JP2002030239A - Printing ink composition for laminate and laminated product using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a printing ink composition for laminates, excellent in adhesion to a silicon oxide laminated film and applicable to boiling and retorting treatments, and to provide a laminated product printed with the printing ink composition and having high laminate strength and gas barrier property. SOLUTION: This printing ink composition for laminates is two-part type one and characterized by containing a polyurethane resin having intramolecular functional group capable of reacting with isocyanate group and a curing agent having an isocyanate group and an alkoxysilyl group.

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, and more particularly, to a plastic film (hereinafter referred to as silicon oxide) having a thin film of silicon oxide laminated on its surface. Laminating printing ink composition having good adhesiveness to boil retort processing, and laminating processing using the same with high lamination strength and gas barrier properties About things.

[0002]

2. Description of the Related Art One of the advanced functions of food packaging containers is to provide a gas barrier property that blocks air and water vapor to prevent deterioration of contents due to oxidation and moisture absorption. A method of providing a gas barrier layer of polyvinylidene chloride or aluminum has been used.

However, recently, the use of chlorine compounds has been shunned due to environmental problems and the like, and there is also a problem that an aluminum laminated plastic film cannot be used for applications requiring transparency of the film. Therefore, a method using a plastic film in which silicon oxide is laminated has been attracting attention as an alternative material.

[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. And a laminated product having gas barrier properties.

[0006]

That is, the invention according to claim 1 comprises a polyurethane resin having a functional group capable of reacting with an isocyanate group in a molecule, and a curing agent having an isocyanate group and an alkoxysilyl group. And a printing ink composition for two-component lamination.

Further, the invention according to claim 2 is characterized in that a reaction product of a polyisocyanate compound represented by the following formula 1 and an amino group-containing alkoxysilane compound is used as the curing agent. And a printing ink composition for two-component lamination described in 1. above. (OCN) p-A- (B) q Formula 1 where A is a residue excluding the isocyanate group of the polyisocyanate compound involved in the reaction, p and q are integers of 1 or more, and p + q is the isocyanate of the polyisocyanate compound. Equal to the number of radicals. B is -NHCON
X is a residue excluding the amino group of the amino group-containing alkoxysilane compound involved in the reaction, and R is hydrogen, an alkyl group, or a phenyl group.

According to a third aspect of the present invention, there is provided the two-component laminate according to the first or second aspect, wherein the content of the curing agent is 0.3 to 5% by weight based on the printing ink composition for a laminate. Printing ink composition.

According to a fourth aspect of the present invention, there is provided a printing method for two-component lamination according to any one of the first to third aspects, wherein the silicon oxide is laminated on a silicon oxide laminated surface of a plastic film having a thin film. The present invention relates to a laminated product obtained by printing an ink composition, applying an anchor coat agent to a printing surface as needed, and laminating a hot-melt polymer.

According to a fifth aspect of the present invention, there is provided a printing method for a two-component lamination according to any one of the first to third aspects, wherein the plastic film on which the silicon oxide is laminated in the form of a thin film is laminated. The present invention relates to a laminated product obtained by printing an ink composition, applying an adhesive to a printing surface, and laminating a polymer film. Hereinafter, the present invention will be described in more detail.

[0011]

DETAILED DESCRIPTION OF THE INVENTION First, pigments usable 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, antimony red, cadmium yellow). , Pigments such as cobalt blue, navy blue, ultramarine blue, carbon black, graphite, and extenders such as calcium carbonate, kaolin, clay, barium sulfate, aluminum hydroxide, and talc) and organic pigments (eg, soluble azo pigments, insoluble Azo pigments, azo lake pigments, condensed azo pigments, copper phthalocyanine pigments, condensed polycyclic pigments, and the like. The appropriate content of these pigments is 0.5 to 50% by weight in the ink composition.

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.).

Among them, it is preferable to use an alicyclic or araliphatic diisocyanate from the viewpoint that the reaction is easily controlled and the performance of the obtained polyurethane resin is well-balanced, and particularly, isophorone diisocyanate or , Α, α, α ', α'-tetramethylxylylene diisocyanate are preferred.

Among the polymer diol compounds available for synthesizing a polyurethane resin, first, as a 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).

The polyether diol compound includes a polyester diol compound obtained by a ring opening reaction of a cyclic ester compound (eg, lactone), a diol compound (eg, a (poly) alkylene glycol compound, bisphenol, etc.) and an oxyalkylene compound. Examples thereof include polyether diol compounds obtained by polyaddition of, for example, ethylene oxide and propylene oxide, and tetrahydrofuran. Further, polycarbonate compounds, polybutadiene glycol compounds, and the like can also be used.

