JP2005178188A - Inkjet recording material and method for manufacturing recorded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a recording material having a high image density when used as an outdoor signboard, capable of recording a high quality image excellent in color developing properties, preparing a recording material high in workability and being used for an aqueous pigment or a pigment ink, in an inkjet recording method or particularly the method using a solvent ink. <P>SOLUTION: The inkjet recording material serves as a recording medium having on an opaque substrate a porous ink receiving layer constituted mainly of particles (A), a water soluble resin (B), a crosslinking agent (C), a non-water soluble resin (D) and a cationic resin (E), and the blending ratio of A to E satisfies expressions (I) to (IV)(all in mass ratio); (I) A/(B+C+D+E)=1.5/1 to 2.5/1; (II) (B+C+D)/E=4/6 to 8/2; (III) (B+C)/D=2/8 to 9/1; (IV) B/C=2/1 to 10/1. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a recording material suitable for an ink jet recording system. Specifically, regarding a recording material used using an ink jet recording method using a solvent-based pigment ink, it is possible to create a high-quality electric signboard with high contrast when viewed by irradiating light from the back, and The present invention relates to a recording material that can be used with water-based pigment inks.

  In recent years, with the improvement of computer performance and the spread of computers, hard copy technology has been rapidly developed. As a hard copy recording method, a sublimation transfer recording method, an electrophotographic method, an ink jet method and the like are known.

  Inkjet printers are printers that use an ink jet system that ejects ink droplets from a nozzle toward recording paper at high speed. They are easy to color and miniaturize and have low printing noise. Recently, it has been rapidly spreading as a terminal such as a personal computer. Furthermore, because of the improvement in recording quality approaching that of silver halide photography and the ease of enlargement, it is expected to be applied to industrial fields such as large signboards, particularly electric signboards.

  As the ink used in the ink jet system, water-based dye ink, that is, one in which various water-soluble dyes are dissolved in water or a mixed solvent of water and a hydrophilic solvent, and various additives are mixed as necessary is mainstream. It is. This is because the water-based ink is capable of vivid color recording, is easy to adjust the viscosity of the ink, and is excellent in safety.

  However, since the water-based dye ink uses a water-soluble dye, there is a disadvantage that water resistance and weather resistance are inferior.

  In order to make up for the drawbacks of the above aqueous dye inks, aqueous pigment inks, that is, organic pigments and / or inorganic pigments are dispersed in water or a mixed solution of water and a hydrophilic solvent, and various additives are used as necessary. There has been proposed an ink containing. In the case of recording using an aqueous pigment ink, it is possible to obtain complete water resistance if the recording material after recording is sufficiently dried, and it has recently been used rapidly.

  However, since water is used as the main dispersion medium of the pigment ink, the concentration of the pigment cannot be increased, the color developability and the vividness of the color tone are inferior, and the head nozzle is easily clogged. There are disadvantages.

  As a measure for solving these problems, oil-based ink has been proposed. Oil-based inks are inks in which oil-soluble dyes are dissolved or organic pigments and / or inorganic pigments are dispersed in solvents such as paraffins. Compared to water-based dye inks and water-based pigment inks, coloring materials (dyes and pigments) Can be selected from dyes and pigments with excellent weather resistance and water resistance, and can be dissolved or dispersed at high concentration in a solvent, so that high image density can be realized, head clogging is unlikely to occur, sheet There is an advantage that cockling due to water absorption is difficult to occur, the surface tension of the ink can be lowered, and ink absorbability to the ink receiving layer is excellent.

  Therefore, oil-based inks are promising as an alternative to water-based inks in fields that require high-speed recording, high-quality recording, and high weather resistance. However, after recording an image on the ink receiving layer using oil-based ink, the solvent remaining in the recording layer (ink receiving layer) is poorly dried and needs to be dried for a long time, which causes various troubles. There are problems such as.

  In recent years, solvent inks have been proposed for the purpose of solving the problems of water-based inks or oil-based inks. The solvent ink is an ink in which a dye or pigment is dispersed in at least one solvent selected from alcohol, glycol, glycol ether, acetate ester, and ketone. When solvent ink is used, there is an advantage that a colorant having excellent weather resistance and water resistance can be selected in the same way as oil-based ink, and a recording layer (ink-receiving layer) after recording than oil-based ink, which is inferior to water-based ink ) There is an advantage that the solvent remaining in the solvent evaporates quickly.

  In order to satisfy the recording quality with respect to the aqueous dye ink and the aqueous pigment ink, a recording material in which a water-soluble resin and a water-insoluble resin are combined has been proposed (for example, see Patent Document 1). This recording material is a recording material designed for water-based inks and is not optimized for solvent inks, but also has a problem of insufficient water resistance because it does not crosslink polyvinyl alcohol, which is a water-soluble resin. .

