JP2001002971A - Printing ink composition for laminate, and laminate- processed product using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a printing ink composition excellent in adhesiveness to silicon oxide laminated films, and also applicable to boil/retort treatment, and to obtain laminated products having high laminate strength and printed with the printing ink composition. SOLUTION: This three-part printing ink composition is such one as to comprise a polyurethane resin having, in the molecule, a functional group reactive with an isocyanate group, a silane coupling agent having, in the molecule, a functional group reactive with an isocyanate group, and an isocyanate-based curing agent, and to be used for printing on plastic films laminated with a silicon oxide in a thin-film fashion.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a printing ink composition for laminating and a laminated product using the same.
More specifically, it has good adhesion to a plastic film having a silicon oxide film laminated on its surface in a thin film form (hereinafter, referred to as a silicon oxide laminated film), and is applicable to boiling and retorting. The present invention relates to a printing ink composition for laminating and a laminated product having high laminating strength using the same.

[0002]

2. Description of the Related Art One of the enhancements in the function of food packaging containers is to provide a gas barrier property for blocking air and water vapor to prevent deterioration of contents due to oxidation and moisture absorption. For this purpose, a method of providing a gas barrier layer of polyvinylidene chloride, aluminum, or the like on the surface of a plastic film has conventionally been used.

However, recently, the use of chlorine-based compounds has been shunned due to environmental problems and the like, and there are some applications in which an aluminum laminated plastic film cannot be used from the viewpoint of transparency.
Attention has been paid to a method using a plastic film in which silicon oxide is laminated.

[0004]

However, in a packaging container obtained by printing a conventional printing ink composition on a silicon oxide laminated film and laminating it, a high lamination strength cannot be obtained, and the boil / retort suitability is not obtained. Also has the problem of becoming scarce.

Accordingly, the present invention provides a printing ink composition for lamination which has excellent adhesion to a silicon oxide laminated film and is applicable to boil and retort treatment, and a high lamination strength on which the printing ink composition is printed. It is an object of the present invention to provide a laminated product having:

[0006]

That is, the invention according to claim 1 provides a polyurethane resin having a functional group capable of reacting with an isocyanate group in a molecule, and a silane cup having a functional group capable of reacting with an isocyanate group in a molecule. The present invention relates to a printing ink composition for three-component lamination, which comprises a ring agent and an isocyanate-based curing agent, and is printed on a plastic film in which silicon oxide is laminated in a thin film. In the present invention, the “three-pack type” means that three components of a polyurethane resin, a silane coupling agent, and an isocyanate-based curing agent are blended as components involved in a resin-based reaction ( Usually, all three components are used in liquid form), and the timing of their combination is not limited to immediately before printing.

[0007] In the invention according to claim 2, the functional group capable of reacting with an isocyanate group in the polyurethane resin and the silane coupling agent is a primary or secondary amino group. The present invention relates to a printing ink composition for mold lamination.

According to a third aspect of the present invention, there is provided a printing ink composition for a three-component laminate according to the first or second aspect, which is provided on a silicon oxide laminated surface of a plastic film on which a silicon oxide is laminated in a thin film form. The present invention relates to a laminated product obtained by applying an anchor coating agent on a printed surface as necessary after printing the resultant, and laminating a hot-melt polymer.

According to a fourth aspect of the present invention, there is provided a printing ink composition for a three-component laminate according to the first or second aspect, wherein the silicon oxide is laminated on a silicon oxide laminated surface of a plastic film having a thin film laminated thereon. And printing an adhesive on the printing surface and laminating a polymer film. Hereinafter, the present invention will be described in more detail.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Conventionally, printing ink compositions for laminating include a one-pack type composed of a pigment, a binder resin represented by polyurethane, an organic solvent, or a two-pack type containing an isocyanate-based curing agent. Although a mold type has been used, the present invention is characterized in that a silane coupling agent is further added to obtain a printing ink composition for three-component lamination.

