JPH07173800A - Processed product of metallized paper - Google Patents

Abstract

PURPOSE:To obtain a processed product of a metallized paper having excellent printability by using a metallized paper. CONSTITUTION:This processed product of a metallized paper is composed of a metallized paper and a transparent paper integrated with each other by using a radiation-curable resin cured by radiation. The transparent paper preferably has a basis weight of 10-45g/m<2> and a transparency of >=70%. A metallic layer having delustered appearance can be produced without applying a matting treatment such as embossing to the metallized surface owing to the presence of the transparent paper covering the metallized layer. The paper is easily printed or pasted since the paper has smooth surface and uniform composition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal vapor-deposited paper processed product, and more particularly to a metal vapor-deposited paper processed product based on metal vapor-deposited paper having smoothness and excellent printability.

[0002]

2. Description of the Related Art Conventionally, as a method of obtaining a metallized metallized paper, for example, a method of laminating a matte-treated aluminum foil on a support, or a method of laminating a non-mattized aluminum foil There are a method of forming a mat by embossing, a method of depositing a metal on the surface of the matted paper, a method of providing a thermally expandable microcapsule layer on a support, forming a metal deposited layer on the layer, and then performing heat treatment. The matte metal vapor-deposited paper obtained by any method has the metal layer or the resin protective layer provided thereon exposed on the surface, and the matte effect reduces the smoothness of the surface in the latter three cases. As a result, the printability on the surface is poor. Further, since the metal layer or the resin protective layer thereof is exposed, the metal layer or the like is easily peeled off due to rubbing or the like.
Further, there is a problem that a glossy feeling remains partially because the treatment for lowering the surface smoothness is not always performed uniformly.

[0003]

SUMMARY OF THE INVENTION The problem to be solved by the present invention is, therefore, in a matte metal vapor-deposited paper processed product, which has a smooth surface and is suitable for printing without impairing the texture, and has a metal vapor deposition layer. It is intended to provide a processed metal vapor-deposited paper product capable of preventing peeling of the metal.

[0004]

The inventor of the present invention has made the following inventions as a result of earnest research for solving the above problems.

That is, the invention is an invention of a processed metal-vapor-deposited paper characterized in that it has a structure in which a metal-vapor-deposited paper and a transparent paper are superposed via a radiation-curable resin and cured by irradiation to be integrated.

The transparent paper is preferably a transparent paper having a basis weight of 10 to 45 g / m ² and a transparency of 70% or more, and it is preferable to use tracing paper, impregnated tracing paper or Japanese paper.

Radiation irradiation is performed by electron beam irradiation or ultraviolet irradiation. Further, the radiation curable resin may be colored.

The details of the present invention will be described below. In the present invention, the transparency is a value represented by 100- (opacity value). The opacity value is the opacity (%) measured by JIS P8138. The thickness is JIS P 811
8 This is the value measured by the test method for the thickness and density of paper and paperboard.

In the present invention, paper having a transparency of 70% or more is called transparent paper. The transparent paper used in the present invention is not particularly limited as long as it has a transparency of 70% or more, such as glassine paper, resin-impregnated paper, typewriter paper, condenser paper, tracing paper, impregnated tracing paper or Japanese paper. However, tracing paper, impregnated tracing paper or Japanese paper is suitable.

The transparent paper having a transparency of 70% or more is suitable as a laminating material, and the transparency of less than 70% is unsuitable because the metallic feeling due to the metal vapor deposition layer is lost.

The tracing paper or impregnated tracing paper referred to here is explained as follows according to the latest paper processing handbook (Tec Times, published August 20, 1988). “Natural trepe is a tracing paper that takes into consideration the trace work and diazo copy work when it comes to original drawing paper. Tracing paper is transparent paper. The reason why paper is opaque and white is that general high-quality paper contains about 50% air in its volume. The paper looks white and becomes opaque due to the distribution of minute voids and the difference in refractive index between cellulose fibers and air. There are two types of tracing paper, natural trepe and impregnated trepe. Natural trepe is a paper made by making pulp fibers highly beaten to reduce voids to 15 to 25%. On the other hand, the impregnated trepe is a transparent paper obtained by impregnating general high-quality paper with a transparent resin having the same refractive index as that of cellulose. ]

