JPH09183266A - Manufacture of ink jet recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink jet recording material which is jointly equipped with excellent gloss, ink absorbing properties, and water-resisting properties. SOLUTION: The recording material is so constituted that a water resisting surface resin coated layer 5 so treated as to be made smooth, and an ink recording layer 1 are laminated on a sheet-like substrate 8. The water resisting surface resin coated layer is preferably constituted by curing a polyolefin resin or unsaturated organic compound containing layer by radiation. The surface is so treated as to be made smooth, and the ink recording layer is composed of fine pigment of colloidal silica or the like, and water soluble resin of polyvinylalcohol or the like. The ink recording layer wherein a film is formed by coating on a forming surface is provided on the water resisting surface resin coated layer via an intermediate layer 4.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an inkjet recording material, and more particularly to an inkjet recording material having excellent gloss, image clarity, ink absorbency and water resistance.

[0002]

2. Description of the Related Art Ink jet recording is a method in which small droplets of ink are ejected from nozzles by various methods to cause ink droplets to adhere to and be absorbed by a recording medium for recording. This method is characterized by low noise, high-speed recording, and color compatibility. In recent years, due to the high performance of personal computers and the spread of multimedia, there is a growing demand for printing out documents including color and color images at the office or at home, and the inkjet recording system is the most suitable recording system for such purposes. It is considered, and there is a demand for an inkjet recording material that is compatible with this system and that is suitable for color print output. Conventional inkjet recording paper is called non-coated type, an inkjet recording material coated with a small amount of chemicals on the surface of pulp paper for the purpose of promoting absorption and fixing of ink, or an average particle size called coated type. An ink jet recording paper in which a coating material prepared by mixing a water-soluble resin such as polyvinyl alcohol, polyvinylpyrrolidone, or gelatin with an absorptive pigment such as silica or calcium carbonate having a particle size of several μm to a dozen μm is applied to the surface of pulp paper Was commonly used.

However, since these ink jet recording materials use pulp paper as a sheet-shaped substrate, it is difficult to eliminate minute irregularities due to pulp fibers or unevenness of the surface generated in the papermaking process. It was In addition, the coating type inkjet recording material has a problem that since the water content of the coating material permeates the paper during coating of the coating material, unevenness of contraction or swelling occurs on the base material, and the glossiness decreases. Even if a finishing treatment such as a treatment is applied, it is difficult to completely repair the shrinkage unevenness and lumps that have once occurred. Therefore, when a color image is printed out by such an inkjet recording material, there is a problem that glossiness is insufficient, sharpness is poor, or image sharpness is insufficient. -When printing a color image such as an image distributed on a medium such as a ROM or created with graphic software, the gloss and image clarity of the resulting inkjet recording material are not satisfactory, and market demands are met. I could not be satisfied.

JP-A-7-25133 discloses that a sheet-shaped support uses a resin-coated paper or polyester film having a center line average roughness of less than 0.4 μm, and an ink receiving layer having a spherical shape with a particle size of 5 to 15 μm. Disclosed is an inkjet recording material containing a fine particle polymer and having a coating amount of 5 to 30 mg / m ² . Alternatively, Japanese Patent Publication 3-253
No. 52 discloses a polyvinyl alcohol having a saponification degree of 50 to 90 mol% and a polyvinyl alcohol on a sheet such as cast coated paper having a surface gloss of 80% or more or a plastic sheet having a Hunter whiteness of 80% or more. Disclosed is an inkjet recording material having high gloss, which is characterized in that a film containing a crosslinking agent of 5 to 50% by weight of alcohol is formed. When a plastic sheet is used as a sheet-shaped substrate, the gloss can be increased relatively easily as compared with the case where pulp paper is used, but a plastic sheet having a specific whiteness does not necessarily provide high gloss and resolution. It was

Generally, when a water-soluble resin such as polyvinyl alcohol is applied as an ink recording layer to a sheet-like substrate such as a plastic sheet, the paper substrate is used for glossiness and image clarity. It's easier to get than in the case,
Since the substrate does not have absorptivity, the ink absorptivity tends to be inferior, the ink absorptivity is slow, and it was necessary to provide a fairly thick resin layer in order to obtain a sufficient absorptivity. Moreover,
A water-soluble resin such as polyvinyl alcohol absorbs due to swelling / expansion of itself when absorbing ink, so that the resin is deformed in the printed portion, so that the gloss is lost and the printed gloss of the printed portion is reduced. Alternatively, there is a problem in that the water resistance is poor, and when the ink recording layer gets wet with water, the ink recording layer elutes or the ink oozes out.

In Japanese Patent Laid-Open No. 7-137431,
A non-absorbent material having a Beck smoothness of 1000 seconds or more is used as a sheet-like support, and the ink receiving layer contains cationic inorganic fine particles having a particle size of less than 0.1 μm, a saponification degree of 85 to 95 mol% and a polymerization degree of 40.
Although an inkjet recording paper using PVA of 00 or more is disclosed, even if the polyolefin resin-coated paper exemplified in the specification is used, the water resistance of the ink recording layer is not satisfactory. In Japanese Patent Laid-Open No. 1-237187, at least a transparent layer, an ink holding layer and an ink transport layer are provided, the ink transport layer has a certain amount of ink holding property, and the ink of a certain amount or more is transported by the ink. A recording material that passes through the layers and is retained by the ink retaining layer is disclosed. Further, JP-A-1-237188 has at least a transparent layer and an ink transport layer, the ink transport layer has a certain amount of ink retention, and the ink of a certain amount or more passes through the ink transport layer. Then, an ink jet recording system using a recording material reaching the interface between the ink transport layer and the transparent layer is disclosed. However, in these methods, since the ink holding layer is mainly composed of a water-soluble resin, it is difficult to achieve both ink absorbency and water resistance. The ink recording layer of the coat type inkjet recording body is
In addition to silica as a pigment, alumina, pseudo-boehmite, calcium carbonate, kaolin and other pigments, as a water-soluble resin,
It has an ink recording layer containing starch, polyvinyl alcohol, a cellulose derivative and the like. Although these ink recording layers are excellent in ink absorbency and water resistance, there is a problem that they are generally lacking in smoothness and gloss.

Japanese Unexamined Patent Publication (Kokai) No. 2-274587 discloses a recording paper in which at least one recording layer having a running property is provided on a support, and the outermost layer of the recording layer is mainly composed of at least synthetic silica and colloidal silica. And a water-soluble binder, and is treated with an aqueous solution containing a cationic polyelectrolyte, and pressed and dried on a mirror surface which is heat-treated while the outermost layer is in a wet state. Is disclosed. However, in order to maintain ink absorbability, it is essential to contain synthetic silica having relatively large particles, but synthetic silica generally has a large particle size, and it has been difficult to achieve both smoothness and glossiness. JP-A-3-215080 discloses that a glass transition point of at least one surface of a plastic film is-
Disclosed is a printing film comprising an ink fixing layer containing a colloidal silica composite emulsion in the range of 30 to 20 ° C. as a main component. JP-A-7-8922
In JP-A-0,096, a coating containing a polymer having a glass transition point of 40 ° C. or higher obtained by polymerizing a monomer having an ethylenic unsaturated bond is provided on a base paper provided with an undercoat coating layer containing a pigment and an adhesive. A cast coated paper for inkjet recording, which is formed by applying a liquid to form a coating layer for casting, and while the coating layer for casting is in a wet state, is brought into pressure contact with a heated mirror surface drum and finished by drying. A manufacturing method is disclosed.

In JP-A-7-101142, in an ink jet recording sheet having an ink receiving layer provided on a support, at least one or more ink receiving layers are provided on the support, and a colloidal having a mean particle size of 300 nm or less as a main component. A glossy layer consisting of particles is laminated in sequence
75% specular gloss specified by Z8741 is 25%
An inkjet recording sheet characterized by the above is disclosed.

