JPH0815772B2 - Sheet - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION "Industrial field of application" The present invention relates to a sheet having excellent surface strength and printability.

"Prior art" Conventionally, a printing sheet that is formed by applying a resin layer that is cured by irradiation with ultraviolet rays or electron beams onto a support such as plastic film, synthetic paper, coated paper, and high-quality paper and cured with ultraviolet rays or electron beams is Are known. However, there is a problem that a peeling phenomenon occurs in which the resin layer is peeled off due to the weak adhesion between the support and the surface layer, and because the wettability of the sheet surface is poor, ink repellency or poor adhesion of the ink after printing, etc. There was a problem. These problems are particularly remarkable when a plastic film, synthetic paper, or coated paper having a binder-rich layer formed thereon is used as a support.

"Problems to be Solved by the Invention" The present invention aims to provide a sheet having excellent surface strength and printability.

"Means for Solving the Problems" The present invention relates to a monofunctional or polyfunctional (meth) acrylate having an amino group or an alkylamino group on a support, and a monofunctional group having a carboxyl group, a sulfonic acid group or a phosphoric acid group. Alternatively, the sheet is characterized in that a surface layer containing a polyfunctional (meth) acrylate is provided and the layer is cured by an electron beam.

"Function" The present invention is to mix a basic group such as an amino group or an alkylamino group, and an acidic group such as a carboxyl group, a sulfonic acid group or a phosphoric acid group in the surface layer, so that the support and the cured layer are cured. It obtains excellent adhesion to the surface layer and excellent printability.

As the support for forming the surface layer, various materials such as plastic films such as polyester, polyethylene, polypropylene and the like, synthetic paper, coated paper, high-quality paper and the like are used.

Among the resins forming the surface layer, as the monofunctional or polyfunctional (meth) acrylate having an amino group or an alkylamino group, NN dimethylaminoethyl (meth) acrylate, 2-vinylpyridine, polyester (meth) acrylate Examples of the amino-modified product, amino-modified product of polyurethane (meth) acrylate, amino-modified product of epoxy (meth) acrylate, and the like.

As the monofunctional or polyfunctional (meth) acrylate having a carboxyl group, a sulfonic acid group or a phosphoric acid group, an ethylenically unsaturated mono- or polycarboxylic acid, a carboxy-modified product of a polyester (meth) acrylate,
Carboxy-modified (meth) acrylates such as carboxy-modified polyurethane (meth) acrylates, carboxy-modified epoxy (meth) acrylates, aliphatic or aromatic vinyl sulfonic acids, (meth) acryloxy phosphates, (meth) acrylics An oxyalkyl phosphate ester etc. can be illustrated.

To 100 parts by weight of a monofunctional or polyfunctional (meth) acrylate having an amino group or an alkylamino group (hereinafter simply referred to as a basic group-containing resin), a carboxyl group,
A monofunctional or polyfunctional (meth) acrylate having a sulfonic acid group or a phosphoric acid group (hereinafter simply referred to as an acidic group-containing resin) is preferably mixed in an amount of about 10 to 1000 parts by weight, more preferably 50 to 150 parts by weight.

Further, a film forming property may be further improved by adding a prepolymer or a monomer other than the above, which is curable by an electron beam.
However, the mixture of the resin containing a basic group and the resin containing an acidic group is at least 1% by weight based on the total resin forming the surface layer.
It is preferably contained, more preferably 2 to 90% by weight, and most preferably 3 to 70% by weight.

Examples of prepolymers and monomers that can be cured by an electron beam other than the above include those listed below.

(A) Poly (meth) of aliphatic, alicyclic, araliphatic polyhydric alcohol having 2 to 6 valences and polyalkylene glycol
Acrylate; (b) Poly (meth) acrylate of polyhydric alcohol obtained by adding alkylene oxide to aliphatic, alicyclic, araliphatic or aromatic polyhydric alcohol of 2 to 6; (c) Polyester poly (Meth) acrylate; (d) Epoxy poly (meth) acrylate; (e) Polyurethane poly (meth) acrylate; (f) Polyamide poly (meth) acrylate; (g) Polysiloxane poly (meth) acrylate; (h) side A vinyl-based or diene-based low polymer having a (meth) acryloyloxy group at the chain and / or the terminal; (i) a modified oligoester (meth) acrylate according to (a) to (i) above; Can be mentioned.