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, diamines having two primary amino groups (for example, ethylenediamine, 1,4-butanediamine, isophoronediamine, etc.) include a primary amino group and a secondary amino group. Diamines having one by one (eg, 2-ethylaminoethylamine, aminoethylethanolamine, etc.) and polyamines having two primary amino groups and one or more secondary amino groups (eg, diethylenetriamine, triethylenetetramine Etc.).

Examples of the hydroxyl group-containing compound include diols having two hydroxyl groups (eg, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, etc.). Examples of the hydrazine residue-containing compound include dihydrazines having two hydrazine groups (eg, ethylene dihydrazine, butylene dihydrazine, etc.) and dihydrazides 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. Specific examples include alkylamines (eg, n-butylamine, di-n-butylamine, etc.), alkanolamines (eg, monoethanolamine, diethanolamine, etc.), and monoalcohols (methanol, ethanol, etc.). The compounds mentioned as the chain extenders can also be used as reaction terminators.

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, aliphatic diamines having two primary amino groups, two primary amino groups and one secondary amino group are used.
A method using an aliphatic polyamine having one or more (in this case, a secondary amino group is also introduced) as a reaction terminator can be used.

In order to obtain a polyurethane resin containing a secondary amino group, an aliphatic polyamine having two primary amino groups and one or more secondary amino groups is used as a chain extender. The method, wherein said primary amino group and 2
For example, a method using aliphatic diamines having one class of amino group 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 an aliphatic diol having two hydroxyl groups, or an alkanolamine as a reaction terminator, etc. Available.

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 for synthesizing a polyurethane resin using the above-mentioned respective reaction components, for example, an organic diisocyanate compound and a polymer diol compound are used in a ratio of 1.3: 1.0 to
3.0: 1.0, more preferably 1.5: 1.0 to 2.
A urethane prepolymer is synthesized by reacting at a molar ratio of 0: 1.0, and a chain extender is allowed to react with the remaining isocyanate groups in a range of generally 0.5 to 0.95 equivalents. Can be used. In addition,
The reaction temperature in each reaction step can be selected from the range of 30 to 140 ° C. according to the material to be used, and a solvent, a catalyst and the like can be used as necessary.

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 curing agent that can be used in the ink composition of the present invention is a compound having an isocyanate group and an alkoxysilyl group in the molecule, and is preferably a polyisocyanate compound represented by the following formula 1, A reaction product with an amino group-containing alkoxysilane compound can be used. (OCN) p-A- (B) q Formula 1 where A is a residue excluding the isocyanate group of the polyisocyanate compound involved in the reaction, p and q are integers of 1 or more, and p + q is the isocyanate of the polyisocyanate compound. Equal to the number of radicals. B is -NHCON
X is a residue excluding the amino group of the amino group-containing alkoxysilane compound involved in the reaction, and R is hydrogen, an alkyl group, or a phenyl group.

The compound represented by the above formula 1 is obtained by firstly using the aliphatic diisocyanate compound, alicyclic diisocyanate compound,
A compound obtained by reacting an aromatic aliphatic diisocyanate compound, an aromatic diisocyanate compound, various buret compounds, isocyanurate compounds, and the like with a silane coupling agent can be used.

In addition, a polyol compound having two or more hydroxyl groups (for example, a diol compound such as alkylene glycol or bisphenol, a triol compound such as glycerin or trimethylolpropane, or a tetraol compound such as pentaerythritol) is added to the number of hydroxyl groups: isocyanate A polyisocyanate compound is prepared by reacting a diisocyanate compound (for example, isophorone diisocyanate, hexamethylene diisocyanate, etc.) in an amount such that the ratio of the number of groups becomes 1: 2, and further, at least one isocyanate group is present in the molecule. It can also be obtained by reacting the remaining amount of the silane coupling agent.

On the other hand, the silane coupling agent to be reacted is a silane coupling agent having a functional group capable of reacting with an isocyanate group and an alkoxysilyl group, specifically, a primary amino group and an alkoxysilyl group. (E.g., γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane), and silane coupling agents having a secondary amino group and an alkoxysilyl group (eg, N-phenyl-γ
-Aminopropyltrimethoxysilane, etc.) are preferred, and monoamine compounds are more preferred from the viewpoint of ease of production and the like.

When the total number of isocyanate groups and alkoxysilyl groups in the curing agent molecule is three or more,
As long as at least one of both the isocyanate group and the alkoxysilyl group is present, any of a large number of functional groups can be used. For example, when the total number of the functional groups is four, three isocyanate groups and one alkoxysilyl group
One, two isocyanate groups and two alkoxysilyl groups,
Alternatively, one isocyanate group and an alkoxysilyl group 3
One of the two. When the isocyanate group is large, the effect of improving the heat resistance and the hot water resistance of the system is increased, while when the alkoxysilyl group is large, the effect of improving the adhesion to the substrate film is increased.