Alternatively, in JP-A-7-117335, in a coat type ink jet recording sheet, at least one or more ink receiving layers are laminated on a support, and a gloss developing layer is sequentially laminated on the ink receiving layer to obtain the gloss. A coating which is made into a mirror gloss finish by being brought into pressure contact with a heated mirror roll while the development layer is in a wet state, and the gloss development layer is mainly composed of colloidal particles having an average particle diameter of 300 nm or less. Disclosed is an inkjet recording sheet comprising a composition. However, colloidal silica or a colloidal silica composite is often used as the main component in these gloss developing layers, but the gloss developing layer that is generally used is provided for the purpose of imparting gloss rather than ink absorbability. In addition, the coating amount is small,
Gloss is developed by a cast treatment (with the gloss developing layer in a wet state, pressure-bonded to a heated mirror roll to give a mirror finish). In addition, since the lower layer has ink absorbability, a pigment having a large particle size, which is relatively easy to obtain voids, is used inside the ink recording layer, so that there is a problem that high-definition recording cannot be obtained. It was That is, in the ink jet recording material having such a structure, when printing, the ink ejected from the nozzle first adheres to the surface of the gloss developing layer, instantaneously moves to the ink receiving layer, and is absorbed and fixed in the ink. Since the voids in the recording layer are large and non-uniform,
The obtained ink dots are large, and their contours are jagged and uneven. Therefore, there is a drawback that the image is considerably lacking in sharpness.

In Japanese Patent Laid-Open No. 62-111782, two different upper and lower porous particle layers are provided on the paper surface, and the degree of polymerization of the pore diameter of the particles forming these porous particle layers is expressed as the pore volume. Is 30% or less, and the average pore size is smaller in the upper layer than in the lower layer. However, in this method, since the porous particles forming the lower layer use a pigment having a relatively large average pore size of 0.05 to 2 μm, when printing with a recent high-definition inkjet printer (for example, printing with 720 dpi × 720 dpi). In a printer that has a head), the dots are dense and dense, so when the dots become large,
Multiple dots are joined together and a delicate image cannot be obtained. Further, since the particles of the ink recording layer are large and have no transparency, it is impossible to obtain a high print density. As an attempt to apply the curing technique by ionizing radiation to an ink jet recording sheet, for example, JP-A-62-22159 is used.
Japanese Unexamined Patent Publication (Kokai) 1 discloses a sheet provided with a transparent ultraviolet-cured cationic acrylic copolymer layer and an anionic acrylic copolymer layer. However, the surface smoothness, glossiness and resolution could not be improved even by simply using the ultraviolet curing method.

[0011]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above problems and provide an ink jet recording material excellent in glossiness, image clarity, ink absorption and water resistance.

The present invention includes the following aspects. [1] An inkjet recording body having a single-layer or multi-layered water-resistant surface resin coating layer and an ink recording layer on a support, wherein the water-resistant surface resin coating layer is a laminated layer of a polyolefin resin composition, or A resin composition containing a saturated organic compound, the layer including at least one layer cured by irradiation with radiation, and at least the surface of the laminate layer or the layer cured by radiation is subjected to a smoothing treatment by a molding surface. A method for manufacturing an inkjet recording material.

[2] The smoothing treatment of the water-resistant surface resin coating layer is carried out by bringing a laminate layer of the polyolefin resin composition into contact with a mirror-finished cooling roll, or by applying a radiation curable layer to a smooth molding surface. The method for producing an ink jet recording material according to [1], which comprises irradiating and curing the composition while being in contact with the ink.

[3] The ink recording layer is formed by coating on the molding surface, and is transferred onto the water-resistant surface resin coating layer via an intermediate layer having adhesiveness or adhesiveness, The method for producing an inkjet recording material according to [1] or [2], which is provided by peeling off the molding surface.

[4] The method for producing an ink jet recording material according to the above item, wherein the water resistant surface resin coating layer has a multilayer structure of two or more layers. . [5] The method for producing an inkjet recording material according to [4], wherein at least one of the multi-layered structures constituting the water resistant surface resin coating layer contains a polyolefin resin. [6] The method for producing an inkjet recording material according to [4], wherein at least one of the multilayer constitutions constituting the water-resistant surface resin coating layer is a radiation-cured unsaturated organic compound-containing layer. .

[7] The water resistant surface resin coating layer containing an unsaturated organic compound which is cured by irradiation with radiation has a multilayer structure, and the outer layer, that is, the layer on the side where the ink recording layer is provided, is not formed on the molding surface. A resin composition containing a saturated organic compound is applied and cured by irradiation with radiation, and the resin composition containing an unsaturated organic compound that subsequently forms an inner layer is applied to the above-mentioned cured coating film or sheet-like substrate. The method for producing an inkjet recording material according to the above item, wherein after coating, the layers are overlapped, and radiation is irradiated again to cure and integrate the coating film. [8] The method for producing an inkjet recording material according to the above items, wherein the water-resistant surface resin coating layer containing a polyolefin has a multilayer structure, and the multilayer structure is formed by a coextrusion melt laminating method.

[9] The water-resistant surface resin coating layer has a multilayer structure, and the outer layer, that is, the layer on the side where the ink recording layer is provided, cures a resin composition containing an unsaturated organic compound by irradiation with radiation, The method for producing an inkjet recording body according to the above items, wherein the inner layer has a polyolefin resin coating layer. [10] The water-resistant resin coating layer has a multi-layered structure consisting of three layers, and the outer layer, that is, the layer on the side where the ink recording layer is provided, comprises the first composition containing an unsaturated organic compound on the molding surface. It is coated and irradiated with radiation to cure it, and the support is coated with a composition containing a polyolefin resin by the melt lamination method, and an unsaturated organic compound that is cured by irradiation with radiation is contained on the composition. The second composition is coated or coated on the coating layer made of the first composition which is cured on the above-mentioned molding surface, and these are overlaid and then cured by radiation to be integrated. The method for producing an inkjet recording material according to the above items.

[11] The method for producing an ink jet recording material according to the above items, wherein the cooling roll used for the melt lamination is mirror-finished. [12] The method for producing an inkjet recording material according to the above item, wherein the cooling roll used for the melt lamination has extremely fine irregularities and provides a substantially smooth surface after the ink recording layer is provided.

[13] The method for producing an ink jet recording material according to the above item, wherein the radiation is an electron beam, the accelerating voltage is 100 to 300 KV, and the absorbed dose of the unsaturated organic compound-containing layer is 0.5 to 15 Mrad. [14] The method for producing an inkjet recording material according to the above items, wherein the water-resistant surface resin coating layer contains a white pigment. [15] The method for producing an inkjet recording material according to the above items, wherein the ink recording layer has a multilayer structure of an ink receiving layer and an ink absorbing layer.

[16] The method for producing an ink jet recording material according to the above items, wherein the ink recording layer contains a fine pigment and a water-soluble resin. [17] The fine pigment is colloidal silica [16]
A method for producing the inkjet recording material described. [18] The white pigment is a titanium dioxide pigment [14]
A method for producing the inkjet recording material described.

[19] The method for producing an ink jet recording material according to the above items, wherein the ink absorbing layer contains silica and / or alumina and a water-soluble resin. [20] The method for producing an inkjet recording material according to the above items, wherein the intermediate layer is one selected from a thermoplastic resin, an adhesive, and a pressure-sensitive adhesive. [21] The method for producing an ink jet recording material according to the above items, wherein the molding surface on which the ink recording layer is coated is a film having a high smooth surface, a laminated paper, a glassine paper, or an inorganic glass surface. .

