JPH1096191A - High gloss printing sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a glazed printing sheet having no exfoliation of an electron radiation curing resin coating layer from a sheet base. SOLUTION: This glazed printing sheet comprises a sheet base and at least one electron radiation curing resin coating layer which is formed by electron radiation curing of an electron radiation curable resin composition at least on one face of the sheet base, in such a way that 100 pts.wt. (solid) of the electron radiation curable resin composition forming at least an inside resin coating layer adjacent to the sheet base contain 10-80 pts.wt. (solid) of electron radiation curable aromatic unsaturated organic compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a sheet for high gloss printing. To elaborate further,
The present invention relates to a sheet for high gloss printing which does not fall off from a sheet-like substrate, has excellent ink adhesion after printing, and has printability.

[0002]

2. Description of the Related Art Conventionally, gloss coated paper called cast coated paper has a coating layer mainly composed of a pigment and an adhesive,
While it is in a plastic state containing water, it is pressed against the heated mirror surface and provided with a high gloss coating layer formed by drying and finishing, but the glossiness as a high gloss coating paper is It is not satisfactory, and a higher glossiness is desired.

In order to solve this problem, a molten resin is laminated on a sheet-like substrate in the form of a film, which is pressed against a metal cylindrical rotating body having a smooth and high-gloss surface and cooled. Instead of a so-called laminate coating method of forming a high gloss coating layer by peeling from a metal cylindrical rotating body or a molten resin of the above-mentioned laminate coating method, an unsaturated organic compound curable by electron beam irradiation is used as a main component. The coating liquid layer formed from the coating composition (hereinafter, referred to as an electron beam-curable resin composition) is pressed against a molding surface or a cylindrical rotating body made of metal, and irradiated with an electron beam to be cured. Electron beam irradiation methods have been used, and printing methods having high glossiness can be obtained by these methods.

However, when these electron beam-curable resin coating layers are subjected to printing, their printability, especially the setting properties of printing inks, are poor, and a satisfactory product as a printing coated paper has not yet been obtained. .

[0005] Therefore, as the electron beam-curable resin composition, an electron beam-curable unsaturated organic compound having a linear or side chain-containing alkyl structure or an electron having a dimer acid structure derived from a dimer of unsaturated higher fatty acid. For printing excellent in printability in offset printing, gravure printing, letterpress printing, etc., especially in setting of printing ink, by containing a line-curable unsaturated organic compound or a polyether structure-containing electron beam-curable unsaturated organic compound. A high gloss sheet is obtained.

Further, in the case of producing a high gloss printing sheet by a cast electron beam irradiation method, the electron beam curable resin coating layer has a laminated structure of two or more layers, and the inner resin coating layer has a pigment-free electron beam curability. A resin composition (hereinafter, referred to as a clear electron beam-curable resin composition) formed from a cured product obtained by electron beam irradiation, and further comprising an outermost resin coating layer provided on the inner resin coating layer, Is formed from a cured product of an electron beam-curable resin composition (hereinafter, referred to as a pigment-containing electron beam-curable resin composition) containing an electron beam, which has high surface whiteness and cosmetics A high-gloss printing sheet with good quality can be obtained.

However, when a paper substrate is used as a sheet-like substrate and the electron beam-curable resin coating layer is provided on the surface of the paper substrate to produce a high gloss printing paper, the paper of this electron beam-curable resin composition is produced. Pigment-coated paper such as cast-coated paper, art paper, and coated paper is usually used as a paper substrate for the purpose of preventing seepage into the substrate. Poorly, there has been a problem that the electron beam cured resin coating layer falls off.

Further, even when a sheet for strong glossy printing is manufactured using a sheet-like substrate such as a plastic film or a so-called synthetic paper, since the electron beam-curable resin composition hardly penetrates, Adhesion between the substrate and the inner resin coating layer is poor, and the electron beam cured resin coating layer falls off.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art and to provide a high gloss printing sheet in which an electron beam curable resin coating layer on a sheet-like substrate does not fall off. Is what you do.

[0010]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that at least one electron beam curable resin coating layer is provided on at least one surface of a sheet-like substrate as a means for solving the above problems. By mixing an organic compound containing at least one specific functional group and / or specific bond into the electron beam-curable resin composition forming the electron beam-curable resin coating layer, The present inventors have found that the resin coating layer has improved adhesion to the sheet-like substrate, and have completed the present invention.

