JP2001138504A - Composition for forming jet ink receiving layer and jet ink receiving layer using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a recording material for printing having an ink receiving layer that is superior in an absorption property of ink, a water absorption property and a coloring or fixing property for ink, is capable of achieving high resolution printing quality and consists of a polymer porous membrane superior in water resistance and to provide a method for manufacturing the recording material. SOLUTION: (1) This composition for forming a jet ink receiving layer includes a polymer chemical substance (a) having a functional group which is made to be polymerized by radiation of an active light beams, (2) a poor solvent (b) for the polymer chemical substance (a), (3) a solvent (c) miscible with the polymer chemical substance (a) and the poor solvent (b) and (4) a hydrophilic polymer chemical substance (d). There is disclosed a jet ink receiving layer consisting of a thin film cured material consisting of the composition and a base material for jet ink recording having the jet ink receiving layer provided on a sheet type basic material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording material for printing such as ink jet printing, planographic printing, letterpress printing, and gravure printing. More particularly, the present invention relates to a water-based ink having improved absorbency, print image characteristics and water resistance. The present invention also relates to a composition for forming a recording material for printing which is excellent in oil-based ink and excellent in absorbency, printed image characteristics and water resistance, and a method for producing the same.

[0002]

2. Description of the Related Art In printing by an ink jet printer, ink is ejected from a nozzle onto a recording material such as paper to form characters and images. According to the ink ejection method, this printing method mainly uses the so-called piezo method, which applies mechanical vibration to the ink using a piezoelectric element to eject the ink, and the pressure generated by heating and foaming the ink. It is divided into the so-called bubble jet method in which ink is ejected.

The ink receiving layer of the recording material must have a function of receiving the ejected ink, absorbing the ink quickly, and fixing the ink in order to obtain clear print image quality.
Conventional ink receiving layers are mainly formed of inorganic particles (pigments) such as silica and a binder such as polyvinyl alcohol. However, this type of ink receiving layer has become insufficient in print characteristics, particularly ink absorption capacity and absorption speed, due to recent improvements in printing speed and image resolution (clarity). In order to obtain clear print image characteristics at higher speeds, the ink receiving layer has high ink absorption,
High color density, high resolution, water resistance, abrasion resistance, and the like have been required.

[0004] The structure of the ink-receiving layer is, for example, that an ink-receiving layer for photographic printing is first provided with a water-absorbing porous layer on a paper substrate, and an ink-absorbing layer is formed on the porous layer. It has a laminated structure. Also, JP-A-10-291363
Japanese Patent Application Laid-Open Publication No. H11-157, discloses that in an ink jet recording sheet provided with one or more ink receiving layers, an ink receiving layer made of a porous hydrophilic polyurethane resin or a porous hydrophilic polyurethane-polyurea resin is provided.

[0005] International Publication WO97 / 44363 and "Omron Technics" (Vol. 38, No. 1, 1)
No. 998) discloses a composition comprising a photopolymerizable monomer, a photopolymerization initiator, an incompatible material of the photopolymerizable monomer, and a common solvent. And that a white coating film can be formed by using this composition without using an inorganic pigment.

[0006]

However, in the ink jet recording sheet having an ink receiving layer described in JP-A-10-291363, the larger the hole diameter, the higher the ink absorption speed. Alternatively, there has been a problem that the pigment easily enters the inside of the porous layer, the color density is reduced, and it is difficult to obtain a clear and vivid image. On the other hand, in the ink jet recording sheet described in the above publication, when the hole diameter decreases, the color density increases, but the ink absorption speed decreases, and ink flow and bleeding easily occur. There was a problem. That is, in the above-described conventional technology, it is difficult to obtain a clear and vivid image while preventing ink from flowing or bleeding.

Further, International Publication WO 97/44363 and “Omron Technics” (Vol. 38, No. 1, 1)
The technique disclosed in No. 998) is intended to express white without using an inorganic pigment such as titanium oxide. It is not intended to be used as an ink receiving layer, and the white coating film obtained by the disclosed method is a porous layer in which aggregates of particles of about 0.5 μm are connected in a net shape. Even when an ink jet recording sheet having such a white coating film as an ink receiving layer is constituted, the ink jet recording sheet having an ink receiving layer described in JP-A-10-291363 is clear and, However, it has not been possible to obtain a vivid image and to prevent the ink from flowing or bleeding.

The problem to be solved by the present invention is to provide a polymer which is excellent in ink absorbency and water absorbency, ink coloring and fixing properties, can realize high-definition print image quality, and is excellent in water resistance. An object of the present invention is to provide a recording material for printing provided with an ink receiving layer composed of a porous film and a method for producing the same.