The ink jet recording material of the present invention is provided with a water resistant surface resin coating layer which is smoothed by a molding surface on the surface of the sheet-shaped substrate on which the ink recording layer is provided, and further a fine pigment and an adhesive. An ink recording layer containing is provided. Support (also called sheet-like substrate)
Examples of the material include paper, synthetic paper, plastic sheet, cloth, non-woven fabric, metal sheet and the like, but paper is preferable. The water-resistant surface resin coating layer may have a single layer or a multilayer structure of two or more layers, and the material is a polyolefin resin or an unsaturated organic compound cured by irradiation with radiation. It is also possible to add a white pigment. When it is a polyolefin resin, it can be obtained by applying it by a melt extrusion laminating method and cooling and solidifying the surface with a cooling roll having a smooth molding surface, that is, a mirror surface. Alternatively, when the resin composition composed of an unsaturated organic compound is cured by irradiation with radiation,
When irradiating with radiation, one surface is in contact with a smooth molding surface to irradiate with radiation to obtain a smooth surface. By such smoothing treatment, the glossiness and smoothness of the finally obtained ink jet recording material are extremely excellent, and a beautiful photograph-like image can be obtained.

A more preferable embodiment of the water-resistant surface resin coating layer is that a polyethylene resin composition containing titanium dioxide is applied to a support (sheet-like substrate) such as paper by a melt extrusion laminating method, and a plated mirror surface is applied. After cooling and solidifying with a cooling roll having a smooth surface to form a smooth surface, a resin composition in which titanium dioxide is mixed and dispersed in an unsaturated organic compound that is cured by radiation irradiation is molded separately into a plastic film or a metal plate. After coating on the surface and irradiating it with an electron beam to cure it, the cured coating film is further coated with a resin composition containing an unsaturated organic compound and titanium dioxide. It also has a function as an intermediate layer), and this coating layer is superposed on the polyethylene coating film described above, and the coating film is cured again by irradiating it with an electron beam. Te, the support (the sheet substrate) / (
Polyethylene and titanium dioxide) / (Unsaturated organic compound and titanium dioxide) / (Unsaturated organic compound and titanium dioxide)
To form a multilayer structure.

The intermediate layer has tackiness or adhesiveness and fixes the ink recording layer to the water resistant surface resin coating layer.
Adhesives, pressure sensitive adhesives, pressure sensitive adhesives, etc. are appropriately selected and configured. The ink recording layer may be composed of a multilayer containing a fine pigment and an adhesive (preferably a water-soluble resin), that is, an ink receiving layer and an ink absorbing layer. The ink receiving layer is a layer for fixing the dye component of the inkjet ink, and has a function of fixing and holding the dye and a function of transparency and gloss. The ink absorbing layer mainly has a function of absorbing the ink solvent that makes up most of the composition of the inkjet ink. Further, when the ink recording layer is applied to the molding surface to form a coating film, and then adhesively transferred to the water-resistant surface resin coating layer via the adhesive or adhesive intermediate layer, excellent gloss can be obtained.

Colloidal silica is a preferable example of the fine pigment, and water-soluble resin is preferable as an adhesive, and polyvinyl alcohol is an example.
A preferable form of the ink recording layer is that a coating prepared from colloidal silica having an average particle diameter of 20 to 200 nm and polyvinyl alcohol is applied on a forming surface to form a film on a polyester film, and then the above-mentioned colloidal silica is used as an average on the upper surface. After coating a coating material prepared from colloidal silica and polyvinyl alcohol having a large particle size to form a two-layer ink recording layer, a coating material prepared from colloidal silica, fine pigment (silica) and polyvinyl alcohol is further prepared. It is applied as an ink absorbing layer to form a three-layer ink recording layer. The ink recording layer is
An adhesive such as a polyester adhesive is applied to the front side surface of the sheet-like support provided with the water-resistant surface resin coating layer, and is pressed against the ink recording layer on the molding surface such as a polyester film. After adhering the ink recording layer and the surface resin coating layer provided on the support, the molding surface is peeled off from the ink recording layer to obtain an inkjet recording body.

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION As the paper support used in the present invention, pulp paper made of wood pulp such as hardwood pulp, softwood pulp, and hardwood mixed softwood pulp is used. Further, it may be a pulp paper made of a commonly used bleached pulp such as kraft pulp, sulfite pulp and soda pulp. If necessary, synthetic pulp and synthetic fibers can be added appropriately. The pulp paper used as the support in the present invention includes various usual additives such as dry paper strengthening agents (cationized starch, cationized polyacrylamide, anionic polyacrylamide, etc.), sizing agents (fatty acid salts, rosin, Maleated rosin, cationized sizing agent, reactive sizing agent, filler (clay, talc, kaolin, etc.), wet paper strengthening agent (melamine resin,
It may contain one or more of an epoxidized polyamide resin), a fixing agent (aluminum sulfate, cationized starch, etc.), a pH adjuster (sodium hydroxide, sodium carbonate, etc.), a conductive agent and a dye.

The pulp paper includes water-soluble polymer additives, sizing agents, inorganic electrolytes, hygroscopic substances, pigments, pH adjusting agents,
It may be tab-sized or size-pressed with a treatment liquid containing at least one of polyvinyl alcohol and carboxy-modified polyvinyl alcohol. The basis weight of the paper support is not particularly limited, but is preferably in the range of 50 to 300 g / m ² , and more preferably 100 to
It is in the range of 200 g / m ² . If the basis weight is low, the rigidity of the base material is insufficient, and when the ink jet recording material is held in the hand and observed, it may cause a great problem, or a problem may occur when the ink jet printer runs a sheet. On the other hand, if it is more than 300 g / m ² , the whole becomes thick and difficult to handle, and it becomes rigid, which may cause inconvenience in paper feeding traveling. There is no particular limitation on the thickness and the tightness, but after the sheet-shaped substrate is manufactured, it is compressed by applying pressure or heat to it with a machine calender, a thermal calender, a soft calender, a super calender, etc. to improve the surface smoothness. Those are preferable. Thickness is about 20-30
About 0 μm, and the tightness is preferably in the range of 0.7 to 1.2 g / cm ³ .

The water resistant surface resin coating layer provided on one surface of the sheet substrate is a polyolefin resin coating layer, or
The unsaturated organic compound-containing layer, which can be cured by irradiation with radiation, is radiation-cured, or these layers have a multilayer structure. The polyolefin resin can be selected from ethylene, α-olefins, for example, homopolymers of propylene and the like, or copolymers of at least two kinds of the above-mentioned olefins, and mixtures of these various polymers.

The preferred polyolefin resins are low density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene and mixtures thereof. The molecular weight of the polyolefin resin is not particularly limited, but 20,
Those in the range of 000 to 200,000 can usually be used. As the polyethylene resin, a commercially available product can be appropriately selected and used, and the density thereof is 0.915 to 0.
950, and the melt index is preferably 2 to 20 g / 10 minutes (JIS K-6760). In addition, blending a pigment into the polyolefin resin can improve the whiteness,
It is preferable in terms of sharpness and image resolution. The pigment is appropriately selected from anatase type titanium dioxide, rutile type titanium dioxide, zinc oxide, talc, calcium carbonate, alumina, silica, synthetic zeolite, etc., and one or two of them can be selected.
It is possible to use a mixture of more than one kind, and it is particularly preferable to use anatase type titanium dioxide or rutile type titanium dioxide in terms of gloss and whiteness. The surface of the pigment may be surface-treated for the purpose of improving dispersibility with the polyolefin resin. Further, a colored pigment, a dye, a fluorescent whitening agent, an antioxidant, a plasticizer, a dispersant and the like can be added to the polyolefin resin coating layer as additives, if necessary.

The polyolefin resin coating layer is formed on the base material on the sheet by a melt extrusion coating method. To carry out melt extrusion coating, a polyolefin resin is usually melt-kneaded with a pigment, and a sheet-like substrate that is running is extrusion-coated in a film form from a slit die of an extruder. Usually, the melt extrusion temperature is preferably 250 to 350 ° C. Further, when the surface is cooled and solidified, it is preferable to use a cooling roll which is mirror-finished by chrome plating or the like in order to improve surface gloss. For example, the surface roughness of the cooling roll (JIS B 06
01) is Ra = 0.5 μm or less, more preferably Ra
= 0.05 μm or less.