That is, the sheet for high gloss printing according to the present invention comprises a sheet-like substrate and an electron beam-curable resin coating layer formed on at least one surface thereof and comprising an electron beam-cured body of an electron beam-curable resin composition. Having a molecular weight of 150 to 100 parts by weight (solid content) in the electron beam-curable resin composition.
1000 electron beam-curable aromatic unsaturated organic compounds
８０80 parts by weight (solid content).

Further, the sheet for high gloss printing according to the present invention comprises:
A sheet-like substrate, having an electron beam-curable resin coating layer formed on at least one surface of the sheet and comprising an electron beam-cured body of an electron beam-curable resin composition, wherein the electron beam-curable resin coating layer has at least 100 parts by weight (solid content) of an electron beam-curable resin composition comprising an inner resin coating layer adjacent to the sheet-like substrate and an outermost resin coating layer disposed on the outermost side, forming the inner resin coating layer Inside, molecular weight 150 to 10
The electron beam-curable aromatic unsaturated organic compound of No. 00 to 10-8
It is characterized in that 0 parts by weight (solid content) is blended.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The electron beam-curable resin composition for forming the electron beam-curable resin coating layer contains an electron beam-curable aromatic unsaturated organic compound. It is considered that the chemical bonding force with the substrate was increased, and the adhesion to the sheet-like substrate was improved.

The electron beam-curable aromatic unsaturated organic compound contained in the electron beam-curable resin composition used in the present invention comprises:
The molecular weight is preferably from 150 to 1,000, and more preferably from 170 to 900. When the molecular weight is less than 150, it is easy to volatilize, has strong skin irritation, and is difficult to handle. On the other hand, if the molecular weight is larger than 1,000, the adhesion to the sheet-like substrate and the adhesion to the printing ink may be poor.

Specifically, as the electron beam-curable aromatic unsaturated organic compound having a molecular weight of 150 to 1,000 contained in the electron beam-curable resin composition, phenol ethylene oxide-modified acrylate, phenoxyethylene glycol acrylate, phenol polyethylene glycol Modified acrylate, propylene oxide-modified acrylate of phenol, propylene glycol-modified acrylate of phenol, ethylene oxide-modified acrylate of alkyl phenol, polyethylene oxide-modified acrylate of alkyl phenol, propylene glycol-modified acrylate of alkyl phenol, polypropylene glycol-modified acrylate of alkyl phenol, monohydroxy phthalate, 2-hydroxy-3
Monofunctional acrylates such as phenoxypropyl acrylate, 2-acryloyloxyethyl-2-hydroxyethyl phthalate.

The electron beam-curable aromatic unsaturated organic compounds having two or more functional groups include acrylates such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, and pyromellitic acid. May be. Also, 2,4-tolylene diisocyanate,
Urethane acrylates such as 2,6-tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, xylylene diisocyanate, tolidine diisocyanate, and naphthylene diisocyanate. Also, bis (p-hydroxyphenyl) methane, bisphenol A
2,2-bis (4-hydroxyphenyl) propane (common name; bisphenol A) acrylate, such as diethylene glycol-modified diacrylate of bisphenol A or polyethylene glycol-modified diacrylate of bisphenol A;
Acrylates of 2,2-bis (4-hydroxyphenyl) butane (common name; bisphenol B), acrylates of 2,2-bis (4-hydroxyphenyl) sulfone (common name; bisphenol S), and the like. The compound may be epoxy-modified or urethane-modified.

These organic compounds may be used in an amount of 10 to 80 parts by weight, preferably 15 to 60 parts by weight, based on 100 parts by weight of the electron beam-curable resin composition.

Further, it is preferable that the electron beam-curable resin coating layer has a laminated structure of two or more layers having an inner resin coating layer and an outermost resin coating layer. The inner resin coating layer adjacent to the sheet-like substrate and the outermost resin coating layer disposed on the outermost layer have a molecular weight of 150 to 1 in 100 parts by weight of the electron beam-curable resin composition.
000 electron beam-curable aromatic unsaturated organic compounds
It is preferred to be composed of a cured product by electron beam irradiation containing 80 parts by weight.

