JPH07195627A - Sheet like support - Google Patents

Abstract

PURPOSE:To provide a sheet like support having a resin coating layer composed of a cured material of an electron beam curable resin and having high glossiness and excellent bending resistance formed thereto. CONSTITUTION:A sheet like support is obtained by forming a resin coating layer composed of a cured material of an electron curable resin having characteristics forming a resin film wherein the product of elongation and tensile strength becomes 70%.kgf/mm<2> or more on at least one surface of a paper support.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a sheet-like support. More specifically, the present invention provides
It relates to protection of the surface of paper, imparting water resistance, polishing, etc., release paper, glossy paper, metal vapor deposition label support,
The present invention relates to the production of supports for photographic printing papers, paper prints, laminated papers, coated papers, thermal papers, pressure-sensitive papers, adhesive papers, decorative papers and the like.

[0002]

2. Description of the Related Art Taking advantage of the characteristics of a sheet-like base material such as paper,
In order to make up for the drawback, a sheet-like support having a resin coating layer on the surface of a base material is widely used, and has permeated every corner of life. That is, as a composite material that takes advantage of the characteristics of each paper and resin sheet, for the purpose of improving the physical properties of the paper substrate,
In addition, many sheet-like supports are used for the purpose of giving a good-looking glossy feeling and for smoothing the rough surface of the paper base material, and the fields of use are information, packaging, and industrial base materials. And it is widespread.

Conventionally, in order to form a resin coating layer on such paper, a resin composition prepared by appropriately selecting and blending various resins is dispersed or dissolved in water or a solvent, and then coated on a sheet-shaped substrate and dried. The method of completing, the method of melting and laminating a resin on a sheet-shaped substrate, and the method of applying hot-melt are widely used.

In general, for coated paper, a method in which a polymer is dissolved in an emulsion or a solvent and applied on the paper, and water or a solvent is dried by heating is used. Typical ones used as the coating material of the coated paper are SBR latex, NBR latex and acrylic latex. In particular, SBR latex is most commonly used because it has a high binding force with the pigment and is advantageous in cost.

In the laminated paper, a polyolefin resin such as polyethylene or polypropylene is laminated on the paper by a melt extrusion method. The polyolefin resin has a skeleton of a repeating structure of an ethylene group of the following formula —CHR ¹ —CH ₂ — [wherein, R ¹ represents a hydrogen atom or a methyl group]. The above-mentioned skeletal structure is chemically stable, has excellent light resistance and water resistance, and the resin has a large elongation rate. Therefore, a sheet-shaped support obtained by coating a polyolefin resin on a paper substrate is bent. However, the coating layer does not crack.

However, the method of dispersing the resin composition in water or a solvent and coating and drying it, or the method of laminating a molten resin is performed at a higher speed as the resin coating amount increases. There is a problem that a larger drying facility and melting facility are required, and the installation area and the thermal energy required for drying and melting increase. Further, in the coating method using a solvent, it is necessary to recover the solvent evaporated in the drying step, but it is difficult to recover all of the solvent, which is not preferable in terms of environmental measures.

Under such circumstances, in recent years, an electron beam curable resin composition containing an unsaturated organic compound (electron beam curable unsaturated organic compound) which can be cured by electron beam irradiation as a main component is applied to a sheet-like substrate. Then, the composition is cured by irradiating the composition with an electron beam to form a resin coating layer to obtain a sheet-like support. A method for producing a sheet-like support using a so-called electron beam curing technique is used. It became so. According to this method, there is an advantage that drying and melting equipment is not required, the apparatus is compact, and the solvent is not released to the atmosphere.

A method of curing an electron beam-curable resin composition using an electron beam curing technique is to irradiate an electron beam having a high energy and penetrate this into the coating layer to cure the resin composition. Thus, the obtained resin coating layer has advantages that it is hard, its surface has high gloss, and it is also excellent in water resistance. However, since the resin coating layer is hard, the resulting sheet-like support is poor in flexibility as a whole and has a drawback that the resin coating layer is cracked when bent. Attempts have been made to improve the flexibility of a cured resin coating film by selecting specific acrylate monomers and acrylate oligomers, but the relationship between the physical properties of the resin coating film and the flexibility of the sheet-shaped support should be optimized. It was not possible to grasp it accurately, and the selection of resin for improving flexibility was limited to a narrow range, making it difficult to improve flexibility.