The polyolefin resin layer may have a multilayer structure of two or more layers, or may have a multilayer structure formed by a coextrusion coating method. The unsaturated organic compound that can be cured by irradiation with radiation and is used as a water-resistant surface resin coating layer that is formed on one surface of the sheet-like substrate includes (1) aliphatic, alicyclic, and araliphatic 1 to 6 Acrylate compounds of polyhydric alcohols and polyalkylene glycols (2) Aliphatic, alicyclic, and araliphatic acrylate compounds obtained by adding alkylene oxide to monohydric alcohols (3) Polyacryloylalkyl Phosphate esters (4) Reaction product of carboxylic acid, polyol and acrylic acid (5) Reaction product of isocyanate, polyol and acrylic acid (6) Reaction product of epoxy compound and acrylic acid (7) Examples include reaction products of an epoxy compound, a polyol, and acrylic acid.

Specifically, polyoxyethylene epichlorohydrin-modified bisphenol A diacrylate, dicyclohexyl acrylate, epichlorohydrin-modified polyethylene glycol diacrylate, 1,
6-hexanediol diacrylate, hydroxybivalic acid ester neopentyl glycol diacrylate, nonylphenoxy polyethylene glycol acrylate, ethylene oxide modified phenoxyphosphoric acid acrylate, ethylene oxide modified phthalic acid acrylate, polybutadiene acrylate, caprolactane modified tetrahydrofurfuryl acrylate, Tris (acryloxyethyl) isocyanurate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, polyethylene glycol diacrylate, 1,4-
Examples thereof include butadiene diol diacrylate, neopentyl glycol diacrylate, neopentyl glycol modified trimethylolpropane diacrylate, and the like.

It is also possible to appropriately select and use one or more of these. Further, for the purpose of adjusting the viscosity or coating property of the paint, an oligomer or a monomer can be appropriately mixed and used. Further, by adjusting the mixing ratio, it is possible to adjust the curability and flexibility of the water resistant surface resin coating layer. However, generally speaking, when the degree of curing is low, it is advantageous for flexibility, but water resistance and coating film strength may be insufficient. Alternatively, the coating film becomes tacky and becomes tacky, which may cause inconvenience. The water-resistant surface resin coating layer of the present invention which is cured by irradiation with radiation preferably exhibits sufficient water resistance and is sufficiently cured in order to prevent tackiness. It is necessary to pay attention to this point when selecting the oligomer and the monomer. Furthermore, it is preferable to add a pigment to the water resistant surface resin coating layer which is cured by irradiation of the present invention in order to improve whiteness, color developability of ink jet recording, image resolution and the like. Examples of the pigment include anatase type titanium dioxide, rutile type titanium dioxide, barium sulfate, calcium carbonate, zinc oxide, silica, satin white, aluminum oxide, magnesium oxide, magnesium hydroxide, etc. It can be mixed and used. Of these, anatase-type titanium dioxide and rutile-type titanium dioxide are preferable from the viewpoint of whiteness and hiding hardening.

To disperse the pigment in the resin composition which is cured by irradiation with the above-mentioned radiation, a three-roll mill (three-roll mill), a two-roll mill (two-roll mill), a cowles dissolver, a homomixer, a sand grinder,
A ball mill, paint conditioner, ultrasonic disperser or the like can be used. When a pigment is contained in a coating layer (hereinafter also referred to as a resin coating layer) obtained by curing an unsaturated organic compound-containing layer with radiation, the blending amount is preferably 250 parts by weight with respect to 100 parts by weight of a resin component cured by irradiation with radiation. It is in the range of not more than parts, more preferably not more than 180 parts by weight. Generally, the larger the amount of white pigment compounded,
Although the whiteness, color developability, and image resolution are improved, if a large amount is blended, the film forming property of the resin coating layer may be deteriorated, and cracks may be generated, or the surface may be roughened to reduce gloss. Further, various additives may be added to the water resistant surface resin coating layer, if necessary. Examples thereof include photopolymerization initiators, photosensitizers, dispersants, colored pigments, dyes, stabilizers, and the like. The water-resistant surface resin coating layer that is cured by irradiation with radiation according to the present invention is one in which the coating material prepared by dispersion is applied to a sheet-like substrate and cured by irradiation with radiation. As the radiation, it is preferable to use an electron beam from the viewpoint of curing performance of the surface resin coating layer and handling. Further, ionizing radiation such as ultraviolet rays, α rays, β rays, γ rays and X rays can also be used. When the resin composition is cured by irradiation with ultraviolet rays, a photopolymerization initiator or a photosensitizer can be added to the resin composition for use. The device used for electron beam irradiation is not particularly limited, but, for example, a device such as an electro curtain system or a scanning system can be used. Surface resin coating layer is 100
It is cured by irradiating with an electron beam at an accelerating voltage of kV or higher, for example, an accelerating voltage of 100 to 300 kV, and an irradiation dose of 0.5 to 15 Mrad. When the irradiation dose is small, the curing may be insufficient, the water resistance may not be exhibited, or the coating film may become tacky. On the other hand, if it is too large, the coating layer may be excessively hard, and the sheet-like substrate may be damaged and become brittle, or it may have a yellowish tint and reduce whiteness. When the water-resistant surface resin coating layer is cured by irradiation with radiation, a casting method is preferred in which the surface of the coating layer is pressed against a smooth molding surface and irradiated with radiation to improve the surface gloss.

As the molding surface, a metal plate plated or mirror-finished, a metal roll, a metal drum, or a plastic film such as a polyester film can be used. It is preferable that the molding surface is smooth in terms of glossiness, and the surface roughness of the molding surface (JIS B 0
601) is Ra = 0.5 μm or less, more preferably R
a = 0.05 μm or less. That is, a coating for a water resistant surface resin coating layer is applied to a sheet-shaped substrate, pressed against a metal roll, and irradiated with radiation from the opposite surface of the paper substrate to cure the coating film. Alternatively, a coating for a water-resistant surface resin coating layer is applied to a radiation transparent polyester film, and the surface coating film is cured by irradiating it with radiation, and then again.
A method of applying a coating for a water-resistant surface resin coating layer, overlaying it on a sheet-shaped substrate, irradiating it again to integrate the surface resin coating layer, and then peeling off the polyester film used as the molding surface. As a result, it is possible to impart even more excellent gloss to the surface of the water resistant surface resin coating layer. The coating material forming the surface resin coating layer which is cured by irradiation with radiation can be applied by a known method. For example, a wire bar coating method, a rod coating method, an air knife coating method, a blade coating method, a gravure coating method, an extrusion coating method, a curtain coating method, a spray coating method or the like is appropriately selected and applied. be able to.

The water-resistant surface resin coating layer of the present invention may have a multilayer structure of one layer or two or more layers, and each layer may be cured by irradiation with radiation. Generally, when a resin composition cured by irradiation with radiation is sufficiently cured to exert water resistance, the coating film becomes stiff and brittle in some cases, and defects occur. Conversely, when the degree of curing is lowered, crosslinking occurs. Is insufficient and the coating film becomes tacky. With a multi-layer structure of two or more layers, the contradictory problems can be solved by disposing the resin layer having a high crosslink density in the upper layer and disposing the flexible resin layer in the lower layer. Alternatively, the white pigment may be concentrated on the upper layer so that a small amount of the white pigment can be effectively used. The support (sheet-shaped substrate) may be provided with an undercoat coating layer for the purpose of improving the adhesion to the water resistant surface resin coating layer.

Further, a backside resin coating layer containing a film-forming synthetic resin can be provided on the back side of the sheet-like substrate, that is, on the side opposite to the side on which the ink recording layer is provided. The backside resin coating layer can be formed in the same manner as the surface on the front side by providing a resin coating layer that is cured by irradiation with radiation or by coating a polyolefin resin-containing layer. It is not always necessary to add a pigment to the backside resin coating layer. Curling and water resistance are improved by the backside resin coating layer. Further, the resin coating layer on the back surface may be further provided with a back surface coating layer for the purpose of preventing blocking with the ink recording layer, imparting writability, preventing electrification, and improving feedability of paper in a printer.

