JP2012001672A - Printing ink composition for alumina vapor-deposited film and application of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a printing ink composition for an alumina vapor-deposited film which has the excellent printability and adhesion to enable decoration printing when printing is performed on a transparent vapor deposition film on a surface of which an alumina is deposited, and has the excellent laminate suitability to expand the applicable field as a packaging container when lamination is performed.SOLUTION: The printing ink composition for the alumina vapor-deposited film contains a pigment, a binder resin, and an organic solvent, wherein the binder resin contained therein is a polyurethane resin (A) and polyvinyl chloride vinyl acetate copolymer resin (B) in a ratio of (A)/(B)=95/5-40/60 (mass ratio).

Description

The present invention relates to a printing ink composition for an alumina vapor-deposited film and its application. More specifically, the present invention has excellent adhesiveness when printed on an alumina vapor-deposited film, and the laminated product obtained is excellent when laminated. The present invention relates to a printing ink composition for an alumina vapor-deposited film having a suitable laminating property.

In recent years, composite films in which inorganic oxides such as metals, silica, and alumina are deposited on the surface of various plastic materials are widely used as flexible packaging materials for food and pharmaceuticals that do not want to be altered or deteriorated by air oxidation or moisture. ing. Such a composite film has a function of suppressing permeation of oxygen and water vapor in the air, and it is possible to manufacture a packaging container having high performance called “gas barrier property” or “fragrance retention”.

Especially in the field of food packaging, gas barrier properties are an important performance in order to maintain freshness, taste and texture over a long period of time. Furthermore, the inorganic oxide-deposited type can maintain transparency, so the contents can be seen well, giving consumers a sense of security, and heating and cooking with a microwave oven in the bag. have.
As concerns about food shortages increase in the future, attempts to extend the expiry date and expiry date to reduce the amount of food discarded will be beneficial to society. From this point of view, it is considered that the use of the composite film is one of the basic technologies.

By the way, when such a packaging container is manufactured, printing with ink is performed on the packaging container in order to improve the display of contents and, more recently, more aggressively design and improve the willingness to purchase products. . And it is divided into two types, front printing and back printing, mainly depending on the difference between the printing places on the outside and inside of the packaging container.
Since surface printing prints ink on the outer side of a packaging container, it does not contact the contents as it is, and is relatively excellent in terms of hygiene even with a simple configuration. However, since the printed surface is rubbed, or directly contacts the hot plate during bag making or sealing, the ink performance is required to have adhesion to the substrate, friction resistance, heat resistance, and the like.
In reverse printing, after ink is printed on the inside of the packaging container, a thin film polymer is laminated on the printing surface through an adhesive or an anchor agent as necessary. By such a laminating process, the ink does not come into contact with the contents on the inner surface of the packaging container, and if the solvent or the like in the ink is sufficiently removed, it becomes very hygienic.
This laminating process may be performed on the printing surface for surface printing, so that the printing surface does not come into contact with the outside.
Furthermore, since the laminating process can stack a number of functional films, it is used for boil and retort applications in addition to ordinary food packaging bags such as snacks.

When using the composite film on which the inorganic oxide is vapor-deposited in a packaging container, the vapor-deposited surface is disposed inside the packaging container in order to protect the vapor-deposited layer of the inorganic oxide. Therefore, there are not many opportunities for ink to be printed on the vapor deposition surface in surface printing, but when the vapor deposition surface is provided on the outer surface or both sides of the composite film, good adhesion to the vapor deposition surface as ink. Is also required. On the other hand, in the case of a packaging container by reverse printing, in most cases, the vapor deposition surface becomes an ink printing surface. Back-printed printed packaging containers have a variety of uses, and some of the performance levels required for these uses are very high. Among them, the gas barrier property can be said to be one of the main purposes, and it is expected that opportunities for using composite films deposited with inorganic oxides will increase further in the future.

Here, as the binder resin for the ink, a polyamide-nitrified cotton type is used for the surface printing, and a polyurethane type resin is used for the back printing. In these resins, the adhesion to the vapor deposition surface made of an inorganic oxide is used. Tended to be generally inferior. In particular, when an ink using a white pigment such as titanium oxide is used as the pigment, the tendency is remarkable. Accordingly, the present applicant has developed an ink composition having good adhesion to a composite film on which various materials are deposited.