In the present invention, the amount of the curing agent added is
Usually, it is about 0.3 to 5 parts by weight with respect to 100 parts by weight of the ink composition. When the amount of the curing agent is small, the adhesiveness to the base film is low. Absent.

Next, examples of the organic solvent that can be used in the ink composition of the present invention include ketone organic solvents (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone) and ester 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, etc.) can be used, and it is preferable to mix and use them in consideration of printability and drying property of the ink.

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

As a method for 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 in which the meat is milled by using a meat machine, for example, a bead mill, a sand mill, a pearl mill, a ball mill, an attritor, a roll mill, and the like, and further, a final formulation is used.

The curing agent according to the present invention is added and mixed immediately before printing as much as possible, for example, when setting the ink in a printing machine, or after setting the ink, in order to prevent the functional group from being lost or the ink from gelling. Is preferred.

A one-pack type ink composition using a polyurethane resin in which a silane coupling agent has been reacted in advance has been known. However, this ink composition is used for reasons such as effectiveness versus economy. 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, since the curing agent of the present invention is used in the form of an additive, when printing on an ordinary plastic film, an ink composition containing no curing agent of the present invention is printed, When printing on an oxide laminated film, a method of adding the curing agent of the present invention can be used. Therefore, this method increases the versatility of the ink, and
There is an advantage that inventory management and the like become easier.

Next, the method of using the printing ink composition for two-pack lamination of the present invention will be described. After the ink composition of the present invention is adjusted to a viscosity suitable for printing with a diluting solvent or the like as necessary, a good effect is obtained by gravure printing or flexographic printing, particularly when printed on a silicon oxide laminated film. It is obtained. Here, as the silicon oxide laminated film, polyester film is currently the mainstream, and Tech Barrier U and Tech Barrier T (the former is used for boiling, the latter is used for retort, both manufactured by Mitsubishi Chemical Kojin Pax Co., Ltd.) , MOS-TB (for boiling use, Oike Kogyo Co., Ltd.), Fine Barrier K (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 heat-fusible polymer called a sealant is performed. Two methods are mainly used for this lamination.
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 one is,
This is a dry lamination process in which an adhesive (for example, an isocyanate type) is applied to the printing surface, and 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 cracks of the silicon oxide film due to heat.

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.

Further, by selecting a silicon oxide laminated film having boilability and 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.

[0044]

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) In a four-necked flask equipped with a stirrer, a cooling pipe and a nitrogen gas introducing pipe, 3-methyl-1,5-pentylene having an average molecular weight of 2,000 was placed. 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.
And the reaction was terminated by adding 2.4 parts of monoethanolamine. Polyurethane resin varnish C (solid content: 30%, weight average molecular weight of polyurethane resin: 16,000, contained in the molecule) (A functional group capable of reacting with an isocyanate group to be obtained = hydroxyl group).

(Production Example 4) 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.
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 Hardener> Preparation of Hardener Solution 1 Trimethylolpropane 3-mol adduct of isophorone diisocyanate (Mytec NY 218A, 75% ethyl acetate solution, manufactured by Mitsubishi Chemical Corporation) 100 parts, γ- 16.7 parts of aminopropyltrimethoxysilane and 66.7 parts of ethyl acetate were reacted while stirring and mixing at 40 ° C. to obtain a curing agent solution 1 (a 50% solution of ethyl acetate, an isocyanate group in one molecule of the curing agent). Two, alkoxysilyl group 1
One).

Preparation of Hardener Solution 2 Trimer of hexamethylene diisocyanate (buret compound, duranate 24A-90E, ethyl acetate 90
% Solution, Asahi Kasei Corporation) 100 parts, γ-aminopropyltrimethoxysilane 56.8 parts, ethyl acetate 13
6.8 parts were reacted while stirring and mixing at 40 ° C. to obtain a curing agent solution 2 (ethyl acetate 50% solution, one isocyanate group and one alkoxysilyl group 2 in one molecule of the curing agent).
One).

Preparation of curing agent solution 3 Trimethylolpropane 3-mol isophorone diisocyanate adduct (Mytec NY 218A, 75% ethyl acetate solution, manufactured by Mitsubishi Chemical Corporation) 100 parts, γ-aminopropyltrimethoxysilane 50 And 10.1 parts of ethyl acetate were reacted at 40 ° C. while stirring and mixing to obtain a curing agent solution 3 (50% solution of ethyl acetate, 1 part of curing agent).
0 isocyanate group and 3 alkoxysilyl group in the molecule
One).