[0009]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems, and in a sheet-like support having a resin coating layer made of a cured product of a resin composition which can be cured by irradiation with an electron beam, it can be bent. An object of the present invention is to provide a sheet-shaped support having flexibility that does not generate cracks and having high gloss, surface smoothness and water resistance.

[0010]

As a result of various studies to solve the problems of the prior art, the present inventors have found that the product of elongation and tensile strength of the resin coating layer is 70 %% kgf / mm ²
By using the resin film as described above, it has been found that the above-mentioned problems can be solved and cracks in the coating layer that occur when the sheet-shaped support is bent can be prevented, and the present invention has been completed.

That is, the sheet-like support of the present invention comprises a sheet-like substrate and a resin containing an unsaturated organic compound which is formed on at least one surface of the sheet-like substrate and is curable by electron beam irradiation as a main component. In a sheet-like support having a resin coating layer made of a cured product of the composition, the product of elongation and tensile strength of the resin film forming the resin coating layer is 70 ·% · kgf / mm ² or more. It is a feature.

The electron beam curable resin composition used in the present invention has a product of elongation and tensile strength of 70 ·% · kgf / mm ² or more when cured into a film. The electron beam curable unsaturated organic compound may be used alone or in combination of several kinds.

Such an electron beam-curable unsaturated organic compound has a terminal group that generates a radical upon irradiation with an electron beam and undergoes a crosslinking reaction. For example, as an oligomer, an acrylic or methacrylic ester of polyurethane,
Acrylic or methacrylic acid ester of polybutadiene,
Examples thereof include acrylic or methacrylic acid esters of polyether alcohol, maleic acid or fumaric acid esters, and the like. Examples of the monomer include an acrylic monomer, a methacrylic monomer, or a vinyl monomer having at least one double bond selected from an acryloyl group, a methacryloyl group, and a vinyl group in one molecule.

More specifically, acrylic, methacrylic, and vinyl monomers having one double bond include styrene, N-vinylpyrrolidone, methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. , 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-
Hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, isooctyl acrylate, lauryl acrylate, tetrahydrofurfuryl acrylate,
Methoxyethylene glycol acrylate, methoxypropylene glycol acrylate, ethyl carbitol acrylate, phenoxyethyl acrylate, cyclohexyl acrylate, cyclohexyl methacrylate, benzyl acrylate, isobornyl acrylate, ethylene oxide modified phenoxy acrylate,
Examples thereof include N, N-dimethylaminoethyl acrylate, and alkylphenoxy polyethylene glycol acrylate.

The acrylic, methacrylic, and vinyl monomers having two or more double bonds include 1,4-
Butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate , Neopentyl glycol diacrylate, bisphenol A, EO modified diacrylate, bisphenol A, PO modified diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, and divinylbenzene. However, the type of the additional compound is not limited to the above.

The coating amount of the resin coating layer of the present invention is 1 to 60.
It is preferably g / m ² . When the coating amount is less than 1 g / m ² , it is difficult to sufficiently exert the effects of the present invention,
In addition, problems such as pinholes may occur during the coating process. Further, if the coating amount exceeds 60 g / m ² , it is not practical in terms of cost.

The electron beam curable resin composition used in the present invention may contain a pigment. As the pigment, titanium dioxide (anatase type and rutile type), barium sulfate, calcium carbonate, aluminum oxide, zinc oxide, magnesium oxide, magnesium hydroxide, kaolin, talc, clay and the like can all be used. The content of the pigment is preferably 80% by weight or less based on the total solid content of the electron beam curable resin composition. If it exceeds 80% by weight, the flexibility of the obtained resin coating layer may be deteriorated and film cracking may occur.

To disperse the pigment in the above electron beam curable resin composition, a three roll mill (three roll mill), a two roll mill (two roll mill), a cowles dissolver, a homomixer, a sand grinder, a planetar. Lee mixer, ultrasonic disperser and the like can be used.

To produce the sheet-like support of the present invention,
It can be manufactured by a conventionally known method. That is, an electron beam curable resin composition is applied onto a sheet-like substrate and the applied layer is pressure-bonded to a highly smooth molding surface (a drum peripheral surface, a plastic film, etc.), or the electron beam curable resin is applied to the molding surface. The composition is applied, the sheet-like substrate is pressure-bonded to the applied layer, the electron beam is then applied to cure the applied layer, and the composition is adhered, and the laminate of the sheet-like substrate and the cured coating is peeled off from the molding surface. It is manufactured.

