JPH0274696A - Substrate for metallized label and metallized label - Google Patents

Abstract

PURPOSE:To obtain the title substrate having good aptitude of washing bottle and curl characteristics and excellent labeling properties and free from crack by applying a radiation curable resin composition containing a radiation curable carboxylic acid and providing a layer cured by irradiation of radioactive rays. CONSTITUTION:A radiation curable resin composition containing a radiation curable carboxylic acid is applied onto at least one surface of a substrate 1 and a layer 3 cured by irradiation of radioactive rays is provided to afford the aimed substrate 4. Furthermore, the above-mentioned radiation is derivative electron beam or ultraviolet ray.

Description

DETAILED DESCRIPTION OF THE INVENTION (A) Field of Industrial Application The present invention relates to a support for metal vapor-deposited labels used for beer bottles and the like. More specifically, the present invention relates to a metal vapor-deposited label support and a metal vapor-deposited label for supplying label paper that has excellent water resistance as a label paper and is suitable for bottle washing after collection.

CB) Conventional technology Label paper used for beer bottles, etc. has traditionally been made of aluminum foil laminated materials, but label paper using aluminum foil is not only expensive to manufacture, but also difficult to wash bottles. In recent years, labels using a support coated with aluminum have come to be used. Generally, in order to produce such vapor-deposited paper, an anchor layer is provided on a support to make the surface smooth and glossy, and then metal vapor deposition is performed. This was necessary in order to accurately reflect the irregularities on the surface of the support, since the metal vapor deposited layer is generally several hundred angstroms thick. For such anchor layers, lacquers of nitrocellulose resin, acrylic resin, urethane resin, or vinyl chloride/vinyl acetate copolymer resin have been used. However, when such resins are used, they are not suitable for bottle washing (recovered bottles are immersed in a high-temperature solution of 1-4% sodium hydroxide and the labels are removed), and the labels on the bottles for collection are difficult to wash. It was inappropriate. In order to improve the suitability for washing bottles, resins made of nitrocellulose resin mixed with fatty acid esters, acrylic resins made of copolymer resins of methacrylic esters, acrylic esters, and acrylic acid, and amino alkyds are used as anchor layers. A resin containing maleic acid was used.

[C] Problems to be Solved by the Invention However, although the use of the above-mentioned anchor layer improves the suitability for bottle washing, when metal vapor deposition is performed, the gloss is insufficient and there are many pinholes. It has disadvantages such as being unsuitable as a support for metal vapor-deposited labels, curling too much and interfering with metal vapor deposition and subsequent processes, and cracking when immersed in water after being made into a label.

CD) Means for Solving the Problems The present inventor has conducted extensive research into means for solving the above-mentioned problems, and as a result has arrived at the following invention. That is, a radiation-curable resin composition consisting of an electron beam or ultraviolet ray (hereinafter, electron beam and ultraviolet rays are collectively referred to as radiation) curable resin and a radiation-curable carboxylic acid is coated on at least one surface of the support. Then, after mixing the photoinitiator, it is cured by radiation irradiation 1! (Hereinafter, simply referred to as a radiation-cured anchor layer) is provided.This is an invention of a support for a metal vapor-deposited label. The present invention will be explained in detail below.

The present invention relates to labels used for collection bottles, and particularly relates to supports for metal vapor-deposited labels.9 The support for metal vapor-deposited labels according to the present invention not only has particularly excellent gloss after metal vapor deposition; It has fewer pinholes and curls, and does not crack when immersed in water.
And the alkaline bath for washing bottles quickly removes them from the bottles! !
It has the property of separating by +1. FIG. 1 is an example of a schematic cross-sectional view of the support for metallized labels of the present invention.

If necessary, a clay coat layer 2 is provided on the upper surface of the support base paper 1, and a radiation-cured anchor layer 3 cured by radiation irradiation is provided thereon to constitute a support 4 for a metal fitting vapor-deposited label. FIG. 2 is an example showing a schematic cross-sectional view of a label 5 using the metal vapor-deposited label support 4 of the present invention.

A metal vapor deposition layer 6 is provided on the metal vapor deposition label support 4, a primer layer 7, printing N8, and overcoat Jl1.
An adhesive layer 10 may be provided on the back surface of the metallized label support 4 as the case may be.

The radiation-curable resin used in the present invention is an unsaturated polyester having a radiation-reactive group at the end of the molecule or in the side chain of the molecule;
Modified unsaturated polyesters, acrylic polymers, single phosphors with unsaturated bonds, etc. can be used alone or with other solvents, and have good compatibility with metal deposited layers and primer layers and with radiation-curable carboxylic acids. You can consider and choose. Representative examples of radiation-curable tM resins are shown below.