Furthermore, a new edition of the printing encyclopedia (edited by the Japan Printing Association)
The Ministry of Finance Printing Bureau's section on transparent paper states, "A type of thin, transparent writing paper. The original image is shown as a transparent copy and used for manuscripts such as the Bandaiq method and blueprints. There are two types, 1) is a raw material that is beaten to a highly viscous state so as to be transparent, or a processed paper that is made transparent by applying a mixture of Canadian balsam, turpentine oil, vegetable oil, etc. to thin paper. 2) is thin-leaf Japanese paper made by the flow drop method using Kozo and Mitsumata. Also called drawing paper. ] Is described.

According to the Paper and Pulp Technology Handbook (1982, Japan Pulp and Paper Technology Association), "general term for thin leaf, dictionary paper, rice paper, type paper, printing paper, etc. have various types depending on the application, and the basis weight is 40 g / m ² or less. So, thin paper is 20g / m
² or less. ] Is described.

Based on the above description, in the present invention, paper having a transparency of 70% or more is called transparent paper for the sake of convenience.
Above all, the transparent paper of the present invention preferably has a basis weight of 10 to 45 g / m ² . For the transparent paper of the present invention, it is possible to use, if necessary, raw materials commonly used in papermaking such as wood pulp, synthetic pulp, fillers, sizing agents, paper strengthening agents and dyes.

When the basis weight of the transparent paper is less than 10 g / m ² , the dimensional stability is poor and it is difficult to control the tension when laminating.
Even if a solventless radiation curable resin is used, wrinkles are likely to be formed, and it may be broken during writing with a pen plotter, which is not preferable. Also, if the basis weight is more than 45 g / m ² , the thickness after laminating becomes thick and the suppleness of the paper disappears,
It is not preferable because it lowers the metallic feeling of the most important metal vapor deposition layer.

As a precedent for laminating a support and a transparent paper, Japanese Patent Publication No. 62-28465 discloses an ultra thin paper laminated on both sides of a transparent synthetic resin film, and the ultra thin paper is made of a thermoplastic synthetic resin. The method of impregnation is described in
Further, Japanese Patent Application Laid-Open No. 4-18200 describes a method of superposing a Japanese paper on one side or both sides of a plastic film with an adhesive interposed therebetween and performing a super calender treatment. All of these are intended for use as recording paper, and there is no description about fancy properties such as metal deposition on a support.

The metal vapor-deposited paper is generally a paper, a coated paper, an art paper, a cast paper, or the like, which is subjected to a sealing treatment with a resin layer, and then a metal such as aluminum is temporarily placed in a vacuum apparatus. By evaporating and vapor depositing this on the resin layer, metal vapor deposition is performed to obtain metal vapor deposition paper. Or
As shown in pages 10 to 16 of the magazine Convertec August 1988, the metal vapor-deposited film can be peeled off by laminating the metal vapor-deposited surface, and after curing the resin, the sheet is peeled off to form the metal vapor-deposited film. A method using a metal-deposited transfer foil for transferring onto a support is known. As such a support, ordinary natural pulp paper such as high-quality paper, glassine paper, cast paper, coated paper and the like is used. Of course, transparent paper such as tracing paper can also be used as the support. Although it is different from the expression of processed metal vapor-deposited paper, so-called synthetic paper, which is made of synthetic fiber or synthetic resin film as pseudo paper, fiber structure (woven cloth, knitted cloth, non-woven cloth), inorganic sheet such as glass fiber sheet, etc. , Synthetic resin film, glass, metal surface, board or plywood, laminated board, etc. can be used. There is no problem even if these are subjected to a sealing process or colored for the purpose of preventing omission or unevenness of metal vapor deposition.

There are a vacuum vapor deposition method and a transfer method for forming the metal vapor deposition layer in the present invention. When the vacuum vapor deposition method is adopted, a resin for sealing is applied to a support, dried, and then a metal such as aluminum is once evaporated in a vacuum apparatus, and this is vapor-deposited on the coating layer. Also, when the transfer method is adopted, the metal vapor deposition surface of the metal vapor deposition film, from which the metal vapor deposition film can be peeled off, is bonded via a sealing resin, and after the resin is cured, the sheet is peeled off to support the metal vapor deposition film. Transfer to the body.