There is no particular limitation on the type of sheet-like substrate used in the present invention, and a relatively thin substrate such as a paper substrate such as a high-quality paper, a plastic film, a cloth, a nonwoven fabric, or an aluminum foil may be used. Preferably, a paper substrate is used. As a paper substrate, usually 50 to
A paper substrate having a weight of 300 g / m ² and a smooth surface is used. The type of paper substrate used in the present invention is not particularly limited. As the pulp forming the paper substrate, generally, softwood pulp, maple, beech, etc. manufactured from fir, toga, etc.
Those containing natural pulp as a main component, such as hardwood pulp and softwood hardwood mixed pulp, manufactured from poplar and the like are widely used, and bleached chemical pulp such as kraft pulp, sulfite pulp, and soda pulp can be used. Further, paper bases manufactured from pulp including synthetic fibers and synthetic pulp can also be used.
The paper base may contain various conventional additives such as a dry strength agent, a sizing agent, a filler, a wet strength agent, a fixing agent, and a pH.
One or more types of modifiers can be included.

The sheet-like substrate of the present invention is not particularly limited in its material. For example, clay, talc, kaolin, calcium carbonate, aluminum hydroxide may be coated on one or both sides of a paper substrate such as high quality paper. , Titanium dioxide, magnesium hydroxide, pigments such as plastic pigment, acrylic resin, polyurethane resin, ethylene-acrylic acid copolymer resin, vinyl acetate-ethylene copolymer resin, styrene-butadiene copolymer resin, vinylidene chloride Coated paper having a pigment coated layer mainly composed of synthetic resin such as resin, cast coated paper, pigment coated paper such as art paper, laminated paper on which one or both sides are laminated with polyolefin resin such as polyethylene May be used, and when a paper substrate is used, the electron beam-curable resin composition may be used. To prevent moisture, separately polyvinyl alcohol, hydroxyethyl cellulose, may be provided undercoat layer barrier agent such as oxidized starch. For the sheet-like substrate having such a coating layer, the outermost resin coating layer may be formed directly on the resin coating layer of the sheet-like substrate without using the inner resin coating layer.

Further, it is not a problem to use a sheet substrate such as a plastic film or a so-called synthetic paper in place of the paper substrate used in the present invention. For example, a film formed by a melt extrusion method of a thermoplastic resin composition containing a polyolefin-based resin such as a polypropylene resin or a polyethylene resin can be used as the sheet-like substrate. Also, so-called synthetic paper obtained by converting synthetic resin film into pseudo paper can be used as the sheet-like substrate. Plastic films used as sheet-like substrates and so-called synthetic paper include pigments such as clay, talc, kaolin, calcium carbonate, titanium dioxide, magnesium hydroxide, metal soaps such as zinc stearate, and various surfactants. And one or more kinds of colored pigments and the like.

In order to enhance the smoothness and glossiness of the high gloss printing sheet according to the present invention, it is preferable to manufacture the sheet using a cast electron beam irradiation method. It is preferable to incorporate a pigment into the electron beam-curable resin composition used for the resin coating layer.
In this case, the electron beam curable resin coating layer has a laminated structure of two or more layers, that is, the inner resin coating layer is formed from an electron beam cured body of a clear electron beam curable resin composition,
The outermost resin coating layer is formed from an electron beam-cured body of the pigment-containing electron beam-curable resin composition, and is preferably manufactured using a casting method.

That is, in the method for producing a sheet for high gloss printing according to the present invention, a clear electron beam-curable resin composition is applied on one surface of a sheet-like substrate to form an inner coating liquid layer, and a molded article is separately formed. On the surface, a pigment-containing electron beam curable resin composition is applied to form an outermost coating liquid layer, and the surface of the molded body is cured by irradiating it with an electron beam to form an outermost resin coating layer. Superimposing the inner coating liquid layer on the sheet-like substrate, irradiating the multilayer body formed thereby with an electron beam to bond and harden the inner coating liquid layer and the outermost resin coating layer, and to coat the inner resin coating layer. There is a method in which a sheet-like substrate and an outermost resin coating layer are joined via a layer to form a laminate, and the laminate is separated from the surface of the molded body.

In another method for producing a sheet for high gloss printing according to the present invention, a clear electron beam curable resin composition is applied on one surface of a sheet-like substrate to form an inner coating liquid layer. On the surface of the molded product, a pigment-containing electron beam-curable resin composition is applied to form an outermost coating liquid layer, and is superimposed on the inner coating liquid layer on the sheet-like substrate, to form a multilayer body formed thereby. The inner coating liquid layer and the outermost coating liquid layer are subjected to electron beam irradiation to adhere and cure to each other, and the sheet-like substrate and the outermost resin coating layer are joined via the inner resin coating layer to form a laminate. Then, there is a method of peeling the laminate from the surface of the molded body.

