JP4186089B2 - Printing ink composition for laminating, and laminate product using the same. - Google Patents

Description

【００４８】
なお、シランカップリング剤としては、Ａ：Ｎ−β（アミノエチル）γ−アミノプロピルトリメトキシシラン、Ｂ：γ−アミノプロピルトリメトキシシラン、Ｃ：Ｎ−フェニル−γ−アミノプロピルトリメトキシシラン（いずれも５０％酢酸エチル溶液）、そして、イソシアネート系硬化剤としては、コロネートＨＬ（４０％酢酸エチル溶液、日本ポリウレタン（株）製）を用いた。
【００４９】
接着性
各試験インキ１００部に表１記載の混合溶媒３０部を加えて希釈し、粘度調整を行った後、グラビア校正機（（株）東谷製作所製、版深度３２μｍ）にて、片面にシリカ蒸着処理が施こされたポリエステルフィルム（テックバリアＴ、フィルム厚１２μｍ、三菱化学興人パックス（株）製）の蒸着面に印刷した。室温で１日経時させた印刷物の印刷面に、セロファンテープを貼り付け、すばやく剥がした時にインキが印刷面から剥離した面積（インキ剥離面積）により、インキのフィルムに対する接着性を評価した。
Ａ：インキが全く剥離しないもの。
Ｂ：インキ剥離面積がテープ接着面積の２０％未満のもの。
Ｃ：インキ剥離面積がテープ接着面積の２０〜７０％のもの。
Ｄ：インキ剥離面積がテープ接着面積の７０％を超えるもの。
【００５０】
ラミネート強度
さらに、印刷面にイソシアネート系接着剤（ディックドライＬＸ−７０３Ａ／ＫＲ−９０、大日本インキ化学工業（株））を、固形分として３ｇ／ｍ^２となる塗布量で塗布した後、ドライラミネート機を用いて無延伸ポリエチレンフィルム（ＲＸＣ−３、フィルム厚６０μｍ、東セロ（株）製）を積層し、４０℃で３日経時させた。このラミネート物を１５ｍｍ幅の試料片に切断し、剥離試験機（安田精機（株）製）を用いてＴ字剥離強度を測定した。評価結果には、強度の実測値（ｇ／１５ｍｍ）を記載した。なお、５０００ｏｖ．は測定上限値５００ｇ／１５ｍｍを超える数値である事を示す。
【００５１】
ボイル適性、レトルト適性
上記の方法で得たラミネート物を製袋し、水を詰めた後に端部を溶封し、ボイル適性試験では９０℃の熱水中に３０分、レトルト適性試験では１２０℃の加圧熱水中に１５分間浸漬し、ラミ浮きの有無からボイル適性およびレトルト適性を評価した。
Ａ：全くラミ浮きが見られないもの。
Ｂ：ピンホール状もしくは一部に細くて短いラミ浮きがみられるもの。
Ｃ：長い筋状のラミ浮きが全面にみられるもの。
Ｄ：完全にＣＰＰフィルムが印刷面から剥がれているもの。
【００５２】
以上の評価結果を表１に記載した。なお、接着性、ボイル適性およびレトルト適性についてはＢ評価以上、また、ラミネート強度については２００ｇ／１５ｍｍ以上のものを、良好な性能を有すると判断した。
【表１】
【００５３】
【発明の効果】
以上、実施例を挙げて具体的に説明したように、本発明のインキ組成物は、珪素酸化物積層フィルムに対する接着性に優れ、ボイル・レトルト用途にも適用可能で、さらに、後加工して得られたラミネート加工物は、高いラミネート強度を有するものである。[0001]
[Industrial application fields]
The present invention relates to a printing ink composition for laminating and a laminated product using the same, and more specifically, a plastic film (hereinafter referred to as a silicon oxide laminated film) in which silicon oxide is laminated in a thin film shape on the surface. The present invention relates to a laminating printing ink composition that has good adhesion to (represents a film) and can be applied to boil retort processing, and a laminated product having high laminating strength using the same.