[0009]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have received ink comprising a cured product of a thin film composed of the following composition on a substrate on a sheet. A recording material for printing characterized by having a layer and a method for producing the same, the finding that the above problem can be solved,
The present invention has been completed.

That is, in order to solve the above-mentioned problems, the present invention provides (I) (1) a polymerizable compound (a) having a functional group polymerizable by irradiation with actinic rays, and (2) a polymerizable compound (a). (B), (3) a polymerizable compound (a), a solvent (c) compatible with the poor solvent (b), and (4) a hydrophilic polymer compound (d). Provided is a composition for forming a jet ink receiving layer.

In order to solve the above problems, the present invention provides (II) applying the composition for forming a jet ink receiving layer described in (I) above onto a sheet-like substrate, and irradiating the composition with actinic rays. The present invention provides a method for producing a printing recording material having an ink-receiving layer produced by polymerizing a polymerizable compound by the method.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The polymerizable compound (a) having a functional group capable of being polymerized by irradiation with actinic rays, which is used in the composition for forming a jet ink receiving layer of the present invention, is not limited to organic or inorganic compounds. In the presence or absence of an initiator, an actinic ray, for example, ultraviolet light, visible light, may be polymerized by irradiation with infrared rays or the like, as long as it becomes a polymer, such as radical polymerizable, anionic polymerizable, and cationic polymerizable. , May be arbitrary. As such a polymerizable compound (a), for example, a vinyl group, a vinylidene group, an acryloyl group, a methacryloyl group [hereinafter, an acryloyl group and a methacryloyl group are collectively referred to as a (meth) acryloyl group. The same applies to (meth) acrylic, (meth) acrylate and the like. And a monomer or oligomer having a maleimide group. Of these, a monomer or oligomer having a (meth) acryloyl group is preferable because the polymerization rate by irradiation with actinic rays is high.

As such a polymerizable compound (a),
For example, ethyl (meth) acrylate, butyl (meth)
Acrylate, hexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, phenyl (meth) acrylate, phenyl cellosolve (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, isobornyl (meth) acrylate, dicyclo Compounds having one (meth) acryl group in one molecule such as pentanyl (meth) acrylate; 1,6-hexanediol di (meth)
Acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate hydroxypivalate, 3-acryloyloxyglycerin monomethacrylate, 2,2′-bis (4-
(Meth) acryloyloxypolyethyleneoxyphenyl) propane 2,2'-bis (4- (meth) acryloyloxypolypropyleneoxyphenyl) propane, dicyclopentanyldi (meth) acrylate, bis [(meth) acryloyloxyethyl] hydroxy Compounds having two (meth) acryl groups in one molecule such as ethyl isocyanate, phenylglycidyl ether acrylate tolylene diisocyanate, divinyl adipate;
Three (meth) acrylic groups in one molecule such as trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, tris [(meth) acryloyloxyethyl] isocyanate, and pentaerythritol tri (meth) acrylate Compounds having four (meth) acryl groups in one molecule such as pentaerythritol tetra (meth) acrylate and glycerin di (meth) acrylate hexamethylene diisocyanate; dipentaerythritol monohydroxypenta (meth) acrylate Compounds having five (meth) acryl groups in one molecule such as; compounds having six (meth) acryl groups in one molecule such as dipentaerythritol hexa (meth) acrylate.

Examples of the polymerizable compound (a) include (meth) acrylic esters of epoxy resins such as bisphenol A-diepoxy- (meth) acrylic acid adducts and (meth) acrylic esters of polyether resins. It is also possible to use a (meth) acrylic acid ester of a polybutadiene resin, a polyurethane resin having a (meth) acrylic group at a molecular terminal, or the like. Further, a maleimide-based monomer or oligomer having a photopolymerization initiator function can also be used.

These polymerizable compounds (a) can be used alone or as a mixture of two or more materials, for example, a mixture of monomers or oligomers, or a mixture of monomers and oligomers. It can also be used.

Further, as the polymerizable compound (a), it is preferable to use a polymerizable compound having a hydrophilic group for the purpose of improving ink absorbency, fixability, color density (brightness) and the like. Examples of the polymerizable compound having a hydrophilic group include (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N-methylenebis (Meth) acrylates having an amino group such as (meth) acrylamide; (meth) acrylates having an anion such as sodium sulfonate ethoxy (meth) acrylate and sodium 2-methylpropane-2-acrylamide;
(Meth) acrylate having a cation such as tri-butyl {2- (meth) acryloyloxyethyl} phosphonium chloride and dimethylaminoethyl (meth) acrylate quaternary; 2- (meth) acryloyloxypropyl hydrogen phthalate; (Meth) having a carboxyl group such as acryloyloxyethyl succinic acid, (meth) acrylic acid, and 2- (meth) acryloyloxypropyl hexahydrohydrogen phthalate
Acrylate; (meth) acrylate having a hydroxyl group such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate; mono {2- (meth) acryloyloxyethyl} acid phosphate, 10- (meth) acryloyloxydecyl dihydrogen phosphate Having a phosphoric acid group such as β- (meth) acryloyloxyethylphenylphosphoric acid
Acrylates: sugar (meth) acrylates and amino acid (meth) acrylates, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate, and the like. Further, as a polymerizable compound having a hydrophilic group, a maleimide having a hydrophilic group can also be used.
These polymerizable compounds having a hydrophilic group can be used alone or as a mixture of two or more materials.