For example, in a back printing ink, in a system using a polyurethane resin as a binder, a number average molecular weight of 200 to 5000, an acid value of 20 to 350, and a hydroxyl value of 20 to 350 are used in order to improve adhesion to a metal aluminum vapor deposition film. In order to improve the adhesion to the silica vapor deposited film, the technology for containing hydroxycarboxylic acid in the above (for example, see Patent Document 1), finally introduces a silane coupling agent and an isocyanate curing agent into the urethane resin molecule. (For example, refer to Patent Documents 2 and 3).
However, the present situation is that a technique for improving the adhesion to an alumina deposited film having high utility value has not yet been obtained in terms of both transparency and gas barrier properties.

JP 09-118855 A JP 2001-002971 A JP 2002-030239 A

As described above, a technology that enables long-term storage using a packaging container having a high gas barrier property, regardless of whether it is fresh food or processed food, is socially beneficial. Furthermore, with the increase in the elderly, the demand for processed foods will increase, and the importance of packaging containers will only increase. On the other hand, the technology to improve purchasing motivation by decorating ink also has the aspect of providing resources to promote further research on long-term preservation for manufacturers involved in food and packaging materials.
Therefore, the problem of the present invention is that, when printed on a transparent vapor-deposited film having alumina deposited on its surface, it has excellent printability and adhesiveness, thereby enabling cosmetic printing and laminating. In some cases, the present invention is to provide a printing ink composition for an alumina vapor-deposited film that has an excellent laminating ability and expands the field applicable as a packaging container.

As a result of intensive studies to solve the above problems, the present inventors have found that a polyurethane resin as a binder resin of a printing ink composition for an alumina vapor-deposited film (hereinafter sometimes simply referred to as an ink composition) It has been found that all of the above problems can be solved by using a vinyl chloride-vinyl acetate copolymer resin in a specific mixing ratio, and the present invention has been completed.

That is, this invention is a printing ink composition for alumina vapor deposition films containing a pigment, binder resin, and an organic solvent, Comprising: Polyurethane resin (A) and vinyl chloride-vinyl acetate type copolymer resin (B) as said binder resin ) Is contained at (A) / (B) = 95/5 to 40/60 (mass ratio).
In the present invention, the organic solvent is preferably a mixed solvent of an ester organic solvent, an alcohol organic solvent, and a ketone organic solvent.
The organic solvent is preferably a mixed solvent of an ester organic solvent and an alcohol organic solvent.
The pigment is preferably a white pigment.
The white pigment is preferably titanium oxide.
Moreover, this invention relates to the printed matter obtained by printing the printing ink composition for alumina vapor deposition film of this invention on the said alumina vapor deposition film.
The present invention also relates to a laminate product obtained by printing the alumina vapor-deposited film on the alumina vapor-deposited film and further laminating it.
Hereinafter, the printing ink composition for an alumina vapor deposition film of the present invention and its application will be described in more detail.

First, the printing ink composition for alumina vapor deposition film of this invention is demonstrated.
The ink composition of the present invention contains a pigment, a binder resin, and an organic solvent.
<Pigment>
As the pigment, for example, various inorganic pigments, organic pigments, or extender pigments generally used in printing inks can be used.
Examples of the inorganic pigment include colored pigments such as titanium oxide, bengara, antimony red, cadmium yellow, cobalt blue, bitumen, ultramarine, carbon black, graphite, silica, calcium carbonate, kaolin, clay, barium sulfate, aluminum hydroxide. And extender pigments such as talc.
Examples of the organic pigment include soluble azo pigments, insoluble azo pigments, azo lake pigments, condensed azo pigments, copper phthalocyanine pigments, and condensed polycyclic pigments.
Furthermore, examples of the extender pigment include calcium carbonate, kaolin clay, barium sulfate, aluminum hydroxide, and talc.
The content of these pigments in the ink composition is usually about 1 to 50% by mass.

<Binder resin>
The binder resin is not particularly limited, and for example, a polyurethane resin or a vinyl chloride-vinyl acetate copolymer resin can be used.

(Polyurethane resin)
As the polyurethane resin, a polyurethane resin obtained by synthesizing a urethane prepolymer by a reaction between an organic diisocyanate compound and a polymer diol compound and reacting with a chain extender and a reaction terminator as necessary is suitably used. it can.