As the resin for sealing the support used in the present invention, an overprinting resin or a varnishing resin generally used in the paper field can be used. For example, a rubber resin, a synthetic rubber resin, Modified rubber resin, polyvinyl acetate resin, polyurethane resin, nitrocellulose resin, polyester resin, urea resin, phenol resin, melamine resin, resorcinol resin, polyvinyl alcohol resin, sodium silicate resin , Epoxy resin, cyanoacrylic resin, acrylic resin,
Silicone resins, unsaturated polyester resins, ethylene / vinyl acetate resins, polyamide resins, aliphatic or aromatic polyurethane resins, copolymer nylon resins, etc. are used. The coating shape of the sealing resin may be an organic solvent type, an aqueous solution type, an emulsion type, a reaction curing type, or a hot melt type. Further, a radiation curable resin may be used for sealing.

The coating amount of the sealing resin is not limited, but for the purpose of sufficiently exerting the sealing effect on the metal vapor deposition surface,
Preferably in the range of ^{2g / m 2 ~45g / m 2} .
If the coating amount of the resin is smaller than this range, the deposition surface will not be sufficiently filled, and pinholes will remain. If it is larger than this range, the filling effect will not be improved.

In the present invention, the electron beam curable resin and the ultraviolet curable resin are collectively referred to as a radiation curable resin. As the radiation curable resin used in the present invention, unsaturated polyester having a radical polymerization curable functional group at the molecular end or in the molecular side chain, modified unsaturated polyester, an acrylic polymer and a polymer having an ethylenically unsaturated bond, The monomers and the like can be used alone or together with other solvents. It can be roughly classified as follows regardless of the number of radiation-curable functional groups.

(1) Aliphatic, alicyclic, aromatic, araliphatic polyhydric alcohol and (meth) acrylate of (poly) alkylene glycol (2) Aliphatic, alicyclic, aromatic, araliphatic (Meth) acrylate of polyhydric alcohol obtained by adding alkylene oxide to polyhydric alcohol of (3) (poly) ester (meth) acrylate (4) (poly) urethane (meth) acrylate (5) epoxy (meth) acrylate ( 6) (Poly) amide (meth) acrylate (7) (meth) acryloyloxyalkyl phosphate ester and salts thereof (8) Vinyl-based or diene-based compound having a (meth) acryloyloxy group at the side chain or terminal (9) ) Monofunctional (meth) acrylate, vinylpyrrolidone, (meth) acryloyl compound (10) Ethylenically unsaturated bond (11) Mono- or polycarboxylic acids having an ethylenically unsaturated bond, and their alkali metal salts, ammonium salts, amine salts, etc. (12) Vinyllactam and polyvinyllactam compounds (13) Acrylamide compounds (14) ) (Poly) ether having an ethylenically unsaturated bond and its ester (15) Ester of alcohol having an ethylenically unsaturated bond (16) Polyalcohol having an ethylenically unsaturated bond and its ester (17) Styrene, divinylbenzene Aromatic compound having one or more ethylenically unsaturated bonds (18) (Poly) organosiloxane compound having a (meth) acryloyloxy group at the side chain or terminal (19) Silicone having an ethylenically unsaturated bond Compound (20) Amino modification Or a carbamate-modified (meth) acrylate (21) A multimer or oligoester (meth) acrylate-modified product of the compounds described in (1) to (20) above. These resins may be used alone or in combination. You may use it.

The coating amount of the radiation curable resin is not limited, but it is preferably in the range of ^{2 to} 45 g / m ^{2 for} the purpose of sufficiently maintaining the adhesive strength between the transparent paper and the support. If the coating amount of the radiation curable resin is smaller than this range, the adhesiveness between the metal vapor-deposited paper and the transparent paper will not be sufficient, and if it exceeds this range, not only will it not contribute to the improvement of the adhesiveness, but also in terms of transparency, rigidity, etc. Fancy may deteriorate. The radiation curable resin may be colorless or colored from the viewpoint of not deteriorating the metallic feel of the metal vapor deposition layer, but it is preferably as transparent as possible. The radiation curable resin may be colored and used so that the color can be discriminated from the transparent paper side. At that time, the colorant used is not particularly limited as long as it is a colorant used in a general paper field.