(a) Polyester acrylate, polyester methacrylate.

For example, Aronix M-5700, Aronix M-
6100, Aronix M-6201 Aronix M-
6300, Aronix M-6500, Aronix M
-7100, Aronix M-8030, Aronix M-8060, Aronix M-8100 (trade names of Toagosei Chemical Co., Ltd.), Visco-Door 00, Viscoat 3700 (trade names of Osaka Organic Chemical Industry Co., Ltd.) ), Kayarad HX-220, Kayarad HX-62
0C or higher, Nippon Tokei Co., Ltd. (product name), etc.

(b) Urethane acrylate, urethane methacrylate, e.g. Aronix M-1100, Aronix M-
1200, Aronix M-1210, Aronix M
-1250, Aronix M-1260, Aronix M-1300, Aronix M-1310 (trade names of Toagosei Chemical Co., Ltd.), Viscoat 812. Viscoat 823, Viscoat 823 (trade names of Osaka Organic Chemical Industry Co., Ltd.), NK ester + U-108-A
, NK ester, U-48A (the above are trade names of Shin-Nakamura Chemical Co., Ltd.), and the like.

(C) Monofunctional acrylate, monofunctional methacrylate, such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate,
2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, cyclohexyl acrylate,
Cyclohexyl methacrylate, benzyl acrylate, glycidyl methacrylate, JN-dimethylaminoethyl acrylate, N,N-dimethylaminoethyl methacrylate, N-N-diethylaminoethyl methacrylate, butoxyethyl acrylate, etc., ethylene oxide modified phenoxylated phosphoric acid acrylate, ethylene oxide modified butoxy In addition to phosphoric acid acrylate, the product name of Toagosei Kagaku Kogyo Co., Ltd. is Aronix M-.
101, Aronix M-102, Aronix M-1
11 Aronix M-113, Aronix M-114
．． 70 Nix M-117, Aronix M-152,
Examples include Aronix M-154.

(d) polyfunctional acrylate, polyfunctional methacrylate, e.g. 1,6-hexanediol diacrylate,
1,6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, pentaerythritol diacrylate, trimethylol allopane hexa Acrylate, isocyanuric acid diacrylate, pentaerythritol triacrylate, isocyanuric acid triacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethylene oxide modified pentaerythritol tetraacrylate, propylene oxide modified pentaerythritol tetraacrylate, propylene oxide modified trimethylolpropane Examples include polyacrylate, ethylene oxide-modified trimethylolpropane polyacrylate, and the like. The product name of Toagosei Chemical Industry Co., Ltd. is Aronix M-.
210, Aronix M-215, Aronix M-2
20, Aronix M-233, Aronix M-24
0, Aronix M-245, Aronix M-305
, Aronix M-309, Aronix M-310,
Examples include Aronix M-315, Aronix M-320, Aronix M-325, Aronix M-400, Aronix M-450, and the like.

(e) Epoxy compounds such as glycidyl methacrylate, 1,3-bis(N,
N-jepoxypropylaminomethyl)cyclohexane, 1,3-bis(N,N-jepoxypropylaminomethyl)benzene, and the like. Mitsubishi Gas Chemical Co., Ltd.
In terms of product name, GE-510-TETRAD-X
, TETRAD-C, etc.

Next, radiation-curable carboxylic acids have both a radiation-curable functional group and a carboxyl group at the molecular end or side chain, and include trimethylolpropane diacrylate fumarate, trimethylolpropane sifumarate monoacrylate, and pentaerythritol diacrylate. Polyfunctional acrylates such as acrylate monofumarate, polyfunctional carboxylic acids or complexes thereof, monoacrylates with carboxyl groups, and product names of Toagosei Chemical Industry Co., Ltd., such as Aronix M-5300 and Aronix M-
5400, Aronix M-5500, Aronix M
-5600, etc. When using a mixture of radiation-curable carboxylic acid and radiation-curable fat-resistant resin as described above, the radiation-curable carboxylic acid is used in an amount of 5% or more by weight based on the solid content of the anchor layer. This is because if the proportion of radiation-curable carboxylic acid is less than 5%, the bottle is not suitable for washing when placed in an alkaline bath after labeling. Further, since such radiation-curable carboxylic acids generally have a small volumetric shrinkage upon curing, the curling properties after providing the radiation-curable anchor layer are extremely poor.