[0002]
[Prior art]
One of the enhancements in the functionality of food packaging containers is the provision of gas barrier properties that block air and water vapor and prevent the contents from being altered by oxidation or moisture absorption. Therefore, a method of providing a gas barrier layer such as polyvinylidene chloride or aluminum on the surface of a plastic film has been conventionally used.
[0003]
However, recently, the use of chlorinated compounds has been shunned due to environmental problems, and there are applications where aluminum laminated plastic films cannot be used due to their transparency, so silicon oxide is an alternative material. A method using a laminated plastic film is attracting attention.
[0004]
[Problems to be solved by the invention]
However, a packaging container obtained by printing a conventional printing ink composition on a silicon oxide laminated film and laminating it has a problem that a high laminate strength cannot be obtained and the suitability for boil and retort is poor.
[0005]
Accordingly, the present invention provides a printing ink composition for laminating that has excellent adhesion to a silicon oxide laminated film and can be applied to boil / retort processing, and a laminate having high laminating strength on which the printing ink composition is printed. The purpose is to provide a processed product.
[0006]
[Means for Solving the Problems]
That is, the invention according to claim 1 includes a polyurethane resin having a functional group capable of reacting with an isocyanate group in the molecule, a silane coupling agent having a functional group capable of reacting with the isocyanate group in the molecule, and an isocyanate curing agent. The present invention relates to a three-component laminating printing ink composition characterized in that it is printed on a plastic film in which a silicon oxide is laminated in a thin film shape. The “three-component type” in the present invention means that three components of a polyurethane resin, a silane coupling agent, and an isocyanate curing agent are blended as components involved in the resin-based reaction ( Usually, all three components are used in a liquid state), but the blending time is not limited to just before printing.
[0007]
Further, in the invention according to claim 2, 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. The present invention relates to a printing ink composition.
[0008]
According to a third aspect of the invention, the three-component laminating printing ink composition according to the first or second aspect is printed on a silicon oxide laminated surface of a plastic film in which silicon oxide is laminated in a thin film shape. Thereafter, the present invention relates to a laminate product obtained by applying an anchor coating agent to the printing surface as necessary and laminating a hot-melt polymer.
[0009]
According to a fourth aspect of the present invention, the three-component laminating printing ink composition according to the first or second aspect is printed on a silicon oxide laminated surface of a plastic film in which silicon oxide is laminated in a thin film shape. Thereafter, the present invention relates to a laminate product obtained by applying an adhesive to the printing surface and laminating a polymer film. The present invention is described in further detail below.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
Conventionally, as a printing ink composition for laminating, a one-component type composed of a pigment, a binder resin typified by polyurethane, an organic solvent, or the like, or a two-component type added with an isocyanate curing agent has been used. However, in the present invention, a silane coupling agent is further added to form a three-component laminating printing ink composition.
[0011]
First, as pigments that can be used in the ink composition of the present invention, various inorganic pigments generally used in printing inks and paints (for example, titanium oxide, bengara, antimony red, cadmium yellow, cobalt blue, bitumen, ultramarine blue). , Colored pigments such as carbon black and graphite, and extender pigments 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, condensation) Azo pigments, copper phthalocyanine pigments, condensed polycyclic pigments, etc.). The content of these pigments is 0.5 to 50% by weight in the ink composition.
[0012]
Next, the polyurethane resin that can be used in the ink composition of the present invention is obtained by reacting an organic diisocyanate compound with a polymer diol compound to synthesize a urethane prepolymer, and further reacting with a chain extender and a reaction terminator. It is what
[0013]
Examples of organic diisocyanate compounds that can be used to synthesize polyurethane resins include aliphatic diisocyanate compounds (eg, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate), alicyclic diisocyanate compounds (eg, isophorone diisocyanate). , Hydrogenated xylylene diisocyanate, etc.), araliphatic diisocyanate compounds (xylylene diisocyanate, α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.), aromatic diisocyanate compounds (eg, toluylene diisocyanate, diphenylmethane diisocyanate) Etc.).
