the above problem has been solved by the following means <1>, preferably <2> to <12>.
<1> A support and an ink receiving layer on at least one surface of the support,
The ink receiving layer includes at least one resin selected from polyester resins, polyurethane resins, and acrylic resins, and a crosslinking agent of at least one of an oxazoline compound and a carbodiimide compound. Inkjet recording sheet.
<2> The inkjet recording sheet according to <1>, wherein the crosslinking agent contained in the ink receiving layer is contained in an amount of 3 to 30% by mass with respect to the resin component.
<3> An intermediate layer is provided between the support and the ink receiving layer, and the intermediate layer has a thickness of 0.1 μm or more and a polyolefin resin of 10% by mass or more <1> Or <2> an inkjet recording sheet.
<4> The inkjet recording sheet according to <3>, wherein the elastic modulus of the intermediate layer is 500 MPa or less.
<5> The intermediate layer includes a crosslinking agent, and the crosslinking agent is at least one selected from an oxazoline compound, a carbodiimide compound, an epoxy compound, an isocyanate compound, and a melamine compound. <3> or <4> an inkjet recording sheet.
<6> The inkjet recording sheet according to any one of <3> to <5>, wherein the intermediate layer contains an acrylic resin.
<7> The inkjet recording sheet according to any one of <3> to <6>, wherein the intermediate layer has a thickness of 0.3 to 5 μm.
<8> A step of ejecting the ink composition onto the ink jet recording sheet of any one of <1> to <7> by an ink jet recording apparatus, and irradiating the ejected ink composition with radiation to form an ink composition A method for producing a printed material comprising: curing the printed material.
<9> The method for producing a printed material according to <8>, wherein the ink composition is a radiation curable ink composition.
<10> The method for producing a printed matter according to <8> or <9>, wherein the ink composition is a solvent-free radiation curable ink composition.
<11> The method for producing a printed material according to any one of <8> to <10>, wherein the ink jet recording apparatus uses a wide format ink jet printer system.
<12> A printed material produced by the method for producing a printed material according to any one of <8> to <11>.

  According to the present invention, when printing is performed with a wide format ink jet printer using radiation curable ink, an ink jet recording sheet having good ink adhesion immediately after printing and ink adhesion after aging, printed matter, and production of the printed matter. It became possible to provide a method.

It is a schematic cross section showing an example of an ink jet recording sheet of the present invention. It is a schematic cross section which shows another example of the recording sheet for inkjets of this invention. It is a schematic cross section which shows an example of the printed matter of this invention. It is a schematic cross section which shows another example of the printed matter of this invention. It is explanatory drawing of an example of the shape change of the recording sheet for inkjets of this invention.

  Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

Inkjet recording sheet:
The inkjet recording sheet of the present invention has a support and an ink receiving layer on at least one surface of the support, and the ink receiving layer is selected from a polyester resin, a polyurethane resin, and an acrylic resin. And at least one cross-linking agent of an oxazoline-based compound and a carbodiimide-based compound.

The inkjet recording sheet of the present invention has a support 1 and an ink receiving layer 2 on at least one surface of the support 1 as shown in FIG. 1, and as shown in FIG. An ink composition is ejected onto the ink receiving layer 2 to form the image layer 4. Further, as shown in FIG. 2, an intermediate layer 3 may be provided between the support 1 and the ink receiving layer 2.
Hereinafter, each member will be described.

<Support>
A well-known thing can be used for a support body. For example, paper, paper laminated with plastic (for example, polyester, polyethylene, polypropylene, polystyrene, etc.), metal plate (for example, aluminum, zinc, copper, etc.), paper or plastic film on which the above-mentioned metal is laminated or deposited. Etc.

  Especially, it is preferable that a support body is a plastic film, it is preferable that it is a film which contains polyester as a main component, and additives, such as a pigment and a plasticizer, may be contained. The polyester is not particularly limited, and for example, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate, or the like is used. Among these, polyethylene terephthalate is particularly preferable from the viewpoint of cost and mechanical strength. A main component means the component contained 50 mass% or more of a support body.

  Further, from the viewpoint of improving the mechanical strength as a support, it is preferable that the film has been subjected to stretching treatment, and particularly preferably biaxially stretched. The draw ratio is not particularly limited, but is preferably in the range of 1.5 to 7 times. If the draw ratio is less than 1.5 times, the mechanical strength may be insufficient. Conversely, if it exceeds 7 times, the thickness may not be uniform. The draw ratio is more preferably in the range of 2 to 5 times. The particularly preferred stretching direction and magnification are in the range of 2 to 5 times in two directions orthogonal to each other.

  The thickness of the support is, for example, constant in the range of 30 μm to 500 μm, more preferably constant in the range of 50 μm to 300 μm. If the thickness of the support is less than 30 μm, it may be difficult to handle due to lack of waist. On the other hand, when the thickness of the support exceeds 500 μm, it is difficult to reduce the size and weight of the display device, and it is disadvantageous in terms of cost.

  In addition, it is preferable to use a support on which at least one of the one surface and the other surface is subjected to a surface treatment such as a corona discharge treatment, a vacuum glow discharge treatment, or a flame treatment. One side and / or the other side of the support can be hydrophilized by surface treatment to improve the wettability of various aqueous coating solutions. Furthermore, functional groups such as a carboxyl group and a hydroxy group can be introduced. Thereby, the adhesive force between the one surface of the support and the ink receiving layer or the intermediate layer can be further increased.

<Ink receiving layer>
The ink receiving layer contains at least one binder resin selected from a polyester resin, a polyurethane resin, and an acrylic resin, and at least one of an oxazoline compound and a carbodiimide compound. Moreover, you may have another component as needed.

(Binder resin)
The resin contained in the ink receiving layer functions as a binder and is selected from a polyester resin, a polyurethane resin, and an acrylic resin, and two or more kinds may be selected.

[Polyester resin]
A polyester resin is a general term for polymers having an ester bond in the main chain, and is usually obtained by the reaction of a polycarboxylic acid and a polyol. Examples of the polycarboxylic acid include fumaric acid, itaconic acid, adipic acid, sebacic acid, terephthalic acid, isophthalic acid, sulfoisophthalic acid, and naphthalenedicarboxylic acid. Examples of the polyol include ethylene glycol, propylene glycol, glycerin, hexanetriol, Examples include butanediol, hexanediol, and 1,4-cyclohexanedimethanol. The polyester resin and its raw materials are described in, for example, “Polyester resin handbook” (Eiichiro Takiyama, Nikkan Kogyo Shimbun, published in 1988), and this description can also be applied to the present invention.
Examples of the polyester resin include polyhydroxybutyrate (PHB), polycaprolactone (PCL), polycaprolactone butylene succinate, polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), Polybutylene succinate carbonate, polyethylene terephthalate succinate, polybutylene adipate terephthalate, polytetramethylene adipate terephthalate, polybutylene adipate terephthalate, polyethylene succinate (PES), polyglycolic acid (PGA), polylactic acid (PLA) series, aliphatic polyester carbonate copolymer, copolymer of aliphatic polyester and polyamide, and the like. The polyester resins are Finetex ES650, ES2200 (manufactured by DIC Corporation), Bironal MD1245, MD1400, MD1480 (manufactured by Toyobo Co., Ltd.), Pesresin A-110, A-124GP, A-520, A-640 (Takamatsu Oils and Fats). Manufactured by Co., Ltd.), plus coats Z561, Z730, Z687, Z592 (manufactured by Kyodo Chemical Co., Ltd.).

[Polyurethane resin]
Polyurethane is a general term for polymers having a urethane bond in the main chain, and is usually obtained by the reaction of polyisocyanate and polyol. Examples of the polyisocyanate include TDI (toluene diisocyanate), MDI (diphenylmethane diisocyanate), NDI (naphthalene diisocyanate), TODI (tolidine diisocyanate), HDI (hexamethylene diisocyanate), IPDI (isophorone diisocyanate), and the like. Examples of the polyol include ethylene glycol, propylene glycol, glycerin and hexanetriol. As the isocyanate of the present invention, a polymer obtained by subjecting a polyurethane polymer obtained by the reaction of polyisocyanate and polyol to chain extension treatment to increase the molecular weight can also be used. The polyisocyanate, polyol, and chain extension treatment described above are described in, for example, “Polyurethane Handbook” (edited by Keiji Iwata, Nikkan Kogyo Shimbun, published in 1987). Polyurethane resins are Superflex 470, 210, 150HS, Elastron H-3 (Daiichi Kogyo Seiyaku Co., Ltd.), Hydran AP-20, AP-40F, WLS-210 (DIC Corporation), Takelac W -6061, Olester UD-350 (manufactured by Mitsui Chemicals, Inc.) is also available as a commercial product.

[Acrylic resin]
The acrylic resin is a polymer composed of a polymerizable monomer having a carbon-carbon double bond, as typified by acrylic and methacrylic monomers. These may be either a homopolymer or a copolymer. Moreover, the copolymer of these polymers and other polymers (for example, polyester, polyurethane, etc.) is also included. For example, a block copolymer or a graft copolymer. Alternatively, a polymer (possibly a mixture of polymers) obtained by polymerizing a polymerizable monomer having a carbon-carbon double bond in a polyester solution or a polyester dispersion is also included. Similarly, a polymer (in some cases, a mixture of polymers) obtained by polymerizing a polymerizable monomer having a carbon-carbon double bond in a polyurethane solution or polyurethane dispersion is also included. Similarly, a polymer obtained by polymerizing a polymerizable monomer having a carbon-carbon double bond in another polymer solution or dispersion (in some cases, a polymer mixture) is also included. Moreover, in order to improve adhesiveness, it is also possible to contain a hydroxyl group and an amino group. Although it does not specifically limit as a polymerizable monomer which has a carbon-carbon double bond, Especially as a typical compound, for example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, citraconic acid Various carboxyl group-containing monomers such as, and salts thereof; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, monobutyl hydroxyl fumarate, mono Various hydroxyl group-containing monomers such as butylhydroxy itaconate; various (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate ) Acrylic acid esters; ) Various nitrogen-containing compounds such as acrylamide, diacetone acrylamide, N-methylol acrylamide or (meth) acrylonitrile; various styrene derivatives such as styrene, α-methylstyrene, divinylbenzene, vinyltoluene, vinyl propionate, etc. Various vinyl esters; various silicon-containing polymerizable monomers such as γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, etc .; phosphorus-containing vinyl-based monomers; various kinds such as vinyl chloride and biridene chloride Examples of vinyl halides include various conjugated dienes such as butadiene. An acrylic ester copolymer such as Jurimer ET-410 (manufactured by Toa Gosei Chemical Co., Ltd.) or EM-48D (manufactured by Daicel Chemical Industries, Ltd.) is preferably used as a commercial product.