As for the jet ink receiving layer, from the viewpoint of improving the fixing property and color density (brightness) of the ink,
It is preferable to use a mixture of a (meth) acrylate having higher functionality (hereinafter, polyfunctional acrylate) and a (meth) acrylate having a cation (hereinafter, cationic acrylate).

The poor solvent (b) of the polymerizable compound (a) used in the composition for forming a jet ink receiving layer of the present invention does not dissolve when mixed with the polymerizable compound (a).
This refers to a substance that separates when left unattended even when stirred. The poor solvent (b) for the polymerizable compound varies depending on the type of monomer and / or oligomer.
When the polymerizable compound (a) is a mixture of a polyfunctional acrylate and a cationic acrylate, it is preferable to use water, a polyhydric alcohol such as propylene glycol, triethanolamine, glycerin, ethylene glycol, diethylene glycol, or the like. These poor solvents (b) may be a mixture of two or more.

The solvent (c) compatible with the polymerizable compound (a) and the poor solvent (b) used in the composition for forming a jet ink receiving layer of the present invention includes the polymerizable compound (a) and the poor solvent ( It refers to a substance that dissolves when mixed with b). When the polymerizable compound (a) is a mixture of a polyfunctional acrylate and a cationic acrylate, and the poor solvent (b) is water or propylene glycol, the solvent (c) may be a monohydric alcohol solvent such as 2-propanol. A ketone solvent such as acetone is preferred. The solvent (c) in this case is a monohydric alcohol-based solvent and a ketone-based solvent.
It may be a mixture of more than one species.

The hydrophilic polymer compound (d) used in the composition for forming a jet ink receiving layer of the present invention includes, for example, polyvinyl pyrrolidone, hydrophilic polyurethane, polyvinyl alcohol, cellulose derivatives such as hydroxycellulose, and polyacrylic acid. Acrylic acid polymer such as, silk derivative, protein such as gelatin, poly [(meth) acryloyloxyethyltrimethylammonium chloride], quaternary ammonium salt of polystyrene, polyethyleneimine salt, polyvinylamine salt, diallylamine acrylamide copolymer, diallyldimethyl Cationic polymers such as ammonium chloride-sulfur dioxide copolymer salts; polyamino acid salts such as sodium polyaspartate; and the like. Further, the hydrophilic polymer compound (d) may be a mixture of two or more of those exemplified above.

In the composition for forming a jet ink receiving layer of the present invention, water-absorbing fine particles (e) can be added in order to improve the ink absorbency and water absorbency.
Examples of the water-absorbing fine particles (e) to be added for such purpose include silica, clay, diatomaceous earth, kaolin,
Water-absorbing inorganic fine particles such as synthetic mica, calcium hydroxide, calcium carbonate, and alumina hydrate; water-absorbing organic fine particles such as cellulose-based, protein-based, and acrylic-based fine particles. Among these, printing performance is improved. For this purpose, it is preferable to use inorganic fine particles. Further, the water-absorbing fine particles (e) can be added as a mixture of two or more materials.

In the composition for forming a jet ink receiving layer according to the present invention, the polymerizable compound (a) contains 50 to 90% by weight of a polyfunctional acrylate and a cation (meth).
It is preferable to contain 10 to 50% by weight of acrylate.
The proportion of the poor solvent (b) is preferably in the range of 5 to 150 parts by weight, and the proportion of the solvent (c) is in the range of 80 to 250 parts by weight, based on 100 parts of the polymerizable compound (a). The water-absorbing polymer compound (d) is preferably used in a proportion of 1 to 25 parts by weight. Further, when water-absorbing fine particles (e) are used together, the proportion is preferably 1 to 20 parts by weight.
A range of parts by weight is preferred.

The jet ink receiving layer of the present invention can be obtained by applying a composition for forming a jet ink receiving layer on a sheet-like substrate, and then irradiating with an actinic ray to polymerize the polymerizable compound. After the polymerization, post-treatments such as drying and washing may be performed to remove the poor solvent and the solvent. When water is used as the poor solvent (b), the receiving layer can be formed without performing a post-treatment step after polymerization.