The coating amount of the water resistant surface resin coating layer of the present invention is preferably in the range of 5 to 50 g / m ² as a whole, regardless of whether it has a single layer or a multilayer structure of two or more layers. If the amount is small, the effect of the present invention is not sufficiently exhibited, and conversely if the amount is large, the effect is saturated, and the cost is unnecessarily increased, and the sheet-like support becomes thick.

The ink recording layer contains a fine pigment and an adhesive (preferably a water-soluble resin). The ink recording layer may be a single layer (FIG. 1), or may have a two-layer structure composed of an ink receiving layer and an ink absorbing layer, and the ink receiving layer may be further divided into an upper layer and a lower layer and further below the ink absorbing layer. May be provided (FIG. 2). As the fine pigment, colloidal silica, anionic colloidal silica, cationic colloidal silica, alumina sol, pseudo-boehmite alumina sol, amorphous silica, vapor phase synthetic silica, synthetic fine particle silica, synthetic fine particle alumina silicate, kaolin, clay, calcined clay, Magnesium sulfate, aluminum oxide, aluminum hydroxide, calcium carbonate, satin white, aluminum silicate, smectite, zeolite,
Diatomaceous earth, montmorillonite group minerals, hydrotalcite group minerals, smectite group minerals, bentonite clay minerals,
Synthetic calcium carbonate, titanium sol, zinc oxide, tin oxide,
Zinc carbonate, calcium silicate, magnesium silicate, magnesium carbonate, magnesium oxide, polyaluminum hydroxide compound, alumina hydrate, plastic pigment,
Urea resin pigments, styrene resin pigments, benzoguanamine resin pigments, grain starch particles such as corn starch particles and potato starch particles, modified starch particles, crystallized cellulose particles, inorganic or organic cellulose particles A pigment can be illustrated. These can be appropriately selected or used in combination.

As the preferred fine pigment, anionic, cationic or acidic colloidal silica is preferred. When other pigments are used together in the colloidal silica, the average particle diameter of the other pigments is preferably 2 μm or less. The amount of the other pigment used is preferably 25 parts by weight or less in terms of dry weight with respect to 100 parts by weight of colloidal silica. Examples of the adhesive include the following adhesives as the lower layer of the ink receiving layer.

The case where the ink recording layer is composed of at least two ink receiving layers will be described below.
The lower layer of the ink receiving layer contains a fine pigment and an adhesive. Average particle size of fine pigments such as colloidal silica used in the lower layer (the surface area is measured by the BET method,
Calculate the average particle size. The following average particle diameters are all measured by this method unless otherwise specified. ) Is 10 to 300 nm. Preferably 20-200n
It was prepared to m. Of course, if necessary, two or more kinds of fine pigments may be mixed and used. As a preferred example, it is effective to use a cationic colloidal silica because of its water resistance and the effect of suppressing blurring of ink dyes during storage at high humidity. In addition, acidic colloidal silica is one in which impurities of general anionic colloidal silica have been removed and stabilized in the acidic region, but in the preparation of a coating with a water-soluble resin, the film forming property or transparency of the coating film is excellent. It can be used effectively. Examples of the adhesive include completely saponified polyvinyl alcohol, incompletely saponified polyvinyl alcohol, cationized polyvinyl alcohol, silicon-containing polyvinyl alcohol, modified polyvinyl alcohol, silanol modified polyvinyl alcohol, cationized polyvinyl alcohol, polyvinylpyrrolidone, casein, soybean casein. , Modified soybean casein, synthetic proteins, gelatin, starch, cationized starch,
Water-soluble resins such as phosphate esterified starch and modified starch, styrene-butadiene copolymer, methyl methacrylate-
Conjugated diene latex of butadiene copolymer, acrylic polymer latex such as polymer or copolymer of acrylic acid ester and methacrylic acid ester, vinyl type polymer such as ethylene-vinyl acetate copolymer, or various of these Various water-based adhesives such as latexes such as functional group-containing modified polymer latexes with functional group-containing monomers such as carboxyl groups and cationic groups of polymers, and thermosetting resins such as melamine resins and urea resins. Maleic anhydride copolymer, polyacrylamide, polymer or copolymer resin of polymethylmethacrylate, polyurethane resin, unsaturated polyester resin, vinyl chloride-vinyl acetate copolymer, acrylic acid ester such as polyvinyl butyral, An alkyd resin system and the like are also exemplified. Among them, polyvinyl alcohol is most effective because of its dispersibility with the fine pigment. The solid content weight ratio of the fine pigment to the water-soluble resin is in the range of 2 to 25 parts by weight, preferably 5 to 15 parts by weight, based on 100 parts by weight of the fine pigment such as colloidal silica. If it is more than 25 parts by weight, the ink absorption rate required by the lower layer cannot be obtained, while if it is less than 2 parts by weight, the ink receiving layer is cracked, which is unsuitable.

Generally, for inkjet paper,
It is known to add a cationic resin to the ink recording layer for the purpose of improving the color density of printing. A cationic resin may be added to the ink recording layer of the present invention. Examples of the cationic resin to be added include polyalkylene polyamines such as polyethylene amine and polypropylene polyamine, or derivatives thereof,
Examples thereof include acrylic resins having a primary amino group and a title ammonium group, and diacrylamine. The amount of the cation resin added is 1 with respect to 100 parts by weight of the pigment.
-30 parts by weight, more preferably 5-20 parts by weight. In addition, various auxiliary agents such as a dispersant, a viscosity modifier, an antifoaming agent, a colorant, an antistatic agent and an antiseptic agent used in the production of general coated paper may be appropriately added. The coating amount of the lower layer of the ink receiving layer is in the range of ^{3 to} 60 g / m ² , preferably 5 to 40 g / m ² . If it is less than 3 g / m ² , there is little ink absorption layer and it is meaningless to provide a lower layer. If it exceeds 40 g / m ² , the effect is saturated and meaningless. In order to obtain a high coating amount of 15 g / m ² or more, in addition to thickening and increasing the concentration of the coating, it is also possible to realize it by coating twice or more.

Next, the upper layer of the ink receiving layer (the layer farther from the support) will be described. The upper layer is laminated adjacent to the lower layer. The basic structure of the upper layer is the same as that of the lower layer, but it is effective that the particle size of the fine pigment is smaller than that of the lower layer in order to obtain the print density. 10 to 300 nm is preferable,
More preferably, it is in the range of 20 to 200 nm. Other,
If necessary, the above-mentioned pigments, water-soluble resins, cationic resins, and dispersants, viscosity modifiers, thickeners, defoamers, colorants, antistatic agents used in the production of general coated papers. , Various auxiliaries such as preservatives are appropriately added. The coating amount of the upper layer of the ink receiving layer is 3 to 60 g / m ² , preferably 5 to 40.
It is preferably in the range of g / m ² .

Next, a mode of providing the ink absorbing layer will be described. In the case where the two ink receiving layers cannot absorb the ink in a printed portion having a large amount of ink (that is, a portion having a high printing density), an ink absorbing layer can be provided adjacent to the lower layer. Even if the ink absorbing layer has the same composition as that of the ink receiving layer containing a fine pigment and an adhesive, it has good ink absorption rate, high print density, high gloss, good printability, and good water resistance, which are the objects of the present invention. An inkjet recording material is obtained. However, it is preferable that the ink dye in the inkjet ink composition stays near the surface of the ink recording layer from the viewpoint of print density and glossiness, and the ink absorbing layer of the above-mentioned ink recording layer of the present invention has the purpose of exhibiting such performance. It is provided in. Further, the ink absorption layer is provided mainly for the purpose of absorbing excess ink solvent.