In addition, a recording material mainly composed of a water-insoluble resin has been proposed (see, for example, Patent Document 2). This recording material is also a recording material designed for water-based inks and is not optimized for solvent inks. In addition, since the solvent resistance of water-insoluble resins is weak, the film strength is increased by absorbing the solvent ink. There is a problem of weakening.
Japanese Patent Laid-Open No. 10-52971 JP 2001-105717 A

  An object of the present invention is to enable high-quality recording with high image density and excellent color developability when used as an outdoor signboard in an inkjet recording system, particularly an inkjet recording system using a solvent ink. An object of the present invention is to provide a recording material that can produce a good recording material and can be used for water-based dyes and pigment inks.

  The present invention is a porous material mainly composed of particles (A), a water-soluble resin (B), a crosslinking agent (C), a water-insoluble resin (D), and a cationic resin (E) on an opaque substrate. A recording medium having a high quality ink-receiving layer, wherein the mixing ratio of A to E satisfies the following formulas I to IV (all mass ratios).

A / (B + C + D + E) = 1.5 / 1 to 2.5 / 1 (I)
(B + C + D) / E = 4/6 to 8/2 (II)
(B + C) / D = 2/8 to 9/1 (III)
B / C = 2/1 to 10/1 (IV)
In one embodiment, the coating amount of the recording layer on the opaque base material is 20 g / m ² or more and 40 g / m ² or less.

  In one embodiment, the particles (A) contain two kinds having different average particle diameters.

  In one embodiment, the molecular weight of the cationic resin (E) is 100,000 or more and 300,000 or less.

  In one embodiment, the total light transmittance of the said opaque base material is 30 mass% or less.

  In one embodiment, the opaque substrate is a white polyester film stretched at least uniaxially.

  According to the method for producing a recorded matter of the present invention, a solvent ink containing at least one solvent and pigment selected from the group consisting of alcohol, glycol, glycol ether, acetate ester, and ketone is formed on the ink receiving layer of the recording material. And recording by an ink jet method.

  In one embodiment, the solvent comprises dipropylene glycol monomethyl ether.

  The recording material of the present invention is designed especially for an ink jet recording method using a solvent ink, and a recorded matter in which a solvent-based pigment ink is recorded on the recording material by an ink jet recording method is used as an outdoor signboard. In addition, the image density is high, the recording quality is excellent, and the recording material is excellent in workability, and it can be used for water-based dyes and pigment inks.

(Opaque substrate)
In the present invention, the opaque substrate is not particularly limited, but for example, a polyester film, polystyrene film, polypropylene film, nylon, polycarbonate, norbornene, vinylon, acrylic, etc. Opaque resin film mixed with foaming agent, polyester cloth, polyester / cotton mixed cloth, cotton cloth, non-woven fabric, pulp, resin impregnated paper, cast coated paper, resin coated paper, glass and any two or more of these are pasted The combination is mentioned. An opaque polyester film excellent in heat resistance is preferable, and an opaque polyester film having a cavity inside that is excellent in flexibility is more preferable. A preferable opacity is that the total light transmittance measured by JIS K-7105 is 30% by mass or less. When the opacity is inferior, there is a problem that the lining can be seen when pasted on a wall or the like.

  The polyester film is an esterification reaction between an aromatic dicarboxylic acid or an ester thereof such as terephthalic acid, isophthalic acid or naphthalenedicarboxylic acid and a glycol such as ethylene glycol, diethylene glycol, 1,4-butanediol or neopentyl glycol. A polymer chip obtained by performing a transesterification reaction and then a polycondensation reaction is melted, and an unstretched sheet obtained by extruding into a sheet form from a T-die is stretched in at least a uniaxial direction, followed by heat setting treatment and relaxation treatment. It is a film manufactured by performing.

  The film is particularly preferably a biaxially stretched film from the viewpoint of strength. Examples of the stretching method include a tubular stretching method, a simultaneous biaxial stretching method, a sequential biaxial stretching method, and the like, but a sequential biaxial stretching method is preferable in view of flatness, dimensional stability, thickness unevenness, and the like. The sequential biaxially stretched film is, for example, roll-stretched 2.0 to 5.0 times in the longitudinal direction at a glass transition temperature (Tg) to (Tg + 30 ° C.) of polyester, and then the magnification is 1 at 120 to 150 ° C. Tenter stretching (stretching in the width direction) to 2 to 5.0 times. Furthermore, it can manufacture by performing a heat setting process at the temperature of 220 degreeC or more after biaxial stretching, and relaxing 3-8 mass% next in the width direction.

  There is no particular limitation on the method for developing the voids in the polyester film. Preferably, an unstretched sheet obtained by mixing, melting, and extruding polyester incompatible thermoplastic resin is stretched in at least one axial direction. By doing so, it is a method of containing many fine cavities inside.

  Examples of thermoplastic resins that are incompatible with polyester include polystyrene resins, polyolefin resins, polyacrylic resins, polycarbonate resins, polysulfone resins, and cellulose resins. Particularly preferred are polyolefin resins such as polystyrene resin, polymethylpentene, and polypropylene.