The electron beam curable resin composition may be applied to the molding surface or the surface of a sheet substrate such as paper or plastic by a bar coating method, a blade coating method, a squeeze coating method, an air knife coating method or a roll coating method. Any of the method, gravure coating method, transfer coating method and the like may be used. For this purpose, a fountain coater or slit die coater system can be used. Especially when the surface of a metal drum is used as the molding surface, a roll coating method using a rubber roll or an offset gravure coating method is used to prevent damage to the molding surface. The fountain coater or slit die coater method is advantageously used.

The electron beam accelerator for irradiating the coating layer of the electron beam curable resin composition with an electron beam is not particularly limited, and examples thereof include a Van de Graaff scanning system, a double scanning system and a curtain beam system. The electron beam irradiating device can be used, but among them, the curtain beam system, which is relatively inexpensive and has a large output, is effectively used. The acceleration voltage at the time of electron beam irradiation is preferably 100 to 300 KV, and the absorbed dose is preferably 0.1 to 6 Mrad,
0.5-5 Mrad is particularly preferred.

The oxygen concentration in the atmosphere during electron beam irradiation is preferably 500 ppm or less. Oxygen concentration is 5
If it exceeds 00 ppm, oxygen may act as a retarder for the polymerization reaction and the resin composition may be insufficiently cured. However, for the purpose of obtaining the surface smoothness of the electron beam curable sheet-like support, an appropriate molding surface such as a metal drum or a plastic film is pressed against the electron beam curable resin composition coating liquid applied on a paper substrate. In the case of exposure, the electron beam curable resin composition coating liquid does not come into direct contact with air during electron beam irradiation, and therefore it is not necessary to particularly reduce the oxygen concentration in the atmosphere during electron beam irradiation. There is of course no problem in using an inert gas for the purpose of suppressing the generation of ozone due to irradiation, or for the purpose of cooling a window that generates heat when an electron beam passes.

There is no particular limitation on the kind of the sheet-like base material used in the present invention, and a base paper having natural pulp as a main component, for example, a base paper made of wood pulp such as hardwood pulp, softwood pulp, hardwood mixed softwood pulp, and the like, Base paper made of bleached pulp such as kraft pulp, sulfite pulp and soda pulp can be preferably used. Further, it is possible to use a base paper produced from synthetic pulp or pulp containing synthetic fibers.

Various chemicals used for ordinary papermaking can be added to the base paper. For example, dry paper strengthening agents (cationized starch, cationized polyacrylamide,
And anionic polyacrylamide), sizing agents (such as fatty acid salts, rosins, maleated rosins, cationic sizing agents, and reactive sizing agents), fillers (clay,
Talc, kaolin, calcium carbonate, magnesium hydroxide, magnesium oxide, etc.), wet strength agents (such as melamine resin and epoxidized polyamide resin), fixing agents (such as aluminum sulfate and cationized starch), pH regulators One or more types (such as caustic soda and sodium carbonate) can be included.

The base paper may be one or more of water-soluble polymer additives, surface sizing agents, inorganic electrolytes, hygroscopic substances, pigments, pH adjusters, dyes, antistatic agents, polyvinyl alcohol, and carboxy-modified polyvinyl alcohol. It may be a tab-sized or size-pressed treatment liquid containing.

Furthermore, there is no problem in using a plastic film or so-called synthetic paper as a sheet-like substrate. A film formed by a melt extrusion method of a thermoplastic resin composition containing a polyolefin resin such as polypropylene resin or polyethylene resin can also be used as a sheet-shaped substrate.

For the plastic film or synthetic paper used as the sheet-shaped substrate, pigments (clay, talc, kaolin, calcium carbonate, titanium dioxide, magnesium hydroxide, etc.), dispersants (metal soap such as zinc stearate, etc.) Various kinds of surfactants), colored pigments and the like can be contained in one or more kinds.

The back surface of the sheet-shaped support of the present invention can also be coated with the resin composition. The resin coating layer on the back surface may be a cured product of a resin composition that is cured by electron beam irradiation, or a resin coating layer applied by another method, for example, a resin composition containing a water-soluble resin as a main component. Or a coating layer of a resin composition containing a solvent-based resin as a main component, or a coating layer obtained by applying a resin composition containing a thermoplastic resin as a main component by a melt extrusion method.