The ink absorbing layer contains a fine pigment and an adhesive (preferably a water-soluble resin), and the particle size of the fine pigment is preferably larger than the particle size of the ink receiving layer composition. The pigment used in the ink absorbing layer can be appropriately selected from the above-mentioned fine pigments or various pigments such as amorphous silica, clay, alumina, and smectite. Silica and alumina are preferably used from the viewpoints of print density and ink absorbability, and the particle size of these is preferably 0.1 to 10 μm. Examples of the adhesive used in combination with the pigment include polyvinyl alcohol, casein, and the like described above (as an adhesive for the ink receiving layer).
Water-soluble resins such as starch can be exemplified. The amount of the adhesive added is in the range of 5 to 150 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the pigment. It is also possible to add a cation resin used for the purpose of improving the ink fixing property. For example, various compounds such as the aforementioned amine compounds can be exemplified. The amount of the cationic resin added is in the range of 1 to 30 parts by weight, more preferably 5 to 20 parts by weight, based on 100 parts by weight of the pigment.

In addition, various auxiliaries such as a dispersant, a viscosity agent, a defoaming agent, a colorant, an antistatic agent and an inhibitor which are used in general coated paper are appropriately added. The coating amount of the ink absorbing layer is not particularly limited, but is preferably in the range of ^{3 to} 30 g / m ² . If it is too small, the ink absorption is insufficient, which is not preferable. On the other hand, if the amount is too large, the effect is saturated and meaningless. The coating method for obtaining the ink recording layer, the ink receiving layer, and the ink absorbing layer of the present invention includes a blade coater, an air knife coater, a roll coater, a bar coater, a gravure coater, a rod blade coater, a lip coater, and a curtain coater. Various coating methods are exemplified.

Next, a mode in which the ink recording layer is applied on the molding surface to form a film and then transferred to a support through an adhesive or tacky intermediate layer will be described. As a bonding method, various laminating methods (a known laminating method such as a dry laminating method, a wet laminating method, a hot melt laminating method, and a melt laminating method can be exemplified) are effective. In the wet laminating method, dry laminating method, and hot melt laminating method, an adhesive resin, an adhesive, or a pressure-sensitive adhesive is applied to a support to form an intermediate layer, and the intermediate layer and the ink recording layer are laminated so that they face each other. After pressure bonding, the molding surface is peeled off to obtain a desired inkjet recording sheet. Alternatively, it is possible to apply an adhesive resin, an adhesive or a pressure-sensitive adhesive to the ink recording layer.

In the melt laminating method, a polyolefin resin such as polyethylene or a composition which is heated and melted at 250 to 350 ° C. or a composition is applied on the surface in a melt extruder,
The desired ink jet recording material is obtained by sticking the ink recording layer provided on the molding surface, cooling and pressure bonding with a cooling roll, and peeling off the molding. When using an adhesive resin, an adhesive, or a pressure-sensitive adhesive as the intermediate layer, after coating and drying the support or the ink recording layer by using various coating methods such as a bar coater, a roll coater, and a lip coater. After bonding the ink recording layer or the support, the molding surface can be peeled off to obtain a desired inkjet recording material. The coating amount of the intermediate layer is not particularly limited as long as the ink recording layer and the support can be adhered, but it is 2 to 50 g / when using any of a thermoplastic resin, an adhesive, a pressure sensitive adhesive and a pressure sensitive adhesive. It is in the range of m ² . When the coating amount is small, it is difficult to obtain a sufficient adhesive force, while when the coating amount is large, the effect is saturated, and the thickness of the ink jet recording material is unnecessarily increased, which is meaningless.

The material used for the intermediate layer is, for example, ethyl cellulose, vinyl acetate resin and its derivatives, polyethylene, ethylene vinyl acetate copolymer, polyisobutylene, hydrocarbon resin, polypropylene, polyamide resin, polyester resin or the like. Plastic resin. Thermosetting resin such as urea resin, phenol resin, epoxy resin, polyisocyanate resin, polyvinyl acetal / phenol resin, rubber = phenol resin, epoxy /
Various adhesives such as composite polymer type adhesives such as nylon resin, rubber type adhesives such as latex type rubber bases, hydrophilic natural polymer adhesives such as starch, glue and casein. Examples include various pressure-sensitive adhesives such as solvent-based pressure-sensitive adhesives, emulsion-type pressure-sensitive adhesives, hot-melt pressure-sensitive adhesives, delayed-type pressure-sensitive adhesives, and various pressure-sensitive adhesives.
It can be used as appropriate. Materials used as the molding surface of the ink recording layer include cellophane having high surface smoothness, polyethylene, polypropylene, soft polyvinyl chloride, high-humidity polyvinyl chloride, films such as polyester, polyethylene laminated paper, glassine paper, and the like. Invasion paper,
Various papers such as vapor-deposited paper, sheets such as metal foil and synthetic paper, and plates having a high smooth surface such as inorganic glass, metal and plastic are appropriately used. In particular, from the viewpoints of coating suitability and proper separation of the molding surface and the ink recording layer, polymer films (polyethylene, polypropylene, polyester, etc.), polyethylene laminated paper,
Glassine paper and inorganic glass are preferred. At this time, the surface roughness Ra (JIS B 0601) of the molding surface is preferably 1 μm or less, and more preferably 0.1 μm or less. Even if the molding surface remains untreated, in order to improve the peeling property between the molding surface and the ink recording layer, it is also possible to coat the molding surface with a resin having releasability such as silicone or fluororesin. It is possible.

The step of applying the ink recording layer when transferring to the support through the intermediate layer is carried out when the uppermost layer of the ink recording layer (that is, when the ink recording layer having a multilayer structure is provided on the molding surface). The upper layer of the ink receiving layer is coated first), and the lower layer of the ink recording layer is coated on the upper surface thereof. Further, if necessary, an ink absorption layer is coated and laminated on this upper surface. The ink recording layer of the ink jet recording material obtained by transferring to the support is (upper layer of ink receiving layer) / (lower layer of ink receiving layer) / (ink absorbing layer) / (intermediate layer) / (sheet-like substrate) ) Are laminated in this order.

The ink used in the ink jet recording system of the present invention contains a dye for forming an image and a liquid medium for dissolving or dispersing the dye as essential components, and if necessary, various dispersants and surface active agents. It is adjusted by adding an agent, a viscosity adjusting agent, a friction adjusting agent, an antistatic agent, a pH adjusting agent, an antifungal agent, a recording agent dissolving or dispersion stabilizing agent, and the like. Examples of the recording agent used in the ink include direct dyes, acid dyes, basic dyes, reactive dyes, food dyes, disperse dyes, oil dyes, and various pigments, but conventionally known ones are not particularly problematic. Can be used. The content of the recording agent is determined depending on the type of liquid medium component, the characteristics required for the ink, etc., but is usually about 0.1 to 20% by weight.

As the solvent of the ink used in the present invention, water and various water-soluble organic solvents such as methyl alcohol, ethyl alcohol, n-propyl alcohol,
C1-C4 alkyl alcohols such as isopropyl alcohol, n-butyl alcohol and isobutyl alcohol, ketones or ketone alcohols such as acetone and diacetone alcohol, polyalkylene glycols such as polyethylene glycol and polypropylene glycol, ethylene glycol, Propylene glycol, butylene glycol, triethylene glycol, thiodiglycol, hexylene glycol, diethylene glycol and other alkylene groups having 2 to 6 alkylene groups, dimethylformamide and other amides, tetrahydrofuran and other ethers, glycerin, ethylene glycol Such as methyl ether, diethylene glycol methyl (ethyl) ether, triethylene glycol monomethyl ether, etc. Such as a lower alkyl ethers of polyhydric alcohols can be exemplified.

[0052]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Unless otherwise specified,% indicates weight%,
Parts are parts by weight.