Examples of the sheet substrate include paper, synthetic paper, polymer film, polymer sheet, nonwoven fabric, woven fabric such as cloth, glass, metal and the like. Among these, a polymer film is preferable in terms of strength, water resistance, weather resistance, and the like. Examples of the material of the polymer film include polyethylene terephthalate, polyester, polystyrene, polyvinyl chloride, polyacrylate, polypropylene, polyethylene, polyamide, polysulfone, polyimide, and cellulose acetate.

The thickness of the jet ink receiving layer of the present invention is:
The range of 10 to 200 μm is preferable, and the range of 20 to 70 μm is preferable because better printing performance can be obtained.

The actinic ray for irradiating the composition for forming a jet ink receiving layer of the present invention includes, for example, an electron beam, γ
Rays, X-rays, ultraviolet rays, visible rays and the like. Among these, ultraviolet rays are preferred from the viewpoint of simplicity of the apparatus and handling. The intensity of the irradiated ultraviolet light is 10 to 500 mW / cm ²
(100 to 5000 W / m ² ) is preferable, and the irradiation time is preferably in the range of 0.1 to 100 seconds. When ultraviolet light or visible light is used as the actinic ray, a photopolymerization initiator can be contained in the polymerizable solution for the purpose of increasing the polymerization rate. The polymerization rate can be further increased by irradiating ultraviolet rays in an inert gas atmosphere. An electron beam is also a preferred actinic ray as an actinic ray for irradiating the composition for forming a jet ink receiving layer of the present invention. With the use of electron beams, solvents, non-solvents, and other additives (eg, thickeners, brighteners, antibacterial agents, etc.) are not affected by ultraviolet absorption, so that the range of these options is expanded, The film forming speed is also improved.

The ultraviolet polymerization initiator that can be mixed with the composition for forming a jet ink receiving layer of the present invention includes:
For example, p-tert-butyltrichloroacetophenone,
Acetophenones such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one; benzophenone, 4,4'-bisdimethylaminobenzophenone, 2-chlorothioxanthone, 2-methyl Ketones such as thioxanthone, 2-ethylthioxanthone and 2-isopropylthioxanthone; benzoin ethers such as benzoin, benzoin methyl ether, benzoin isopropyl ether and benzoin isobutyl ether; benzyl ketals such as benzyl dimethyl ketal and hydroxycyclohexyl phenyl ketone; Is mentioned.

As the UV polymerization initiator that can be mixed with the composition for forming a jet ink receiving layer of the present invention, a polymer type polymerization initiator, maleimide or the like can also be used. As the polymer type polymerization initiator, for example, "Esacure KIP150" (manufactured by Lamberti) and the like can be mentioned. As the maleimide, for example, tetramethylene glycol (average molecular weight 650) maleimide acetate (Japanese Unexamined Patent Publication No. 11-124403) can be used. Publication Synthesis Example 1
8) and the like.

Further, in order to further improve the ink absorbency, fixability, color density (brightness), etc., depending on the type and composition of the ink, the surface of the polymer film of the present invention, the inside of the pores (and A thin layer comprising a surfactant, a hydrophilic polymer, a protein or an inorganic compound may be provided between the polymer film and the substrate. The thin layer may be a single layer or a plurality of layers. For example, a protein layer may be further provided on the thin layer of the hydrophilic polymer. Further, for the purpose of improving weather resistance, water resistance, printing durability, and the like, an ultraviolet absorbing layer, a layer of an inorganic compound, or the like may be provided.

Examples of the hydrophilic polymer used herein include, for example, cellulose derivatives such as polyvinyl virolidone, hydrophilic polyurethane, polyvinyl alcohol, and hydroxycellulose; acrylic acid polymers such as polyacrylic acid; silk derivatives and gelatin. Proteins; cationic polymers such as poly [(meth) acryloyloxyethyltrimethylammonium chloride], quaternary ammonium salts of polystyrene, polyethyleneimine salts, polyvinylamine salts, and salts of diallylamine acrylamide copolymer.

In the composition for forming a jet ink receiving layer of the present invention, when a salt of diallyl dimethyl ammonium chloride-sulfur dioxide copolymer is selected as the hydrophilic polymer compound (d), the poor solvent after irradiation with actinic light is selected. Further, post-processes such as drying and washing of the solvent can be omitted.

[0032]

The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to the scope of these examples. In the following Examples and Comparative Examples, “parts” means “parts by weight”.

[Definition of Measurement Items] The measurement in the following examples was performed according to the following method.