Preparation of Curing Agent Solution 4 100 parts of trimethylolpropane 3 mol adduct of isophorone diisocyanate (Mytec NY 218A, 75% solution of ethyl acetate, manufactured by Mitsubishi Chemical Corporation) and 50 parts of ethyl acetate are mixed with stirring. To obtain a curing agent solution 4 (50% solution of ethyl acetate, 3 isocyanate groups in one molecule of the curing agent).
And an alkoxysilyl group 0).

<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]

<Evaluation of Performance> Examples 1 to 8 and Comparative Example 1
Toluene: methyl ethyl ketone: isopropanol = 40: 40: 20 with respect to 100 parts of test inks
(Weight ratio) 30 parts of the mixed solvent was added and diluted, and then a gravure calibrator (manufactured by Higashiya Seisakusho Co., Ltd., plate depth 32μ)
m), printed on a polyester film (Tech Barrier T, film thickness 12 μm, manufactured by Mitsubishi Kagaku Kojin Pax Co., Ltd.) on one side subjected to silica evaporation treatment, and evaluated for adhesiveness, laminating strength, and boiling retort suitability Was done. The results are shown in Table 1.

[Table 1]

Adhesive property A cellophane tape was stuck to the printed surface of the printed matter after one day, and when peeled off quickly, the adhesiveness of the ink to the film was evaluated based on the area where the ink was peeled off from the printed surface (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 Isocyanate-based adhesive (Dick Dry LX
-703A / KR-90, Dainippon Ink and Chemicals, Inc. at a coating amount of 3 g / m ² as a solid content, and then using a dry laminator, a non-stretched polyethylene film (RXC-3, film) (Thickness: 60 μm, manufactured by Tocelo Co., Ltd.) 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, 500 ov. Is the upper limit of measurement 500g / 15m
Indicates that the value is greater than m.

Boil suitability, retort suitability The laminate obtained by the above method is made into a bag, filled with water, and then sealed. In a boil suitability test, 30% in hot water at 90 ° C.
Minutes, in the retort aptitude test, 15
After immersion for a minute, boil suitability and retort suitability were evaluated from 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.

[0058]

[Table 1]

[0059]

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.

Continued on the front page F-term (reference) 4F100 AA20B AH03H AH06H AK01A AK01D AK04 AK41 AK51C AK51G AK51H AL01H BA04 BA07 BA10A BA10D CA02C CB00 CC03C GB23 HB31C JD02 JJ03 JK06 CA04 CA04J04 CA14J04 CD16 DA01 DA03 DB03 DB04 DB07 DF01 DF02 DF16 DF20 DF22 DG04 DG05 DG06 DG14 DH05 DQ09 HA01 HB16 HC03 HC12 HC17 HC22 HC46 HC52 HC61 HC64 HC67 HC71 HC73 JA44 JA46 KA02 KA04 KD12 RA07 4J039 AE04 BC06 BC44 BC04

Claims (5)

[Claims] 1. A two-component laminating printing ink composition comprising: a polyurethane resin having a functional group capable of reacting with an isocyanate group in a molecule; and a curing agent having an isocyanate group and an alkoxysilyl group. . 2. The two-component laminate according to claim 1, wherein a reaction product of a polyisocyanate compound represented by the following formula 1 and an amino group-containing alkoxysilane compound is used as the curing agent. Printing ink composition. (OCN) p-A- (B) q Formula 1 where A is a residue excluding the isocyanate group of the polyisocyanate compound involved in the reaction, p and q are integers of 1 or more, and p + q is the isocyanate of the polyisocyanate compound. Equal to the number of radicals. B is -NHCON
X is a residue excluding the amino group of the amino group-containing alkoxysilane compound involved in the reaction, and R is hydrogen, an alkyl group, or a phenyl group. 3. The two-part printing ink composition for lamination according to claim 1, wherein the content of the curing agent is 0.3 to 5% by weight based on the printing ink composition for lamination. 4. After printing the printing ink composition for two-component lamination according to any one of claims 1 to 3, on a silicon oxide laminated surface of a plastic film on which silicon oxide is laminated in a thin film form, A laminated product obtained by applying an anchor coat agent to the printing surface as needed and laminating a hot-melt polymer. 5. The printing ink composition for two-component lamination according to any one of claims 1 to 3, wherein the printing ink composition according to any one of claims 1 to 3 is printed on a silicon oxide laminated surface of a plastic film on which silicon oxide is laminated in a thin film form. A laminated product obtained by applying an adhesive to the printing surface and laminating a polymer film.