The binder resin contained in the ink receiving layer only needs to contain any one of a polyester resin, a polyurethane resin, and an acrylic resin, and may contain other resins.
Examples of other resins include polystyrene resin, polyolefin resin, and polyamide resin.

  The binder resin contained in the ink receiving layer may contain at least one of a polyester resin, a polyurethane resin, and an acrylic resin, and may contain two or more of these. The weight ratio (mass% of polyester resin: mass% of polyurethane resin: mass% of acrylic resin) in the case of including two or more kinds is 0.1 to 0.9: 0.1 to 0.9: 0 to 0.0. 3 is preferable, 0.3 to 0.7: 0.3 to 0.7: 0 to 0.2 is more preferable, and 0.4 to 0.6: 0.4 to 0.6: 0 is particularly preferable.

  The binder resin contained in the ink receiving layer is preferably 67 to 97% by mass, more preferably 77 to 97% by mass, and 87 to 97% by mass with respect to the total solid content contained in the ink receiving layer. It is particularly preferred that When two or more kinds of resins are included, the total amount of the resin may be within the above range.

(Crosslinking agent)
The ink receiving layer contains a crosslinking agent of at least one of an oxazoline compound and a carbodiimide compound, and may contain two or more kinds.

[Oxazoline compounds]
The oxazoline-based compound is a compound having an oxazoline group represented by the following formula (1).

  As the oxazoline-based compound, a polymer having an oxazoline group, for example, a polymerizable unsaturated monomer having an oxazoline group, if necessary, other polymerizable unsaturated monomers and known methods (for example, solution polymerization, emulsification) And a polymer obtained by copolymerization by polymerization or the like. Examples of the polymerizable unsaturated monomer having an oxazoline group include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2- Examples of the monomer unit include isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline, and the like. Two or more of these may be used in combination. Oxazoline-based compounds are commercially available products such as Epocross K-2020E, Epocross K-2010E, Epocross K-2020E, Epocross K-2030E, Epocross WS-300, Epocross WS-500, Epocross WS-700, etc. (Made by Co., Ltd.).

[Carbodiimide compounds]
A carbodiimide compound is a compound having a functional group represented by -N = C = N-. Polycarbodiimide is usually synthesized by condensation reaction of organic diisocyanate, but the organic group of the organic diisocyanate used in this synthesis is not particularly limited, either aromatic or aliphatic, or a mixture thereof It can be used. However, aliphatic systems are particularly preferred from the viewpoint of reactivity. As a raw material for synthesis, organic isocyanate, organic diisocyanate, organic triisocyanate, and the like are used. As examples of organic isocyanates, aromatic isocyanates, aliphatic isocyanates, and mixtures thereof can be used.
Specifically, 4,4′-diphenylmethane diisocyanate, 4,4-diphenyldimethylmethane diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, cyclohexane Diisocyanate, xylylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,3-phenylene diisocyanate, etc. are used. As organic monoisocyanates, isophorone isocyanate, phenyl isocyanate are used. Cyclohexyl isocyanate, butyl isocyanate, naphthyl isocyanate and the like are used. The carbodiimide compound is also available as a commercial product such as Carbodilite V-02-L2 (Nisshinbo Co., Ltd.).

  The crosslinking agent is preferably added in a range of 3% by mass to 30% by mass, more preferably 3% by mass to 15% by mass with respect to the binder (resin) component. By adding the cross-linking agent within the above range, the adhesive force with the support is further improved. When the cross-linking agent is 3% by mass or more with respect to the binder (resin) component, the ink permeates into the ink receiving layer is good, and the ink adhesion immediately after the image formation is easily improved. If the cross-linking agent is 30% by mass or less based on the binder (resin) component, the ink-receiving layer does not proceed too much and the ink-receiving layer does not have too high hardness. Easy to improve sex. In addition, when the addition amount exceeds 30% by mass, the cost is excessively increased.

(Other)
In addition to the binder resin and the crosslinking agent, the ink receiving layer may be a surfactant, a slip agent, an antifoaming agent, a foam suppressor, a dye, a fluorescent whitening agent, a preservative, a water-resistant agent, particles, or a distillation. It may contain water or the like.

  Examples of the surfactant include known anionic, nonionic, cationic, fluorine, and silicone surfactants. The surfactant is described in, for example, “Surfactant Handbook” (Nishi Ichiro, Imai Seiichiro, Kasai Shozo Edition, Sangyo Tosho Co., Ltd., 1960). Particularly preferred are anionic and nonionic surfactants.

  Examples of commercially available anionic surfactants include Lapisol A-90, Lapisol A-80, Lapisol BW-30, Lapisol B-90, Lapisol C-70 (trade name: manufactured by Nippon Oil & Fats Co., Ltd.), NIKKOL OTP-100 (trade name: manufactured by Nikko Chemical Co., Ltd.), Kohakuru ON, Kolacool L-40, Phosphanol 702 (Toho Chemical), Viewlight A-5000, Viewlight SSS (Sanyo Kasei), etc. it can.

  Commercially available nonionic surfactants include, for example, NAROACTY CL-95, HN-100 (trade name: manufactured by Sanyo Chemical Industries, Ltd.), Risolex BW400 (higher alcohol industry), EMALEX ET-2020 (Japan Emulsion Stock) Company), Unilube 50MB-26, Nonion IS-4 (Nichio Corporation), and the like.

  Examples of commercially available fluorosurfactants include MegaFuck F171, F172, F173, F176, F177, F141, F141, F142, F143, F144, R30, F437, F475, and the like. F479, F482, F554, F780, F780, F781 (above, manufactured by DIC Corporation), Fluorard FC430, FC431, FC171 (above, manufactured by Sumitomo 3M Limited), Surflon S-382, SC- 101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, SC-383, S393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.), PF636, PF656 PF6320, PF6520, PF7002 (manufactured by OMNOVA) and the like.

  Specific examples of commercially available cationic surfactants include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid. (Co) polymer polyflow No. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.

Examples of commercially available silicone surfactants include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Tore Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA” manufactured by Toray Dow Corning Co., Ltd. “Tole Silicone SH29PA”, “Tole Silicone SH30PA”, “Tole Silicone SH8400”, “TSF-4440”, “TSF-4300”, “TSF-4445”, “TSF-4460”, manufactured by Momentive Performance Materials, “TSF-4452”, “KP341”, “KF6001”, “KF6002” manufactured by Shin-Etsu Silicone Co., Ltd., “BYK307”, “BYK323”, “BYK330” manufactured by BYK Chemie, and the like can be mentioned.
Only one type of surfactant may be used, or two or more types may be combined.

As the slip agent, an aliphatic wax or the like is preferably used.
Specific examples of the aliphatic wax include plant-based waxes such as carnauba wax, candelilla wax, rice wax, wood wax, jojoba oil, palm wax, rosin modified wax, cucumber wax, sugar cane wax, esparto wax, and bark wax. Animal waxes such as beeswax, lanolin, whale wax, ibota wax, shellac wax, mineral waxes such as montan wax, ozokerite, ceresin wax, petroleum waxes such as paraffin wax, microcrystalline wax, petrolactam, and fishertro push wax And synthetic hydrocarbon waxes such as polyethylene wax, oxidized polyethylene wax, polypropylene wax, and oxidized polypropylene wax. Among these, carnauba wax, paraffin wax, and polyethylene wax are particularly preferable. These are also preferably used as aqueous dispersions because they can reduce the environmental burden and are easy to handle. Examples of commercially available products include Cellosol 524 (manufactured by Chukyo Yushi Co., Ltd.).
Only 1 type may be used for a slip agent and it may combine 2 or more types.

As the particles, either organic or inorganic fine particles can be used. For example, polymer fine particles such as polystyrene, polymethyl methacrylate (PMMA), silicone resin, and benzoguanamine resin, and inorganic fine particles such as silica, calcium carbonate, magnesium oxide, and magnesium carbonate can be used. Examples of commercially available products include cross-linked PMMA particles MR-2G (manufactured by Soken Chemical Co., Ltd.), silica particle seahoster KE-W10 (manufactured by Nippon Shokubai Co., Ltd.), and the like.
Only 1 type may be used for particle | grains and it may combine 2 or more types.

  Examples of preservatives include sodium dehydroacetate, sodium benzoate, sodium pyridinethion-1-oxide, p-hydroxybenzoic acid ethyl ester, 1,2-benzothiazolin-3-one, sodium sorbate, sodium pentachlorophenol, etc. Can be mentioned.

The thickness of the ink receiving layer is, for example, preferably 0.1 to 10 μm, more preferably 0.1 to 5 μm, and particularly preferably 0.1 to 1 μm.
The thickness of the ink receiving layer when the intermediate layer is provided is preferably 0.1 to 1 μm, and more preferably 0.2 to 0.6 μm.

<Intermediate layer>
The inkjet recording sheet of the present invention may have an intermediate layer between the support and the ink receiving layer.