(1) Printing Test As a pigment-based inkjet printer, "DesignJet 2500CP" manufactured by Hewlett-Packard Company was used.

(2) Surface Smoothness The surface smoothness was evaluated.

(3) Adhesion to Base Material Cellophane tape was applied to the unprinted and printed areas, and the degree of peeling of the receiving layer when peeled off in the 90 ° direction was visually evaluated.

(4) Ink Absorption The time required for the printed ink to dry was measured and evaluated.

(5) Printed Image Properties A test pattern (color bar) was printed with the above printer, and the color development, presence or absence and degree of bleeding of the printed matter were visually observed. Also, for gray (a part represented by a dot density of 20% K (black)), a microscope (100 ×)
And the shape of the dot was observed.

(6) Color density The color bars K (black), C (cyan), M (magenta), and Y (yero) were measured using a Macbeth reflection densitometer Macbeth RD918 (Macbeth). .

(7) Water Resistance Test The test print was immersed in water at 60 ° C. for 10 minutes, and bleeding and ink elution were visually observed.

Example 1 (Preparation of Polymerizable Solution) As a polymerizable compound (a), "Unidick V-4263" (an average of three molecules per molecule manufactured by Dainippon Ink and Chemicals, Inc.) 60 parts of urethane acrylate having an acrylic group) and “Light acrylate DQ
-75 "(a quaternary ammonium salt of dimethylaminoethyl methacrylate manufactured by Kyoeisha Chemical Co., Ltd.), 40 parts of" Irgacure 184 "(a UV polymerization initiator manufactured by Ciba Geigy Japan) as a polymerization initiator, 3 parts of a poor solvent ( 50 parts of propylene glycol as b), 110 parts of 2-propanol as the solvent (c), and 20 parts of polyvinylpyrrolidone having a molecular weight of 120,000 as the hydrophilic polymer compound (d) were uniformly mixed to obtain a polymerizable solution 1. .

(Preparation of Polymer Film) A polymer solution 1 was placed on a 100 μm-thick white polyethylene terephthalate sheet (hereinafter referred to as a PET sheet) using a bar coater.
Was applied so that the thickness after curing became 44 μm. This was replaced with a nitrogen atmosphere by leaving it in a nitrogen stream for 180 seconds, and then 360 nm with a metal halide lamp.
UV rays having an intensity of 60 mW / cm ² (600 W / m ² )
Irradiated for 0 seconds. The irradiated film was vacuum-dried at room temperature for 3 hours and at 70 ° C. for 3 hours to obtain a polymer film 1.

(Printing Test) The polymer film 1 was cut into an A4 size and was subjected to printing. In the printing test, a test pattern was printed using a pigment-based printer “DesignJet 2500CP”. Table 1 shows the evaluation results of the printed matter.

Example 2 (Preparation of Polymerizable Solution) 60 parts of “Unidick V-4263” and 40 parts of “Light Acrylate DQ-75” as the polymerizable compound (a), and “Irgacure 184” as a polymerization initiator 5 parts, 40 parts of water as the poor solvent (b), 170 parts of 2-propanol as the solvent (c), and 20 parts of polyvinylpyrrolidone having a molecular weight of 120,000 as the hydrophilic polymer compound (d) are uniformly mixed and polymerized. An ionic solution 2 was obtained.

(Preparation of Polymer Film) A polymer solution 2 was placed on a white PET sheet having a thickness of 100 μm using a bar coater.
Was applied so that the thickness after curing was 53 μm. This was replaced with a nitrogen atmosphere by leaving it in a nitrogen stream for 180 seconds, and then 360 nm with a metal halide lamp.
UV rays having an intensity of 60 mW / cm ² (600 W / m ² )
Irradiated for 0 seconds. The irradiated film was vacuum-dried at room temperature for 3 hours and at 70 ° C. for 3 hours to obtain a polymer film 2.

(Printing Test) The polymer film 2 was cut into an A4 size and was subjected to printing. In the printing test, a test pattern was printed using a pigment-based printer “DesignJet 2500CP”. Table 1 shows the evaluation results of the printed matter.

Example 3 (Preparation of Polymerizable Solution) As the polymerizable compound (a), 60 parts of "Unidick V-4263", 40 parts of "Light Acrylate DQ-75", and "Irgacure 184" 4
Parts, 80 parts of propylene glycol as the poor solvent (b),
A polymerizable solution 3 was obtained by uniformly mixing 30 parts of acetone and 70 parts of 2-propanol as the solvent (c) and 20 parts of polyvinylpyrrolidone having a molecular weight of 120,000 as the hydrophilic polymer compound (d).