Example 1 (1) Production of sheet-like support Canadian Standard Freeness (JIS P-8
121) bleached softwood kraft pulp (NBKP) beaten to 250 ml, and similarly hardened bleached kraft pulp (LBKP) beaten to a Canadian Standard Freeness of 280 ml were mixed at a weight ratio of 2: 8, A pulp slurry having a concentration of 0.5% was prepared. The following papermaking additives were added to this pulp slurry in the following addition amounts with respect to the absolute dry weight of the pulp, and they were sufficiently stirred and dispersed. Cationized starch 2.0%, alkyl ketene dimer 0.4%, anionized polyacrylamide resin 0.1%, polyamide polyamine epichlorohydrin resin 0.7%, pH of 7. by adding caustic soda.
Adjust to 5. The pulp slurry having the above composition is paper-made by a Fourdrinier machine, passed through a drier, size press and machine calender, and has a basis weight of 170 g / m ² , a tenacity of 1.0 g / cm ² , and a moisture content of 8.0%. Was manufactured. The size press liquid used in the size press step is a 2: 1 mixture of carboxyl-modified polyvinyl alcohol and sodium chloride.
It was mixed at a weight ratio of 5%, and was added to water to dissolve it by heating to adjust the concentration to 5%.
g / m ² .

High-density polyethylene resin (density 0.954
g / m ² , melt index 20 g / 10 min) 65 parts by weight, low density polyethylene resin (density 0.924 g / m
² , melt index 4 g / 10 min) 35 parts by weight of the back surface polyolefin resin coating layer composition was dispersed with a Banbury mixer. After performing corona discharge treatment on both front and back surfaces of the pulp paper, a polyolefin resin coating layer composition mixed and dispersed in a Banbury mixer is applied to the wire side of pulp paper (paper base) at a coating amount of 25 g / m ^2. Was applied by a melt extruder having a T-die (melting temperature 320 ° C.).

(2) Coating of Water-Resistant Surface Resin Coating Layer Subsequently, the felt surface of pulp paper was subjected to melt extrusion laminating coating by the following procedure to provide a water-resistant surface resin coating layer of polyolefin resin. First, a surface polyolefin resin coating composition composed of a polyolefin resin and a white pigment, a linear low-density polyethylene resin (density 0.926, melt index 20 g
/ 10 minutes) 35 parts by weight, low density polyethylene resin (density 0.919, melt index 2 g / 10 minutes) 50 parts by weight, anatase type titanium dioxide (trademark: A-220,
Ishihara Sangyo) 15 parts by weight, zinc stearate 0.1 parts by weight, antioxidant (trademark: Irganox 1010, manufactured by Ciba Geigy) 0.03 parts by weight, ultramarine blue (Daiichi Kasei, trademark: blue mouth ultramarine blue No. 2000). 0.09 part by weight and 0.3 part by weight of a fluorescent whitening agent (trademark: UVITEX OB, manufactured by Ciba Geigy) were prepared. Then, 20 g / m ^{2 was} coated on the surface of the pulp paper by the melt extrusion laminating method. At this time, the molten resin surface was cooled and solidified by using a cooling roll having a chromium-plated mirror-finished surface (surface roughness Ra = 0.05 μm).

(3) Coating of ink recording layer Cation-modified colloidal silica having an average particle diameter of 45 nm (trademark: Snowtex AK-XL, manufactured by Nissan Chemical Industries) 10
8 parts by weight of silicon-containing modified polyvinyl alcohol (trademark: R-2105, manufactured by Kuraray) was mixed with 0 parts by weight 15
% Aqueous solution was applied to a PET film (trademark: Lumirror T type, surface roughness Ra = 0.02 μm) used as a molding surface so as to have a coating amount of 8 g / m ² with a Mayer bar and dried. Next, 100 parts by weight of cation-modified colloidal silica having an average particle diameter of 85 nm (trademark: Snowtex AK-ZL, manufactured by Nissan Kagaku Co., Ltd.) on the coating layer, and silicon-containing polyvinyl alcohol (trademark: R-2105, manufactured by Kuraray). A 15% aqueous solution mixed with 15 parts by weight was applied and dried with a Meyer bar so that the applied amount was 15 g / m ² .

(4) Manufacture of inkjet recording material A polyester adhesive (trade name: AD-, manufactured by Toyo Morton Co., Ltd.) used as an intermediate layer is added to the laminate of the sheet-like substrate and the water-resistant surface resin coating layer prepared by the above procedure. 578A) 10
A composition of 0 parts by weight and 15 parts by weight of a polyisocyanate-based cross-linking agent (Toyo Morton, trademark: CAT-50) was dissolved in 10% by weight with ethyl acetate, and a dry coating amount was 10 g / m ² with a Mayer bar. The coating was dried. Then, the ink recording layer provided on the PET film is faced and overlapped, and pressed by a pair of metal rolls (linear pressure 15 kg /
cm) It adhered. After promoting adhesive curing at a temperature of 50 ° C. for 1 week, the PET film was peeled off to complete an ink jet recording material.

Example 2 Example 1 except that the water resistant surface resin coating layer was obtained by curing the unsaturated organic compound containing layer by irradiation with radiation.
An ink jet recording material was completed in the same manner as in. (2) Coating of Water-Resistant Surface Resin Coating Layer First, 80 parts by weight of a 6-functional polyacrylic oligomer (pentaerythritol oligomer, trademark: Beamset 700, manufactured by Arakawa Chemical Industry), anatase type titanium dioxide (trademark: A220, Ishihara Sangyo) 20 parts by weight of a resin coating layer composition for a surface which is cured by irradiation with radiation was prepared by mixing and dispersing for 1 hour with a paint conditioner. This coating material was applied to the same sheet-like substrate as in Example 1 using a wire bar so that the coating amount after curing was 30 g / m ^2, and then a metal plate plated with chrome (surface roughness) (Ra = 0.02 μm), and the coating film was cured by irradiating it with an electron beam from the paper substrate side (electron beam irradiation condition: accelerating voltage 165 KV, irradiation dose 2 Mrad), and the metal plate was removed after curing.

Example 3 The same sheet-like substrate (support) as in Example 1 was used, and the water-resistant surface resin coating layer was a polyolefin layer and the unsaturated organic compound-containing layer was a layer cured by irradiation. The coating layer was constructed. Further, the ink recording layer was composed of three layers including an ink receiving layer (upper layer / lower layer) and an ink absorbing layer. For the intermediate layer, the same adhesive as in Example 1 was used.

(2) Coating of Water-Resistant Surface Resin Coating Layer In the same manner as in Example 1, a sheet-shaped support was coated with a polyolefin resin. The sheet-like support, the back surface polyolefin resin coating layer composition, the composition of the water resistant surface resin coating layer made of polyolefin, and the manufacturing method are the same as in Example 1. In this example, a layer made of a surface resin coating layer composition which was cured by irradiation with radiation was further laminated on the upper surface of the polyolefin waterproof resin coating layer. That is, a resin coating layer composition for a surface which is cured by irradiation with radiation, a hexafunctional polyacrylic oligomer (pentaerythritol oligomer, trademark: Beamset 700, manufactured by Arakawa Chemical Industry) 80
Parts by weight, anatase titanium dioxide (trademark: A220,
20 parts by weight of Ishihara Sangyo Co., Ltd. was mixed and dispersed in a paint conditioner for 1 hour, and this composition was used as a molding surface. A chrome-plated metal plate (surface roughness R
a = 0.02 μm) using a wire bar on the surface,
Coating was performed so that the coating amount after curing was 10 g / m ² , and this coating layer had an accelerating voltage of 165 KV and an irradiation dose of 2 Mrad.
The coating layer was cured by irradiating it with an electron beam so that Then, a composition for surface resin coating layer coated in the same manner, 36 parts by weight of a trifunctional polyurethane oligomer (urethane acrylate oligomer having a molecular weight of 1200, trademark: Beamset 550B, manufactured by Arakawa Chemical Industry Co., Ltd.), a trifunctional acrylate monomer. This composition was prepared by mixing 24 parts by weight of propylene glycol diacrylate (trademark: M-220, manufactured by Toagosei) and 40 parts by weight of anatase titanium dioxide (trademark: A220, manufactured by Ishihara Sangyo) with a paint conditioner for 1 hour. On the cured film described above, a wire bar is used to apply a coating amount of 20 g /
m ² and the coating layer is superposed on the above-mentioned sheet substrate coated with the polyolefin resin composition, and an electron beam is applied from the back of the paper substrate under the conditions of an acceleration voltage of 175 KV and an irradiation dose of 2 Mrad. Irradiation was performed and the laminate was cured and adhered to be integrated. Next, the metal plate was peeled off to form a water resistant surface resin coating layer.