  The intermediate layer adheres the support and the ink receiving layer. The elastic modulus of the intermediate layer is preferably at most 500 MPa, that is, 500 MPa or less. The elastic modulus of the intermediate layer is more preferably in the range of 10 MPa to 500 MPa, and still more preferably in the range of 50 MPa to 500 MPa. The conventional intermediate layer has an elastic modulus of 600 MPa or more, whereas the intermediate layer has such a very low elastic modulus. Thereby, when the support and the ink receiving layer are elastically deformed, the intermediate layer expands and contracts at a very micro level so as to follow the change in the shape of the support and the ink receiving layer. For example, when the ink receiving layer 3 is deformed so as to be pressed against the support 1 as indicated by a two-dot broken line (A) in FIG. 5, the intermediate layer 3 shrinks so that the thickness T becomes small. Further, when the shape of the deformed ink receiving layer 2 returns as shown by the solid line (B) in FIG. 5, the intermediate layer 3 returns to the original thickness and shape. Thus, the intermediate layer 3 has a property of changing its thickness and restoring its shape. By providing the intermediate layer 3 with elasticity, even if the shape of the ink receiving layer 2 is changed, the ink receiving layer 2 is maintained in an adhesive state without being peeled off from the support 1 and remains in close contact. Note that the ink receiving layer 2 and the support 1 are peeled off means that the ink receiving layer 2 is peeled off from the intermediate layer 3, the intermediate layer 3 is destroyed from the inside, or the intermediate layer 3 is peeled off from the support 1. Means one of them.

  The intermediate layer 3 preferably has a breaking elongation of 10% or more and 300% or less, whereas the conventional intermediate layer has a breaking elongation of less than 5%. Thereby, even if the ink receiving layer 2 is elastically deformed, the intermediate layer 3 extends more reliably and without breaking.

(resin)
The intermediate layer preferably contains at least 10% by mass of a polyolefin resin. 10 mass% means that the mass ratio is at least 10, that is, 10 or more, when the mass excluding additives that occupy 5% or less of the total mass from the total mass of the intermediate layer is 100. By including 10 mass% or more of the polyolefin resin, the intermediate layer has the above elastic modulus. The intermediate layer preferably contains a polyolefin resin in the range of 10% by mass to 90% by mass, and more preferably in the range of 20% by mass to 80% by mass.

[Polyolefin resin]
Polyolefin resins are generally known to have low adhesive strength with polyester, and conventionally, they have not been used as a main component in an intermediate layer that bonds an ink receiving layer made of polyester and a support. Further, the use of polyolefin resin for the intermediate layer is limited to the case where polyolefin is used for the support or the ink receiving layer.
However, in the present invention, polyolefin is used in the intermediate layer between the support and the ink receiving layer. Thus, in order to prevent the ink receiving layer and the support from being peeled off even though the polyolefin is the main component of the intermediate layer, the thickness T of the intermediate layer is at least 0.1 μm, that is, 0.1 μm or more. It is said. When the thickness of the intermediate layer is smaller than 0.1 μm or more, the ink receiving layer and the support are easily peeled off, and particularly easily in a high density printing portion where the ink discharge amount is large. Furthermore, by setting it as said thickness, the stress applied as a load by the crosscut etc. to the ink receiving layer or the support body in the crosscut test, for example, is relieved by the intermediate layer. The thickness T of the intermediate layer is preferably in the range of 0.1 μm to 5.0 μm, more preferably in the range of 0.3 μm to 5.0 μm, and in the range of 0.2 μm to 4 μm. More preferably. The thickness T of the intermediate layer is preferably constant.
In addition, since the stress is dispersed by having the intermediate layer, the ink adhesion can be improved even if the ink receiving layer does not sufficiently soak the ink composition.

  Furthermore, by using a resin that is not easily deteriorated under high temperature and high humidity, in a state of being subjected to wet heat aging (e.g., dried at 85 ° C. or at an aging temperature of 65 ° C. and a relative humidity of 95% for 100 to 500 hours). Also, the above elastic modulus and elongation at break are maintained. Since the polyolefin-based resin is a resin that hardly deteriorates under high temperature and high humidity, the above-described elastic modulus and elongation at break are maintained by using the polyolefin-based resin even in a state of wet heat aging.

The polyolefin is a polymer obtained by polymerizing alkenes such as ethylene, butylene, and propylene, and may be a copolymer having such a structure. These are collectively referred to as a polyolefin-based polymer. Specifically, such a polyolefin polymer is preferably any of the following.
-Copolymer consisting of ethylene or polypropylene and acrylic monomer or methacrylic monomer-Copolymer consisting of ethylene or polypropylene and carboxylic acid (including anhydride)-Ethylene or polypropylene and acrylic monomer or methacrylic monomer, Copolymer comprising carboxylic acid (including anhydride)

  Specific examples of the acrylic monomer or methacrylic monomer constituting the polyolefin polymer preferably include methyl methacrylate, ethyl acrylate, butyl acrylate, 2-hydroxyethyl acrylate and the like.

  The carboxylic acid constituting the polyolefin polymer is preferably acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride and the like. These may be used alone or in combination of a plurality of types.

  The total of ethylene or polypropylene in the polyolefin-based polymer is preferably 80 to 98 mol%, more preferably 85 to 95 mol%. Further, the acrylic monomer or methacrylic monomer is preferably in the range of 0 to 20 mol%, more preferably 3 to 10 mol% in total. Furthermore, the total amount of carboxylic acid is preferably 0 to 15 mol%, more preferably 1 to 10 mol%. By setting the monomer composition within this range, both good adhesion and durability can be achieved.

  The molecular weight of the polyolefin polymer is preferably about 2000 to 200000. The polyolefin-based polymer may have a linear structure or a branched structure. The polyolefin polymer is preferably in the form of an aqueous polymer dispersion (so-called latex). As for the method for producing a water-based polymer dispersion for a polyolefin-based polymer, there are a method by emulsification and a method by emulsification dispersion, the former being preferred. For a specific method, for example, the method described in Japanese Patent No. 3699935 can be referred to.

  The polyolefin polymer preferably has a water-affinity functional group such as a carboxyl group or a hydroxyl group when the aqueous polymer is in the form of latex. Also, when using polyolefin polymers in the form of latex, emulsification stability of surfactants (eg, anionic and nonionic surfactants) and polymers (eg: polyvinyl alcohol) to improve stability An agent may be included. Further, if necessary, a pH adjuster (eg, ammonia, triethylamine, sodium hydrogen carbonate, etc.), an antiseptic (eg, 1,3,5-hexahydro- (2-hydroxyethyl) -s-triazine, 2- (4 -Thiazolyl) benzimidazole, etc.), thickeners (eg, sodium polyacrylate, methylcellulose, etc.), film-forming aids (eg, butyl carbitol acetate, etc.), etc. Good.

  Some polyolefin-based polymer-based latexes that can be used in the present invention are commercially available. Specific examples of commercially available products include Bondine HX-8210, HX-8290, TL-8030, LX-4110 (manufactured by Sumitomo Chemical Co., Ltd.), Arrow Base SA-1200, SB-1010, SE-1013N, SE-1200 (above, Unitika Ltd.), Nippon UFN1008 (manufactured by Nippon Zeon Co., Ltd.), and the like.

[acrylic resin]
Moreover, it is preferable that an intermediate | middle layer contains an acrylic resin. The acrylic resin is for increasing the elongation at break of the intermediate layer by compounding with polyolefin. The acrylic resin preferably has a mass ratio with respect to the polyolefin of 0% to 700%, more preferably 5% to 700%, and even more preferably 30% to 300%.
As the acrylic resin, the same acrylic resin contained in the ink receiving layer can be used, and the preferred range is also the same.

[Polyester resin]
The intermediate layer may contain a polyester resin. As the polyester resin, the same polyester resin as that contained in the ink receiving layer can be used, and the preferred range is also the same.

(Crosslinking agent)
The intermediate layer preferably contains a crosslinking agent. The cross-linking agent is used to further increase the adhesive force between the ink receiving layer and the support. The cross-linking agent is not particularly limited as long as it causes a cross-linking reaction when forming the intermediate layer, and does not need to remain as a cross-linking agent in the formed intermediate layer. That is, in the obtained ink jet recording sheet of the present invention, a crosslinking agent is incorporated into a part of a crosslinked structure in which other molecules are crosslinked, and has already finished the reaction and action as a crosslinking agent. Good. The cross-linking agent increases the number of molecules in the intermediate layer and the cross-linking points in the molecule, thereby ensuring the property of restoring the shape of the intermediate layer, and improving the adhesion of the intermediate layer to the ink receiving layer and the support. More improved.

As the crosslinking agent to be included in the intermediate layer, oxazoline compounds, carbodiimide compounds, epoxy compounds, isocyanate compounds, and melamine compounds (C ₃ N ₆ H ₆ ) are preferable. It may be included. As the crosslinking agent, an oxazoline-based compound and a carbodiimide-based compound are particularly preferable. As the carbodiimide compound and the oxazoline compound, the same crosslinking agents as those contained in the ink receiving layer can be used, and preferred ranges thereof are also the same. Details of the epoxy compound, the isocyanate compound, and the melamine compound will be described later.
As addition amount of a crosslinking agent, it is preferable to contain 1-50 mass%, It is more preferable to contain 3-30 mass%, It is more preferable to contain 5-25 mass%.
If the addition amount of the cross-linking agent is less than 1% by mass, it may be insufficient to cross-link the polyolefin resin, and if it exceeds 50% by mass, there is no adverse effect from the viewpoint of adhesion, but costs increase. Too much.

[Epoxy compounds]
The epoxy compound is a compound having an epoxy group in the molecule and a compound obtained as a result of reaction of the epoxy group. Examples of the compound having an epoxy group in the molecule include condensates of epichlorohydrin and ethylene glycol, polyethylene glycol, glycerin, polyglycerin, bisphenol A, and the like with hydroxyl groups and amino groups, such as polyepoxy compounds and diepoxy compounds. Compounds, monoepoxy compounds, glycidylamine compounds, and the like. Examples of the polyepoxy compound include sorbitol, polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, triglycidyl tris (2-hydroxyethyl) isocyanate, glycerol polyglycidyl ether, trimethylol. Examples of the propane polyglycidyl ether and diepoxy compound include neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, resorcin diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether. Ether, polypropylene glycol diglycidyl ether, Ritetramethylene glycol diglycidyl ether and monoepoxy compounds include, for example, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, and glycidyl amine compounds such as N, N, N ′, N ′,-tetraglycidyl-m. -Xylylenediamine, 1,3-bis (N, N-diglycidylamino) cyclohexane and the like. Specific examples of the water-soluble monomer having an epoxy group include, for example, “Denacol-614B” (sorbitol polyglycidyl ether, epoxy equivalent 173, trade name, manufactured by Nagase ChemteX Corporation), “Denacol-EX-313” (glycerol poly). Glycidyl ether, epoxy equivalent 141, trade name, manufactured by Nagase ChemteX Corporation), “Denacol-EX-521” (polyglycerol polyglycidyl ether, epoxy equivalent 168, trade name, manufactured by Nagase ChemteX Corporation), and “Denacol-EX -830 "(polyethylene glycol diglycidyl ether, epoxy equivalent 268, trade name, manufactured by Nagase ChemteX Corporation).