  An unstretched sheet in which a polyester and a polyester incompatible thermoplastic resin are mixed is, for example, a method obtained by mixing each resin chip, melt-kneading in an extruder, and then extruding and solidifying, or in advance kneading A method in which both resins are kneaded by a machine is further melt-extruded from an extruder and solidified, or incompatible polyester resin is added to the polyester in the polyester polymerization step, and the chips obtained by stirring and dispersing are melt-extruded. It can also be obtained by a solidifying method. The unstretched sheet obtained by solidification is usually in a non-oriented or weakly oriented state. Further, thermoplastic resins that are incompatible with polyester exist in various forms such as spherical, elliptical, or thread-like dispersion in polyester.

  The amount of the thermoplastic resin incompatible with the polyester mixed with the polyester is preferably 3 to 39% by weight, particularly 6 to 35% by weight based on the total amount of the mixture, although it depends on the amount of the target cavity. preferable. If it is less than 3% by weight, there is a limit to increasing the amount of generated cavities, and the desired flexibility, lightness, and drawability cannot be obtained. On the other hand, if it exceeds 39% by weight, the heat resistance and strength of the polyester film, particularly the waist strength, are markedly impaired.

  The film can contain inorganic particles in order to improve concealment and drawing properties as required. Examples of inorganic particles for this purpose include, but are not limited to, titanium dioxide, silicon dioxide, calcium carbonate, barium sulfate, aluminum oxide, kaolin, and talc.

  A colorant, an ultraviolet absorber, a fluorescent agent, an antistatic agent, a viscosity reducing agent, an antioxidant and the like can be added to the polymer mixture depending on the application.

  The opaque base material used in the present invention may be a single layer film or a composite film having two or more layers in which a surface layer and a center layer are laminated. In the case of a composite film, there is an advantage that the functions of the surface layer and the center layer can be designed independently. The method for producing the composite film is not particularly limited. However, in consideration of productivity, the raw material for the surface layer and the central layer are extruded from separate extruders, led to one die, and after obtaining an unstretched sheet, at least Lamination by the so-called coextrusion method that is oriented in a uniaxial direction is particularly preferable.

As a base material, it is preferable that it is white, and a preferable range is a measured value by JISZ-8730, L *> = 80, -5 <= a * <= 5, -5 <= b * <= 5. When the base material is not white, the recording material after the ink receiving layer is provided is not white due to the influence of the base material, and the quality of the recorded material is lowered.
(Anchor coat layer)
The recording material of the present invention has an opaque base material and an ink receiving layer provided on the base material. In order to improve the adhesion between the base material and the ink receiving layer, the base material and the ink receiving layer are used. An anchor coat layer may be provided between them.

  As the binder resin constituting the anchor coat layer, it is preferable to use at least one kind of polyester resin, polyurethane resin, polyester urethane resin, acrylic resin, melamine resin and the like.

  In the anchor coat layer, various particles may be contained in order to improve the slipperiness by forming irregularities on the surface and to improve the adhesion with the ink receiving layer. Examples of the particles to be contained in the anchor coat layer include silica, kaolinite, talc, calcium carbonate, zeolite, alumina, barium sulfate, carbon black, zinc oxide, titanium oxide, and other inorganic particles, acrylic, nylon, styrene. Organic particles such as polyester, benzoguanamine / formalin condensate, and the like. Furthermore, in order to impart various functions to the anchor coat layer, a crosslinking agent, a surfactant, an antistatic agent, a fluorescent dye, a fluorescent whitening agent, an ultraviolet absorber, and the like may be included.

In addition, as a method of providing an anchor coat layer, using a known method such as a gravure coat method, a kiss coat method, a dip method, a spray coat method, a curtain coat method, an air knife coat method, a blade coat method, a reverse roll coat method, It can be provided by an in-line coating method in which an anchor coat layer is provided in the film production process, or an offline coating method in which an anchor coat layer is provided after film production. Of these methods, the in-line coating method is preferable in terms of cost.
(Ink receiving layer)
In the recording material of the present invention, it is necessary to provide an ink receiving layer having a porous structure directly on an opaque substrate or via an anchor layer.

  The ink receiving layer is mainly composed of particles, a water-soluble resin, a cross-linking agent, a water-insoluble resin, and a cationic resin, and needs to have a porous structure. The method for forming the porous structure is not particularly limited, but a coating solution containing a large amount of particles with respect to a water-soluble resin, a cross-linking agent, a water-insoluble resin, and a cationic resin is prepared, applied on a substrate, and dried. Is preferred. Further, the above-mentioned “the ink receiving layer is mainly composed of particles, water-soluble resin, cross-linking agent, water-insoluble resin, and cationic resin” means that the ink receiving layer is composed of particles, water-soluble resin, cross-linking agent, non-water-soluble resin. It means containing 70% by mass or more, preferably 80% by mass or more of water-soluble resin and cationic resin.

  In the present invention, the porous structure means a structure in which a large number of voids exist inside and communicates from the surface to the inside.