First, pigments that can be used in the ink composition of the present invention include various inorganic pigments generally used in printing inks and paints (for example, titanium oxide, red iron oxide,
Colored pigments such as antimony red, cadmium yellow, cobalt blue, dark blue, ultramarine, carbon black, graphite, and extenders such as calcium carbonate, kaolin, clay, barium sulfate, aluminum hydroxide, and talc) and organic pigments (for example, Soluble azo pigment, insoluble azo pigment, azo lake pigment, condensed azo pigment, copper phthalocyanine pigment, condensed polycyclic pigment, and the like. The content of these pigments is 0.5 to 5 in the ink composition.
0% by weight is an appropriate amount.

Next, as a polyurethane resin that can be used in the ink composition of the present invention, an urethane prepolymer is synthesized by reacting an organic diisocyanate compound with a high molecular weight diol compound, and further reacted with a chain extender and a reaction terminator. It is obtained by doing.

Examples of the organic diisocyanate compound usable for synthesizing the polyurethane resin include aliphatic diisocyanate compounds (eg, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate) and alicyclic diisocyanate compounds (eg, , Isophorone diisocyanate, hydrogenated xylylene diisocyanate), araliphatic diisocyanate compounds (xylylene diisocyanate, α, α,
α ′, α′-tetramethylxylylene diisocyanate) and aromatic diisocyanate compounds (eg, toluylene diisocyanate, diphenylmethane diisocyanate, etc.).

Above all, it is preferable to use an alicyclic or araliphatic diisocyanate compound from the viewpoint that the reaction is easily controlled and the performance of the obtained polyurethane resin is well balanced. α, α, α ′, α′-Tetramethylxylylene diisocyanate is preferred.

As the high molecular diol compound usable for synthesizing the polyurethane resin, first, as the polyester diol compound, a low molecular diol component (for example, ethylene glycol, 1,3-propanediol,
Linear glycols such as 1,4-butanediol,
1,2-propanediol, neopentyl glycol,
Branched glycols such as 3-methyl-1,5-pentanediol and 2,4-diethyl-1,5-pentanediol; ether diols such as diethylene glycol and triethylene glycol); and a dicarboxylic acid component (for example, succinic acid) Polyester diol compounds obtained by reacting with an acid, adipic acid, maleic acid or other saturated and unsaturated aliphatic dicarboxylic acids, or phthalic acid or other aromatic dicarboxylic acids).

As the polyether diol compound, a polyester diol compound obtained by subjecting a cyclic ester compound (for example, lactone or the like) to a ring opening reaction, a diol compound (for example, a linear or branched polyalkylene glycol compound, Alkylene glycol,
Examples thereof include polyether diol compounds obtained by polyaddition of oxyalkylenes (eg, ethylene oxide, propylene oxide, etc.) and tetrahydrofuran to bisphenols and the like. Further, polycarbonate diol compounds, polybutadiene glycol compounds, and the like can also be used. is there.

Among them, it is preferable to use a polyester diol compound in order to improve the boil retort suitability of the obtained ink composition.

The molecular weight of these high molecular weight diol compounds is preferably 400 or more from the viewpoint of film properties of the obtained polyurethane resin, and 10,000 or less from the viewpoint of reactivity, more preferably 1,000 to 1,000. 6,000.

The chain extender usable for synthesizing the polyurethane resin is a compound having two or more functional groups capable of reacting with an isocyanate group. Specifically, as the amino group-containing compound, a diamine compound having two primary amino groups (for example, ethylenediamine, 1,4-butanediamine, isophoronediamine, etc.) includes a primary amino group and a secondary amino group. Diamine compounds having one by one (eg, 2-ethylaminoethylamine, aminoethylethanolamine, etc.) and polyamine compounds having two primary amino groups and one or more secondary amino groups (eg, diethylenetriamine, triethylenetetramine Etc.).

Examples of the hydroxyl group-containing compound include diol compounds having two hydroxyl groups (eg, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, etc.). Examples of the hydrazine residue-containing compound include dihydrazine compounds having two hydrazine groups (eg, ethylenedihydrazine, butylenedihydrazine, etc.) and dihydrazide compounds having two hydrazide groups (eg, succinic dihydrazide, adipic dihydrazide). Etc.), and hydrazine can also be used.