[Isocyanate compounds]
An isocyanate compound is a compound having a partial structure of -N = C = O. Examples of the organic isocyanate compound include aromatic isocyanate and aliphatic isocyanate, and these may be used in combination. Specifically, 4,4′-diphenylmethane diisocyanate, 4,4-diphenyldimethylmethane diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, cyclohexane Diisocyanate, xylylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,3-phenylene diisocyanate, etc. are used. As organic monoisocyanates, isophorone isocyanate, phenyl isocyanate are used. Cyclohexyl isocyanate, butyl isocyanate, naphthyl isocyanate, and the like are used. Moreover, an isocyanate type compound is also available as Elastron H-3 (Daiichi Kogyo Seiyaku Co., Ltd.), DP9C214 (Baxenden Co., Ltd.), Takenate XWD-HS30 (Mitsui Chemicals Co., Ltd.).

[Melamine compounds]
A melamine-based compound is a compound having two or more methylol groups in the molecule, and these compounds can be used without particular limitation in the present embodiment. Examples of melamine compounds include hexamethylol melamine. Examples of commercially available melamine compounds include becamine PM-N, becamine J-101, and becamine M-3 (manufactured by DIC Corporation).

(Other)
The intermediate layer contains a surfactant, an antifoaming agent, an antifoaming agent, a dye, a fluorescent whitening agent, a preservative, a water-resistant agent, an antistatic agent, and the like as necessary in addition to the resin and the crosslinking agent. Also good.

Method for producing inkjet recording sheet:
The ink jet recording sheet of the present invention can be produced without any particular limitation on the production method thereof. For example, a coating liquid for forming an intermediate layer and a coating liquid for forming an ink receiving layer are formed on a support. It can be suitably produced by a production method provided with a step of forming an intermediate layer or an ink-receiving layer by sequentially applying or simultaneously applying multiple layers so as to be sequentially laminated and drying, and if necessary, A process may be provided.

  The application can be performed by, for example, a blade coater, an air knife coater, a roll coater, a bar coater, a gravure coater, a reverse coater or the like. In the case of a simultaneous multilayer coating method in which a plurality of coating liquids are applied simultaneously without providing a drying step, for example, a slide bead coater, a slide curtain coater, a curtain flow coater, an extrusion die coater or the like can be used. Further, for example, the “Wet-On-Wet method” (WOW method) described in paragraph Nos. 0016 to 0037 of JP-A-2005-14593 may be used.

The coating amount of the coating liquid used for forming the ink receiving layer is preferably from 5 to 20 g / m ^2, more preferably 7~10g / m ^2.
Moreover, as an application quantity of the coating liquid used for formation of an intermediate | middle layer, 5-20 g / m < ² > is preferable and 7-10 g / m < ² > is more preferable.

Manufacturing method of printed matter:
The method for producing a printed material according to the present invention includes a step of ejecting an ink composition onto the ink jet recording sheet of the present invention by an ink jet recording apparatus, and irradiating the ejected ink composition with ultraviolet rays to thereby form the ink composition. And a step of curing.

The ink composition used in the present invention is not particularly limited as long as it is a known one, but is preferably a radiation curable ink composition, and a solvent is used for curing after ejection on the inkjet recording sheet of the present invention. A solvent-free radiation-curable ink composition that does not contain is particularly preferred.
The radiation is not particularly limited as long as it can impart energy capable of generating a starting species in the ink composition by irradiation, and is widely α-ray, γ-ray, X-ray, ultraviolet ray, visible ray, Includes electron beams and the like. Of these, ultraviolet rays and electron beams are preferred from the viewpoint of curing sensitivity and device availability, and ultraviolet rays are particularly preferred. Therefore, in the present invention, an ultraviolet curable ink composition is preferred.

As the radiation curable ink composition, for example, descriptions in JP 2010-47015 A, JP 5-214280 A, and the like can be referred to, and the contents thereof are incorporated in the present specification.
As the solvent-free radiation curable ink composition, for example, descriptions in JP-A Nos. 2004-131725 and 2009-299057 can be referred to, and the contents thereof are incorporated in the present specification.

  The method for producing a printed material according to the present invention includes the above-described steps, whereby an image layer is formed from the ink composition cured on the inkjet recording sheet, and the printed material is formed as shown in FIGS. .

Examples of the ink jet recording apparatus that can be used in the present invention include an apparatus including an ink supply system, a temperature sensor, and an actinic radiation source.
The ink supply system includes, for example, an original tank containing the ink composition of the present invention, a supply pipe, an ink supply tank immediately before the inkjet head, a filter, and a piezo-type inkjet head. The piezo-type inkjet head preferably has a multi-size dot of 1 to 100 pl, more preferably 8 to 30 pl, preferably 320 × 320 to 4,000 × 4,000 dpi, more preferably 400 × 400 to 1,600 ×. It can be driven so that it can discharge at a resolution of 1,600 dpi, more preferably 720 × 720 dpi. In the present invention, dpi represents the number of dots per 2.54 cm.

Ink such as radiation curable ink desirably has a constant temperature for the ejected ink. Therefore, the ink jet recording apparatus preferably includes a means for stabilizing the ink composition temperature. The parts to be kept at a constant temperature are all the piping systems and members from the ink tank (intermediate tank if there is an intermediate tank) to the nozzle ejection surface. That is, heat insulation and heating can be performed from the ink supply tank to the inkjet head portion.
The temperature control method is not particularly limited, but for example, it is preferable to provide a plurality of temperature sensors at each piping site and perform heating control according to the ink flow rate and the environmental temperature. The temperature sensor can be provided near the ink supply tank and the nozzle of the inkjet head. Moreover, it is preferable that the head unit to be heated is thermally shielded or insulated so that the apparatus main body is not affected by the temperature from the outside air. In order to shorten the printer startup time required for heating, or to reduce the loss of heat energy, it is preferable to insulate from other parts and reduce the heat capacity of the entire heating unit.

Using the above-described ink jet recording apparatus, the ink composition is ejected by heating the ink composition to preferably 25 to 80 ° C., more preferably 25 to 50 ° C., so that the viscosity of the ink composition is preferably 3 to 15 mPa. It is preferable to carry out after lowering to s, more preferably 3 to 13 mPa · s. In particular, in the present invention, it is preferable to use an ink composition having an ink viscosity at 25 ° C. of 50 mPa · s or less because the ink composition can be discharged satisfactorily. By using this method, high ejection stability can be realized.
Since the radiation curable ink composition generally has a higher viscosity than the water-based ink usually used in ink jet recording ink, the viscosity variation due to temperature variation during ejection is large. Viscosity fluctuation of the ink composition has a great influence on the change of the droplet size and the change of the droplet discharge speed, and thus causes the image quality deterioration. Therefore, it is necessary to keep the temperature of the ink composition during ejection as constant as possible. Therefore, in the present invention, the temperature control range of the ink composition is preferably set to ± 5 ° C. of the set temperature, more preferably ± 2 ° C. of the set temperature, and further preferably set temperature ± 1 ° C. .

Next, a process of irradiating the ejected ink composition with radiation to cure the ink composition will be described.
The ink composition discharged on the inkjet recording sheet of the present invention is cured by irradiation with radiation. This is because the radical polymerization initiator contained in the ink composition is decomposed by irradiation with radiation to generate radicals, and the polymerization reaction of the radical polymerizable compound is caused and accelerated by the radicals. At this time, if a sensitizer is present together with the radical polymerization initiator in the ink composition, the sensitizer in the system absorbs radiation and enters an excited state, and the radical polymerization initiator is decomposed by contact with the radical polymerization initiator. And a more sensitive curing reaction can be achieved.

  Here, although the peak wavelength of the radiation used depends on the absorption characteristics of the sensitizer, for example, it is preferably 200 to 600 nm, more preferably 300 to 450 nm, and 350 to 420 nm. Is more preferable.

In addition, the ink composition has sufficient sensitivity even with low output radiation. Therefore, it is appropriate that the exposure surface illuminance is cured at 10 to 4,000 mW / cm ² , more preferably 20 to 2,500 mW / cm ² .

Mercury lamps and gas / solid lasers are mainly used as radiation sources, and mercury lamps and metal halide lamps are widely known as light sources used for curing UV photocurable ink jet recording inks. . However, from the viewpoint of environmental protection, mercury-free is strongly desired, and replacement with a GaN-based semiconductor ultraviolet light-emitting device is very useful industrially and environmentally. Furthermore, LED (UV-LED) and LD (UV-LD) are small, have a long lifetime, high efficiency, and low cost, and are expected as light sources for photo-curable ink jet recording.
Further, a light emitting diode (LED) and a laser diode (LD) can be used as a radiation source. In particular, when an ultraviolet light source is required, an ultraviolet LED and an ultraviolet LD can be used. For example, Nichia Corporation has introduced a purple LED whose main emission spectrum has a wavelength between 365 nm and 420 nm. If even shorter wavelengths are required, US Pat. No. 6,084,250 discloses an LED that can emit radiation centered between 300 nm and 370 nm. Other ultraviolet LEDs are also available and can emit radiation in different ultraviolet bands. A particularly preferred radiation source in the present invention is a UV-LED, and a UV-LED having a peak wavelength of 350 to 420 nm is particularly preferred.
Incidentally, it is preferable that maximum illumination intensity of the LED on a recording medium is 10 to 2,000 mW / cm ^2, more preferably 20 to 1,000 mW / cm ^2, is 50 to 800 mW / cm ² It is particularly preferred.