The method of applying the radiation-curable resin or sealing resin of the present invention includes gravure coater, gravure offset coater, bar coater, roll coater, air knife coater, U comma coater and AKKU.
Coater, smoothing coater, micro gravure coater, reverse roll coater, 4 or 5 roll coater, blade coater, dip coater, falling curtain coater, slide coater, die coater,
Any coater such as a squeeze coater may be used.

The electron beam irradiation used for curing the electron beam irradiating resin in the present invention has an accelerating voltage of 100 to 1000 KV, more preferably 100, from the viewpoint of transmission power and curing power.
It is preferable to use an electron beam accelerator of up to 300 KV so that the absorbed dose in one pass is 0.5 to 20 Mrad.
If the accelerating voltage or the electron beam irradiation dose is lower than this range, the electron beam penetrating power is too low to perform sufficient curing, and
If the amount is larger than this range, not only the energy efficiency is deteriorated, but also unfavorable effects on quality such as decomposition of transparent paper, resin and additives, coloring, strength reduction of processed metal vapor-deposited paper and the like appear.

The electron beam accelerator may be, for example, an electro curtain system, a scanning type, a double scanning type or the like.

During electron beam irradiation, if the oxygen concentration is high, the curing of the electron beam curable resin is hindered, so replacement with an inert gas such as nitrogen, helium, carbon dioxide, etc. is carried out, and the oxygen concentration is 600 ppm or less, Preferably 400 pp
Irradiation is preferably performed in an atmosphere suppressed to m or less.

In the present invention, the radiation-curable resin can be cured by irradiation with ultraviolet rays, if necessary. Examples of the ultraviolet irradiation device used include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, and a metal halide lamp.
There is also an ozoneless type that produces less ozone. Generally, a plurality of lamps having an output of 80 w / cm or more are used in parallel.

In the present invention, as the photoinitiator used for curing by ultraviolet irradiation, acetophenones such as di- and trichloroacetophenone, benzophenone, Michler's ketone, benzyl, benzoin, benzoin alkyl ether, benzyl dimethyl ketal, tetramethyl are used. There are thiuram monosulfides, thioxanthones, azo compounds and the like, which are selected from the viewpoints of the type of curing reaction of the curable resin, stability, suitability with an ultraviolet irradiation device, and the like. The amount of the photoinitiator used is usually in the range of 0.1 to 5% with respect to the ultraviolet curable resin. Further, a storage stabilizer such as hydroquinone may be used in combination with the photoinitiator.

As the sensitizer used in the present invention, an aliphatic amine, an amine containing an aromatic group, a nitrogen heterocyclic compound,
Allyl urea, O-tolylthiourea, sodium diethyldithiophosphate, soluble salts of aromatic sulfinic acid,
N, N-disubstituted-P-aminobenzonitrile compounds, tree n
-Butylphosphine, sodium diethylthiophosphate, Michler's ketone, N-nitrosohydroxylamine derivatives, oxazoline compounds, carbon tetrachloride, hexachloroethane, etc. are available, and commonly used as a photoinitiator, the curing rate can be improved.

[0031]

Since the processed metal vapor-deposited paper of the present invention has a structure in which transparent paper is attached to the metal vapor-deposited paper, the metal vapor-deposited surface is not exposed on the surface, and therefore the metal vapor-deposited layer is not rubbed even if strongly rubbed. The problem of peeling does not occur. Further, since the surface is transparent paper, it has smoothness and is uniform in terms of material, so printing and gluing are easy. It is a processed metal vapor-deposited paper product that has a calm texture. In addition, even when manufacturing the transparent paper, without contact with the solvent or solution,
Since the transparent paper is not heated, wrinkles and irregularities do not occur and curling does not occur, and a processed metal vapor-deposited paper product having good dimensional stability can be obtained.

[0032]

EXAMPLES Next, the present invention will be described in more detail by way of examples, but the contents of the present invention are not limited to the examples.