A reaction terminator usable for synthesizing a polyurethane resin is a compound having at least one functional group capable of reacting with an isocyanate group, in a ratio of 2 mol per mol of the polyurethane resin after chain extension. Is to react. Specifically, an alkylamine compound (for example, n
-Butylamine, di-n-butylamine, etc.), alkanolamine compounds (e.g., monoethanolamine,
Diethanolamine, etc.) and monoalcohol compounds (methanol, ethanol, etc.). Further, the compounds mentioned as the chain extenders can also be used as the reaction terminator.

Further, the polyurethane resin used in the present invention needs to contain a functional group capable of reacting with an isocyanate group in the molecule, and the following method can be used for that purpose. For example, in order to obtain a polyurethane resin containing a primary amino group, a diamine compound having two primary amino groups, a polyamine having two primary amino groups and one or more secondary amino groups are required. Compound (in this case, 2
Or a method of using an amino group of the same type) as a reaction terminator.

In order to obtain a polyurethane resin containing a secondary amino group, two primary amino groups and two
A method using a polyamine compound having one or more primary amino groups as a chain extender, a method using a diamine compound having one primary amino group and one secondary amino group each as a reaction terminator, and the like can be used. .

Further, in order to obtain a polyurethane resin containing a hydroxyl group, a method using aminoethylethanolamine as a chain extender, a method using a diol compound having two hydroxyl groups, or an alkanolamine compound as a reaction terminator are used. it can.

From the viewpoint of high reactivity with the isocyanate-based curing agent, one molecule is contained in the polyurethane resin molecule.
Those having a primary or secondary amino group are preferred, and those having a primary amino group are more preferred.

As a method of synthesizing a polyurethane resin using the above reaction components, for example, an organic diisocyanate compound and a high molecular diol compound are used in a ratio of 1.3: 1.0 to 3.0.
0: 1.0, more preferably 1.5: 1.0 to 2.0:
A urethane prepolymer is synthesized by reacting at a molar ratio of 1.0, a chain extender is reacted with the remaining isocyanate groups in a range of approximately 0.5 to 0.95 equivalents, and a reaction terminator is further reacted. And a method in which a chain extender and a reaction terminator are reacted at once. In addition, the reaction temperature in each reaction stage is 3 depending on the material used.
It can be selected from the range of 0 to 140 ° C., and if necessary, a solvent, a catalyst, and the like can be used.

In the ink composition of the present invention, the molecular weight of the polyurethane resin is 5,000 as a weight average molecular weight.
~ 50,000 is preferable, and 10,000 ~ 30,000
0 is more preferred. Further, the content in the ink composition is preferably from 1 to 40% by weight.

Next, the silane coupling agent that can be used in the ink composition of the present invention is a silane coupling agent having a functional group capable of reacting with an isocyanate group in the molecule. Silane coupling agents are preferred. Specifically, silane coupling agents having primary and secondary amino groups (for example, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane , N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, N-β (aminoethyl)
γ-aminopropyltriethoxysilane) a silane coupling agent having a primary amino group (eg, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane), and a silane coupling agent having a secondary amino group ( For example, N-phenyl-γ-aminopropyltrimethoxysilane and the like can be mentioned. further,
From the viewpoint of high reactivity with the isocyanate curing agent, those having a primary amino group are more preferable.

The preferred amount of the silane coupling agent in the present invention is from 0.1 to 5% by weight, more preferably from 0.3 to 3% by weight, based on the ink composition. If the amount is reduced, the adhesiveness to the silicon oxide laminated film and the suitability for boiling and retorting become low. On the other hand, if it is added in an amount of more than 5% by weight, the effect does not change and it is economically disadvantageous.

A one-pack type ink composition using a polyurethane resin in which a silane coupling agent has been previously reacted with a silane coupling agent has been known from the past. However, it is disadvantageous in that it is limited to the use of the silicon oxide laminated film from the beginning.

On the other hand, in the present invention, since the silane coupling agent is used as an individual material, first, a non-additive type ink composition is manufactured and used as it is when printing on a normal plastic film. After the printing on the silicon oxide laminated film is determined, a method of adding a silane coupling agent can be used.

For example, when a method of adding a silane coupling agent for imparting appropriateness is used when shipping an ink upon receiving an order for the above-mentioned application or when the ink is set in a printing machine, There is an advantage that the versatility of the device is increased, and inventory management and the like are facilitated. Of course, an ink composition to which a silane coupling agent is added may be manufactured from the beginning for use as a silicon oxide laminated film.