[0014]
Among them, it is preferable to use an alicyclic or araliphatic diisocyanate compound from the viewpoint that the reaction control is simple and the performance balance of the obtained polyurethane resin is good, and in particular, isophorone diisocyanate and α, α , Α ′, α′-tetramethylxylylene diisocyanate is preferred.
[0015]
As a high molecular diol compound that can be used for synthesizing a polyurethane resin, first, as a polyester diol compound, a low molecular diol component (for example, ethylene glycol, 1,3-propanediol, 1,4-butanediol, etc.) Chain glycols, 1,2-propanediol, neopentyl glycol, branched glycols such as 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, diethylene glycol, triethylene glycol Obtained by reacting a dicarboxylic acid component (for example, saturated and unsaturated aliphatic dicarboxylic acids such as succinic acid, adipic acid, and maleic acid, and aromatic dicarboxylic acids such as phthalic acid). List polyester diol compounds .
[0016]
Further, as the polyether diol compound, a polyester diol compound obtained by ring-opening reaction of a cyclic ester compound (for example, lactone), a diol compound (for example, a polyalkylene glycol compound having a linear or side chain, alkylene glycol, Polyether diol compounds obtained by polyaddition of oxyalkylene (for example, ethylene oxide, propylene oxide, etc.) or tetrahydrofuran to bisphenol, etc., and polycarbonate diol compounds, polybutadiene glycol compounds, etc. are also available. is there.
[0017]
Among these, in order to improve the boil / retort suitability of the obtained ink composition, it is preferable to use a polyester diol compound.
[0018]
The molecular weight of these polymer diol compounds is preferably 400 or more from the viewpoint of the film properties of the obtained polyurethane resin, and 10,000 or less from the viewpoint of reactivity, more preferably 1,000 to 6,000. It is.
[0019]
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.), a primary amino group and a secondary amino group are used. Diamine compounds having one each (for example, 2-ethylaminoethylamine, aminoethylethanolamine, etc.), and polyamine compounds having two primary amino groups and one or more secondary amino groups (for example, diethylenetriamine, triethylenetetramine) Etc.).
[0020]
Examples of the hydroxyl group-containing compound include diol compounds having two hydroxyl groups (for example, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, etc.). Further, examples of the hydrazine residue-containing compound include dihydrazine compounds having two hydrazine groups (for example, ethylene dihydrazine, butylene dihydrazine, etc.), dihydrazide compounds having two hydrazide groups (for example, succinic dihydrazide, adipic dihydrazide). Etc.) and hydrazine can also be used.
[0021]
A reaction terminator that can be used for synthesizing a polyurethane resin is a compound having at least one functional group capable of reacting with an isocyanate group, and is reacted at a ratio of 2 mol with respect to 1 mol of the polyurethane resin after chain extension. Is. Specific examples include alkylamine compounds (eg, n-butylamine, di-n-butylamine), alkanolamine compounds (eg, monoethanolamine, diethanolamine), and monoalcohol compounds (methanol, ethanol, etc.). it can. Furthermore, the compounds mentioned as the chain extender can also be used as a reaction terminator.
[0022]
Furthermore, the polyurethane resin used in the present invention needs to contain a functional group capable of reacting with an isocyanate group in the molecule. For this purpose, the following method can be used. For example, in order to obtain a polyurethane resin containing a primary amino group, the diamine compound having two primary amino groups, a polyamine having two primary amino groups and one or more secondary amino groups. A method of using a compound (in this case, a secondary amino group is also introduced) as a reaction terminator can be used.
[0023]
In order to obtain a polyurethane resin containing a secondary amino group, a method using a polyamine compound having two primary amino groups and one or more secondary amino groups as a chain extender, the primary A method using a diamine compound having one amino group and one secondary amino group as a reaction terminator can be used.
[0024]
Furthermore, in order to obtain a polyurethane resin containing a hydroxyl group, a method using aminoethylethanolamine as a chain extender, a diol compound having two hydroxyl groups, a method using an alkanolamine compound as a reaction terminator, and the like can be used.