[0029]

EXAMPLES The constitution and effects of the present invention will be described in more detail with reference to the following examples, but of course the present invention is not limited to these modes.

Example 1 An electron beam curable resin composition (composition 1) was prepared by mixing and dispersing a mixture having the following composition for 1 hour with a paint conditioner.
Was prepared. Composition 1 Ingredient weight difunctional urethane acrylate oligomer 60.0 parts by weight (trademark: New Frontier R-1204, manufactured by Dai-ichi Kogyo Seiyaku Co.) acryloylmorpholine (Trademark: ACMO, manufactured by Kojin) 20.0 parts by weight of bisphenol A, EO adduct 20.0 parts by weight diacrylate (Trademark: Viscoat 700, Osaka Organic Chemical)

The above composition was applied onto one surface of a paper substrate having a basis weight of 180 g / m ² using a wire bar so that the coating amount after curing was 25 g / m ² , and this coating layer was formed. After laying it on a metal plate molding surface with chrome plating on the surface, irradiating an electron beam from the back side of the paper substrate at an acceleration voltage of 300 KV and an absorbed dose of 2 Mrad to cure the coating layer, and then mold the metal plate. The laminate of the paper base and the cured coating was peeled from the surface to prepare a sheet-like support. Using the obtained sheet-shaped support, flexibility was evaluated as follows. That is, the sheet-like support was bent 180 ° in the direction opposite to the resin coating layer, and the degree of cracking of the resin coating layer was visually evaluated. 2 points for items and 1 point for broken items 3
The grade was evaluated. Three and two points are practical, but
One point is not practical. The evaluation results are shown in Table 1.

The elongation and tensile strength of the resin film, which is a cured product of the above composition, were measured by the following methods. That is, the above composition was applied onto one surface of a PET film having a thickness of 100 μm using a wire bar so that the thickness after curing was 25 μm, and this applied layer was formed into a metal plate by plating the surface with chrome. After overlapping with the surface, electron beam is irradiated from the back of the PET film under the conditions of accelerating voltage: 300 KV and absorbed dose: 2 Mrad to cure the coating layer to form a resin coating, and then peel the resin coating layer from the metal plate molding surface. Then, a laminate composed of the resin coating layer and the PET film was produced. Then, the resin coating layer was peeled off from this laminate to obtain a resin film for measuring elongation and tensile strength. A sample with a width of 10 mm was prepared from this resin film, and a tensile tester (trademark: ST
ROGRAPH M-2, manufactured by Toyo Seiki)
A tensile test was carried out according to SP-8113, and the elongation rate and tensile strength were measured at the same time. For the measurement, the distance between the two grips at the beginning of the sample (length of the measured part of the sample) is 10 mm.
And the pulling speed: 5 mm / min.

The elongation and tensile strength of the resin film were calculated from the following equations. Elongation rate = 100 × ΔL / L (%) Tensile strength = F / S (kgf / mm ² ) Product of elongation rate and tensile strength = 100 × (ΔL · F) / (L ·
S) (% · kgf / mm ² ) L: Length of sample S: Cross-sectional area of sample ΔL: Length of elongation until sample is cut F: Tensile force when sample is expanded and cut by ΔL

Example 2 A sheet-like support was prepared in the same manner as in Example 1. However, the following electron beam curable resin composition (composition 2) was separately prepared and used in place of the composition 1. Composition 2 Ingredient weight bifunctional hydrogenated polybutadiene acrylate oligomer 50.0 parts by weight (average molecular weight of about 3000, trademark: NISSO PB TEAI-3000, manufactured by Nippon Soda) 2-hydroxypropyl acrylate 25.0 parts by weight (trademark: Light Ester HOP- A, manufactured by Kyoeisha Oil & Fat Co., Ltd. Lauryl acrylate (trademark: LA, manufactured by Osaka Organic Chemical Co., Ltd.) 25.0 parts by weight Table 1 shows the evaluation results obtained in the same manner as in Example 1.

Example 3 A sheet-like support was prepared in the same manner as in Example 1. However, the following electron beam curable resin composition (composition 3) was separately prepared and used in place of the composition 1. Composition 3 Ingredient weight trifunctional urethane acrylate oligomer 70.0 parts by weight (trademark: New Frontier R-1301, manufactured by Dai-ichi Kogyo Seiyaku) alkyl phenoxy polyethylene glycol acrylate 30.0 parts by weight (trademark: New Frontier NP-2, the first industrial Pharmaceutical products) Table 1 shows the evaluation results obtained in the same manner as in Example 1.