(3) Coating of ink recording layer Cation-modified colloidal silica having an average particle diameter of 45 nm (trademark: Snowtex AK-XL, manufactured by Nissan Kagaku) 10
8 parts by weight of silicon-containing modified polyvinyl alcohol (trademark: R-2105, manufactured by Kuraray) was mixed with 0 parts by weight 15
% Aqueous solution was applied to a PET film (trademark: Lumirror T type, surface roughness Ra = 0.02 μm) used as a molding surface so as to have a coating amount of 8 g / m ² with a Mayer bar and dried. Next, 100 parts by weight of cation-modified colloidal silica having an average particle diameter of 85 nm (trademark: Snowtex AK-ZL, manufactured by Nissan Kagaku Co., Ltd.) on the coating layer, and silicon-containing polyvinyl alcohol (trademark: R-2105, manufactured by Kuraray). A 15% aqueous solution mixed with 15 parts by weight was applied and dried with a Meyer bar so that the applied amount was 15 g / m ² . Furthermore, 100 parts by weight of amorphous silica (trademark: Fineseal X-45, manufactured by Tokuyama), 30 parts by weight of polyvinyl alcohol (trademark: PVA-117, manufactured by Kuraray), an ink-fixing cationic resin agent (on the coated surface) Trademark: SR-1
(001, manufactured by Sumitomo Chemical Co., Ltd.) 15% by weight, 15%
Coating amount is 15g / m ^{2 with} wire bar using aqueous solution
The coating was dried so that

Comparative Example 1 100 parts by weight of amorphous silica (trademark: Fineseal X-45, manufactured by Tokuyama), 30 parts by weight of polyvinyl alcohol (trademark: PVA-117, manufactured by Kuraray) were added to the same sheet-like paper substrate as in Example 1. Part, and a 15% aqueous solution in which 15 parts by weight of an ink-fixing cationic resin (trademark: SR-1001, manufactured by Sumitomo Chemical Co., Ltd.) are mixed, and the coating amount is 2 with a wire bar.
It was coated so as to be 0 g / m ² and dried.

The ink jet recording materials of the respective Examples and Comparative Example 1 produced by the above procedure were evaluated as follows. The glossiness and the ink absorbency were evaluated by printing and recording with a commercially available inkjet printer (trademark: Deskjet 560J, manufactured by Hewlett Packard).
Glossiness: The specular glossiness at an incident angle of 60 degrees and 20 degrees was measured for solid portions of black, yellow, magenta, and cyan inks by the method of JIS Z 8714. Ink absorbency: The ink absorbency is evaluated every 5 seconds immediately after printing by overlaying a high-quality paper on the printed surface and observing whether the ink is transferred to the high-quality paper. It was measured. The measured number of seconds was evaluated in four stages (⊚: 5 seconds or less, ◯: 5 to 10 seconds, Δ: 10 to 3)
0 seconds, x: 30 seconds or more).

Printing Density: The density of solid black portions was measured using a Macbeth densitometer (trademark: Macbeth RD-920). The values in the table are average values of 5 measurements.

[0065]

[Table 1]

As is clear from Table 1, the ink jet recording materials obtained in Examples 1 to 3 had glossiness, image clarity, and
The print density and water resistance were excellent.

[0067]

The ink jet recording material according to the present invention has a structure in which a water resistant surface resin coating layer, an intermediate layer and an ink recording layer are laminated on a sheet substrate.
The surface resin coating layer includes a layer obtained by curing a polyolefin resin or an unsaturated organic compound-containing layer by irradiation with radiation, and further has at least one smoothed interface thereof. The ink recording layer is mainly composed of a fine pigment such as colloidal silica and polyvinyl alcohol and a water-soluble resin, and after the ink recording layer is formed on the molding surface, the water-resistant surface resin is applied through the intermediate layer. It was transferred to the coating layer. The reason why high glossiness is achieved in the present invention is that first, by coating the surface of the paper substrate with the water-resistant resin composition, the unevenness caused by the pulp fiber is covered to obtain a smooth surface property. Further, the surface of the water-resistant resin coating layer or the interface when it is composed of multiple layers was pressed against a cooling roll or a smooth surface to be mirror-finished, and radiation was applied from the back surface to obtain a publicly smooth surface. Can be given. The second reason is that the surface of the ink recording layer is smoothed by transferring the ink recording layer to the surface resin coating layer through the intermediate layer after coating and forming the ink recording layer. . Thirdly, since the ink recording layer and the surface resin coating layer are formed in this way, the overall multilayer structure composed of the ink absorbing layer and the surface resin coating layer is smooth and parallel from the surface. It is speculated that optical scattering is reduced. 4th
It is presumed that since the ink recording layer is composed of colloidal silica and a water-soluble resin, a transparent ink recording layer can be obtained, which contributes to high gloss. The reason why the high ink absorbency is obtained by the present invention is that the ink recording layer is composed of a fine pigment and a water-soluble resin to obtain appropriate voids to obtain an ink absorbing speed and an ink absorbing capacity. Guessed. Further, since the ink receiving layer of the present invention is transparent, it can be observed without interfering with the dye inside the ink recording layer, and it is presumed that it contributes to the achievement of high print density. The reason why the water resistance is obtained by the present invention is that the water-soluble resin is contained in an appropriate amount in the ink recording layer composed of colloidal silica and the water-soluble resin, so that it does not dissolve even when wet with water and suppresses the start-up of the coating film. It is presumed that

[Brief description of the drawings]

FIG. 1 is an example in which the present invention comprises an ink recording layer, an intermediate layer, and a water resistant surface resin coating layer.

FIG. 2 shows an ink recording layer comprising two ink receiving layers and one ink absorbing layer, an intermediate layer, two layers containing an unsaturated organic compound which is cured by irradiation with radiation, and one layer. An example comprising a water resistant surface resin coating layer comprising a polyolefin resin layer.

[Explanation of symbols]

1: Ink recording layer 2A: Ink receiving layer (upper layer) 2B: Ink receiving layer (lower layer) 3: Ink absorbing layer 4: Intermediate layer 5: Water-resistant surface resin coating layer 6A: Water-resistant surface resin coating layer Cured unsaturated organic compound layer (upper layer) 6B: Radiation irradiation that is a water resistant surface resin coating layer Curing unsaturated organic compound layer (lower layer) 7: Polyolefin resin composition layer that is a water resistant surface resin coating layer 8: Support Body (sheet-like substrate) 9: Backside coating layer

Claims (3)

[Claims] 1. An ink jet recording body comprising a support, on which a single-layer or multi-layer water-resistant surface resin coating layer and an ink recording layer are provided, wherein the water-resistant surface resin coating layer is a laminate layer of a polyolefin resin composition, Alternatively, at least one layer formed by curing a resin composition containing an unsaturated organic compound by irradiation with radiation is included, and at least the surface of the laminate layer or the layer cured by radiation is subjected to a smoothing treatment by a molding surface. A method for producing an ink jet recording material, which is characterized. 2. The smoothing treatment of the water resistant surface resin coating layer comprises:
By contacting a cooling roll with a mirror finish to the laminate layer of the polyolefin resin composition,
Alternatively, the method for producing an inkjet recording material according to claim 1, wherein the radiation-curable layer is irradiated with radiation and cured in a state of being in contact with a smooth molding surface. 3. An ink recording layer, which is formed by coating on a molding surface, which is transferred onto a water-resistant surface resin coating layer via an adhesive or adhesive intermediate layer and molded. The method for manufacturing an inkjet recording body according to claim 1 or 2, wherein the surface is provided by peeling.