Example 1 A commercially available tracing paper having a basis weight of 45 g / m ² was used as a support, an alkyd resin (Melan 46D manufactured by Hitachi Chemical Co., Ltd.) was used as a sealing resin, and a dry weight was 10 g with a direct gravure coater. / M ² and coated with hot air. Next, aluminum was vapor-deposited by a vacuum vapor deposition method to obtain a metal vapor-deposited paper. An electron beam curable resin (Shin-Nakamura Chemical Co., A-TMM-
3) is applied with a direct gravure coater and the coating weight is 10 g
/ M ² so that the transparent paper has a basis weight of 12 g /
m ^2, superimposed the transparency 82% of tracing paper, at an accelerating voltage of 200kv transparent sheet side, 2 Mrad
The electron beam curable resin was cured by irradiating it with an electron beam so that the absorbed dose would be to obtain a desired metal-deposited paper processed product.

Example 2 Commercially available high-quality paper having a basis weight of 70 g / m ² was used as a support,
An electron beam curable resin (Aronix M210, manufactured by Toagosei Kagaku Kogyo Co., Ltd.) was used as a sealing resin, and was applied by a roll coater to a coating weight of 20 g / m ² to form a vapor deposition film (25 μm polyethylene terephthalate film). After peeling treatment and vacuum deposition of aluminum having a thickness of 0.05 µm)
At an accelerating voltage of kv, an electron beam is irradiated so that the absorbed dose becomes 2 Mrad to cure the electron beam curable resin, the sheet and the film are peeled off, the metal vapor deposition film is transferred to a support, and the metal vapor deposition paper is Obtained. An electron beam curable resin (Kayarad MAN, manufactured by Nippon Kayaku Co., Ltd.) as a radiation curable resin was applied to the metal vapor-deposited paper.
Applying DA) as coating weight in a roll coater is 20 g / m ^2, a basis weight 18 g / m ² as a transparent sheet, the overlay transparency 80% of tracing paper, at an accelerating voltage of 200kv transparent sheet side, The electron beam curable resin was cured by irradiating it with an electron beam so that the absorbed dose was 1.5 Mrad to obtain a desired metal-deposited paper processed product.

Example 3 A metal-deposited paper was obtained in the same manner as in Example 1 except that a commercially available white cast paper having a basis weight of 100 g / m ² was used as the support. A UV-curable resin (made by Toagosei Kagaku Kogyo Co., Ltd., Aronix M80
30% of 2% by weight of a photoinitiator, manufactured by Ciba Geigy Co., Ltd., Irgacure 651 is mixed) by a roll coater so that the coating weight becomes 20 g / m ^2, and the ultraviolet curing resin is partially cured by preliminary ultraviolet curing. After adjusting the viscosity by using a transparent paper, superimpose it on a tracing paper with a basis weight of 12 g / m ² and a transparency of 82%, and further irradiate ultraviolet rays on the tracing paper to cure the resin, which is the objective. A processed metal vapor deposition paper product was obtained.

Example 4 The transparent paper used in Example 1 has a basis weight of 18 g / m ² and a transparency of 7
An intended processed metal vapor-deposited paper product was obtained in the same manner as in Example 1 except that the impregnated tracing paper was changed to 9%.

Example 5 The transparent paper used in Example 1 has a basis weight of 45 g / m ² and a transparency of 7
A target processed metal vapor-deposited paper product was obtained in the same manner as in Example 1 except that 0% washi was used.

Example 6 A target processed metal vapor-deposited paper product was obtained in the same manner as in Example 1 except that the red edible dye Rose Bengal was mixed with the radiation curable resin and colored.

Example 7 The transparent paper used in Example 1 had a basis weight of 8 g / m ² and a transparency of 84.
% A target processed metal vapor-deposited paper product was obtained in the same manner as in Example 1 except that the content of the tracing paper was changed to 100%. Although the adhesiveness was good, it was difficult to handle the transparent paper, and the resulting processed paper product had wrinkles.

Comparative Example 1 The metallized paper obtained in the same manner as in Example 1 was passed through an embossing roll for embossing to obtain a matt metallized paper.