Further, as the monomer, (a) an amide group-containing monomer represented by vinyllactams such as ethylenically unsaturated (meth) acrylamide or alkyl-substituted (meth) acrylamide, N-vinylpyrrolidone; (b) ethylene (C) Alkyl ester of ethylenically unsaturated carboxylic acid; (d) Nitrile group-containing monomer such as (meth) acrylonitrile; (e) Styrene; f) esters of ethylenically unsaturated alcohols such as vinyl acetate and (meth) allyl acetate; (g) mono (meth) acrylates of alkylene oxide addition polymers of compounds containing active hydrogen (h) polybasic acids and An ester group-containing bifunctional monomer represented by a diester with saturated alcohol; (i) a compound containing active hydrogen Bifunctional monomer consisting of diester of alkylene oxide addition polymer and (meth) acrylic acid; (j) Bisacrylamide such as N, N-methylenebisacrylamide; (k) Divinylbenzene, divinylethylene glycol, divinyl sulfone , Divinyl ether, divinyl ketone, and other bifunctional monomers; (l) ester group-containing polyfunctional monomers represented by polyesters of polycarboxylic acids and unsaturated alcohols; (m) active hydrogen-containing compounds Polyfunctional monomer comprising polyester of alkylene oxide addition polymer and (meth) acrylic acid; (n) Polyfunctional unsaturated monomer such as trivinylbenzene.

Etc.

Incidentally, in the surface layer component, in addition to the electron beam curable prepolymers and monomers as described above, if necessary, for example, an inorganic pigment, an organic pigment, a non-electron beam curable resin, an antifoaming agent, a leveling agent, a lubricant, an interface Additives such as an activator, a plasticizer, an ultraviolet absorber, a fluorescent dye, a coloring dye, a fluorescent pigment, and a coloring pigment can be appropriately added.

The surface layer components as described above are thoroughly mixed by an appropriate mixing stirrer such as a mixer, and then coated on the support by various known methods. If necessary, the resin component may be heated to adjust the viscosity. Further, the coating amount is not necessarily limited, but if the coating amount is less than 0.1 g / m ² , the desired effect of the present invention cannot be expected, and if the coating amount exceeds 20 g / m ² , there is an economical problem, so it is preferable. Is 0.1-20g
/ m ² , more preferably in the range of about 0.3 to 15 g / m ² .

The surface layer formed on the support is cured by irradiation with an electron beam, and the amount of the electron beam to be irradiated is preferably 0.1 to 15 Mrad, more preferably 0.5 to 10 Mrad. Because
If it is less than 0.1 Mrad, the resin component cannot be sufficiently cured, and excessive electron beam irradiation exceeding 15 Mrad may cause deterioration or discoloration of the support.

In addition, as a method of irradiating an electron beam, for example, a scanning method, a curtain beam method, a broad beam method, or the like can be adopted, and an acceleration voltage for irradiation is suitably about 100 to 300 KV. If necessary, the sheet provided with the surface layer can be smoothed with a super calender or the like.

The sheet thus obtained is printed by, for example, UV printing and used in various fields such as posters, wallpaper and packaging.

UV printing is printing in which ink is cured by ultraviolet rays, and is characterized in that the printed matter is excellent in water resistance, chemical resistance, and abrasion resistance.

"Examples" Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. Unless otherwise specified, parts and% in the examples are parts by weight and% by weight, respectively.
Indicates.

Example 1 A mixture of carboxy-modified acrylate and polyester acrylate (trade name; FS) on a polypropylene film.
-3030, Mitsubishi Rayon Co., Ltd.) 50 parts and a mixture of amino-modified synthetic acrylate and polyester acrylate (trade name: F
S-3054, manufactured by Mitsubishi Rayon Co., Ltd.) 50 parts of the mixed solution was applied so that the dry coating amount was 5 g / m ^2, and an electron curtain type electron beam irradiation device (CB: 150 type, manufactured by ESI Co.) A sheet was obtained by treating with an irradiation dose to cure the resin component.