Examples of the organic diisocyanate compound include aromatic diisocyanate compounds such as tolylene diisocyanate, alicyclic diisocyanate compounds such as 1,4-cyclohexane diisocyanate and isophorone diisocyanate, aliphatic diisocyanate compounds such as hexamethylene diisocyanate, and α, Examples include araliphatic diisocyanate compounds such as α, α ′, α′-tetramethylxylylene diisocyanate. These organic diisocyanate compounds can be used alone or in combination of two or more. Of these, alicyclic diisocyanates, aliphatic diisocyanates and araliphatic diisocyanates are more preferred.

Examples of the polymer diol compound include polyalkylene glycols such as polyethylene glycol and polypropylene glycol, polyether diol compounds such as alkylene oxide adducts such as ethylene oxide and propylene oxide of bisphenol A, adipic acid, sebacic acid, and anhydrous phthal 1 type or 2 types or more of dibasic acids, such as an acid, and 1 type of glycols, such as ethylene glycol, propylene glycol, 1, 4- butanediol, neopentyl glycol, 3-methyl-1, 5-pentanediol, or And polyester diol compounds such as polyester diols and polycaprolactone diols obtained by condensation reaction of two or more. These high molecular diol compounds can be used alone or in admixture of two or more.
Furthermore, in addition to the above polymer diol compounds, alkane diols such as 1,4-pentanediol, 2,5-hexanediol, 3-methyl-1,5-pentanediol, ethylene glycol, propylene glycol, 1,4- Low molecular diol compounds such as butanediol and 1,3-butanediol can be used alone or in admixture of two or more.

In the case of using a mixed solvent system of an ester solvent and an alcohol solvent as an organic solvent to be described later, the use of a polyether diol compound as the polymer diol compound increases the solubility of the resulting polyurethane resin. This is preferable in that it has a tendency and a wide range of ink designs can be made according to the required performance.
The organic diisocyanate compound and the polymer diol compound are used in an equivalent ratio of isocyanate group to hydroxyl group (isocyanate index) of usually 1.2: 1 to 3.0: 1, more preferably 1.3: The range is 1 to 2.0: 1. When the above isocyanate index is smaller than 1.2, there is a tendency to be a flexible polyurethane resin, and when the ink composition of the present invention is printed, the blocking resistance may be low. In this case, other hard resins May need to be used together.

As the chain extender, known chain extenders used in polyurethane resins as ink binders can be used, for example, aliphatic diamines such as ethylenediamine, propylenediamine, tetramethylenediamine, hexamethylenediamine, Isophorone diamine, cycloaliphatic diamines such as 4,4′-dicyclohexylmethane diamine, aromatic diamines such as toluylenediamine, araliphatic diamines such as xylene diamine, N- (2-hydroxyethyl) ethylenediamine, N -(2-hydroxyethyl) propylenediamine, diamines having a hydroxyl group such as N, N'-di (2-hydroxyethyl) ethylenediamine, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, diethyleneglycol Le, diol compounds such as triethylene glycol.
Furthermore, polyamines such as diethylenetriamine and triethylenetetramine can be used in combination as long as the polyurethane resin does not gel.

As the reaction terminator, known reaction terminators used in polyurethane resins as ink binders can be used. For example, monoalkylamines such as n-propylamine and n-butylamine, di-n- Examples thereof include dialkylamines such as butylamine, alkanolamines such as monoethanolamine and diethanolamine, and monoalcohols such as ethanol.

As a method for producing the polyurethane resin, a known method for producing a polyurethane resin can be used as it is, using the above materials. In addition, when the molecular weight, chemical structure, and equivalent ratio of each component are different, the hardness of the obtained polyurethane resin is also different. Therefore, it is possible to adjust printability and laminate suitability by appropriately combining these components.

The mass average molecular weight of the polyurethane resin is preferably 10,000 to 70,000, and more preferably 20,000 to 60,000.

(Vinyl chloride-vinyl acetate copolymer resin)
As the vinyl chloride-vinyl acetate copolymer resin, a vinyl chloride monomer and vinyl acetate are essential components, and if necessary, vinyl propionate, vinyl monochloroate, vinyl versakate, vinyl laurate, vinyl stearate, A fatty acid vinyl monomer such as vinyl benzoate or a monomer having a functional group such as a hydroxyl group produced by a conventionally known method can be used.