The basis weight of the radiation-cured anchor layer used in the present invention is preferably 1 g/I+'12 to 10 g/rr+2. If the amount of the radiation-cured anchor layer is less than this amount, it will not be possible to fill in the unevenness of the support, and when gold melon vapor deposition is performed. low gloss,
The result is a metal vapor layer that is likely to flicker, and if the radiation-cured anchor layer is more than this, the yIM in an alkaline bath will be poor and the suitability for bottle washing will deteriorate.

In the present invention G, when the resin is cured by ultraviolet irradiation, a photoreaction initiator is mixed and used.

Examples of photoinitiators include acetophenones such as di- and trichloroacetophenone, benzophenone, Michler's ketone, benzyl, benzoin, benzoin alkyl ether, benzyl dimethyl ketal, tetramethylthiuram monosulfide, thioxanthone, azo compounds, various silver salts, etc. The amount of photoreaction initiator used is usually in the range of 0.1 to 10% based on the ultraviolet curable resin.

Further, a storage stabilizer such as hydroquinone may be used in combination with the photoinitiator.

The base paper used as a support in the present invention may be ordinary natural valve paper, so-called synthetic paper made of synthetic fiber or composite RL resin film, or resin-coated paper with a water-resistant resin coating layer provided on the surface of the base paper. can be done, but
Natural valve papers based on wood valves of softwood valves, hardwood valves, mixed softwood and hardwood valves are advantageously used.

The thickness of the base paper is not particularly limited, but paper with good smoothness is preferred, and its basis weight is preferably 40 g/mF to 150 g/mF.

The base paper containing natural valve as a main component, which is advantageously used in the method of the present invention, can contain various polymeric compounds and additives. For example, starch derivatives, polyacrylamides, polyvinyl alcohol derivatives, dry paper strength agents such as gelatin, fatty acid salts, rosin derivatives, sizing agents such as dialkyl ketene dimer emulsions, melamine resins, urea vI! A suitable combination of oils, wet paper strength agents such as epoxidized polyamide, stabilizers, pigments, dyes, antioxidants, optical brighteners, various latexes, non-alpha electrolyte-pH adjusters, etc. can be contained.

Furthermore, in the present invention, the surface of the base paper may be subjected to surface treatment such as corona treatment in order to improve the adhesion and wettability between the base paper and the radiation-curable resin composition.

Examples of methods for applying the radiation-curable resin composition onto base paper include blade coating, air knife coating-spray coating, squeeze coating, reverse roll coating, gravure roll coating, and transfer roll coating.
Methods such as E-barcode 2 curtain coating and die coating are used.

In the present invention, since a radiation irradiation method is used to cure the anchor layer, the support on which the anchor layer is provided is not exposed to high temperatures, making it difficult to curl, and it only takes a few seconds from applying the anchor layer to curing it. Therefore, the anchor layer does not seep into the inside of the support. Therefore, the anchor layer is not lost from the surface and pinholes do not occur when metal is deposited. When curing by electron beam irradiation, the surface of the anchor layer becomes even more mirror-like. To finish, the surface to be treated can be brought into contact with a mirror-finished roll and irradiated with an electron beam from the back side to harden and give a mirror-finished surface. Although it is significantly less economical than the method of completely curing with irradiation at 300-degrees of irradiation, it is possible to perform preliminary electron beam irradiation in advance to partially harden the surface, contact it with a mirror roll, peel it off, and then perform secondary irradiation. There is also a way to completely cure it.

When molding is performed, a molding roll can be used instead of a mirror-finished roll to obtain a desired molded surface such as a slightly rough surface, and the volumetric shrinkage of the resin during polymerization and curing can be used. A micro-rough surface may also be created.

In addition, for mirror finishing and molding, after applying an electron beam curable resin composite acid onto the support, for mirror finishing and molding, a synthetic resin or metal sheet having a surface shape is layered on top of the support. Electron beam irradiation is performed from the front side or sheet side,
There is also a method of peeling off the sheet after the electron beam curable resin composition is cured to obtain a surface with a predetermined shape.