  Particles A in the ink receiving layer are (1) silica, kaolinite, talc, light calcium carbonate, heavy calcium carbonate, zeolite, alumina, barium sulfate, carbon black, zinc oxide, zinc sulfate, zinc carbonate, titanium dioxide, Satin white, aluminum silicate, diatomaceous earth, calcium silicate, aluminum hydroxide, hydrous halloysite, magnesium carbonate, magnesium hydroxide, inorganic particles, (2) acrylic or methacrylic, vinyl chloride, vinyl acetate, nylon, Styrene / acrylic, styrene / butadiene, polystyrene / acrylic, polystyrene / isoprene, polystyrene / isoprene, methyl methacrylate / butyl methacrylate, melamine, polycarbonate, urea, epoxy, urethane , Phenolic, diallyl phthalate, and a resin particles polyester or the like. Among these, particles having pores on the surface excellent in ink absorbability are preferable, and synthetic amorphous silica having a small refractive index difference from the resin is particularly preferable.

  As the synthetic amorphous silica, those having an average particle diameter of 1 to 20 μm and a pore volume of 0.2 to 3.0 ml / g are suitable. Further, although only one type of silica may be used, it is preferable to mix two types of silica having a pore volume of 1.0 ml / g or more, an average particle size of 1 to 10 μm, and an average particle size of 10 to 20 μm. By using particles with a large pore volume, the ink absorption capacity can be increased, and by mixing two kinds, the ink receiving layer becomes bulky, and the ink absorption capacity can be increased even with the same coating amount. . The ratio of the two types of mixing is preferably in the range of 10/90 to 90/10, more preferably 30/70 to 70/30. The synthetic amorphous silica may be surface-modified if necessary. Examples of the surface treatment include chemical treatment using organic silane, organic titanate, etc., and physical treatment for attaching paraffin wax or glycol to the surface.

  A commercially available product can be suitably selected as such silica. Examples include Mizusawa Chemical Mizukasil, Tokuyama Soda Toxeal, Fine Seal, Shionogi Pharmaceutical Carplex, Fuji Silysia Silicia, Grace Devison Cyloid, Silojet, Nippon Silica Nipgel, and the like.

  As the water-soluble resin B used in the present invention, known resins can be used, such as polyester, polyurethane, polyester urethane, polyvinyl alcohol, acrylic, starch, polyvinyl butyral, gelatin, casein, ionomer, gum arabic, carboxymethyl cellulose, Among resins such as polyvinylpyrrolidone, polyacrylamide, and styrene-butadiene rubber, one or more kinds can be used as desired. For ink-jet recording, polyvinyl alcohol is preferable because it has good solvent resistance.

  The crosslinking agent C used in the present invention preferably contains at least one selected from urea, epoxy, melamine, isocyanate and the like. Among these, melamine type is preferable from the viewpoint of operability. Moreover, in order to promote a crosslinking reaction, a catalyst etc. are used suitably as needed.

  The water-insoluble resin D used in the present invention is a resin that does not dissolve in room temperature water and does not absorb 10% by mass or more of room temperature water with respect to the resin solid, more preferably. It is a resin that does not absorb water by 5 mass% or more. As a method for evaluating water absorption, a method of measuring a change in volume when a resin solid is immersed at room temperature for 24 hours can be used. Specifically, a resin layer is applied in a thickness of several tens of μm on a substantially non-water-absorbing support, for example, aluminum foil, glass, etc., dried, and immersed in 18 ° C. ion exchange water for 24 hours. It can be calculated from the thickness change rate of the resin layer ((thickness after immersion / thickness before immersion) × 100).

  As water-insoluble resin, one kind of resin such as acrylic, polypropylene, polyethylene, polyethylene oxide, polyvinyl chloride, polyester, polycarbonate, alkyd, polyurethane, methyl methacrylate, vinyl acetate, ethylene vinyl acetate copolymer, etc. The above can be used as desired. Of these, polyurethane resins and ethylene vinyl acetate copolymers having a low glass transition temperature for forming a flexible film are preferred.

  The cationic resin E can be used without limitation as long as it is cation-modified, such as cation-modified polyvinyl alcohol, cation-modified polyester, cation-modified polyamide, diallylamine polymer, dimethyldiallylammonium chloride polymer, and cation-modified surfactant. However, a resin containing a quaternary ammonium salt is highly effective in improving the printing characteristics of an aqueous pigment ink. Among these, poly (dimethyldiallylammonium chloride), poly (trimethylaminoethyl methacrylate / methyl sulfate), dimethyl Amine ammonium epichlorohydrin polycondensate and dicyandiamide polyalkylene polyamine polycondensate are preferred.

  The molecular weight of the cationic resin is preferably from 100,000 to 300,000. If the molecular weight is too smaller than this range, there is a problem that the water resistance and film strength of the ink receiving layer are lowered. On the other hand, when the molecular weight is too large, the effect of improving the printing characteristics is lost.

  The ink receiving layer may contain a surfactant for the purpose of improving leveling properties during coating and defoaming the coating liquid. The surfactant may be any of cationic, anionic and nonionic, but is preferably a silicon-based or fluorine-based surfactant. These surfactants are preferably contained in the ink receiving layer to such an extent that the ink absorption performance of the ink receiving layer does not extremely decrease.