The vinyl chloride-vinyl acetate copolymer resin preferably has a mass average molecular weight of 10,000 to 70,000.
Such vinyl chloride-vinyl acetate copolymer resins are commercially available. For example, Solvein A, AL, TA5R, TA2, TA3, TAO, TAOL, C, CH, CN manufactured by Nissin Chemical Industry Co., Ltd. , CNL and the like.

The vinyl chloride-vinyl acetate copolymer resin used in the printing ink composition for an alumina vapor-deposited film of the present invention has various functional groups in the molecule from the viewpoint of solubility in organic solvents and printability. You may have.
In addition, when a polar solvent is frequently used as the organic solvent, the vinyl chloride-vinyl acetate copolymer may have a hydroxyl group or the like in the molecule. As a commercially available polymer, for example, sorbine A, AL, TA5R, TA2, TA3, TAO, TAOL are preferably used.

The printing ink composition for an alumina vapor-deposited film of the present invention comprises a polyurethane resin (A) and a vinyl chloride-vinyl acetate copolymer resin (B), preferably (A) / (B) = 95 / 5-40. / 60 (mass ratio). By containing the polyurethane resin (A) and the vinyl chloride-vinyl acetate copolymer resin (B) at such a ratio, the printing ink composition for an alumina vapor-deposited film of the present invention is superior to the alumina vapor-deposited film. It will have printability and adhesiveness. Furthermore, when it is printed on an alumina vapor-deposited film and further laminated, it has excellent laminating properties. When the above (A) / (B) is less than 95/5, the ratio of the vinyl chloride-vinyl acetate copolymer resin (B) is decreased, and the adhesiveness to the alumina vapor-deposited film is insufficient. . On the other hand, when the above (A) / (B) exceeds 40/60, the ratio of the vinyl chloride-vinyl acetate copolymer resin (B) increases, and a printed matter formed using the ink composition of the present invention. It becomes hard and the adhesiveness to an alumina vapor deposition film is also insufficient.
The above (A) / (B) is preferably 85/15 to 45/55, more preferably 70/30 to 60/40 (mass ratio).
In addition, the content of the polyurethane resin (A) and the vinyl chloride-vinyl acetate copolymer resin (B) in the ink composition of the present invention is preferably 5 to 20% by mass.

(Other resins)
Furthermore, as long as the target performance of the present invention is not deteriorated, the ink composition of the present invention can supplementarily add a cellulose resin, a vinyl copolymer, a polyamide resin, etc. as other binder resins. .

<Organic solvent>
Examples of the organic solvent include ketone organic solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, ester organic solvents such as methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, and isobutyl acetate, methanol, and ethanol. Alcohol organic solvents such as n-propanol, isopropanol and butanol, and hydrocarbon solvents such as toluene and methylcyclohexane can be used.
From recent environmental issues, ester organic solvents, alcohol organic solvents and ketone organic solvents are mixed, or ester organic solvents and alcohol organic solvents that are more environmentally friendly. Is preferably used.

<Other materials>
Various additives such as a pigment dispersant, an antistatic agent, a wax, a leveling agent, a surfactant, and a plasticizer can be further added to the printing ink composition for vapor deposited alumina films of the present invention.

As a method for producing an ink composition using the above constituent materials, known methods can be used. Specifically, for example, a mixture of a pigment, a binder resin, an organic solvent and, if necessary, a pigment dispersant is kneaded using a high speed mixer, a ball mill, a sand mill, an attritor, etc. Can be obtained by adding and mixing.

Next, the printed matter obtained by printing the printing ink composition for an alumina vapor deposition film of the present invention and its use will be described.

<Alumina deposition film>
The printing ink composition for an alumina vapor-deposited film of the present invention has good performance when the alumina vapor-deposited film is used as a base material.
The alumina vapor-deposited film is obtained by providing a vapor-deposited layer of alumina (aluminum oxide) or a mixture of alumina and silica (silicon oxide) on various plastic film substrates.
Here, examples of the plastic substrate include polyester films such as polyethylene terephthalate and polyethylene naphthalate, polyolefin films such as polypropylene film and polyethylene film, polyamide films, polyvinyl chloride films, polyacrylonitrile films, and polycarbonate films. Can be mentioned.
The above-mentioned plastic film is a stretched or unstretched film. If necessary, an additive such as an antistatic agent or an ultraviolet ray inhibitor, or a material obtained by corona treatment or plasma treatment on the surface of the substrate can also be used.