Example 4 A sheet-like support was prepared in the same manner as in Example 1. However, the following electron beam curable resin composition (composition 4) was separately prepared and used in place of the composition 1. Composition 4 Ingredient weight difunctional urethane acrylate oligomer 60.0 parts by weight (trademark: New Frontier R-1204, manufactured by Dai-ichi Kogyo Seiyaku Co.) Bisphenol A, EO adduct diacrylate 40.0 parts by weight (trademark: Viscoat 700, Osaka Organic Chemical Manufacture) Table 1 shows the evaluation results obtained in the same manner as in Example 1.

Example 5 A sheet-like support was prepared in the same manner as in Example 1. However, the following electron beam curable resin composition (composition 5) was separately prepared and used in place of the composition 1. Composition 5 Ingredient weight difunctional urethane acrylate oligomer 50.0 parts by weight (trademark: Beam Set 505B manufactured by Arakawa Chemical) acryloyl morpholine (Trademark: ACMO, Kohjin Co., Ltd.) 40.0 parts by weight of lauryl acrylate (trademark: LA, Osaka Organic Chemical Co. ) 10.0 parts by weight Table 1 shows the evaluation results obtained in the same manner as in Example 1.

Example 6 A sheet-like support was prepared in the same manner as in Example 1. However, the following electron beam curable resin composition (composition 6) was separately prepared and used in place of the composition 1. Composition 6 Ingredients amount difunctional urethane acrylate oligomer 70.0 parts by weight (trademark: Beam Set 551B, manufactured by Arakawa Chemical) ethyl carbitol acrylate 30.0 parts by weight (trademark: Viscoat # 190, manufactured by Osaka Organic Chemical Industry) Example 1 Table 1 shows the evaluation results obtained in the same manner.

Example 7 A sheet-like support was prepared in the same manner as in Example 1. However, the following electron beam curable resin composition (composition 7) was separately prepared and used in place of the composition 1. Composition 7 Ingredients amount difunctional urethane acrylate oligomer 60.0 parts by weight (trademark: New Frontier R-1204, manufactured by Dai-ichi Kogyo Seiyaku Co.) 2-hydroxypropyl acrylate 30.0 parts by weight (trademark: Light Ester HOP-A, manufactured by Kyoeisha Yushi ) Alkylphenoxy polyethylene glycol acrylate 10.0 parts by weight (Trademark: New Frontier NP-2, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) Table 1 shows the evaluation results obtained in the same manner as in Example 1.

Example 8 A sheet-like support was prepared in the same manner as in Example 1. However, the following electron beam curable resin composition (composition 8) was separately prepared and used in place of the composition 1. Composition 8 Ingredients amount difunctional urethane acrylate oligomer 50.0 parts by weight (trademark: Beam Set 505B manufactured by Arakawa Chemical) acryloyl morpholine (Trademark: ACMO, manufactured by Kojin) 30.0 parts by weight of 2-ethylhexyl acrylate 20.0 parts by weight (trademark: Acrylic Acid 2-ethylhexyl acid, monomer, manufactured by Wako Pure Chemical Industries, Ltd.) Table 1 shows the evaluation results obtained in the same manner as in Example 1.

Example 9 A sheet-like support was prepared in the same manner as in Example 1. However, the following electron beam curable resin composition (composition 9) was separately prepared and used in place of the composition 1. Composition 9 Ingredients amount difunctional urethane acrylate oligomer 56.0 parts by weight (trademark: Beam Set 505B manufactured by Arakawa Chemical) N- vinyl-2-pyrrolidone (trademark: Aronix M-0.99, manufactured by 28.0 parts by Toagosei Chemical Industry) 2- 16.0 parts by weight of ethylhexyl acrylate (trademark: 2-ethylhexyl acrylate, monomer, manufactured by Wako Pure Chemical Industries, Ltd.) Table 1 shows the evaluation results obtained in the same manner as in Example 1.

Examples 10-18 In Examples 1-9, the paper substrate used had a basis weight of 60 g /
A sheet-like support was prepared in the same manner as in Examples 1 to 9 except that the paper substrate of m ² was used instead. Table 1 shows the evaluation results obtained in the same manner as in Examples 1-9.