The ink composition is appropriately irradiated with such radiation for 0.01 to 120 seconds, more preferably for 0.1 to 90 seconds.
Radiation irradiation conditions and a basic irradiation method are disclosed in JP-A-60-132767. Specifically, the light source is provided on both sides of the head unit including the ink ejection device, and the head unit and the light source are scanned by a so-called shuttle method. Irradiation is performed after a certain period of time (preferably 0.01 to 0.5 seconds, more preferably 0.01 to 0.3 seconds, and still more preferably 0.01 to 0.15 seconds) after ink landing. Will be done. In this way, by controlling the time from ink landing to irradiation to an extremely short time, it is possible to prevent the ink that has landed on the recording medium from spreading before curing. In addition, since it can be exposed to the porous recording medium before the ink penetrates to a deep part where the light source does not reach, it is preferable because residual unreacted monomer can be suppressed.
Further, the curing may be completed by another light source that is not driven. International Publication No. 99/54415 pamphlet discloses a method using an optical fiber or a method of irradiating a recording unit with UV light by applying a collimated light source to a mirror surface provided on the side of the head unit, as an irradiation method. Such a curing method can also be applied to the production method of the present invention.

The inkjet recording apparatus using the inkjet recording apparatus preferably uses a wide format inkjet printer system, and preferably uses a wide format UV inkjet printer system. A wide format inkjet printer system is a system that cures the ejected ink composition by irradiating the ink composition almost simultaneously with the ejection of the ink composition from the inkjet recording apparatus, and produces a large print in a short time. Is possible. Wide format printers are generally defined as printers capable of printing 24 inches (61 cm) or more in width. Printers with a width of 44 inches (111.7 cm) to 64 inches (162.5 cm) are the mainstream, but some printers can print up to a width of 197 inches (500 cm).
As the wide format UV inkjet printer system, LuxelJet UV360GTW / XTW and UV550GTW / XTW series, Accuracy LED 1600 (both manufactured by FUJIFILM Corporation), inca SP320 / SP320e / SP320S / SP320W (made by Inca Digital Printers Lim etc.) be able to.

In the method for producing a printed matter of the present invention, an ink set containing an ink composition can be suitably used. For example, a cyan ink composition, a magenta ink composition, and a black composition may be combined with a yellow ink composition and used as an ink set. In order to obtain a full-color image using the ink composition, an ink set in which four dark ink compositions of yellow, cyan, magenta, and black are combined is preferable. More preferably, the ink set is a combination of a dark ink composition group of five colors consisting of yellow, cyan, magenta, black and white and a light cyan and light magenta ink composition group. The “dark ink composition” means an ink composition in which the pigment content exceeds 1% by weight of the entire ink composition.
In order to obtain a color image by the method for producing a printed material according to the present invention, it is preferable to use an ink composition (ink set) of each color, and to superimpose in order from a color with low brightness. Specifically, when using an ink set composed of yellow, cyan, magenta, and black ink compositions, it may be applied onto the inkjet recording sheet of the present invention in the order of yellow → cyan → magenta → black. preferable. Further, when an ink set including at least a total of seven colors of light cyan and light magenta ink composition groups and cyan, magenta, black, white, and yellow dark ink composition groups is used, In this case, it is preferable to apply the ink in the order of white → light cyan → light magenta → yellow → cyan → magenta → black on the inkjet recording sheet of the present invention.
In this way, by superimposing the inks in the order of low lightness, it becomes easier for the irradiation line to reach the lower ink, and good curing sensitivity, reduction of residual monomers, and improvement in adhesion can be expected. In addition, irradiation can be performed by discharging all colors and collectively exposing, but exposure for each color is preferable from the viewpoint of promoting curing.

Printed matter:
The printed matter of the present invention is recorded by the method for producing a printed matter of the present invention. In the printed matter of the present invention, the image layer 4 is formed on the ink jet recording sheet of the present invention, and an example is shown in FIGS. The printed matter of the present invention is excellent in adhesiveness and becomes a high-quality printed matter.
The thickness of the image layer 4 is preferably 1 to 800 μm, more preferably 100 to 800 μm, and further preferably 500 to 750 μm.
Although there is no restriction | limiting in particular in the width | variety of printed matter, It is preferable to record with a wide format inkjet printer system, 0.3-5m is preferable, 0.5-4m is more preferable, 1-3m is especially preferable. In addition, the preferable width | variety of the recording sheet for inkjets of this invention is the same as the preferable width | variety of the above-mentioned printed matter of this invention.
When the printed material of the present invention is used as an electrical decoration printed material, the printed material of the present invention is preferably installed so that the opposite side of the image layer and the ink receiving layer is the viewing side. That is, it is preferable that a light source is provided on the image layer side formed on the ink receiving layer of the ink jet recording sheet of the present invention, and the printed material of the present invention is viewed from the support side.
Various functional layers can be provided on the support opposite to the printing surface. For example, the scratch-resistant layer described in WO09 / 001629, the hard coat layer with antistatic performance described in JP-A-5-186534, the antiglare layer described in JP-A-1-46701, and JP-A-2001-2001 Examples thereof include an antireflection layer described in 330708, and a weather resistant layer described in JP2011-146659A. In addition, various films having scratch resistance, antiglare property, etc. can be laminated. By providing the above various functional layers on the opposite side of the printing surface, the printed matter of the present invention can be made into a particularly preferable form when viewed from the support side.

The printed matter of the present invention can be used as an electric signboard. The electric signboard has a light source and a printed matter for electric decoration, and the printed matter for electric decoration is preferably arranged between two kinds of acrylic resins having excellent transparency and weather resistance.
The printed matter of the present invention is preferably arranged so that the viewing side is the mat layer, that is, the light source side is the easy adhesion layer.
The light source is not particularly limited, and for example, a light bulb, a fluorescent lamp, a light emitting diode (LED), an electroluminescence panel (ELP), one or a plurality of cold cathode fluorescent lamps (CCFL), a hot cathode fluorescent lamp (HCFL), etc. are used. be able to.

The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.
Examples 1-7, 11, 12, 14 and 15 are reference examples.

Example 1
A polyethylene terephthalate (hereinafter referred to as PET) resin having an intrinsic viscosity of 0.64 polycondensed using a Ti compound as a catalyst is dried to a moisture content of 50 ppm or less and melted in an extruder with a heater temperature of 270 to 300 ° C. It was. The melted PET was extruded from a die part onto a chill roll electrostatically applied to obtain a band-shaped amorphous base. The obtained amorphous base was stretched 3.3 times in the longitudinal direction and then stretched 3.8 times in the width direction to obtain a film support having a thickness of 250 μm.

The support was transported at a transport speed of 45 m / min, and both surfaces were subjected to corona discharge treatment under the condition of 955 J / m ² , and then the following coating solution A was applied to one surface by the bar coating method. And this was dried at 145 degreeC for 1 minute, and the recording sheet (2.1 m width roll winding form) with which the ink receiving layer was provided in the single side | surface of the support body was obtained. The thickness of the ink receiving layer was 0.9 μm.

The composition of the coating liquid A is as follows.
(Coating liquid A)
Polyester resin aqueous solution 182.0 parts by mass (manufactured by Kyoyo Chemical Co., Ltd., plus coat Z592 solid content 25%)
119.8 parts by mass of an aqueous polyurethane resin dispersion (Superflex 150HS, solid content 38%, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Cross-linking agent (oxazoline compound) 25.0 parts by mass (Epocross K-2020E, solid content 40%, manufactured by Nippon Shokubai Co., Ltd.)
Surfactant A 29.7 parts by mass (manufactured by Sanyo Chemical Industries, Ltd., 1% aqueous solution of NAROACTY CL-95)
Surfactant B 12.3 parts by mass (1% aqueous solution of Rapisol B-90 manufactured by NOF Corporation)
1.8 parts by weight of slip agent (Canaba wax dispersion cellosol 524, solid content 30%, manufactured by Chukyo Yushi Co., Ltd.)
0.7 parts by mass of particles (manufactured by Soken Chemical Co., Ltd., crosslinked PMMA particles MR-2G, aqueous dispersion having an average particle diameter of 1 μm, solid content of 15%)
Preservative 0.7 parts by mass (manufactured by Daito Chemical Co., Ltd., 1,2-benzothiazolin-3-one, solid content 3.5% methanol solvent)
Distilled water α part by mass (α: the amount was adjusted so that the whole coating liquid A was 1000 parts by mass)

In each of Examples and Comparative Examples, solvent-free radiation curable ink (manufactured by FUJIFILM Special Ink System Limited, product numbers UVIJET KO 021 Black, UVIJET KO 004JI KO 215 KY 215 JK 052 Yellow) was used.
Use a "wide format UV inkjet press LuxelJet UV550GTW, manufactured by Fuji Film" as a printing machine and print a color image twice in roll-to-roll fine art mode (wavelength 365 to 405 nm, printing speed 22 m ² / hr). Thus, a printed matter having a width of about 2 m and a size of 1.5 m was obtained. The thickness of the image layer after drying was 500 to 720 μm.