(Preparation of Polymer Film) A polymer solution 3 was placed on a white PET sheet having a thickness of 100 μm using a bar coater.
Was applied so that the thickness after curing became 36 μm. This was replaced with a nitrogen atmosphere by leaving it in a nitrogen stream for 180 seconds, and then 360 nm with a metal halide lamp.
UV rays having an intensity of 60 mW / cm ² (600 W / m ² )
Irradiated for 0 seconds. The irradiated film was vacuum-dried at room temperature for 3 hours and at 70 ° C. for 3 hours to obtain a polymer film 3.

(Printing Test) The polymer film 3 was cut into an A4 size and was subjected to printing. In the printing test, a test pattern was printed using a pigment-based printer “DesignJet 2500CP”. Table 1 shows the evaluation results of the printed matter.

Example 4 (Preparation of Polymerizable Solution) 60 parts of "Unidick V-4263" and 40 parts of "Light Acrylate DQ-75" as the polymerizable compound (a), and "KIP-7" as a polymerization initiator
5B "(polymer type ultraviolet polymerization initiator manufactured by Lamberti), 4 parts of poor solvent (b), 5 parts of water, 95 parts of 2-propanol as solvent (c), hydrophilic polymer compound (d)
-Based polymer “PAS-A5” (Nitto Boseki Co., Ltd.)
3 parts of diallyldimethylammonium chloride-sulfur dioxide copolymer (average molecular weight: 4000) and 20 parts of polyvinylpyrrolidone having a molecular weight of 120,000 were uniformly mixed to obtain a polymerizable solution 4.

(Preparation of Polymer Film) A polymer solution 4 was formed on a white PET sheet having a thickness of 100 μm using a bar coater.
Was applied so that the thickness after curing became 51 μm. This was replaced with a nitrogen atmosphere by leaving it in a nitrogen stream for 180 seconds, and then 360 nm with a metal halide lamp.
UV rays having an intensity of 60 mW / cm ² (600 W / m ² )
The polymer film 4 was obtained by irradiation for 0 second. After the ultraviolet irradiation, the printing test was performed without drying or the like.

(Printing Test) The polymer film 4 was cut into an A4 size and was subjected to printing. In the printing test, a test pattern was printed using a pigment-based printer “DesignJet 2500CP”. Table 2 shows the evaluation results of the printed matter.

Example 5 (Preparation of Polymerizable Solution) As a polymerizable compound (a), 60 parts of "Unidick V-4263", 40 parts of "Light Acrylate DQ-75" and "NK ester AM-90G"
(Monoacrylate manufactured by Shin-Nakamura Chemical Co., Ltd.) 20 parts, Irgacure 184 (ultraviolet polymerization initiator manufactured by Nippon Ciba Geigy) 5 parts as a polymerization initiator, propylene glycol 70 parts as a poor solvent (b), solvent (C) 2-
A polymerizable solution 5 was obtained by uniformly mixing 94 parts of propanol, 20 parts of polyvinylpyrrolidone having a molecular weight of 120,000 as the hydrophilic polymer compound (d), and 10 parts of kaolin as the water-absorbing inorganic fine particles (e).

(Preparation of Polymer Film) A polymer solution 5 was formed on a white PET sheet having a thickness of 100 μm using a bar coater.
Was applied to a thickness of 44 μm. This was left in a nitrogen stream for 180 seconds to replace the atmosphere with a nitrogen atmosphere, and then irradiated with ultraviolet rays having a 60 nm / cm ² (600 W / m ² ) intensity of 360 nm for 90 seconds by a metal halide lamp. The irradiated film was vacuum-dried at room temperature for 3 hours and at 70 ° C. for 3 hours to obtain a polymer film 5.

(Printing Test) The polymer film 5 was cut into an A4 size and was subjected to printing. In the printing test, a test pattern was printed using a pigment-based printer “DesignJet 2500CP”. Table 2 shows the evaluation results of the printed matter.

Example 6 (Preparation of Intermediate Layer) A solution prepared by dissolving 10 parts by weight of polyacrylic acid having an average molecular weight of 25,000 in 90 parts by weight of water was used to form a layer having a thickness of 1%.
It was applied to a 00 μm white PET sheet using a bar coater so that the thickness after drying was 9 μm. The coated film was vacuum-dried at 70 ° C. for 3 hours to obtain a polymer film 6.

(Preparation of Polymer Film) The polymerizable solution 1 described in Example 1 was applied to the polymer film 6 using a bar coater so that the thickness after curing was 64 μm (including the intermediate layer). did. This was left in a nitrogen stream for 180 seconds to replace the atmosphere with a nitrogen atmosphere, and then irradiated with ultraviolet rays having a 60 nm / cm ² (600 W / m ² ) intensity of 360 nm for 90 seconds by a metal halide lamp. After irradiation, the film is kept at room temperature for 3 hours.
The polymer film 7 was obtained by vacuum drying at 70 ° C. for 3 hours.