Example 19 A sheet-like support was prepared in the same manner as in Example 1. However, the following electron beam curable resin composition (composition 10) was prepared by adding zinc oxide to the composition 1 and used in place of the composition 1. Composition 10 Ingredient weight difunctional urethane acrylate oligomer 60.0 parts by weight (trademark: New Frontier R-1204, manufactured by Dai-ichi Kogyo Seiyaku Co.) acryloylmorpholine (Trademark: ACMO, manufactured by Kojin) 20.0 parts by weight of bisphenol A, EO adduct Diacrylate 20.0 parts by weight (Trademark: Biscoat 700, Osaka Organic Chemistry) Zinc oxide (Trademark: No. 1 Zinc Hua General Product, manufactured by Mitsui Mining & Smelting Co., Ltd.) 60.0 parts by weight Table 1 shows the evaluation results obtained in the same manner as in Example 1. Show.

Example 20 A sheet-like support was prepared in the same manner as in Example 7. However, composition 7 was mixed with titanium dioxide to prepare the following electron beam curable resin composition (composition 11), which was used instead of composition 7. Composition 11 Ingredient weight difunctional urethane acrylate oligomer 60.0 parts by weight (trademark: New Frontier R-1204, manufactured by Dai-ichi Kogyo Seiyaku Co.) 2-hydroxypropyl acrylate 30.0 parts by weight (trademark: Light Ester HOP-A, manufactured by Kyoeisha Yushi ) Alkylphenoxy polyethylene glycol acrylate 10.0 parts by weight (Trademark: New Frontier NP-2, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) Titanium dioxide (crystal system: anatase, 60.0 parts by weight Trademark: Taipaque A-220, manufactured by Ishihara Sangyo) Example 7 and Table 1 shows the evaluation results obtained in the same manner.

Example 21 A sheet-like support was prepared in the same manner as in Example 6. However, the following electron beam curable resin composition (composition 12) was prepared by adding titanium dioxide to the composition 6 and used in place of the composition 6. Composition 12 Ingredient weight difunctional urethane acrylate oligomer 70.0 parts by weight (trademark: Beam Set 551B, manufactured by Arakawa Chemical) ethyl carbitol acrylate 30.0 parts by weight (trademark: Viscoat # 190, manufactured by Osaka Organic Chemical Industry) titanium dioxide (crystalline System: rutile, trademark: Taipaque 60.0 parts by weight CR-58, manufactured by Ishihara Sangyo) Table 1 shows the evaluation results obtained in the same manner as in Example 6.

Example 22 A sheet-like support was prepared in the same manner as in Example 9. However, the composition 9 was blended with kaolin clay to prepare the following electron beam curable resin composition (composition 13).
Used instead of. Composition 13 Ingredient weight difunctional urethane acrylate oligomer 56.0 parts by weight (trademark: Beam Set 505B manufactured by Arakawa Chemical) N- vinyl-2-pyrrolidone (trademark: Aronix M-0.99, manufactured by 28.0 parts by Toagosei Chemical Industry) 2- Ethylhexyl acrylate 16.0 parts by weight (Trademark: 2-ethylhexyl acrylate, monomer, Wako Pure Chemical Industries) Kaolin clay (Trademark: NN Kaolin clay, 60.0 parts by weight Tsuchiya Kaolin Kogyo)

Comparative Example 1 A sheet-shaped support was prepared in the same manner as in Example 1. However, separately, the following electron beam curable resin composition (composition 14)
Was prepared and used in place of Composition 1. Composition 14 Ingredient weight difunctional urethane acrylate oligomer 60.0 parts by weight (trademark: New Frontier R-1204, manufactured by Dai-ichi Kogyo Seiyaku) 1,9-nonanediol diacrylate 40.0 parts by weight (trademark: L-C9A, first industrial Pharmaceutical products) Table 1 shows the evaluation results obtained in the same manner as in Example 1.

[0048]Comparative example 2 A sheet-shaped support was prepared in the same manner as in Example 3. However
And acrylate oligomer and acrylate of composition 3
Change the ratio of monomers to 50:50 and cure with the following electron beam
Of the resin composition (composition 15) is prepared in place of the composition 3.
I used it. Composition 15 Component Compounding amount Trifunctional urethane acrylate oligomer 50.0 parts by weight (trademark: New Frontier R-1301, manufactured by Dai-ichi Kogyo Seiyaku) Alkylphenoxy polyethylene glycol acrylate 50.0 parts by weight (trademark: New Frontier NP-2, manufactured by Dai-ichi Kogyo Seiyaku) Example 3 and Table 1 shows the evaluation results obtained in the same manner.