(Example 2)
A printed matter was obtained in the same manner as in Example 1 except that the coating liquid A of Example 1 was changed to the coating liquid B shown below.
The composition of the coating liquid B is as follows.
(Coating solution B)
Polyester resin aqueous solution 196.2 parts by mass (manufactured by Kyoyo Chemical Co., Ltd., plus coat Z592 solid content 25%)
Polyurethane resin aqueous dispersion 129.1 parts by mass (Daiichi Kogyo Seiyaku Co., Ltd. Superflex 150HS solid content 38%)
Cross-linking agent (oxazoline compound) 7.5 parts by mass (Epocross K-2020E, solid content 40%, manufactured by Nippon Shokubai Co., Ltd.)
Surfactant A 29.7 parts by mass (manufactured by Sanyo Chemical Industries, Ltd., 1% aqueous solution of NAROACTY CL-95)
Surfactant B 12.3 parts by mass (1% aqueous solution of Rapisol B-90 manufactured by NOF Corporation)
1.8 parts by weight of slip agent (Canaba wax dispersion cellosol 524, solid content 30%, manufactured by Chukyo Yushi Co., Ltd.)
0.7 parts by mass of particles (manufactured by Soken Chemical Co., Ltd., crosslinked PMMA particles MR-2G, aqueous dispersion having an average particle diameter of 1 μm, solid content of 15%)
Preservative 0.7 parts by mass (manufactured by Daito Chemical Co., Ltd., 1,2-benzothiazolin-3-one, solid content 3.5% methanol solvent)
Distilled water α part by mass (α; the amount was adjusted so that the whole coating liquid B was 1000 parts by mass)

(Example 3)
A printed matter was obtained in the same manner as in Example 1 except that the coating liquid A of Example 1 was changed to the coating liquid C shown below.
The composition of the coating liquid C is as follows.
(Coating liquid C)
Polyester resin aqueous solution 141.6 parts by mass (manufactured by Kyoyo Chemical Co., Ltd., plus coat Z592 solid content 25%)
93.2 parts by mass of a polyurethane resin aqueous dispersion (Daiichi Kogyo Seiyaku Co., Ltd. Superflex 150HS solid content 38%)
Cross-linking agent (oxazoline compound) 75.0 parts by mass (Epocross K-2020E, solid content 40%, manufactured by Nippon Shokubai Co., Ltd.)
Surfactant A 29.7 parts by mass (manufactured by Sanyo Chemical Industries, Ltd., 1% aqueous solution of NAROACTY CL-95)
Surfactant B 12.3 parts by mass (1% aqueous solution of Rapisol B-90 manufactured by NOF Corporation)
1.8 parts by weight of slip agent (Canaba wax dispersion cellosol 524, solid content 30%, manufactured by Chukyo Yushi Co., Ltd.)
0.7 parts by mass of particles (manufactured by Soken Chemical Co., Ltd., crosslinked PMMA particles MR-2G, aqueous dispersion having an average particle diameter of 1 μm, solid content of 15%)
Preservative 0.7 parts by mass (manufactured by Daito Chemical Co., Ltd., 1,2-benzothiazolin-3-one, solid content 3.5% methanol solvent)
Distilled water α part by mass (α; the amount was adjusted so that the entire coating liquid C was 1000 parts by mass)

Example 4
A printed matter was obtained in the same manner as in Example 1 except that the coating liquid A in Example 1 was changed to the coating liquid D.

The composition of the coating liquid D is as follows.
(Coating liquid D)
Polyester resin aqueous solution 161.7 parts by mass (manufactured by Kyoyo Chemical Co., Ltd., plus coat Z592 solid content 25%)
106.5 parts by mass of aqueous polyurethane resin dispersion (Superflex 150HS, solid content 38%, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Acrylic resin aqueous dispersion 36.4 parts by mass (Daicel Chemical Industries, Ltd. EM-48D solid content 27.5%)
Cross-linking agent (oxazoline compound) 25.0 parts by mass (Epocross K-2020E, solid content 40%, manufactured by Nippon Shokubai Co., Ltd.)
Surfactant A 29.7 parts by mass (manufactured by Sanyo Chemical Industries, Ltd., 1% aqueous solution of NAROACTY CL-95)
Surfactant B 12.3 parts by mass (1% aqueous solution of Rapisol B-90 manufactured by NOF Corporation)
1.8 parts by weight of slip agent (Canaba wax dispersion cellosol 524, solid content 30%, manufactured by Chukyo Yushi Co., Ltd.)
0.7 parts by mass of particles (manufactured by Soken Chemical Co., Ltd., crosslinked PMMA particles MR-2G, aqueous dispersion having an average particle diameter of 1 μm, solid content of 15%)
Preservative 0.7 parts by mass (manufactured by Daito Chemical Co., Ltd., 1,2-benzothiazolin-3-one, solid content 3.5% methanol solvent)
Distilled water α part by mass (α; the amount was adjusted so that the whole coating liquid D was 1000 parts by mass)

(Example 5)
A printed matter was obtained in the same manner as in Example 1 except that the coating liquid A in Example 1 was changed to the coating liquid E.

(Coating fluid E)
The composition of the coating liquid E is as follows.
186.4 parts by mass of polyurethane resin aqueous dispersion (Daiichi Kogyo Seiyaku Co., Ltd. Superflex 150HS solid content 38%)
Cross-linking agent (oxazoline compound) 75.0 parts by mass (Epocross K-2020E, solid content 40%, manufactured by Nippon Shokubai Co., Ltd.)
Surfactant A 29.7 parts by mass (manufactured by Sanyo Chemical Industries, Ltd., 1% aqueous solution of NAROACTY CL-95)
Surfactant B 12.3 parts by mass (1% aqueous solution of Rapisol B-90 manufactured by NOF Corporation)
1.8 parts by weight of slip agent (Canaba wax dispersion cellosol 524, solid content 30%, manufactured by Chukyo Yushi Co., Ltd.)
0.7 parts by mass of particles (manufactured by Soken Chemical Co., Ltd., crosslinked PMMA particles MR-2G, aqueous dispersion having an average particle diameter of 1 μm, solid content of 15%)
Preservative 0.7 parts by mass (manufactured by Daito Chemical Co., Ltd., 1,2-benzothiazolin-3-one, solid content 3.5% methanol solvent)
Distilled water α part by mass (α; the amount was adjusted so that the whole coating liquid E was 1000 parts by mass)

(Example 6)
A printed matter was obtained in the same manner as in Example 1 except that the coating liquid A in Example 1 was changed to the coating liquid F.

The composition of the coating liquid F is as follows.
(Coating fluid F)
Polyester resin aqueous solution 182.0 parts by mass (manufactured by Kyoyo Chemical Co., Ltd., plus coat Z592 solid content 25%)
119.8 parts by mass of an aqueous polyurethane resin dispersion (Superflex 150HS, solid content 38%, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Cross-linking agent (carbodiimide compound) 25.0 parts by mass (Nisshinbo Co., Ltd. Carbodilite V-02-L2 solid content 40%)
Surfactant A 29.7 parts by mass (manufactured by Sanyo Chemical Industries, Ltd., 1% aqueous solution of NAROACTY CL-95)
Surfactant B 12.3 parts by mass (1% aqueous solution of Rapisol B-90 manufactured by NOF Corporation)
1.8 parts by weight of slip agent (Canaba wax dispersion cellosol 524, solid content 30%, manufactured by Chukyo Yushi Co., Ltd.)
0.7 parts by mass of particles (manufactured by Soken Chemical Co., Ltd., crosslinked PMMA particles MR-2G, aqueous dispersion having an average particle diameter of 1 μm, solid content of 15%)
Preservative 0.7 parts by mass (manufactured by Daito Chemical Co., Ltd., 1,2-benzothiazolin-3-one, solid content 3.5% methanol solvent)
Distilled water α part by mass (α; the amount was adjusted so that the whole coating solution F was 1000 parts by mass)

(Example 7)
A polyethylene terephthalate (hereinafter referred to as PET) resin having an intrinsic viscosity of 0.64 polycondensed using a Ti compound as a catalyst is dried to a moisture content of 50 ppm or less and melted in an extruder with a heater temperature of 270 to 300 ° C. It was. The melted PET was extruded from a die part onto a chill roll electrostatically applied to obtain a band-shaped amorphous base. The obtained amorphous base was stretched 3.3 times in the longitudinal direction, then subjected to corona discharge treatment in air, and the following coating solution G was applied to one side by a bar coating method. The coated uniaxially stretched film is guided to a preheating zone while being gripped with a clip, dried at 90 ° C., continuously stretched 3.8 times in the width direction in a heating zone at 100 ° C., and further 215 ° C. Heat treatment was applied in the heating zone to obtain a recording sheet having a thickness of 250 μm. The thickness of the ink receiving layer was 0.1 μm.

The composition of the coating liquid G is as follows.
(Coating liquid G)
Polyester resin aqueous solution 63.0 parts by mass (manufactured by Kyoyo Chemical Co., Ltd., plus coat Z592 solid content 25%)
41.4 parts by mass of polyurethane resin aqueous dispersion (Superflex 150HS, solid content 38%, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Cross-linking agent (oxazoline compound) 8.7 parts by mass (Epocross K-2020E, solid content 40%, manufactured by Nippon Shokubai Co., Ltd.)
Surfactant B 16.0 parts by mass (1% aqueous solution of Rapisol B-90 manufactured by NOF Corporation)
8.0 parts by mass of slip agent (Carnava wax dispersion cellosol 524 solid content 30%, manufactured by Chukyo Yushi Co., Ltd.)
1.2 parts by mass of particles (Silica Particle Seahoster KE-W10 0.15 μm, solid content 15% manufactured by Nippon Shokubai Co., Ltd.)
Distilled water α part by mass (α; the amount was adjusted so that the entire coating solution G was 1000 parts by mass)

  In the same manner as in Example 1, using a “wide format UV inkjet press LuxelJet UV550GTW, manufactured by Fuji Film” as a printing machine and printing a color image twice in a roll-to-roll fine art mode, an approximately 2 m width × 1. A printed matter having a size of 5 m was obtained.

(Example 8)
A polyethylene terephthalate (hereinafter referred to as PET) resin having an intrinsic viscosity of 0.64 polycondensed using a Ti compound as a catalyst is dried to a moisture content of 50 ppm or less and melted in an extruder with a heater temperature of 270 to 300 ° C. It was. The melted PET was extruded from a die part onto a chill roll electrostatically applied to obtain a band-shaped amorphous base. The obtained amorphous base was stretched 3.3 times in the longitudinal direction and then stretched 3.8 times in the width direction to obtain a film support having a thickness of 250 μm.