Next, as the isocyanate-based curing agent which can be used in the ink composition of the present invention, a polyol compound (for example, trimethylolpropane, etc.) and a diisocyanate compound (for example, isophorone diisocyanate, toluylene diisocyanate, etc.) corresponding to the number of hydroxyl groups are used. There are, for example, isocyanate adducts of polyol compounds, various buret compounds, isocyanurate compounds, and the like, and the amount thereof is usually about 1 to 10 parts by weight based on 100 parts by weight of the ink composition.

The isocyanate-based curing agent is added and mixed immediately before printing, for example, when setting the ink in a printing machine, or after setting the ink, in order to prevent lapse of the functional group and gelation of the ink. Is preferred.

Next, examples of the organic solvent that can be used in the ink composition of the present invention include ketone-based organic solvents (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) and ester-based organic solvents (eg, methyl acetate, ethyl acetate, and the like). N-propyl acetate, n-butyl acetate, isobutyl acetate, etc.), aliphatic hydrocarbon-based organic solvents (for example, n
-Hexane, n-heptane, n-octane, etc.), aromatic hydrocarbon-based organic solvents (eg, toluene, xylene, etc.), alicyclic hydrocarbon-based organic solvents (eg, cyclohexane, methylcyclohexane, cyclooctane, etc.),
Alcohol-based organic solvents (eg, methanol, ethanol, n-propanol, isopropanol, butanol, etc.), and diol compounds and derivatives thereof (eg,
Ethylene glycol, propylene glycol, ethylene glycol monoethyl ether, etc.) can be used, and it is preferable to mix and use them in consideration of printability and drying property of the ink.

Further, addition of various ink additives such as a hard resin, a pigment dispersant, and a surfactant is optional.

As a method of producing a printing ink using these materials, first, a pigment, a polyurethane resin, an organic solvent, and if necessary, a pigment dispersant, a surfactant and the like are stirred and mixed, and then various kinds of kneading are performed. A method is used in which the meat is milled using a meat mill, for example, a bead mill, a sand mill, a pearl mill, a ball mill, an attritor, a roll mill, and the like, and further, the remaining ingredients are added and mixed.

Next, the method of using the printing ink composition for three-component lamination of the present invention will be described. The ink composition of the present invention is adjusted to a viscosity suitable for printing with a diluting solvent or the like, if necessary, and then printed on a silicon oxide laminated film mainly by a gravure printing method. here,
At present, polyester films are mainly used as silicon oxide laminated films, and Tech Barrier U and Tech Barrier T (the former is used for boiling, the latter is used for retort, both are manufactured by Mitsubishi Chemical Kojin Pax Co., Ltd.), MOS- TB
(Boil application, Oike Industry Co., Ltd.), Fine Barrier K
(Manufactured by Reiko Co., Ltd.) and the like are commercially available.

Further, in the present invention, after the ink composition is printed, lamination processing for laminating a polymer called a sealant is performed, and mainly two methods are used. One of them is extrusion lamination in which an anchor coating agent (for example, an imine-based resin) is applied to a printing surface as needed, and a hot-melt polymer (for example, polyethylene, polypropylene, or the like) is laminated in a thin film. The other is a dry lamination process in which an adhesive (for example, an isocyanate system) is applied to a printing surface, and then a non-stretched plastic film (for example, a non-stretched polyethylene film, a non-stretched polypropylene film, etc.) is laminated. Among them, dry lamination is preferred from the viewpoint of preventing the silicon oxide layer from cracking due to thermal stress.

The laminated product obtained by such a method is finally sealed with a heat sealer or the like on the sealant surfaces to form a packaging container.

Furthermore, by selecting a silicon oxide laminated film having a boilability and a retort suitability, the contents packed in the packaging container can be boiled and retorted. Usually, the packaging container is immersed in hot (pressurized) water at 60 to 95 ° C. for boil treatment and 110 to 130 ° C. for retort treatment for several minutes to 1 hour. It has good boiling retort suitability.

[0042]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In Examples, “parts” and “%” represent “parts by weight” and “% by weight” unless otherwise specified.