In the pigment-containing electron beam-curable resin composition used in the outermost resin coating layer (when the electron beam-curable resin coating layer is a single layer, this layer), the pigment used is not particularly limited. Not known as inorganic pigments such as clay, kaolin, talc, magnesium hydroxide, aluminum hydroxide, heavy calcium carbonate, light calcium carbonate, titanium dioxide (anatase type and rutile type), zinc white, barium sulfate, etc., and plastic pigments Organic pigments, such as polystyrene, can be used. These pigments are usually white and may be used without any treatment on the surface, but those treated with siloxane, alumina, alcohol, silane coupling agent or the like may be used. The pigment may be composed of a single kind, or may be used as a mixture of two or more kinds. In addition, a known auxiliary agent such as a dispersant, a releasing agent, an antifoaming agent, a coloring agent, a dye, and a preservative is optionally added to the electron beam-curable resin composition containing such a pigment. You can also.

The amount of the pigment is preferably 10 to 80 parts by weight, more preferably 20 to 60 parts by weight, based on 100 parts by weight of the electron beam-curable resin composition. If the amount of the pigment is less than 10 parts by weight, the concealability of the pigment may be poor. If the amount is more than 80 parts by weight, the viscosity of the paint may be excessively high and the fluidity may be poor. .

The electron beam-curable unsaturated organic compound used in the pigment-containing electron beam-curable resin composition is not particularly limited, but the following electron beam-curable unsaturated organic compound is used for the purpose of imparting printability. It is preferred to incorporate a compound.

(1) An electron beam-curable unsaturated organic compound having a linear or side chain and having a molecular weight of 300 to 10,000 and containing an alkyl structure. (2) An electron beam-curable unsaturated organic compound containing a structure of a reaction product of an alkyl diol having a molecular weight of 30 to 300 and hydrogenated castor oil. (3) An electron beam-curable unsaturated organic compound containing a dimer acid structure derived from a dimer of an unsaturated higher fatty acid. (4) An electron beam-curable unsaturated organic compound containing a polyether structure having a molecular weight of 1,000 to 10,000. Can be mentioned. If these compounds have any of the above structures, they may be urethane-modified, ester-modified, epoxy-modified, or the like.

In order to disperse the white pigment in the electron beam-curable unsaturated organic compound, a three-roll mill (three-roll mill), a two-roll mill (two-roll mill), a Cowles dissolver, a homomixer, a sand grinder, A planetary mixer, an ultrasonic disperser, or the like can be used.

When the high gloss printing sheet of the present invention has two or more electron beam-curable resin coating layers, the electron beam-curable unsaturated organic compound used for the inner resin coating layer in contact with the sheet-like substrate includes an electron-curable unsaturated organic compound. A line-curable aromatic unsaturated organic compound is an essential component, and the other components are not particularly limited. One or more of the following compounds may be used in combination.

(1) Aliphatic, alicyclic and aromatic
Acrylate compounds of hexahydric alcohol and polyalkylene glycol. (2) Acrylic compounds obtained by adding polyalkylene oxide to aliphatic, alicyclic and aromatic mono- to hexavalent alcohols. (3) Polyacryloyl alkyl phosphates. (4) Reaction products of polybasic acid, polyol and acrylic acid. (5) Reaction products of isocyanate, polyol and acrylic acid. (6) A reaction product of an epoxy compound and acrylic acid. (7) A reaction product of an epoxy compound, a polyol and acrylic acid. And the like.

If the above additional components are specifically described, monofunctional monomers include methyl acrylate, ethyl acrylate, lauryl acrylate, stearyl acrylate, N-vinylpyrrolidone, acryloyl morpholine, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, tetrahydrofurfuryl acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, cyclohexyl acrylate, cyclohexyl methacrylate, dicyclohexyl acrylate, isobornyl acrylate, benzyl acrylate, ethoxydiethylene glycol acrylate, methoxytriethylene glycol Acrylate,
Methoxypropylene glycol acrylate, N, N-
Dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, 2-ethylhexyl carbitol acrylate, ω-carboxypolycaprolactone monoacrylate, monohydroxyethyl phthalate, dimer acrylate, acrylic acid-9,
10-epoxidized oleyl, methacrylic acid-9,10-
Epoxidized oleyl, ethylene glycol monoacrylate maleate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, dicyclopentenyloxyethylene acrylate, 4,4-dimethyl-1,3
Acrylates of dioxolane caprolactone adducts, acrylates of 3-methyl-5,5-dimethyl-1,3-dioxolane caprolactone adducts, polybutadiene acrylates, ethylene oxide-modified phenoxylated phosphoric acid acrylates and the like are used.