  Silicone surfactants include dimethyl silicon, amino silane, acrylic silane, vinyl benzyl silane, vinyl benzyl silyl amino silane, glycid silane, mercapto silane, dimethyl silane, polydimethyl siloxane, polyalkoxy siloxane, hydrodiene modified siloxane, vinyl modified siloxane, Vitroxy modified siloxane, amino modified siloxane, carboxyl modified siloxane, halogenated modified siloxane, epoxy modified siloxane, methacryloxy modified siloxane, mercapto modified siloxane, fluorine modified siloxane, alkyl group modified siloxane, phenyl modified siloxane, alkylene oxide modified siloxane, etc. .

  Fluorosurfactants include ethylene tetrafluoride, perfluoroalkyl ammonium salt, perfluoroalkyl sulfonic acid amide, sodium perfluoroalkyl sulfonate, perfluoroalkyl potassium salt, perfluoroalkyl carboxylate, perfluoroalkyl sulfone. Acid salts, perfluoroalkyl ethylene oxide adducts, perfluoroalkyl trimethyl ammonium salts, perfluoroalkyl amino sulfonates, perfluoroalkyl phosphate esters, perfluoroalkyl alkyl compounds, perfluoroalkyl alkyl betaines, perfluoroalkyl halides, etc. Is mentioned.

  In order to impart other functionalities to the ink receiving layer, various additives may be contained within a range that does not impair the ink absorbing ability and other physical properties. Examples of the additive include fluorescent dyes, fluorescent brighteners, plasticizers, ultraviolet absorbers, pigment dispersants, foam suppressors, antifoaming agents, preservatives, and the like.

  In the present invention, the ratio of the added amount of the particles A, the water-soluble resin B, the cross-linking agent C, the water-insoluble resin D, and the cationic resin E is important. The mass ratio of the particles A to the water-soluble resin B, the crosslinking agent C, the water-insoluble resin D, and the cationic resin E satisfies the following formulas (I) to (IV).

A / (B + C + D + E) = 1.5 / 1 to 2.5 / 1 (I)
(B + C + D) / E = 4/6 to 8/2 (II)
(B + C) / D = 2/8 to 9/1 (III)
B / C = 2/1 to 10/1 (IV)
Formula (I) represents a mass ratio of the particles A to the water-soluble resin B, the cross-linking agent C, the water-insoluble resin D, and the cationic resin E. A / (B + C + D + E) = 1.5 / 1 to 2.5 / 1 Preferably, A / (B + C + D + E) = 1.5 / 1 to 2/1. If it is less than 1.5 / 1, voids due to particles are reduced, ink absorbability becomes poor, and blurring increases. If it exceeds 2.5 / 1, since the dot diameter is small, the solid image will not be filled and the print density will be low.

  Formula (II) represents a mass ratio of the water-soluble resin B, the crosslinking agent C, the water-insoluble resin D and the cationic resin E, and is (B + C + D) / E = 4/6 to 8/2, preferably (B + C + D ) / E = 5/5 to 7/3. If it is less than 4/6, the amount of water-soluble cation increases, so the water resistance becomes weak. If it exceeds 8/2, the dot diameter is too large and the print density is low.

  Formula (III) represents a mass ratio of the water-soluble resin B, the crosslinking agent C and the water-insoluble resin D, and is (B + C) / D = 2/8 to 9/1, preferably (B + C) / D = 4. / 6 to 7/3. If it is less than 2/8, the resin with good solvent resistance decreases, so the print density becomes low. If it exceeds 9/1, the film becomes too hard, and the cut property is deteriorated.

  Formula (IV) represents the mass ratio of the water-soluble resin B and the crosslinking agent C, and the ratio of B and C is B / C = 2/1 to 10/1. If it is less than 2/1, the film becomes too hard, so that the cut property is deteriorated. If the ratio exceeds 10/1, the water-soluble resin film is flexible, so the water resistance is lost.

In the recording material of the present invention, the coating amount of the ink receiving layer after drying is not limited, but is preferably 20 g / m ² or more and 40 g / m ² or less. If it is less than 20 g / m ² , the pores due to the particles are reduced, the ink absorption rate is slow, and the bleeding becomes large. If it exceeds 40 g / m ² , the ink absorption capacity increases and the ink sinks into the receiving layer, so that the print density becomes low.

The recording material of the present invention is an ink jet method using a solvent ink in which a dye or a pigment is dissolved or dispersed in at least one solvent selected from alcohol, glycol, glycol ether, acetate ester, and ketone. It is particularly suitable as a recorded matter recorded by
(Solvent ink)
As the solvent used in the solvent ink, various solvents are selected from the viewpoints of compatibility with the characteristics of the head nozzle, safety, and drying properties, and a plurality of solvents are mixed and used as necessary. Examples of such solvents include (1) alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, tridecyl alcohol, cyclohexyl alcohol, 2-methylcyclohexyl alcohol, and (2) ethylene. Glycols such as glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, glycerin, (3) ethylene glycol monomethyl ether, ethylene glycol monoethylene ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether , Diethylene glycol butyl ether, ethylene glycol monomer Ether ether, ethylene glycol monoethyl acetate, ethylene glycol monobutyl acetate, diethylene glycol monomethyl acetate, diethylene glycol monoethyl acetate, diethylene glycol monobutyl acetate, and other glycol ethers, (4) ethyl acetate, isopropylene acetate, n-butyl acetate, etc. Examples include esters, (5) ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone, and diacetone alcohol.