<Production of polyurethane resin varnish> (Production Example 1) 3-methyl-1,5-pentylene having an average molecular weight of 2,000 was placed in a four-necked flask equipped with a stirrer, a cooling pipe and a nitrogen gas introducing pipe. 200 parts of adipate diol and 44.4 parts of isophorone diisocyanate were charged and reacted at 100 to 105 ° C for 6 hours while introducing nitrogen gas. Cool to near room temperature, 243 parts of toluene,
243 parts of methyl ethyl ketone, 122 of isopropanol
After adding 13.6 parts of isophoronediamine, a chain extension reaction is performed by adding 13.6 parts of isophoronediamine, and 2.4 parts of ethylenediamine is further added to stop the reaction. Polyurethane resin varnish A (solid content: 30%, weight average molecular weight of polyurethane resin) 16,0
00, a functional group capable of reacting with an isocyanate group contained in the molecule = primary amino group).

(Production Example 2) A four-necked flask equipped with a stirrer, a cooling tube and a nitrogen gas introducing tube was charged with an average molecular weight of 2,0.
200 parts of 3-methyl-1,5-pentylene adipate diol and isophorone diisocyanate
4 parts, 100-105 while introducing nitrogen gas
The reaction was carried out at 6 ° C. for 6 hours. After allowing to cool to near room temperature and adding 243 parts of toluene, 243 parts of methyl ethyl ketone and 122 parts of isopropanol, 13.6 parts of isophorone diamine was added.
And the reaction was terminated by adding 3.4 parts of 2-ethylaminoethylamine. The polyurethane resin varnish B (solid content 30%, polyurethane resin weight average molecular weight 16,000, The functional group capable of reacting with the isocyanate group contained therein was a secondary amino group).

(Production Example 3) A four-necked flask equipped with a stirrer, a cooling pipe and a nitrogen gas introducing pipe was charged with an average molecular weight of 2,0.
200 parts of 3-methyl-1,5-pentylene adipate diol and isophorone diisocyanate
4 parts, 100-105 while introducing nitrogen gas
The reaction was carried out at 6 ° C. for 6 hours. After allowing to cool to near room temperature and adding 243 parts of toluene, 243 parts of methyl ethyl ketone and 122 parts of isopropanol, 13.6 parts of isophorone diamine was added.
Part of the mixture, a chain elongation reaction was carried out, and 2.4 parts of monoethanolamine was further added to stop the reaction. Polyurethane resin varnish C (solid content: 30%, polyurethane resin weight average molecular weight: 16,000, contained in the molecule) A functional group capable of reacting with an isocyanate group = hydroxyl group) was obtained.

(Production Example 4) A four-necked flask equipped with a stirrer, a cooling pipe and a nitrogen gas introduction pipe was charged with an average molecular weight of 2,0.
200 parts of 3-methyl-1,5-pentylene adipate diol and isophorone diisocyanate
4 parts, 100-105 while introducing nitrogen gas
The reaction was carried out at 6 ° C. for 6 hours. After allowing to cool to near room temperature and adding 243 parts of toluene, 243 parts of methyl ethyl ketone and 122 parts of isopropanol, 13.6 parts of isophorone diamine was added.
3) and a chain extension reaction was carried out.
The reaction was stopped by adding 8 parts, to obtain a polyurethane resin varnish D (solid content: 30%, weight average molecular weight of the polyurethane resin: 16,000, no functional group capable of reacting with an isocyanate group contained in the molecule = none).

<Preparation of Examples 1 to 8 and Comparative Examples 1 to 4> Titanium oxide (R-960, manufactured by DuPont) 40
Parts, a mixture of 15 parts of a polyurethane resin varnish and 10 parts of a mixed solvent were kneaded using a paint conditioner manufactured by Red Devil Co., and the remaining ingredients of the formulation shown in Table 1 were added. 1 to 4 test inks were prepared.

[Table 1]

As the silane coupling agent,
A: N-β (aminoethyl) γ-aminopropyltrimethoxysilane, B: γ-aminopropyltrimethoxysilane, C: N-phenyl-γ-aminopropyltrimethoxysilane (all in 50% ethyl acetate solution), And, as the isocyanate-based curing agent, Coronate HL is used.
(40% ethyl acetate solution, manufactured by Nippon Polyurethane Co., Ltd.)
Was used.