(Printing Test) The polymer film 7 was cut into an A4 size and was subjected to printing. In the printing test, a test pattern was printed using a pigment-based printer “DesignJet 2500CP”. Table 2 shows the evaluation results of the printed matter.

[0059]

[Table 1]

[0060]

[Table 2]

From the results shown in Tables 1 and 2, even when printing directly on the porous polymer film of the present invention using a pigment-based ink jet printer, ink absorption is high, color density is high, and fine print image quality is high. It can be understood that they are excellent in water resistance and weather resistance.

Comparative Example 1 (Preparation of Polymerizable Solution) 60 parts of "Unidick V-4263" and 40 parts of "Light Acrylate DQ-75" as the polymerizable compound (a), and "Irgacure 184" as the polymerization initiator 3 parts, 50 parts of propylene glycol as the poor solvent (b), and 2-propanol 92 as the solvent (c).
The parts were uniformly mixed to obtain a polymerizable solution 6.

(Preparation of Polymer Film) A polymer solution 6 was formed on a white PET sheet having a thickness of 100 μm using a bar coater.
Was applied so that the thickness after curing was 33 μm. This was replaced with a nitrogen atmosphere by leaving it in a nitrogen stream for 180 seconds, and then 360 nm with a metal halide lamp.
UV rays having an intensity of 60 mW / cm ² (600 W / m ² )
Irradiated for 0 seconds. The irradiated film was vacuum dried at room temperature for 3 hours and at 70 ° C. for 3 hours to obtain a transparent polymer film 8.

(Printing Test) The polymer film 8 was cut into an A4 size and was subjected to printing. In the printing test, a test pattern was printed using a pigment-based printer “DesignJet 2500CP”. Table 3 shows the evaluation results of the printed matter.

Comparative Example 2 (Preparation of Polymerizable Solution) 60 parts of "Unidick V-4263" and 40 parts of "Light Acrylate DQ-75" as the polymerizable compound (a), and "Irgacure 184" as the polymerization initiator 5 parts, 96 parts of 2-propanol as the solvent (c), and 10 parts of polyvinylpyrrolidone having a molecular weight of 120,000 as the hydrophilic polymer compound (d) were uniformly mixed to obtain a polymerizable solution 7.

(Preparation of polymer film) PE having a thickness of 100 μm
The polymerizable solution 7 was applied on the T sheet using a bar coater so that the thickness after curing became 51 μm. This was left in a nitrogen stream for 180 seconds to replace the atmosphere with a nitrogen atmosphere, and then irradiated with ultraviolet rays having a 60 nm / cm ² (600 W / m ² ) intensity of 360 nm for 90 seconds by a metal halide lamp. The irradiated film was vacuum dried at room temperature for 3 hours and at 70 ° C. for 3 hours to obtain a transparent polymer film 9.

(Printing Test) The polymer film 9 was cut into an A4 size and was subjected to printing. In the printing test, a test pattern was printed using a pigment-based printer “DesignJet 2500CP”. Table 3 shows the evaluation results of the printed matter.

Comparative Example 3 (Preparation of Polymerizable Solution) 60 parts of "Unidick V-4263" and 40 parts of "Light Acrylate DQ-75" as the polymerizable compound (a), and "Irgacure 184" as the polymerization initiator 5 parts, 33 parts of propylene glycol as the poor solvent (b), and 2-propanol 98 as the solvent (c).
Part, polystyrene “Hymer ST-95” having a molecular weight of 4000 as a hydrophobic polymer compound (Sanyo Chemical Industry Co., Ltd.)
20 parts) were uniformly mixed to obtain a polymerizable solution 9.

(Preparation of Polymer Film) A polymer solution 9 was formed on a white PET sheet having a thickness of 100 μm using a bar coater.
Was applied so that the thickness after curing became 39 μm. This was replaced with a nitrogen atmosphere by leaving it in a nitrogen stream for 180 seconds, and then 360 nm with a metal halide lamp.
UV rays having an intensity of 60 mW / cm ² (600 W / m ² )
Irradiated for 0 seconds. The irradiated film was vacuum-dried at room temperature for 3 hours and at 70 ° C. for 3 hours to obtain a transparent polymer film 11.

(Printing Test) The polymer film 11 was cut into an A4 size and was subjected to printing. In the printing test, a test pattern was printed using a pigment-based printer “DesignJet 2500CP”. Table 3 shows the evaluation results of the printed matter.