As the polyfunctional monomers, ethanediol diacrylate, 1,3-propanediol diacrylate, 1,4-butanediol diacrylate,
6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 1,14-tetradecanediol diacrylate, 1,15-pentadecanediol diacrylate, diethylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, neopentyl Glycol diacrylate, 2-butyl-2-ethylpropanediol diacrylate, polyethylene oxide-modified hydrogenated bisphenol A diacrylate, hydroxypivalate neopentyl glycol ester diacrylate, hydroxypivalate ester neopentyl glycol ester caprolactone adduct Acrylate, ethylene oxide-modified isocyanuric acid diacrylate, pentaerythri Diacrylate monostearate, 1,6-hexanediol diglycidyl ether acrylic acid adduct, tricyclodecane dimethanol diacrylate, trimethylolpropane triacrylate, ethylene oxide-modified trimethylolpropane triacrylate, polyethylene oxide-modified trimethylol Pan triacrylate, propylene oxide-modified trimethylol propylene triacrylate, polypropylene oxide-modified trimethylol propylene triacrylate, pentaerythritol triacrylate, ethylene oxide-modified isocyanuric acid triacrylate, ethylene oxide-modified glycerol triacrylate, polyethylene oxide-modified glycerol triacrylate, propylene Oxide-modified glycerol triacrylate Over DOO, polypropylene oxide-modified glycerol triacrylate,
Pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, caprolactone-modified dipentaerythritol hexaacrylate, and polycaprolactone-modified dipentaerythritol hexaacrylate are used. .

The metal cylindrical rotary body used as the molded body is not particularly limited in its material shape, but is formed of, for example, stainless steel, copper, chromium, etc. and has a mirror-finished smooth peripheral surface. Is used. Further, in order to facilitate the separation between the outermost resin coating layer and the surface of the molded product, a release aid such as silicone oil or wax can be supplied to the surface of the metal cylindrical rotary member.

The molding sheet material used as the molding is not limited as long as it is smooth and flexible, but specific examples thereof include a plastic film such as polyester, a metal sheet, and a resin-coated paper. A metal-deposited film, a metal-deposited paper, or the like is preferable, and a release aid such as silicone or wax may be supplied to the surface of the sheet-like material for molding to facilitate release of the outermost resin coating layer. . Further, the surface of the sheet-shaped material may be subjected to an appropriate treatment in advance, for example, a treatment such as a silicone treatment, so that the cured outermost resin coating layer can be easily separated. The sheet-like material used as a molded article may be processed into an endless belt shape. The sheet-like material used as a molded article can be used repeatedly. However, since the repeated impact of electron beam irradiation deteriorates the sheet-like material, the number of repetitive uses is limited.

As a method of applying the electron beam-curable resin composition to the surface of a metal cylindrical rotary member, a sheet-like material, or the surface of a sheet-like substrate as a molded body, for example, a bar coating method, Air doctor coating, blade coating, squeeze coating, air knife coating, roll coating, gravure coating, transfer coating, comma coating, smoothing coating, micro gravure coating, reverse roll coating, multi-roll Coating methods such as a coating method, a dip coating method, a kiss coating method, a gate roll coating method, a drop curtain coating method, a slide coating method, a fountain coating method, and a slit die coating method can be used. In particular, when a metal cylindrical rotating body is used as a molded body, a roll coating method using a rubber roll for application or an offset gravure coating method should be used in order not to damage the surface of the metal cylindrical rotating body. Preferably, a non-contact fountain coater, a slit die coater or the like is advantageously used.

In the high gloss printing sheet of the present invention, the coating amount of the entire electron beam curable resin coating layer composed of at least one layer is preferably ³ to 60 g / m ² after curing, more preferably 5 to 60 g / m ^2. ４０40 g / m ² . If the coating amount is less than 3 g / m ² , the surface smoothness of the obtained coated body will be insufficient, aesthetics cannot be obtained, and the glossiness may be reduced. On the other hand, when the coating amount is more than 60 g / m ² , the effect is saturated and the cost may be increased.

When the electron beam-curable resin coating layer comprises at least one inner resin coating layer and an outermost resin coating layer,
In order to impart aesthetics and printability of the outermost resin coating layer, the coating amount after curing is preferably 0.1 g / m ² or more, more preferably 0.3 to 20 g / m ² . is there. When the coating amount of the outermost resin coating layer is less than 0.1 g / m ² , the concealing property may be insufficient even if the blending amount of the pigment is large. In order to secure the function of the inner resin coating layer, the coating amount after curing is preferably 3 g / m ² or more, more preferably 5 to 20 g / m ² .
If the coating amount of the inner resin coating layer is less than 3 g / m ² , the unevenness of formation of the paper substrate cannot be filled, and the surface smoothness of the obtained printing sheet may be insufficient.