Comparative Example 3 A sheet-like support was prepared in the same manner as in Example 1. However, separately, the following electron beam curable resin composition (composition 16)
Was prepared and used in place of Composition 1. Composition 16 Ingredient weight trifunctional urethane acrylate oligomer 100.0 parts by weight (trademark: New Frontier R-1301, manufactured by Dai-ichi Kogyo Seiyaku Co.) Table 1 shows the results of evaluation conducted in the same manner as in Example 1.

Comparative Example 4 A sheet-like support was prepared in the same manner as in Example 1. However, separately, the following electron beam curable resin composition (composition 17)
Was prepared and used in place of Composition 1. Composition 17 Ingredient weight difunctional urethane acrylate oligomer 50.0 parts by weight (trademark: New Frontier R-1204, manufactured by Dai-ichi Kogyo Seiyaku) alkyl phenoxy polyethylene glycol acrylate 50.0 parts by weight (trademark: New Frontier NP-2, the first industrial Pharmaceutical products) Table 1 shows the evaluation results obtained in the same manner as in Example 1.

Comparative Example 5 A sheet-like support was prepared in the same manner as in Example 1. However, separately, the following electron beam curable resin composition (composition 18)
Was prepared and used in place of Composition 1. Composition 18 Ingredient weight trifunctional urethane acrylate oligomer 50.0 parts by weight (trademark: New Frontier R-1301, manufactured by Dai-ichi Kogyo Seiyaku Co.) acryloylmorpholine (Trademark: ACMO, manufactured by Kojin) 30.0 parts by weight of an alkyl phenoxy polyethylene glycol acrylate 20.0 Parts by weight (Trademark: New Frontier NP-2, manufactured by Dai-ichi Kogyo Seiyaku) Titanium dioxide (crystal system: rutile, trademark: Taipaque 60.0 parts by weight CR-58, manufactured by Ishihara Sangyo)

Comparative Example 6 A sheet-shaped support was prepared in the same manner as in Example 1. However, separately, the following electron beam curable resin composition (composition 19)
Was prepared and used in place of Composition 1. Composition 19 Ingredient weight trifunctional urethane acrylate oligomer 60.0 parts by weight (trademark: Beam Set 550B, Arakawa Chemical Industries, Ltd.) 1,9-nonanediol diacrylate (trademark: L-C9A, 40.0 parts by weight produced by Dai-ichi Kogyo Seiyaku) Titanium dioxide (Crystal system: Anatase, 60.0 parts by weight Trademark: Typake A-220, manufactured by Ishihara Sangyo) Table 1 shows the evaluation results obtained in the same manner as in Example 1.

Comparative Example 7 A sheet-like support was prepared in the same manner as in Comparative Example 1. However, composition 14 was mixed with titanium dioxide to prepare the following electron beam curable resin composition (composition 20).
Used in place of 4. Composition 20 Ingredient weight difunctional urethane acrylate oligomer 60.0 parts by weight (trademark: New Frontier R-1204, manufactured by Dai-ichi Kogyo Seiyaku Co.) 1,9-nonanediol diacrylate (trademark: L-C9A, 40.0 parts by weight of the first industrial Pharmaceutical) Titanium dioxide (crystal system: anatase, 60.0 parts by weight Trademark: Typake A-220, manufactured by Ishihara Sangyo Co., Ltd.) Table 1 shows the evaluation results obtained in the same manner as in Comparative Example 1.

[0054]

[Table 1]

[0055]

The sheet-like support having a resin coating layer made of a cured product of a resin composition curable by electron beam irradiation according to the present invention has a flexible coating which does not crack when bent. It also has high gloss, high smoothness, and water resistance, and is extremely useful industrially.

Claims (1)

[Claims] 1. A resin coating comprising a sheet-like substrate and a cured product of a resin composition which is formed on at least one surface of the sheet-like substrate and has an unsaturated organic compound which is curable by electron beam irradiation as a main component. And the product of elongation and tensile strength of the resin film forming the resin coating layer is 70.
% -Kgf / mm ² or more, a sheet-like support.