[0025]
From the viewpoint of high reactivity with the isocyanate curing agent, those having a primary or secondary amino group in the molecule of the polyurethane resin are preferred, and those having a primary amino group are more preferred. It is.
[0026]
As a method of synthesizing a polyurethane resin using the above reaction components, for example, an organic diisocyanate compound and a polymer diol compound are 1.3: 1.0 to 3.0: 1.0, more preferably 1.5: 1. The urethane prepolymer is synthesized by reacting at a molar ratio of 0.0 to 2.0: 1.0, and the chain extender is reacted in the range of approximately 0.5 to 0.95 equivalent to the remaining isocyanate group. Further, a method of reacting a reaction terminator, a method of reacting a chain extender and a reaction terminator in a lump can be used. In addition, the reaction temperature in each reaction stage can be selected from the range of 30-140 degreeC according to the material to be used, and a solvent, a catalyst, etc. can also be used as needed.
[0027]
In the ink composition of the present invention, the molecular weight of the polyurethane resin is preferably 5,000 to 50,000, more preferably 10,000 to 30,000 as a weight average molecular weight. Furthermore, as content in an ink composition, 1 to 40 weight% is suitable.
[0028]
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. From the practical aspect, a silane coupling agent having an amino group. A ring agent is 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 (for example, γ-aminopropyl) Examples thereof include silane coupling agents having a secondary amino group (for example, N-phenyl-γ-aminopropyltrimethoxysilane). Furthermore, those having a primary amino group are more preferred from the viewpoint of high reactivity with isocyanate curing agents.
[0029]
The preferred amount of the silane coupling agent used in the present invention is 0.1 to 5% by weight, more preferably 0.3 to 3% by weight, based on the ink composition. When the amount used is less than the above range, Adhesiveness to the silicon oxide laminated film and suitability for boil and retort are lowered. On the other hand, it may be added in an amount of more than 5% by weight, but the effect is not changed and it is economically disadvantageous.
[0030]
In addition, from the past, a one-component ink composition using a polyurethane resin that has been reacted with a silane coupling agent in advance has been known. This is disadvantageous in that it is limited to the use of the silicon oxide laminated film.
[0031]
On the other hand, in the present invention, since a silane coupling agent is used as an individual material, first, an unadded ink composition is manufactured and used as it is when printing on a normal plastic film. A method of adding a silane coupling agent can be used after it is determined that the oxide laminated film is printed.
[0032]
For example, when a method of adding a silane coupling agent for imparting suitability when an ink is shipped in response to an order for the above application or when the ink is set in a printing machine, the versatility of the ink is obtained. There is an advantage that the stock management becomes high and inventory management becomes easy. Of course, you may manufacture the ink composition which added the silane coupling agent from the beginning for a silicon oxide laminated film use.
[0033]
Next, as an isocyanate curing agent that can be used in the ink composition of the present invention, a diisocyanate compound (for example, isophorone diisocyanate, toluylene diisocyanate, or the like) is reacted with a polyol compound (for example, trimethylolpropane) by the number of hydroxyl groups. In addition, there are isocyanate adducts of polyol compounds, various burette compounds and isocyanurate compounds, and the addition amount is usually about 1 to 10 parts by weight with respect to 100 parts by weight of the ink composition.
[0034]
The isocyanate curing agent may be added and mixed as much as possible immediately before printing, for example, when setting ink in a printing machine or after setting ink, in order to prevent functional group expiration and ink gelation. preferable.
[0035]
Next, examples of the organic solvent that can be used in the ink composition of the present invention include ketone organic solvents (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), ester organic solvents (for example, methyl acetate, ethyl acetate, n-acetate). Propyl, n-butyl acetate, isobutyl acetate, etc.), aliphatic hydrocarbon organic solvents (eg, n-hexane, n-heptane, n-octane, etc.), aromatic hydrocarbon organic solvents (eg, toluene, xylene, etc.) ), Alicyclic hydrocarbon organic solvents (eg, cyclohexane, methylcyclohexane, cyclooctane, etc.), alcohol organic solvents (eg, methanol, ethanol, n-propanol, isopropanol, butanol, etc.), and diol compounds and derivatives thereof (Eg, ethylene glycol, propylene Recall, ethylene glycol monoethyl ether, etc.) are available, in consideration of printability and drying of the ink, it is preferred to mix utilized.