The support was transported at a transport speed of 45 m / min, and both surfaces were subjected to corona discharge treatment under the condition of 955 J / m ² , and then the following coating solution H was coated on one surface by the bar coating method. Then, this was dried at 145 ° C. for 1 minute and further subjected to a corona discharge treatment on both sides under the condition of 288 J / m ² , and then the coating liquid I was applied to one side by a bar coating method. And this was dried at 145 degreeC for 1 minute, and the recording sheet with which the intermediate | middle layer and the ink receiving layer were provided in the single side | surface of the support body was obtained. The thicknesses of the intermediate layer and the ink receiving layer were each 0.45 μm.

The composition of the coating liquid H is as follows.
(Coating liquid H)
Acrylic ester copolymer 63.4 parts by mass (manufactured by Toagosei Chemical Co., Ltd., Jurimer ET-410 solid content 30%)
95.1 parts by mass of polyolefin (manufactured by Unitika Ltd., Arrow Base SE-1013N solid content: 20% by mass)
Crosslinking agent (carbodiimide compound) 31.5 parts by mass (Nisshinbo Co., Ltd. Carbodilite V-02-L2 solid content 40%)
Surfactant A 16.7 parts by mass (1% aqueous solution of NAROACTY CL-95 manufactured by Sanyo Chemical Industries, Ltd.)
6.9 parts by mass of surfactant B (1% aqueous solution of Rapisol B-90 manufactured by NOF Corporation)
Polystyrene latex aqueous dispersion 1.2 parts by mass (Nippol UFN1008 manufactured by Zeon Corporation)
Preservative 0.8 parts by mass (Daito Chemical Co., Ltd., 1,2-benzothiazolin-3-one, solid content 3.5% methanol solvent)
Distilled water α part by mass (α; the amount was adjusted so that the entire coating liquid H was 1000 parts by mass)

(Coating liquid I)
The composition of the coating liquid I is as follows.
Polyester resin aqueous solution 91.0 parts by mass (manufactured by Kyoyo Chemical Co., Ltd., plus coat Z592 solid content 25%)
59.9 parts by mass of an aqueous polyurethane resin dispersion (Superflex 150HS, solid content 38%, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Cross-linking agent (oxazoline compound) 12.5 parts by mass (Epocross K-2020E, solid content 40%, manufactured by Nippon Shokubai Co., Ltd.)
Surfactant A 29.7 parts by mass (manufactured by Sanyo Chemical Industries, Ltd., 1% aqueous solution of NAROACTY CL-95)
Surfactant B 12.3 parts by mass (1% aqueous solution of Rapisol B-90 manufactured by NOF Corporation)
1.8 parts by weight of slip agent (Canaba wax dispersion cellosol 524, solid content 30%, manufactured by Chukyo Yushi Co., Ltd.)
Preservative 0.7 parts by mass (manufactured by Daito Chemical Co., Ltd., 1,2-benzothiazolin-3-one, solid content 3.5% methanol solvent)
Distilled water α part by mass (α; the amount was adjusted so that the whole coating liquid I was 1000 parts by mass)

  In the same manner as in Example 1, using a “wide format UV inkjet press LuxelJet UV550GTW, manufactured by Fuji Film” as a printing machine and printing a color image twice in a roll-to-roll fine art mode, an approximately 2 m width × 1. A printed matter having a size of 5 m was obtained.

Example 9
A printed matter was obtained in the same manner as in Example 8 except that the coating liquid H of Example 8 was changed to the coating liquid J.

The composition of the coating liquid J is as follows.
(Coating liquid J)
Acrylic ester copolymer 8.5 parts by mass (Jurimer ET-410, solid content 30%, manufactured by Toagosei Co., Ltd.)
228.3 parts by mass of polyolefin (manufactured by Unitika Ltd., Arrow Base SE-1013N solid content: 20% by mass)
Cross-linking agent (carbodiimide compound) 6.3 parts by mass (manufactured by Nisshinbo Co., Ltd. Carbodilite V-02-L2 solid content 40%)
Surfactant A 16.7 parts by mass (1% aqueous solution of NAROACTY CL-95 manufactured by Sanyo Chemical Industries, Ltd.)
6.9 parts by mass of surfactant B (1% aqueous solution of Rapisol B-90 manufactured by NOF Corporation)
Polystyrene latex aqueous dispersion 1.2 parts by mass (Nippol UFN1008 solid content 20%, manufactured by Zeon Corporation)
Preservative 0.8 parts by mass (Daito Chemical Co., Ltd., 1,2-benzothiazolin-3-one, solid content 3.5% methanol solvent)
Distilled water α part by mass (α; the amount was adjusted so that the whole coating liquid J was 1000 parts by mass)

(Example 10)
A printed matter was obtained in the same manner as in Example 8, except that the coating liquid H in Example 8 was changed to the coating liquid K.

The composition of the coating liquid K is as follows.
(Coating liquid K)
190.2 parts by mass of polyolefin (available from Unitika Ltd., Arrow Base SE-1013N solid content: 20% by mass)
Crosslinking agent (carbodiimide compound) 31.5 parts by mass (Nisshinbo Co., Ltd. Carbodilite V-02-L2 solid content 40%)
Surfactant A 16.7 parts by mass (1% aqueous solution of NAROACTY CL-95 manufactured by Sanyo Chemical Industries, Ltd.)
6.9 parts by mass of surfactant B (1% aqueous solution of Rapisol B-90 manufactured by NOF Corporation)
Polystyrene latex aqueous dispersion 1.2 parts by mass (Nippol UFN1008 solid content 20%, manufactured by Zeon Corporation)
Preservative 0.8 parts by mass (Daito Chemical Co., Ltd., 1,2-benzothiazolin-3-one, solid content 3.5% methanol solvent)
Distilled water α part by mass (α; the amount was adjusted so that the entire coating liquid K was 1000 parts by mass)

(Example 11)
A printed matter was obtained in the same manner as in Example 8 except that the coating liquid H of Example 8 was changed to the coating liquid L.

The composition of the coating liquid L is as follows.
(Coating liquid L)
Acrylic ester copolymer 109.9 parts by mass (manufactured by Toagosei Chemical Co., Ltd., Jurimer ET-410 solid content 30%)
25.3 parts by mass of polyolefin (manufactured by Unitika Ltd., Arrow Base SE-1013N solid content: 20% by mass)
Crosslinking agent (carbodiimide compound) 31.5 parts by mass (Nisshinbo Co., Ltd. Carbodilite V-02-L2 solid content 40%)
Surfactant A 16.7 parts by mass (1% aqueous solution of NAROACTY CL-95 manufactured by Sanyo Chemical Industries, Ltd.)
6.9 parts by mass of surfactant B (1% aqueous solution of Rapisol B-90 manufactured by NOF Corporation)
Polystyrene latex aqueous dispersion 1.2 parts by mass (Nippol UFN1008 solid content 20%, manufactured by Zeon Corporation)
Preservative 0.8 parts by mass (Daito Chemical Co., Ltd., 1,2-benzothiazolin-3-one, solid content 3.5% methanol solvent)
Distilled water α part by mass (α; the amount was adjusted so that the entire coating liquid L was 1000 parts by mass)

(Example 12)
A printed matter was obtained in the same manner as in Example 8, except that in Example 8, the thickness of the intermediate layer was 0.1 μm.

(Example 13)
A printed matter was obtained in the same manner as in Example 8 except that the thickness of the intermediate layer was changed to 3.0 μm in Example 8.

(Example 14)
A printed matter was obtained in the same manner as in Example 8 except that the coating liquid H in Example 8 was changed to the coating liquid M.

The composition of the coating liquid M is as follows.
(Coating liquid M)
Acrylic ester copolymer 126.8 parts by mass (Jurimer ET-410, solid content 30%, manufactured by Toagosei Co., Ltd.)
Crosslinking agent (carbodiimide compound) 31.5 parts by mass (Nisshinbo Co., Ltd. Carbodilite V-02-L2 solid content 40%)
Surfactant A 16.7 parts by mass (1% aqueous solution of NAROACTY CL-95 manufactured by Sanyo Chemical Industries, Ltd.)
6.9 parts by mass of surfactant B (1% aqueous solution of Rapisol B-90 manufactured by NOF Corporation)
Polystyrene latex aqueous dispersion 1.2 parts by mass (Nippol UFN1008 solid content 20%, manufactured by Zeon Corporation)
Preservative 0.8 parts by mass (Daito Chemical Co., Ltd., 1,2-benzothiazolin-3-one, solid content 3.5% methanol solvent)
Distilled water α part by mass (α; the amount was adjusted so that the whole coating liquid M was 1000 parts by mass)

(Example 15)
A printed matter was obtained in the same manner as in Example 8 except that the coating liquid H of Example 8 was changed to the coating liquid N.

The composition of the coating liquid N is as follows.
(Coating liquid N)
Acrylic ester copolymer 63.4 parts by mass (manufactured by Toagosei Chemical Co., Ltd., Jurimer ET-410 solid content 30%)
Polyester aqueous dispersion 76.1 parts by mass (Plus Coat Z-687, solid content: 25% by mass)
Crosslinking agent (carbodiimide compound) 31.5 parts by mass (Nisshinbo Co., Ltd. Carbodilite V-02-L2 solid content 40%)
Surfactant A 16.7 parts by mass (1% aqueous solution of NAROACTY CL-95 manufactured by Sanyo Chemical Industries, Ltd.)
6.9 parts by mass of surfactant B (1% aqueous solution of Rapisol B-90 manufactured by NOF Corporation)
Polystyrene latex aqueous dispersion 1.2 parts by mass (Nippol UFN1008 solid content 20%, manufactured by Zeon Corporation)
Preservative 0.8 parts by mass (Daito Chemical Co., Ltd., 1,2-benzothiazolin-3-one, solid content 3.5% methanol solvent)
Distilled water α part by mass (α; the amount was adjusted so that the whole coating liquid N was 1000 parts by mass)

(Comparative Example 1)
A printed matter was obtained in the same manner as in Example 1 except that the coating liquid A in Example 1 was changed to the coating liquid O.