Comparative Example 2 A target processed metal vapor-deposited paper product was obtained in the same manner as in Example 1 except that a commercially available tracing paper having a basis weight of 50 g / m ² was used as the transparent paper.

Comparative Example 3 A target metallized paper processed product was obtained in the same manner as in Example 1 except that an impregnated tracing paper having a basis weight of 45 g / m ² and a transparency of 60% was used as the transparent paper.

The processed metal vapor-deposited paper products obtained in the above Examples and Comparative Examples were all good with no defective adhesion.

Test Method Printability: Printability was observed on the obtained metal-vapor-deposited paper processed product and the printability was observed. A product having a uniform surface and capable of being printed in the same manner as general paper was judged to have excellent printability, and when the ink was repelled or the printing was disturbed due to unevenness, the printability was poor.

Scratch resistance: The obtained metal-vapor-deposited paper processed product was strongly rubbed with a dry gauze, and those in which the metal-vapor-deposited layer was not peeled were judged as excellent in scratch resistance, and those in which the metal-vapor-deposited layer was removed were judged as poor in scratch resistance. did.

Wrinkles and unevenness: The obtained metal-deposited paper processed product was subjected to a sampling inspection, and it was excellent when no wrinkles and unevenness were found. Normal occurrence, 1 per 100
The case where wrinkles and unevenness were observed at a rate higher than the number of sheets was judged as poor.

Metallic feeling: The processed metal vapor-deposited paper product was visually observed, and those with a metallic feeling were judged excellent, those with a strong paper impression and paper with a strong whiteness were judged poor. did.

[0048]

[Table 1]

Evaluation: As is clear from the results shown in Table 1,
The processed metal vapor-deposited paper obtained by laminating transparent paper on the metal vapor-deposited paper of the present invention does not lose its metallic feel due to the action of the transparent paper provided thereon, and has good surface properties and excellent printability.
The metal vapor deposition layer is protected by the transparent paper on the surface while maintaining its metallic feel, so the metal vapor deposition layer may fall off even if the surface is strongly rubbed, or it may detach during printing and reduce printability. Since there is no matte or embossing for matting, it has surface smoothness and good printability. Since the radiation curable resin has fluidity when superposed on the transparent paper, the tension can be easily controlled, bubbles or the like are not caught, and unevenness and wrinkles do not occur. Further, since the transparent paper does not come into contact with the solvent or the solvent at the time of coating and is not heated, curling and wrinkling are suppressed.

On the other hand, when there is no transparent paper and the metal vapor deposition layer is exposed on the surface or embossed,
Since there are many irregularities on the surface, the ink paste during printing becomes uneven and peeling of the metal deposition layer due to rubbing occurs,
Poor quality. If the transparency of the transparent paper is 70% or less, the metallic feeling of the processed metal vapor-deposited paper product is lost. Even if the transparency is 70% or more, if the basis weight is less than 10 g / m ² , wrinkles are likely to occur during production, which is not preferable in terms of quality.

[0051]

EFFECTS OF THE INVENTION Since the metal vapor-deposited paper product of the present invention has a metal vapor-deposition layer covered with transparent paper, a matte metal layer can be obtained in a textured manner without performing treatment such as embossing on the metal vapor-deposition surface. Since the surface is smooth and the material is uniform, printing and gluing are easy. Since it has an appropriate barrier property and air permeability, a processed metal vapor-deposited paper product having a good curl balance can be obtained.

Claims (5)

[Claims] 1. A processed metal-vapor-deposited paper, characterized in that the metal-vapor-deposited paper and the transparent paper are superposed on each other via a radiation-curable resin and cured by irradiation to be integrated. 2. The processed metal vapor-deposited paper according to claim 1, wherein the transparent paper has a basis weight of 10 to 45 g / m ² and a transparency of 70% or more. 3. The processed metal vapor-deposited paper according to claim 1, wherein the transparent paper is tracing paper, impregnated tracing paper or Japanese paper. 4. The processed metal vapor-deposited paper product according to claim 1, wherein the radiation irradiation is electron beam irradiation or ultraviolet irradiation. 5. The processed metal vapor-deposited paper according to claim 1, wherein the radiation curable resin is colored.