In the printing sheet of the present invention, in order to improve the smoothness and to improve the adhesion between the sheet-like substrate and the electron beam-curable resin coating layer in contact with the sheet-like substrate, the sheet-like substrate and the electron beam-curable film in contact therewith are improved. An undercoat layer containing a synthetic resin as a main component may be provided between the resin coating layer. Examples of the synthetic resin used for the undercoat layer include alkyd resins, (meth) acrylic resins, vinyl resins, cellulose resins, urethane resins, polyester resins, and copolymer resins thereof. The solution is applied by dissolving or dispersing in a solvent-based or aqueous medium. An electron beam curable resin or an ultraviolet curable resin can also be used for forming the undercoat layer. Providing such an undercoat layer is a means generally used in the field of forming a resin coating layer by coating an electron beam-curable resin composition on a sheet-like substrate. Photographic paper support coated with the resin composition,
It is used in the production of electrophotographic transfer paper, heat-sensitive base paper, process release paper, thermal transfer receiving paper, ink jet recording paper, wrapping paper, and the like.

The electron beam irradiator used for the electron beam irradiation is not particularly limited, and examples thereof include a hand-graft scanning system, a double scanning system,
An electron beam irradiation apparatus such as a broad beam method and a curtain beam method can be used. Among them, the curtain beam method, which is relatively inexpensive and provides a large output, is effectively used in the present invention.

The acceleration voltage at the time of electron beam irradiation is 100 to 30.
0 kV, and the absorbed dose is 0.1 kV.
1 to 8 Mrad, preferably 0.5 to 5 Mr
ad is particularly preferred.

[0042]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.

Example 1 A sheet for high gloss printing was produced by the following operation. Composition 1 (for electron beam curing resin coating layer formed) Ingredient weight polypropylene glycol urethanes modified bifunctional acrylate oligomer with tolylene diisocyanate (molecular weight 2800) 35 parts by weight 1,9-diacrylate 15 parts by weight (Trademark: New Frontier L-C9A, manufactured by Daiichi Kogyo Seiyaku) 20 parts by weight of phenoxyethylene glycol acrylate (trademark: New Frontier PHE, molecular weight: 192, manufactured by Daiichi Kogyo Seiyaku) Titanium dioxide (trademark: R-23, Sakai) 30 parts by weight of each of the above-mentioned compositions were mixed with a Cowles dissolver for 2 parts.
The composition was prepared by mixing at 000 rpm for 20 minutes.

Preparation of High Gloss Printing Sheet The above composition 1 was used as a synthetic paper having a thickness of 95 μm (trade name: Yupo F
PG-95, manufactured by Oji Yuka Synthetic Paper Co., Ltd.) using a Meyer bar so that the coating amount after curing becomes 10 g / m ^2, and the thickness used as a molded body from above 75
After superimposing a polyester film of μm, an accelerating voltage of 175
An electron beam was irradiated under the conditions of kV, an absorbed dose of 3 Mrad, and an oxygen concentration of 500 ppm or less to cure the coating liquid layer, to form an obtained electron beam cured resin coating layer, and to integrally bond the sheet-like substrate. . Thereafter, the polyester film was peeled off from the electron beam-curable resin coating layer to obtain a high gloss printing sheet having the electron beam-curable resin coating layer. The results of tests and evaluations of the high gloss printing sheet thus obtained are shown below.

Test and Evaluation Method (1) Adhesiveness to Sheet-like Substrate A cut was made on the surface of the electron beam-cured resin coating layer of the obtained sample with a cutter knife so that only the cured coating film was damaged. And a cellophane tape having a width of 18 mm was applied thereto, peeled off by hand at an angle of about 135 degrees, and the surface state of the high-gloss printing sheet was visually evaluated. ○ is practical, but × is not practical. ：: The resin coating layer does not fall off. X: The resin coating layer falls off.

(2) Blank Paper Gloss Blank paper gloss was measured using a gloss meter VGS-1D (manufactured by Nippon Denshoku Industries Co., Ltd.) according to JIS Z8741 at a gloss of 60/60 °. Those having a measured value of 75 or more are judged to be excellent in glossiness.