Moreover, as a method of providing the vapor deposition layer on the plastic film substrate, a known method can be used, such as a vacuum vapor deposition method using a heating means such as an electron beam heating method, a resistance heating method, an induction heating method, or sputtering. It is obtained by forming a vapor-deposited layer of aluminum oxide (alumina) or a mixture of aluminum oxide and silicon oxide (silica) on a plastic substrate by the method, plasma vapor deposition method, ion plating method or the like.
Although the thickness of the said vapor deposition layer is not specifically limited, As a range which has transparency and gas barrier properties, such as oxygen and water vapor | steam, it is 4-350 nm, Preferably it is 8-160 nm.
Specific examples of such an alumina vapor deposition film include GL-AE manufactured by Toppan Printing Co., Ltd. and IB-PET-PUB manufactured by DIC Corporation.

<Printed matter>
A desired printed matter can be obtained by printing the printing ink composition for an alumina vapor deposition film of the present invention on the above alumina vapor deposition film using a gravure printing method, a flexographic printing method, or the like. A printed matter obtained by printing the printing ink composition for an alumina deposited film of the present invention on such an alumina deposited film is also one aspect of the present invention.
In addition, the printed matter obtained by the above method may be subjected to a laminating process to be described later on the printing surface to obtain a laminated product. For example, when the printed matter is a surface printed matter, a conventional method for protecting an alumina vapor deposition layer What coated the well-known overcoat agent can also be utilized for manufacture of a packaging container.

<Laminated product>
In the back-printed printed material, a highly functional packaging container can be produced by applying a lamination process in which a polymer called a sealant is laminated on the printed surface of the printed material. In addition, after printing the printing ink composition for alumina vapor deposition films of this invention on an alumina vapor deposition film, the laminated product obtained by further laminating is also one of this invention.

Here, two methods are mainly used as a method of laminating the sealant. One of them is to apply an anchor coating agent (for example, titanium-based, urethane-based, imine-based, polybutadiene, etc.) to the printed surface as necessary, and heat-melt polymer (for example, low-density polyethylene, ethylene-vinyl acetate copolymer). This is an extrusion laminating process in which coalesced, polypropylene, etc.) are laminated in a thin film shape. The other is a dry laminating process in which an adhesive (eg, urethane, isocyanate, etc.) is applied to the printed surface, and then an unstretched plastic film (eg, unstretched polyethylene film, unstretched polypropylene film, etc.) is laminated. It is. Furthermore, a polymer layer having various functions can be provided between the sealant and the sealant.
The laminated product obtained from such a method is finally sealed with a heat sealer or the like between the sealant surfaces to form a packaging container.

In the present invention, as the binder resin, a printing ink composition dedicated to an alumina vapor deposition film containing a polyurethane resin and a vinyl chloride-vinyl acetate copolymer resin in a specific blending ratio is used. Thereby, when the printing ink composition is printed on the alumina vapor-deposited film, printability and adhesiveness are improved, and further, when laminated, the laminateability is also improved.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Unless otherwise specified, “%” means “% by mass”, and “part” means “part by mass”.

(Manufacture of printing ink composition for alumina vapor deposition film)
Polyurethane resin varnish 100 parts by mass of 3-methyl-1,5-pentylene adipate diol having an average molecular weight of 2000 and polypropylene glycol having an average molecular weight of 2000 in a four-necked flask equipped with a stirrer, a cooling pipe and a nitrogen gas introduction pipe 100 parts by mass and 44.4 parts by mass of isophorone diisocyanate were charged and reacted at 100 to 105 ° C. for 6 hours while introducing nitrogen gas. After cooling to near room temperature, 518 parts by mass of ethyl acetate and 91 parts by mass of isopropyl alcohol were added, then 15.6 parts by mass of isophoronediamine was added to extend the chain, and 1.1 parts by mass of monoethanolamine was further added to react. It was stopped and a polyurethane resin varnish (solid content 30% by mass, viscosity 10 ps / 25 ° C.) was obtained.