  As dyes used in solvent inks, naphthol dyes, azo dyes, metal complex dyes, cyanine dyes, quinoline dyes, nitro dyes, anthraquinone dyes, quinoimine dyes, indigo dyes, nitroso dyes, benzoquinone dyes, carbonium dyes, naphthoquinone dyes, Examples thereof include oil-soluble dyes such as naphthalimide dyes, phthalocyanine dyes, and perinine dyes.

  Pigments used in solvent inks include aluminum powder, bronze powder, carbon black, titanium oxide, iron oxide, zinc white, alumina white, brown rice, barium sulfate, calcium carbonate, magnesium carbonate, clay, ultramarine, yellow lead, cobalt Inorganic pigments such as blue and bitumen, Fast Yellow G, Fast Yellow 10G, Disazo Yellow AAA, Disazo Yellow AAMX, Disazo Yellow AAOT, Disazo Yellow AAA, Orthonitroaniline Orange, Dinitroaniline Orange, Disazo Orange, Disazo Orange, Disazo Orange PMP, Vulcan Orange, Toluidine Red, Chlorinated Para Red, Naphthol Carmine FB, Naphthol Red M, Brilliant Fast Scar Red, Naphthol Red 23, Pyrazolone Red, Bali Mured 2B, Calcium Red 2B, Strontium Red 2B, Manganese Red 2B, Barium Risor Red, Lake Red C, Brilliant Carmine 6B, Pigment Scarlet 3B Rate, Lake Bordeaux 10B, Anthosine 3B Lake, Anthosine 5B Lake, Rhodamine 6G Lake, Eosin Lake , Naphthol Red FGR, Rhodamine B Lake, Methyl Violet Lake, Quinacridone Red K, Dioxazine Violet, Victoria Pure Blue BO Lake, Basic Blue 5B Lake, Basic Blue 6G Lake, Phthalocyan Blue, Fast Sky Blue, Alkaline Blue G Toner, Alkaline Blue R Toner, Peacock Blue Lake, Reflex Blue 2G, Reflex Blue R, Brilli Cement green lake, diamond green thioflavin lake, phthalocyanine green G, green gold, phthalocyanine green Y, aniline black, carbon black, daylight fluorescent pigment, pearl pigment, and the like.

  Solvent inks include, for example, polyacrylic acid esters, linseed oil modified alkyd resins, polystyrene, rosin resins, tempenphenol resins, alkylphenol modified xylene resins, and the like for the purpose of increasing storage stability, scratch resistance, etc. Plasticizer, wax, dryer, dispersant, thickener, gelling agent, thixotropy imparting agent, antifoaming agent, antifoaming agent, anti-settling agent, anti-skinning agent, anti-drying agent, antioxidant Additives such as an agent, a smoothing agent, an antifungal agent, an ultraviolet absorber, a matting agent, an antistatic agent, a stabilizer, a flame retardant, a surface tension adjusting agent, a surfactant, and a viscosity adjusting agent can also be contained.

  In the present invention, the water-based dye ink is an ink in which a dye is mainly dissolved as a coloring material in water or a mixed liquid of water and a hydrophilic solvent, and various additives are contained as necessary.

  In the present invention, the water-based pigment ink is an ink in which pigments are mainly dispersed as a coloring material in water or a mixed liquid of water and a hydrophilic solvent, and various additives are contained as necessary.

Next, although an example and a comparative example of the present invention are given and explained, the present invention is not limited to these examples. First, the measurement / evaluation method used in the present invention is as follows.
Recording characteristics (1) Inkjet printer (manufactured by Roland DG, SC-500) and its genuine solvent ink (SL-BK, SL-CY, SL-MG, SL-YE, SL-LC, SL-LM) Was used, and photographic images and illustrations were recorded under the conditions of Super and visually observed. In any of the above solvent inks, the main solvent is dipropylene glycol monomethyl ether and contains a pigment as a coloring material.

○: Vivid recording with excellent color development Δ: Recording with a level slightly inferior in color development but no problem ×: Recording with dullness or poor color development (2) Inkjet printer ( Using Epson, PM-7000C) and its genuine water-based dye inks (IC1BK07, IC1C07, IC1M07, IC1Y07, IC1LC07, IC1LM07), photographic images and illustrations were recorded and observed under fine conditions.

◯: Vivid and excellent color developability △: Record with a slightly inferior color developability but no problem x: Record with dullness or poor color developability (3) Inkjet printer ( Superland conditions using Roland DG, FJ-500) and genuine water-based pigment inks (EPG-BK, EPG-CY, EPG-MG, EPG-YE, EPG-LC, EPG-LM) Then, photographic images and illustrations were recorded and observed visually.