Example 2 A sheet for high gloss printing was produced by the following operation. Composition 2 (the outermost resin coating layer formed) Ingredient weight polypropylene glycol urethanes modified bifunctional acrylate oligomer with tolylene diisocyanate (molecular weight 2800) 45 parts by weight of 1,9-nonanediol diacrylate 25 parts by weight ( Trademark: New Frontier L-C9A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) Titanium dioxide (trademark: R-23, manufactured by Sakai Chemical Co.) 30 parts by weight

[0048] Composition 3 (for the inner resin coating layer formed) Ingredient weight 1,4-butanediol and polyester urethane-modified diacrylate 50 parts by weight of isophorone Ron diisocyanate and adipic acid (Trademark: OI-13B, the molecular weight 1000, manufactured by Arakawa Chemical Industry Co., Ltd.) Phenoxyethylene glycol acrylate 50 parts by weight (trademark: New Frontier PHE, molecular weight: 192, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Compositions 2 and 3 were prepared by dispersing and mixing at 000 rpm for 20 minutes.

Preparation of High Gloss Printing Sheet The above composition 2 was used as a molded product to a thickness of 75 μm.
Is coated on the surface of the polyester film using a Meyer bar so that the coated amount after curing is 5 g / m ² ,
The outermost coating liquid layer was formed. Next, the composition 3 was treated with a basis weight of 1
On a surface of a sheet-like substrate made of 28 g / m ² cast-coated paper (trade name: Mirror Coated Gold, manufactured by Shin-Oji Paper Co., Ltd.), the coating amount after curing was 10 g /
m ^2, and the outermost coating liquid layer on the surface of the polyester film is superimposed on the inner coating liquid layer. Then, an acceleration voltage of 175 kV is applied to the multilayer body from the back of the polyester film. , Absorbed dose 3Mrad,
The inner coating layer and the outermost coating layer are cured by irradiating an electron beam under an oxygen concentration of 500 ppm or less, and the inner resin coating layer, the outermost resin coating layer, and the sheet-like substrate obtained at the same time are integrally bonded. Was. Thereafter, the polyester film was peeled off from the outermost resin coating layer to obtain a high gloss printing sheet having an electron beam curing resin coating layer. The same tests and evaluations as in Example 1 were performed. The evaluation results are shown in the table.

Example 3 The same operation as in Example 2 was performed. However, the following composition 4 was prepared and used in place of the composition 3. Composition 4 (for the inner resin coating layer formed) Ingredient weight urethane-modified diacrylate 50 parts by weight of 1,4-butane diol and isophorone Ron diisocyanate to the polyester of adipic acid (Trademark: OI-13B, molecular weight 1000, Arakawa 50 parts by weight of diethylene glycol-modified diacrylate of bisphenol A (trade name: KAYARAD R-551, molecular weight 512, manufactured by Nippon Kayaku Co., Ltd.) A high gloss printing sheet was prepared and evaluated in the same manner as in Example 2. The evaluation results are shown in the table.

Example 4 The same operation as in Example 2 was performed. However, the following composition 4 was prepared and used in place of the composition 3. Composition 5 (for the inner resin coating layer formed) Ingredient weight urethane-modified diacrylate 50 parts by weight of 1,4-butane diol and isophorone Ron diisocyanate to the polyester of adipic acid (Trademark: OI-13B, molecular weight 1000, Arakawa Bisphenol A polyethylene glycol-modified diacrylate 50 parts by weight (trade name: New Frontier BPE-10, molecular weight 776, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) A high gloss printing sheet was prepared in the same manner as in Example 2. evaluated. The evaluation results are shown in the table.

Comparative Example 1 The same operation as in Example 1 was performed. However, the following composition 6 was prepared and used in place of composition 1. Composition 6 (for electron beam curing resin coating layer formed) Ingredient weight polypropylene glycol urethanes modified bifunctional acrylate oligomer with tolylene diisocyanate (molecular weight 2800) 45 parts by weight of 1,9-nonanediol diacrylate 25 parts by weight (Trade name: New Frontier L-C9A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) Titanium dioxide (trade name: R-23, manufactured by Sakai Chemical Co.) 30 parts by weight A high gloss printing sheet was prepared and evaluated in the same manner as in Example 1. . The evaluation results are shown in the table.

Comparative Example 2 The same operation as in Example 2 was performed. However, the following composition 7 was prepared and used in place of composition 3. Composition 7 (for the inner resin coating layer formed) Ingredient weight 1,4-butanediol and polyester urethane-modified diacrylate 70 parts by weight of isophorone Ron diisocyanate and adipic acid (Trademark: OI-13B, molecular weight 1000, Arakawa Acryloylmorpholine (trade name: ACMO, manufactured by Kojin Co.) 5 parts by weight Methoxytriethylene glycol acrylate 25 parts by weight (trade name: MTGA, Arakawa Chemical Co., Ltd.) High gloss print sheet as in Example 2 Was prepared and evaluated. The evaluation results are shown in the table.