For electron beam irradiation, the acceleration voltage is 10 from the viewpoint of penetrating power and curing power.
0 to 1000 Kv, more preferably 100 to 30
Using a 0Kv electron beam accelerator, the absorbed dose in one bath is 0.
．． It is preferable to set it to 2 to 51 Jrad.
If the accelerating voltage or electron beam irradiation amount is lower than this range, the penetrating power of the electron beam will be too low and sufficient curing will not occur, and if it is too high than this range, energy efficiency will not only deteriorate, but also the strength of the base paper will decrease. Unfavorable effects on quality, such as decomposition of the resin and decomposition of the resin, may occur. The electron beam accelerator may be, for example, an electrocurtain system, a scanning type, a double scanning type, or the like.

Note that when electron beam irradiation is performed, curing of the electron beam curable resin composition is hindered if the oxygen concentration is high.

Substitute with an inert gas such as nitrogen, helium, or carbon dioxide to reduce the oxygen concentration to 600 pp@ or less, preferably 4
It is preferable to irradiate in an atmosphere controlled to 0.00 ppm or less.

Examples of ultraviolet irradiation devices include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, and metal halide lamps, and there are also ozone-less types that generate less ozone. Generally output 3
Use multiple lamps of 0 w/c+a or higher in parallel.

The support for a metal vapor deposited label produced according to the present invention can be provided with a metal vapor layer, a primer layer, a printing layer, an overcoat layer, and optionally an adhesive layer on the back surface to form a metal vapor deposit label.

[E] Function The support for metal vapor-deposited labels according to the present invention uses a radiation-curable carboxylic acid and a radiation-curable resin in the radiation-curable anchor layer, so that the metal-deposited label support according to the present invention has a high resistance when immersed in an alkaline bath due to the action of the radiation-curable carboxylic acid. It has good label removability and low volume shrinkage, so it has good curling properties.
Crack-resistant, water resistant and glossy thanks to radiation-curable resin.

It has excellent metal deposition properties, and because it uses a radiation curing method, pinholes are less likely to occur, and the anchor layer does not penetrate into the base paper that serves as the support, so opacity does not decrease.

[F] Examples The present invention will be explained in detail below using examples, but the content of the present invention is not covered by the examples.

Practical example 1 Base weight 70g/rn with clay coating on the surface as a support
A radiation-curable m-lipid compound acid was applied using a gravure coater in the following composition ratio using single gloss paper.

As a radiation-curable resin composition, isocyanuric acid diacrylate (manufactured by Toagosei Kagaku Kogyo Co., Ltd., trade name Aronix M-215) is used as a radiation-curable resin, and polyacrylic acid dimer is used as a radiation-curable carboxylic acid.Toagosei Kagaku Kogyo Co., Ltd. product, trade name Aronix M-560
0), and benzyl dimethyl ketal (manufactured by Ciba Geigy Co., Ltd., product name Irgacure 651) was used as a photoreaction initiator.

(Sample A) Radiation curable resin 93 parts Radiation curable carboxylic acid 5 parts Photopolymerization initiator
2 parts (Sample B) Radiation curable resin 68 parts Radiation curable carbon a 30 parts Photopolymerization initiator
2 parts (Sample C) Radiation curable resin 10 parts Radiation curable carboxylic acid 88 parts Photopolymerization initiator
The support coated with two parts of the radiation-curable resin composition thus obtained was heated in an ultraviolet irradiation device (80W).
/cm-ozone condensing type, irradiation amount W10c@),
A metal vapor-deposited label support was obtained by irradiating with ultraviolet rays.

An aluminum vapor-deposited layer with a thickness of 400 angstroms was provided on the prepared support for metal vapor-deposited labels, and then a printing layer using ink using nitrocellulose as a vehicle and an overcoat layer made of nitrocellulose resin were provided to form a predetermined shape. A metal vapor-deposited label was used and evaluated using the following method.

(1) Crackability: A starch paste was applied to the back side of the glossy label, and the label was attached to a beer bottle, dried for 24 hours, and immersed in cold water for 24 hours to observe the condition of the label.

(2) Apply starch glue to the back of the bottle washability label, paste it on the beer bottle, dry it for 24 hours, leave it for 24 hours, leave it at 70℃, 1
Judgment was made based on the time taken for the label to peel off after being immersed in a specified sodium hydroxide solution.

(3) Starch glue was applied to the back of the pinhole label, and it was pasted on a glass plate and dried for 24 hours. After leaving it for 24 hours, the front of the label was wetted with a solvent containing dye and judged based on the degree of coloring on the back. .

(4) Opacity Determined by visual observation after providing a radiation-curable anchor layer or an anchor layer by a conventional method.

(5) Curling Evaluation shall be made based on the radiation-curable anchor layer or the curling property of the sheet during continuous running after providing the anchor layer by a conventional method.