[0036]
Furthermore, the addition of various ink additives such as hard resin, pigment dispersant, and surfactant is optional.
[0037]
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 after stirring and mixing, For example, a method of kneading using a bead mill, a sand mill, a pearl mill, a ball mill, an attritor, a roll mill, etc., and further adding and mixing the remaining materials is used.
[0038]
Next, a method for using the three-component laminating printing ink composition of the present invention will be described. The ink composition of the present invention is printed on a silicon oxide laminated film mainly by a gravure printing method after being adjusted to a viscosity suitable for printing with a diluent solvent or the like as necessary. Here, as the silicon oxide laminated film, polyester films are currently mainstream, and Tech Barrier U and Tech Barrier T (the former is for boil use and the latter is for retort use, both manufactured by Mitsubishi Chemical Kojin Pax Co., Ltd.) MOS-TB (for boil use, Oike Kogyo Co., Ltd.), Fine Barrier K (manufactured by Reiko Co., Ltd.), etc. are commercially available.
[0039]
Furthermore, in the present invention, after the ink composition is printed, a lamination process is performed in which a polymer called a sealant is laminated, and two methods are mainly used. One of them is an extrusion laminating process in which an anchor coating agent (for example, imine type) is applied to the printing surface as needed, and a hot-melt polymer (for example, polyethylene, polypropylene, etc.) is laminated in a thin film. The other is a dry laminating process in which an adhesive (for example, isocyanate type) is applied to the printing surface, and then an unstretched plastic film (for example, unstretched polyethylene film, unstretched polypropylene film, etc.) is laminated. Among these, from the viewpoint of preventing cracking of the silicon oxide layer due to thermal stress, dry laminating is preferable.
[0040]
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.
[0041]
Furthermore, by selecting a silicon oxide laminated film having boil suitability and retort suitability, it is possible to boil and retort the contents packed in the packaging container. Usually, the packaging container is immersed in hot water at 60 to 95 ° C. in the boil treatment and 110 to 130 ° C. in the retort treatment (pressurized) for about several minutes to 1 hour. It has good boil and retort suitability.
[0042]
【Example】
EXAMPLES Hereinafter, although this invention is demonstrated concretely using an Example, this invention is not limited to this. In Examples and the like, “parts” and “%” represent “parts by weight” and “% by weight” unless otherwise specified.
[0043]
<Manufacture of polyurethane resin varnish>
(Production Example 1)
A four-necked flask equipped with a stirrer, a condenser tube and a nitrogen gas inlet tube was charged with 200 parts of 3-methyl-1,5-pentylene adipatediol having an average molecular weight of 2,000 and 44.4 parts of isophorone diisocyanate, The reaction was carried out at 100 to 105 ° C. for 6 hours while introducing gas. Allow to cool to near room temperature, add 243 parts of toluene, 243 parts of methyl ethyl ketone and 122 parts of isopropanol, then add 13.6 parts of isophoronediamine to cause chain extension, and then add 2.4 parts of ethylenediamine to stop the reaction. Polyurethane resin varnish A (solid content 30%, weight average molecular weight of polyurethane resin 16,000, functional group capable of reacting with isocyanate group contained in molecule = primary amino group) was obtained.
[0044]
(Production Example 2)
A four-necked flask equipped with a stirrer, a condenser tube and a nitrogen gas inlet tube was charged with 200 parts of 3-methyl-1,5-pentylene adipatediol having an average molecular weight of 2,000 and 44.4 parts of isophorone diisocyanate, The reaction was carried out at 100 to 105 ° C. for 6 hours while introducing gas. After allowing to cool to near room temperature, 243 parts of toluene, 243 parts of methyl ethyl ketone and 122 parts of isopropanol were added, then 13.6 parts of isophoronediamine was added to cause chain extension reaction, and 3.4 parts of 2-ethylaminoethylamine was further added. The reaction was stopped to obtain polyurethane resin varnish B (solid content 30%, weight average molecular weight of polyurethane resin 16,000, functional group capable of reacting with isocyanate group contained in molecule = secondary amino group).