：: Vivid and very excellent color developability ○: Vivid and excellent color developability △: Slightly inferior color development but no problem level ×: Dull record Or (4) Water resistance. Print blue solid (cyan, yellow mixed color) with the printer (SC-500) in (1) above, leave it for 24 hours, and then point the print section under running water. The friction was added.
○: Image is not lost even with strong friction Δ: Image is lost with strong friction ×: Image is easily lost (5) Cutability Blue solid (mixed cyan and yellow) with the printer (SC-500) in (1) above. After printing and leaving for 24 hours, the recorded matter was cut with a cutter.
○: Powder does not fall off from the cut surface of the receiving layer.
Δ: Powder is slightly removed from the cut surface of the receiving layer.
X: Powder falls from the cut surface of the receiving layer.
(6) Opacity of substrate The recorded matter prepared by the printer (SC-500) of (1) above was attached to a wall and visually observed whether the lining was visible.
○: The lining is not visible Δ: The lining is slightly visible ×: The lining is visible (Example 1)
The following coating liquid was prepared at the ratio shown in Table 1, and 100 g / m ² (30 g / m ^{2 by} weight after drying) on a void-containing white polyester film (K2323-100 μm manufactured by Toyobo Co., Ltd.) having a total light transmittance of 8%. And dried by spraying hot air of 10 m / second at 120 ° C. for 60 seconds to form an ink receiving layer to obtain a recording material. The following silica has a pore volume of 1.2 ml / g and an average particle size of 9.0 μm (silica I) and 12.0 μm (silica II). The following cationic resin has a molecular weight of about 140,000.

51.57% by mass of water
Silica I 9.88 mass%
(Grace Devison 74 * 4500)
Silica II 9.88 mass%
(P612 made by Grace Devison)
Water-soluble resin 14.82% by mass
(RS-117 made by Kuraray, solid content concentration 10% by mass)
Melamine resin 0.62% by mass
(Sumitex M-3 manufactured by Sumitomo Chemical Co., Ltd., solid content concentration 80% by mass)
Catalyst 0.02% by mass
(Sumitex ACX manufactured by Sumitomo Chemical)
Ethylene vinyl acetate copolymer 0.54 mass%
(Sumitomo Chemical Industries Sumikaflex 410, solid content concentration 55% by mass)
Cationic resin 12.67% by mass
(Senka CP103, solid concentration 39% by mass)
(Example 2)
In Example 1, a recording material was obtained in the same manner as in Example 1 except that the coating amount after drying of the ink receiving layer was 15 g / m ² .
(Example 3)
In Example 1, a recording material was obtained in the same manner as in Example 1 except that the coating amount after drying of the ink receiving layer was 50 g / m ² .
Example 4
A recording material was obtained in the same manner as in Example 1 except that the coating liquid was as follows.

51.57% by mass of water
Silica 19.76% by mass
(Grace Devison 74 * 4500)
Water-soluble resin 14.82% by mass
(RS-117 made by Kuraray, solid content concentration 10% by mass)
Melamine resin 0.62% by mass
(Sumitex M-3 manufactured by Sumitomo Chemical Co., Ltd., solid content concentration 80% by mass)
Catalyst 0.02% by mass
(Sumitex ACX manufactured by Sumitomo Chemical)
Ethylene vinyl acetate copolymer 0.54 mass%
(Sumitomo Chemical Industries Sumikaflex 410, solid content concentration 55% by mass)
Cationic resin 12.67% by mass
(Senka CP103, solid concentration 39% by mass)
(Example 5)
A recording material was obtained in the same manner as in Example 1 except that the coating liquid was as follows.

51.57% by mass of water
Silica 19.76% by mass
(P612 made by Grace Devison)
Water-soluble resin 14.82% by mass
(RS-117 made by Kuraray, solid content concentration 10% by mass)
Melamine resin 0.62% by mass
(Sumitex M-3 manufactured by Sumitomo Chemical Co., Ltd., solid content concentration 80% by mass)
Catalyst 0.02% by mass
(Sumitex ACX manufactured by Sumitomo Chemical)
Ethylene vinyl acetate copolymer 0.54 mass%
(Sumitomo Chemical Industries Sumikaflex 410, solid content concentration 55% by mass)
Cationic resin 12.67% by mass
(Senka CP103, solid concentration 39% by mass)
(Example 6)
A recording material was obtained in the same manner as in Example 1 except that the cationic resin having a molecular weight of about 70,000 was changed to the following.

51.57% by mass of water
Silica 9.88 mass%
(Grace Devison 74 * 4500)
Silica 9.88 mass%
(P612 made by Grace Devison)
Water-soluble resin 19.76% by mass
(RS-117 made by Kuraray, solid content concentration 10% by mass)
Melamine resin 0.62% by mass
(Sumitex M-3 manufactured by Sumitomo Chemical Co., Ltd., solid content concentration 80% by mass)
Catalyst 0.02% by mass
(Sumitex ACX manufactured by Sumitomo Chemical)
Ethylene vinyl acetate copolymer 0.54 mass%
(Sumitomo Chemical Industries Sumikaflex 410, solid content concentration 55% by mass)
Cationic resin 12.67% by mass
(Senka CP102, solid concentration 39% by mass)
(Example 7)
A recording material was obtained in the same manner as in Example 1 except that the cationic resin having a molecular weight of about 400,000 was changed to the following.