The composition of the coating liquid O is as follows.
(Coating solution O)
Polyester resin aqueous solution 202.2 parts by mass (manufactured by Kyoyo Chemical Co., Ltd., plus coat Z592 solid content 25%)
Polyurethane resin aqueous dispersion 133.1 parts by mass (Daiichi Kogyo Seiyaku Co., Ltd. Superflex 150HS solid content 38%)
Surfactant A 29.7 parts by mass (manufactured by Sanyo Chemical Industries, Ltd., 1% aqueous solution of NAROACTY CL-95)
Surfactant B 12.3 parts by mass (1% aqueous solution of Rapisol B-90 manufactured by NOF Corporation)
1.8 parts by weight of slip agent (Canaba wax dispersion cellosol 524, solid content 30%, manufactured by Chukyo Yushi Co., Ltd.)
0.7 parts by mass of particles (manufactured by Soken Chemical Co., Ltd., crosslinked PMMA particles MR-2G, aqueous dispersion having an average particle diameter of 1 μm, solid content of 15%)
Preservative 0.7 parts by mass (manufactured by Daito Chemical Co., Ltd., 1,2-benzothiazolin-3-one, solid content 3.5% methanol solvent)
Distilled water α parts by mass (α; the amount was adjusted so that the whole coating solution O was 1000 parts by mass)

(Comparative Example 2)
A printed matter was obtained in the same manner as in Example 1 except that the coating liquid A in Example 1 was changed to the coating liquid P.

The composition of the coating liquid P is as follows.
(Coating liquid P)
Polyester resin aqueous solution 182.0 parts by mass (manufactured by Kyoyo Chemical Co., Ltd., plus coat Z592 solid content 25%)
119.8 parts by mass of an aqueous polyurethane resin dispersion (Superflex 150HS, solid content 38%, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Crosslinking agent (melamine compound) 12.5 parts by mass (DIC Co., Ltd. Becamine M-3 solid content 80%)
Surfactant A 29.7 parts by mass (manufactured by Sanyo Chemical Industries, Ltd., 1% aqueous solution of NAROACTY CL-95)
Surfactant B 12.3 parts by mass (1% aqueous solution of Rapisol B-90 manufactured by NOF Corporation)
1.8 parts by weight of slip agent (Canaba wax dispersion cellosol 524, solid content 30%, manufactured by Chukyo Yushi Co., Ltd.)
0.7 parts by mass of particles (manufactured by Soken Chemical Co., Ltd., crosslinked PMMA particles MR-2G, aqueous dispersion having an average particle diameter of 1 μm, solid content of 15%)
Preservative 0.7 parts by mass (manufactured by Daito Chemical Co., Ltd., 1,2-benzothiazolin-3-one, solid content 3.5% methanol solvent)
Distilled water α part by mass (α; the amount was adjusted so that the whole coating liquid P was 1000 parts by mass)

(Comparative Example 3)
A printed matter was obtained in the same manner as in Example 1 except that the coating liquid A in Example 1 was changed to the coating liquid Q.

The composition of the coating liquid Q is as follows.
(Coating liquid Q)
Polyester resin aqueous solution 182.0 parts by mass (manufactured by Kyoyo Chemical Co., Ltd., plus coat Z592 solid content 25%)
119.8 parts by mass of an aqueous polyurethane resin dispersion (Superflex 150HS, solid content 38%, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Cross-linking agent (epoxy compound) 10.0 parts by mass (Nagase ChemteX Corp. Denacol EX-521 solid content 100%)
Surfactant A 29.7 parts by mass (manufactured by Sanyo Chemical Industries, Ltd., 1% aqueous solution of NAROACTY CL-95)
Surfactant B 12.3 parts by mass (1% aqueous solution of Rapisol B-90 manufactured by NOF Corporation)
1.8 parts by weight of slip agent (Canaba wax dispersion cellosol 524, solid content 30%, manufactured by Chukyo Yushi Co., Ltd.)
0.7 parts by mass of particles (manufactured by Soken Chemical Co., Ltd., crosslinked PMMA particles MR-2G, aqueous dispersion having an average particle diameter of 1 μm, solid content of 15%)
Preservative 0.7 parts by mass (manufactured by Daito Chemical Co., Ltd., 1,2-benzothiazolin-3-one, solid content 3.5% methanol solvent)
Distilled water α part by mass (α; the amount was adjusted so that the whole coating solution Q was 1000 parts by mass)

(Evaluation)
The printed materials of Examples 1 to 15 and Comparative Examples 1 to 3 were evaluated as follows.

[Evaluation of ink adhesion immediately after image formation]
On the printed material immediately after printing the color image, 11 scratches were formed in each direction with a single-blade razor to form 100 squares, and then an adhesive tape (600 manufactured by 3M) was attached. Then, after the tape was rubbed with an eraser and completely adhered, it was peeled off in the direction of 90 degrees with respect to the horizontal plane, and the strength of the adhesive strength with the ink was determined from the following A to E by obtaining the number of peeled squares. Evaluation was made as follows in five stages.
A: When there is no peeling B: When the number of peeled squares is 1 or more and less than 5 C: When the number of peeled squares is 5 or more and less than 15 D: When the number of peeled squares is 15 or more and less than 30 E: When the number of peeled cells is 30 or more The above A to C are acceptable levels on the product, and D to E are unacceptable levels.

[Evaluation of ink adhesion after thermo treatment]
A thermal treatment was performed in which the printed matter on which the color image was printed was left in an environment of 60 ° C. and 90% relative humidity for 240 hours. Adhesion was evaluated after the thermo treatment. The evaluation criteria of the adhesiveness after the thermo treatment were evaluated as follows in the following five stages A to E.
A: When there is no peeling B: When the number of peeled squares is 1 or more and less than 5 C: When the number of peeled squares is 5 or more and less than 15 D: When the number of peeled squares is 15 or more and less than 30 E: When the number of peeled cells is 30 or more The above A to C are acceptable levels on the product, and D to E are unacceptable levels.

[Thickness of ink receiving layer and intermediate layer]
On the recording sheet before printing a color image, a microtome (Leica RM2255) was used to perform cross-section cutting. By observing the obtained cross section with a scanning electron microscope (S-4700, manufactured by HITACHI), the film thicknesses of the ink receiving layer and the intermediate layer of each sample were measured.

[Measurement of Elastic Modulus and Breaking Elongation (Examples 8 to 15)]
Based on ATSM D882, each evaluation sample having a width of 5 mm and a thickness of 20 μm was prepared under the following sample preparation conditions. The thickness of 20 μm is the thickness of the evaluation sample when measuring the elastic modulus and elongation at break of the intermediate layer.

  The coating solution used to form the intermediate layer is applied onto the support, a film is formed under the same conditions as the conditions for forming the intermediate layer, and the film is removed from the support to evaluate the intermediate layer. Was made. As a support, Therapy HP2 (manufactured by Toray Industries, Inc.) was used. Evaluation was made using Tensilon RTM-50 Orientec Co., Ltd., 5 mm wide, 20 mm distance between chucks, 5 mm / min pulling speed, and room temperature (23 ° C., relative humidity 50%). The degree was determined for each evaluation sample.

In Table 1, the numerical values in the “polyolefin”, “acrylic”, “polyester”, and “crosslinking agent” columns of the intermediate layer are as follows when the mass excluding the additive from the total solid amount constituting the intermediate layer is 100. Indicates the solid mass of the component.
In addition, the values in the columns of “polyester”, “polyurethane”, “acrylic”, “oxazoline”, “carbodiimide”, “melamine”, and “epoxy” in the ink receiving layer are 100 masses excluding additives from the total solid amount constituting the receiving layer When indicating the solid mass of each component.

  From the table, an example in which the ink receiving layer includes at least one resin selected from polyester resins, polyurethane resins, and acrylic resins, and a crosslinking agent of at least one of an oxazoline compound and a carbodiimide compound. Nos. 1 to 15 were found to have excellent ink adhesion immediately after image formation and after thermo treatment. On the other hand, it was found that Comparative Examples 1 to 3 in which no oxazoline-based compound or carbodiimide-based compound was used as a crosslinking agent were inferior in ink adhesion immediately after image formation and after thermo treatment to Examples 1-15.

DESCRIPTION OF SYMBOLS 1 Support body 2 Ink receiving layer 3 Intermediate | middle layer 4 Image layer A Two-dot broken line B

Claims (10)

A support and an ink receiving layer on at least one surface of the support;
The ink-receiving layer, viewed contains at least one or more resins selected from polyester resins, polyurethane resins, and acrylic resins, and at least one cross-linking agent of an oxazoline compound and carbodiimide compound,
The mass ratio of the resin contained in the ink receiving layer is the polyester resin: the polyurethane resin: the acrylic resin = 0.3-0.7: 0.3-0.7: 0-0.2,
Having an intermediate layer between the support and the ink receiving layer;
The intermediate layer has a thickness of 0.3 μm or more;
Ink-jet recording sheet in which the intermediate layer is characterized by containing Mukoto least 20 mass% of the polyolefin resin.   2. The inkjet recording sheet according to claim 1, wherein the crosslinking agent contained in the ink receiving layer is contained in an amount of 3 to 30% by mass with respect to the resin component. The inkjet recording sheet according to claim 1 or 2 , wherein the elastic modulus of the intermediate layer is 500 MPa or less. The intermediate layer includes a crosslinking agent, and the crosslinking agent is at least one selected from an oxazoline compound, a carbodiimide compound, an epoxy compound, an isocyanate compound, and a melamine compound. Item 4. The inkjet recording sheet according to any one of Items 1 to 3 . The inkjet recording sheet according to any one of claims 1 to 4 , wherein the intermediate layer contains an acrylic resin. The thickness of the intermediate layer is an ink jet recording sheet according to any one of claims 1 to 5 is 0.3 to 5 m. Discharging the ink composition onto the inkjet recording sheet according to any one of claims 1 to 6 with an inkjet recording apparatus;
Irradiating the ejected ink composition with radiation to cure the ink composition. The method for producing a printed matter according to claim 7 , wherein the ink composition is a radiation curable ink composition. The method for producing a printed matter according to claim 7 or 8 , wherein the ink composition is a solvent-free radiation curable ink composition. It said ink jet recording apparatus, using wide-format inkjet printers systems, methods for producing printed material according to any one of claims 7-9.

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