Comparative Example 3 The cast-coated surface of a single-sided cast-coated paper having a basis weight of 128 g / m ² (trade name: mirror coated platinum, manufactured by Shin-Oji Paper) was evaluated in the same manner as in Example 1. The evaluation results are shown in the table.

[0055]

[Table 1]

As can be seen from the table, the high-gloss printing sheet according to the present invention has excellent adhesion to the sheet-like substrate, does not cause the electron beam-curable resin coating layer to fall off from the sheet-like substrate, and has a very high glossiness of white paper. High (Examples 1-4). However, when the electron beam-curable aromatic unsaturated organic compound resin is not contained in the electron beam-curable resin composition forming the electron beam-curable resin coating layer in contact with the sheet-like substrate, the adhesiveness to the sheet-like substrate is reduced. Is inferior (Comparative Examples 1 and 2). In addition, general cast-coated paper has very low blank gloss (Comparative Example 3).

[0057]

According to the present invention, there is provided an electron beam-curable resin composition having at least one sheet of an electron beam-curable resin coating layer on at least one surface of a sheet-like substrate to form an electron beam-curable resin coating layer in contact with the sheet-like substrate. Molecular weight of 150 to 10 in 100 parts by weight
The electron beam-curable aromatic unsaturated organic compound of No. 00 is 10 to 8
By containing 0 parts by weight, the adhesiveness to the sheet-like substrate is improved, and a high gloss printing sheet in which the electron beam curable resin coating layer does not fall off the sheet-like substrate is obtained, which is extremely useful in practice.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI B05D 7/24 303 B05D 7/24 303E B32B 27/00 B32B 27/00 Z 27/30 27/30 A C09D 4/02 C09D 4 / 02

Claims (3)

[Claims] 1. A sheet-like substrate and an electron beam-curable resin coating layer formed on at least one surface thereof and formed of an electron beam-cured body of a coating composition containing an electron beam-curable unsaturated organic compound as a main component. The coating composition is characterized in that 10 to 80 parts by weight (solid content) of an electron beam-curable aromatic unsaturated organic compound having a molecular weight of 150 to 1000 is blended in 100 parts by weight (solid content) of the coating composition. Glossy printing sheet. 2. A sheet-like substrate and an electron beam-curable resin coating layer formed on at least one surface thereof and comprising an electron beam-cured body of a coating composition containing an electron beam-curable unsaturated organic compound as a main component. Wherein the electron beam-curable resin coating layer includes at least an inner resin coating layer adjacent to the sheet-like substrate, and an outermost resin coating layer disposed on the outermost side, forming the inner resin coating layer. A sheet for high gloss printing characterized in that 10 to 80 parts by weight (solid content) of an electron beam-curable aromatic unsaturated organic compound having a molecular weight of 150 to 1000 is blended in 100 parts by weight (solid content) of a coating composition. . 3. The electron beam-curable aromatic unsaturated organic compound is a phenol ethylene oxide-modified acrylate, phenoxyethylene glycol acrylate, phenol polyethylene glycol-modified acrylate, phenol propylene oxide-modified acrylate, phenol polypropylene glycol-modified acrylate,
Ethylene oxide modified acrylate of alkyl phenol, polyethylene oxide modified acrylate of alkyl phenol, propylene glycol modified acrylate of alkyl phenol, polypropylene glycol modified acrylate of alkyl phenol, 2-hydroxy-3
-Phenoxypropyl acrylate, phthalic acid modified acrylate, isophthalic acid modified acrylate, terephthalic acid modified acrylate, trimellitic acid modified acrylate, pyromellitic acid modified acrylate, 2,4-tolylene diisocyanate modified diacrylate, 2,6-tolylene diisocyanate Modified diacrylate, 4,4-diphenylmethane diisocyanate-modified diacrylate,
Selected from xylylene diisocyanate modified diacrylate, tolidine diisocyanate modified diacrylate, naphthylene diisocyanate modified diacrylate, bis (p-hydroxyphenyl) methane, bisphenol A modified diacrylate, bisphenol B modified diacrylate, bisphenol S modified diacrylate 3. The sheet for high gloss printing according to claim 1, which is at least one kind.