Water 49.70% by mass
Silica 9.88 mass%
(Grace Devison 74 * 4500)
Silica 9.88 mass%
(P612 made by Grace Devison)
Water-soluble resin 14.82% by mass
(RS-117 made by Kuraray, solid content concentration 10% by mass)
Melamine resin 0.62% by mass
(Sumitomo Chemical Industries Smitex M-3, solid content concentration 80 mass%)
Catalyst 0.02% by mass
(Sumitex ACX manufactured by Sumitomo Chemical)
Ethylene vinyl acetate copolymer 0.54 mass%
(Sumitomo Chemical Industries Sumikaflex 410, solid content concentration 55% by mass)
Cationic resin 14.53 mass%
(Senka CP105, solid concentration 34% by mass)
(Example 8)
A recording material was obtained in the same manner as in Example 1 except that the base material was a transparent polyester film (A8300-100 μm, manufactured by Toyobo Co., Ltd.) having a total light transmittance of 91% by mass.

51.57% by mass of water
Silica 9.88 mass%
(Grace Devison 74 * 4500)
Silica 9.88 mass%
(P612 made by Grace Devison)
Water-soluble resin 14.82% by mass
(RS-117 made by Kuraray, solid content concentration 10% by mass)
Melamine resin 0.62% by mass
(Sumitex M-3 manufactured by Sumitomo Chemical Co., Ltd., solid content concentration 80% by mass)
Catalyst 0.02% by mass
(Sumitex ACX manufactured by Sumitomo Chemical)
Ethylene vinyl acetate copolymer 0.54 mass%
(Sumitomo Chemical Industries Sumikaflex 410, solid content concentration 55% by mass)
Cationic resin 12.67% by mass
(Senka CP103, solid concentration 39% by mass)
(Comparative Examples 1-8)
A recording material was obtained in the same manner as in Example 1, except that the composition ratio of the ink receiving layer was as shown in Table 1. The characteristics of the films obtained in Examples 1 to 8 and Comparative Examples 1 to 8 are shown in Tables 1 and 2.

（作用）

(Function)

  For the recording material of Comparative Example 1, only Formula I is outside the scope of the present invention. The voids due to the particles are reduced, ink absorbability becomes poor, and bleeding is increased.

  The recording material of Comparative Example 2 is outside the scope of the present invention only for formula (I). The voids due to the particles increase and the ink absorbency becomes too good, so that the solid is not filled and the print density is low. Moreover, since the space | gap increased, film | membrane intensity | strength becomes weak and water resistance is weak.

  In the recording material of Comparative Example 3, only the formula (II) is out of the scope of the present invention. When the cation amount is small, the dot diameter does not become small, so the color density is low.

  In the recording material of Comparative Example 4, only the formula (II) is outside the scope of the present invention. Since the amount of water-soluble cation increases, the water resistance is weak.

  In the recording material of Comparative Example 5, only the formula (III) is out of the scope of the present invention. Since water-insoluble resins with weak film strength increase, water resistance is weak.

  In the recording material of Comparative Example 6, only the formula (III) is out of the scope of the present invention. Since the amount of the cross-linked polyvinyl alcohol increases, the film strength becomes too strong and the cut property is deteriorated.

  The recording material of Comparative Example 7 is outside the scope of the present invention only for formula (IV). Since there is much quantity of a crosslinking agent, film | membrane intensity | strength becomes strong and cut property worsens.

In the recording material of Comparative Example 8, only the formula (IV) is out of the scope of the present invention. Since there is little quantity of a crosslinking agent, film | membrane intensity | strength becomes weak and water resistance is weak.

Claims (8)

Porous ink reception mainly composed of particles (A), water-soluble resin (B), cross-linking agent (C), water-insoluble resin (D), and cationic resin (E) on an opaque substrate A recording medium having a layer, wherein the mixing ratio of A to E satisfies the following formulas I to V (all mass ratios).
A / (B + C + D + E) = 1.5 / 1 to 2.5 / 1 (I)
(B + C + D) / E = 4/6 to 8/2 (II)
(B + C) / D = 2/8 to 9/1 (III)
B / C = 2/1 to 10/1 (V) ^2. The ink jet recording material according to claim 1, wherein the coating amount of the recording layer on the opaque base material is 20 g / m ² or more and 40 g / m ² or less. The inkjet recording material according to claim 1 or 2, wherein the particles (A) contain two types having different average particle diameters. The inkjet recording material according to claim 1, wherein the cationic resin (E) has a molecular weight of 100,000 or more and 300,000 or less. The inkjet recording material according to claim 1, wherein the opaque base material has a total light transmittance of 30% by mass or less. 6. The ink jet recording material according to claim 1, wherein the opaque base material is a white polyester film stretched at least uniaxially. A solvent ink containing at least one solvent and pigment selected from the group consisting of alcohol, glycol, glycol ether, acetate ester, and ketone is formed on the ink receiving layer of the recording material according to claim 1. A method for producing a recorded matter, characterized by using an ink jet recording method. The method for producing a recorded matter according to claim 7, wherein the solvent contains dipropylene glycol monomethyl ether.