Comparative Example 4 (Preparation of Polymerizable Solution) 100 parts of “KAYARAD TMPTA” (trimethylolpropane triacrylate manufactured by Nippon Kayaku Co., Ltd.) was used as the polymerizable compound (a).
5 parts of "Irgacure 184" as a polymerization initiator, 50 parts of triethanolamine as a poor solvent (b) and 50 parts of 2-propanol as a solvent (c) were uniformly mixed to obtain a polymerizable solution 10.

(Preparation of Polymer Film) A polymer solution 1 was placed on a white PET sheet having a thickness of 100 μm using a bar coater.
0 was applied so that the thickness after curing was 46 μm. This was left in a nitrogen stream for 180 seconds to replace it with a nitrogen atmosphere.
Ultraviolet light having an nm intensity of 60 mW / cm ² (600 W / m ² ) was irradiated for 90 seconds. The irradiated film is kept at room temperature for 3 hours at 70 ° C.
The polymer film 12 was obtained by vacuum drying for 3 hours.

(Printing Test) The polymer film 12 was cut into an A4 size and was subjected to printing. In the printing test, a test pattern was printed using a pigment-based printer, Design Jet 2500CP. Table 3 shows the evaluation results of the printed matter.

[0074]

[Table 3]

From the results shown in Table 3, since the polymer film obtained in Comparative Example 1 did not contain the hydrophilic polymer compound (d) in the composition, ink absorbency and image bleeding occurred. I can understand. In addition, since it is clear that the polymer film obtained in Comparative Example 2 is inferior in surface smoothness, it can be understood that the presence of a poor solvent is indispensable for improving the surface smoothness. Furthermore, the polymer film obtained in Comparative Example 3 was:
It can be understood that since the hydrophobic polymer was used instead of the hydrophilic polymer compound (d), the print image quality and the smoothness were reduced. Furthermore, it can be understood that the polymer film obtained in Comparative Example 4 has problems in adhesion between the receiving layer and the base material and in print image quality.

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EFFECTS OF THE INVENTION The jet ink receiving layer comprising the composition for forming a jet ink receiving layer of the present invention has good ink absorbency, and can provide good color developability, ink fixability, and clear printed image properties. Since there is an advantage that the difference in printing characteristics depending on the type of ink is small, general image quality is
Of course, it is suitable for ultra-fine image quality printing and has excellent water resistance and weather resistance, so that it is particularly suitable as a recording material for outdoor printed matter. Further, the jet ink recording substrate of the present invention, since the ink receiving layer has a cross-linked structure,
It has the advantage of being excellent in strength, heat resistance, weather resistance, chemical resistance and the like.

The jet ink receiving layer of the present invention comprises:
Compared with the conventional production method, the production method is easy to control the type and combination of hydrophilic groups and the amount of introduction according to the type and color of the ink, and can introduce a crosslinked structure into the film, and Since the phase separation is completed instantaneously, the production speed is high.The large-scale equipment is not required, the selection range of the polymer is wide, and the design of the crosslink density and crosslink structure is easy. There is an advantage that there is.

Claims (10)

[Claims] 1. A polymerizable compound (a) having a functional group polymerizable by irradiation with actinic rays, (2) a poor solvent (b) of the polymerizable compound (a), and (3) a polymerizable compound ( A composition for forming a jet ink receiving layer, comprising: a) a solvent (c) compatible with a poor solvent (b); and (4) a hydrophilic polymer compound (d). 2. The composition for forming a jet ink receiving layer according to claim 1, wherein the polymerizable compound (a) is at least one compound selected from the group consisting of acrylic monomers and oligomers. 3. The composition for forming a jet ink receiving layer according to claim 1, wherein the poor solvent (b) is water and / or a polyhydric alcohol. 4. The composition for forming a jet ink receiving layer according to claim 1, wherein the solvent (c) is a monohydric alcohol solvent and / or a ketone solvent. 5. The hydrophilic polymer compound (d) is a vinyl polymer, a polysaccharide polymer, an ethylene oxide polymer,
The composition for forming a jet ink receiving layer according to any one of claims 1 to 4, wherein the composition is at least one hydrophilic polymer selected from the group consisting of a protein polymer, an amine polymer, and an acrylic polymer. . 6. The composition for forming a jet ink receiving layer according to claim 1, further comprising water-absorbing fine particles (e). 7. The composition for forming a jet ink receiving layer according to claim 6, wherein the fine particles (e) are water-absorbing inorganic fine particles. 8. A jet ink receiving layer comprising a cured product of a thin film comprising the composition according to claim 1. Description: 9. A jet ink recording base material comprising the jet ink receiving layer according to claim 8 on a sheet-like base material. 10. The jet ink recording substrate according to claim 9, further comprising an intermediate layer between the sheet-like substrate and the jet ink receiving layer.