Adhesiveness 30 parts of the mixed solvent shown in Table 1 was added to 100 parts of each test ink to dilute the mixture, and the viscosity was adjusted. Then, a gravure calibrator (Higashiya Seisakusho Co., Ltd., plate depth 32 μm) was used. Printing was performed on a vapor-deposited surface of a polyester film (Tech Barrier T, film thickness 12 μm, manufactured by Mitsubishi Chemical Kojin Pax Co., Ltd.) on one side of which a silica vapor deposition treatment was performed. Paste cellophane tape on the printed surface of the printed material aged at room temperature for one day,
The adhesiveness of the ink to the film was evaluated based on the area where the ink was peeled off from the printing surface when the ink was quickly peeled off (ink peeling area). A: The ink does not peel at all. B: The ink peeling area is less than 20% of the tape adhesion area. C: The ink peeling area is 20 to 70% of the tape adhesion area. D: The ink peeling area exceeds 70% of the tape adhesion area.

Laminate strength Further, an isocyanate-based adhesive (Dick Dry LX-703A / KR-90, Dainippon Ink and Chemicals, Inc.) was applied to the printed surface at a coating amount of 3 g / m ² as a solid content. Thereafter, a non-stretched polyethylene film (RXC-3, film thickness 60 μm, manufactured by Tosello Co., Ltd.) was laminated using a dry laminator, and aged at 40 ° C. for 3 days. This laminate was cut into 15 mm wide sample pieces, and the T-shaped peel strength was measured using a peel tester (manufactured by Yasuda Seiki Co., Ltd.). In the evaluation results, measured values of strength (g / 15 mm) are described. In addition, 5000 ov. Is the upper limit of measurement 500g
/ 15 mm.

Boil suitability, retort suitability The laminate obtained by the above method was made into a bag, filled with water, and the end was sealed. In the boil suitability test, the retort suitability test was performed in hot water at 90 ° C. for 30 minutes. Was immersed in hot water at 120 ° C. for 15 minutes, and the suitability for boiling and retort were evaluated based on the presence or absence of laminating. A: No laminating is seen at all. B: Pinhole-shaped or partially thin and short laminar floating is observed. C: Long streak-like laminar floating is observed on the entire surface. D: CPP film completely peeled off from the printing surface.

The above evaluation results are shown in Table 1. In addition,
Adhesion, boiling suitability and retort suitability were rated B or higher, and lamination strength was 200 g / 1.
Those having a size of 5 mm or more were judged to have good performance.

[Table 1]

[0053]

As described above, the ink composition of the present invention has excellent adhesiveness to a silicon oxide laminated film and is applicable to boiling and retorting applications. The laminated product obtained by post-processing has high lamination strength.

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 4F100 AA20B AH06 AK01A AK01D AK42 AK51C AT00A BA03 BA04 BA07 BA10A BA10D EH46 GB23 JK01 JL11 JM02B 4J038 DG001 DG061 DG101 DG261 DG262 DG292 GA04 BC01 FA07

Claims (4)

[Claims] 1. A silicon oxide comprising a polyurethane resin having a functional group capable of reacting with an isocyanate group in a molecule, a silane coupling agent having a functional group capable of reacting with an isocyanate group in a molecule, and an isocyanate-based curing agent. A printing ink composition for three-pack laminating, characterized in that an object is printed on a plastic film laminated in a thin film form. 2. The printing ink composition for three-component lamination according to claim 1, wherein the functional group capable of reacting with the isocyanate group in the polyurethane resin and the silane coupling agent is a primary or secondary amino group. 3. A plastic film on which silicon oxide is laminated in the form of a thin film, on a silicon oxide laminated surface of the plastic film.
A laminated product obtained by printing the printing ink composition for three-component lamination described in 1 above, applying an anchor coat agent on the printed surface as needed, and laminating a hot-melt polymer. 4. A plastic film in which silicon oxide is laminated in a thin film form on a silicon oxide laminated surface of the plastic film.
A laminated product obtained by printing the printing ink composition for three-component lamination described in 1 above, applying an adhesive to a printed surface, and laminating a polymer film.