Example 2 In Example 1, 30 parts of monoacryloxyphthalate (trade name; M-5400, manufactured by Toagosei Kagaku) as resin components and NN dimethylaminoethyl methacrylate (trade name; D)
A sheet was obtained in the same manner except that a mixed solution of 30 parts of M, manufactured by Mitsubishi Rayon Co., Ltd.) and 40 parts of oligoester acrylate (trade name; M-8030, manufactured by Toagosei Kagaku) was used.

Example 3 Monoacryloxyphthalate M- in Example 2
A sheet was obtained in the same manner except that 30 parts of methacrylic oxyphosphate ester (trade name; Phosmer M, manufactured by Unichemical Co., Ltd.) was used instead of 5400.

Example 4 Preparation of coated paper Polyvinyl alcohol (trade name; PVA-117, product of Kuraray Co., Ltd.) 8% aqueous solution 1000 parts Calcium carbonate (trade name; Softon 1800, Bihoku Powder Co., Ltd.) 100 parts Water 100 parts coating The amount of the liquid applied to woodfree paper with a basis weight of 54 g / m ² is
The coated paper was coated and dried to a coating weight of 6 g / m ^2, and smoothed with a super calender to obtain coated paper.

A sheet was obtained in the same manner as in Example 1 except that the above coated paper was used as the support instead of the polypropylene film.

Example 5 A sheet was obtained in the same manner as in Example 2 except that the coated paper used in Example 4 was used as the support instead of the polypropylene film.

Example 6 A sheet was obtained in the same manner as in Example 3 except that the coated paper used in Example 4 was used as the support instead of the polypropylene film.

Comparative Example 1 A mixture FS-3030 of carboxy-modified acrylate and polyester acrylate as a resin component in Example 1.
A sheet was obtained in the same manner except that 100 parts of was used.

Comparative Example 2 In Example 1, a mixture of amino-modified acrylate and polyester acrylate FS-3054 was used as a resin component.
A sheet was obtained in the same manner except that 0 part was used.

Comparative Example 3 A sheet was obtained in the same manner as in Example 1, except that 100 parts of oligoester acrylate (trade name; M-8030, manufactured by Toagosei Kagaku) was used as the resin component.

Comparative Example 4 A sheet was obtained in the same manner as in Comparative Example 1 except that the coated film used in Example 4 was used as the support instead of the polypropylene film.

Comparative Example 5 A sheet was obtained in the same manner as in Comparative Example 2 except that the coated paper used in Example 4 was used as the support instead of the polypropylene film.

Comparative Example 6 A sheet was obtained in the same manner as in Comparative Example 3 except that the coated film used in Example 4 was used as the support instead of the polypropylene film.

The sheets thus obtained were subjected to the following tests, and the respective results are shown in Table 1.

[Evaluation Criteria for Surface Strength (Adhesion to Support)]

Cellophane tape (manufactured by NITT0) was adhered to the surface of the sheet and then peeled off to visually determine the peeled state of the surface layer.

◯: No abnormality in the surface layer ×: Peeling of the surface layer [Evaluation criteria for printability (ink repellency)] Printing was performed by a UV printing machine manufactured by Garasu Co., and the printing effect was visually judged.

UVS-SEL orange manufactured by Moroboshi Ink was used as the printing ink.

○: Completely printed ×: Repelling of the printing ink is observed [Evaluation criteria for printability (ink adhesion)] After printing with a UV printing machine manufactured by Gallus, the same test as the evaluation of surface strength was performed. .

UVS-SEL orange manufactured by Moroboshi Ink was used as the printing ink.

○: No abnormality on the printing surface ×: There is peeling of the printing ink "Effect" As is clear from the results of Table 1, the sheet of the present invention is
The sheet was excellent in surface strength and printability.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication D21H 27/36

Claims (3)

[Claims] 1. A monofunctional or polyfunctional (meth) acrylate having an amino group or an alkylamino group and a monofunctional or polyfunctional (meth) acrylate having a carboxyl group, a sulfonic acid group or a phosphoric acid group on a support. A sheet comprising a surface layer containing the material, the layer being cured by an electron beam. 2. The sheet according to claim 1, wherein the support is a plastic film or synthetic paper. 3. The sheet according to claim 1, wherein the support is coated paper or high-quality paper.