The results of the above evaluation are shown in Table 1.

Example 2 Using the same support as in Example 1, the formulation of the radiation-curable resin composition was changed as follows. The types and coating amounts of the radiation-curable resin and radiation-curable carboxylic acid were the same as in Sample A.

(Sample D) Radiation curable resin 95 parts Radiation curable carboxylic acid 5 parts (Sample E) Radiation curable resin 70 parts Radiation curable carboxylic acid 30 parts (Sample F) Radiation curable resin 10 parts Radiation curable carboxylic acid 90 Part: The support coated with the radiation-curable resin composition thus obtained was replaced with nitrogen (oxygen concentration, 200 ppm) using an electron beam irradiation device (
Electrocurtain (manufactured by ESI) was introduced, and electron beam irradiation was performed under the conditions of an acceleration voltage of 175 kV and an absorption line of N 3 Mra, d to obtain a support for a metal vapor-deposited label. A label was prepared using the obtained support for a metal vapor-deposited label in the same manner as in Example 1.

The results of the evaluation are shown in Table 1.

Comparative Example 1 A support for a metal-deposited label was obtained in the same manner as in Example 1 except that the proportion of the radiation-curable resin composition in Example 1 was changed as follows.

Radiation-curable resin composition (sample G) The types of raw materials used were the same as in sample A, but the composition ratio was changed as follows.

Radiation curable resin 95 parts Radiation curable carboxylic acid 3 parts Photopolymerization initiator
A label was prepared in the same manner as in Example 1 using two copies of the obtained support for a metal vapor-deposited label. Table 1 shows the evaluation results.
Shown below.

Comparative Example 2 A support for a metal-deposited label was obtained in the same manner as in Example 2, except that the proportion of the radiation-curable resin composition in Example 2 was changed as follows.

(Sample H) 97 parts of radiation-curable resin 3 parts of radiation-curable carboxylic acid A label was prepared in the same manner as in Example 1 using the obtained support for a metal-deposited label. The results of the evaluation are shown in Table 1.

Comparative Example 3 A 40% by weight solution of a mixed resin of a nitrocellulose resin and a fatty acid ester resin was coated on the support of Example 1 and dried by heating at -180°C for 15 seconds to form a metal. A support for a vapor-deposited label was obtained (Sample I). A label was prepared using the obtained support for a metal-deposited label in the same manner as in Example 1. The evaluation results are shown in Table 1.

Figure 1 Figure 2 [G] Effects of the Invention As is clear from Table 1, the support for metallized labels according to the present invention has improved bottle washability and curling properties due to the radiation-curable anchor layer containing radiation-curable carboxylic acid. It has extremely excellent suitability for labels, such as being resistant to cracking, excellent in water resistance, gloss, and metal deposition, with little occurrence of pinholes and little decrease in opacity.

[Brief explanation of the drawing]

FIG. 1 is an example of a schematic cross-sectional view of the support for metallized labels of the present invention. FIG. 2 is an example showing a schematic cross-sectional view of a metallized label using the metallized label support of the present invention. 1. Support base paper, 2. 3. Clay coat layer, 3. Radiation curable anchor layer, 4. Support for metallized label, 5. Label, 6. Gold layer vapor deposition layer, 7. Brimer layer. 8. Printing layer; 9. overcoat layer, 10,
Back adhesive layer. November 27, 1999 1゜2゜3゜Indication of the case 1985 Patent Application No. 225883 Name of the invention Support for metal vaporized labels and the person who amends the metal vaporized labels Related Patent Applicant Address 4-2 Marunouchi Otsu-chome, Chiyoda-ku, Tokyo Name (59B) Mitsubishi Paper Mills Co., Ltd. Contact Address 125
Mitsubishi Paper Mills Co., Ltd., 4-1 Toganemachi-chome, Katsushika-ku, Tokyo
Contents of the 5° amendment to the patent division

Claims (4)

[Claims] (1) A support for a metal-deposited label, comprising a layer coated with a radiation-curable resin composition containing a radiation-curable carboxylic acid on at least one surface of the support and cured by radiation irradiation. (2) The metal vapor-deposited label support according to claim (1), wherein the radiation is an electron beam. (3) Claim (1), wherein the radiation is ultraviolet rays, and the radiation-curable resin composition contains a photoreaction initiator.
The support for the metallized label described above. (4) A metallized label produced using a metallized label support provided with an anchor layer made of a radiation-curable resin composition containing the radiation-curable carboxylic acid and cured by radiation irradiation.