Example of production of printing ink composition for alumina vapor-deposited film Pigment (titanium oxide R-960, manufactured by DuPont), polyurethane resin varnish, vinyl chloride-vinyl acetate resin (Solvine T-3, Nisshin Chemical Industry ( The mixture of (made by Co., Ltd.) was kneaded using a paint conditioner manufactured by Red Devil, and further added with a solvent, and the printing inks for alumina vapor deposited films of Examples 1 to 3 and Comparative Examples 1 to 3 shown in Table 1 were used. A composition was prepared.
The performance evaluation of the ink compositions of Examples 1 to 3 and Comparative Examples 1 to 3 obtained above was performed according to the following method, and the evaluation results are shown in Table 1.

<Performance evaluation of ink composition>
1. Adhesiveness After adding 50 parts of a diluent having the same solvent composition shown in Table 1 to the ink compositions of Examples 1 to 3 and Comparative Examples 1 to 3 and adjusting the viscosity, a plate having a plate depth of 28 μm was prepared. In the gravure printing machine equipped (manufactured by Higashitani Seisakusho), on the treated surface of PET film (trade name: GL-LE, thickness 12 μm, manufactured by Toppan Printing Co., Ltd.) on which one side was subjected to alumina deposition treatment, Printing was performed at a printing speed of 50 m / min. The cellophane tape was affixed to the printed surface of each obtained printed matter, and the adhesiveness was evaluated from the ratio of the area where the ink film peeled off the adherend when peeled off.
A: No peeling at all B: Peeling area is less than 20% C: Peeling area is at least 20%

2. Printability From the following method, after printing, whether or not ink adheres to the guide roll (guide roll was taken) was tested to evaluate printability. The ink once adhered to the guide roll is re-transferred to the printing surface and stains occur. Therefore, when “guide roll removal” occurs, it has an adverse effect on obtaining a cosmetic print.
After diluting by adding 50 parts of the diluent having the same solvent composition shown in Table 1 to the printing ink compositions for vapor deposited alumina films of Examples 1 to 3 and Comparative Examples 1 to 3, the plate depth was 28 μm. Surface of PET film (trade name: GL-LE, thickness: 12 μm, manufactured by Toppan Printing Co., Ltd.) that has been subjected to alumina vapor deposition on one side by a gravure printing machine (made by Toya Seisakusho Co., Ltd.) equipped with a plate of In addition, printing was performed at a printing speed of 100 m / min, and the presence or absence of dropping of the printed ink coating film by the guide roll of the gravure printing machine was visually evaluated.

As shown in Table 1, the printing ink composition for an alumina vapor-deposited film according to the example showed good results for both adhesiveness and printing suitability.
On the other hand, none of the printing ink composition for an alumina vapor deposition film according to the comparative example had good adhesiveness and printability.

By using the printing ink composition for an alumina vapor-deposited film according to the present invention, the printability and adhesiveness are good when printed on the alumina vapor-deposited film, and the laminate suitability is also good when laminated. become.

Claims (7)

A printing ink composition for an alumina vapor-deposited film containing a pigment, a binder resin and an organic solvent,
The binder resin contains a polyurethane resin (A) and a vinyl chloride-vinyl acetate copolymer resin (B) at (A) / (B) = 95/5 to 40/60 (mass ratio). A printing ink composition for an alumina vapor-deposited film. The printing ink composition for an alumina vapor-deposited film according to claim 1, wherein the organic solvent is a mixed solvent of an ester organic solvent, an alcohol organic solvent, and a ketone organic solvent. The printing ink composition for an alumina vapor-deposited film according to claim 1, wherein the organic solvent is a mixed solvent of an ester organic solvent and an alcohol organic solvent. The printing ink composition for an alumina vapor-deposited film according to claim 1, 2, or 3, wherein the pigment is a white pigment. The printing ink composition for an alumina vapor-deposited film according to claim 4, wherein the white pigment is titanium oxide. A printed matter obtained by printing the alumina-deposited film printing ink composition according to claim 1, 2, 3, 4, or 5 on an alumina-deposited film. A laminated product obtained by further laminating a printed ink composition for an alumina vapor deposited film according to claim 1, 2, 3, 4 or 5 on an alumina vapor deposited film.