[0045]
(Production Example 3)
A four-necked flask equipped with a stirrer, a condenser tube and a nitrogen gas inlet tube was charged with 200 parts of 3-methyl-1,5-pentylene adipatediol having an average molecular weight of 2,000 and 44.4 parts of isophorone diisocyanate, The reaction was carried out at 100 to 105 ° C. for 6 hours while introducing gas. After cooling to near room temperature, 243 parts of toluene, 243 parts of methyl ethyl ketone and 122 parts of isopropanol were added, then 13.6 parts of isophoronediamine was added to cause chain extension reaction, and then 2.4 parts of monoethanolamine was added to stop the reaction. Thus, polyurethane resin varnish C (solid content 30%, weight average molecular weight of polyurethane resin 16,000, functional group capable of reacting with isocyanate group contained in the molecule = hydroxyl group) was obtained.
[0046]
(Production Example 4)
A four-necked flask equipped with a stirrer, a condenser tube and a nitrogen gas inlet tube was charged with 200 parts of 3-methyl-1,5-pentylene adipatediol having an average molecular weight of 2,000 and 44.4 parts of isophorone diisocyanate, The reaction was carried out at 100 to 105 ° C. for 6 hours while introducing gas. After cooling to near room temperature, 243 parts of toluene, 243 parts of methyl ethyl ketone and 122 parts of isopropanol were added, then 13.6 parts of isophoronediamine was added to cause chain extension reaction, and 4.8 parts of dibutylamine was added to stop the reaction. Thus, polyurethane resin varnish D (solid content 30%, weight average molecular weight of polyurethane resin 16,000, functional group capable of reacting with isocyanate group contained in molecule = none) was obtained.
[0047]
<Preparation of Examples 1-8 and Comparative Examples 1-4>
A mixture of 40 parts of titanium oxide (R-960, manufactured by DuPont), 15 parts of a polyurethane resin varnish, and 10 parts of a mixed solvent was kneaded using a paint conditioner manufactured by Red Devil Co. The remaining materials were added to prepare test inks of Examples 1 to 8 and Comparative Examples 1 to 4.
[Table 1]

[0048]
As silane coupling agents, A: N-β (aminoethyl) γ-aminopropyltrimethoxysilane, B: γ-aminopropyltrimethoxysilane, C: N-phenyl-γ-aminopropyltrimethoxysilane ( Both were 50% ethyl acetate solution), and Coronate HL (40% ethyl acetate solution, manufactured by Nippon Polyurethane Co., Ltd.) was used as the isocyanate curing agent.
[0049]
Adhesiveness After adding 100 parts of each test ink to 30 parts of the mixed solvent shown in Table 1 for dilution and adjusting the viscosity, a gravure proofing machine (manufactured by Toya Seisakusho Co., Ltd., plate depth: 32 μm) is used to prepare silica on one side. It printed on the vapor deposition surface of the polyester film (Tech barrier T, film thickness 12 micrometers, Mitsubishi Chemical Kojin Pax Co., Ltd. product) to which the vapor deposition process was given. Cellophane tape was affixed to the printed surface of the printed matter aged at room temperature for 1 day, and the adhesiveness of the ink to the film was evaluated based on the area where the ink peeled off the printed surface when quickly removed (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.
[0050]
Laminate strength Further, an isocyanate adhesive (Dick Dry LX-703A / KR-90, Dainippon Ink & Chemicals, Inc.) was applied to the printing surface at a coating amount of 3 g / m ² as a solid content, and then dried. Using a laminating machine, an unstretched polyethylene film (RXC-3, film thickness 60 μm, manufactured by Tosero Co., Ltd.) was laminated 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 result, the actually measured value (g / 15 mm) of the strength was described. In addition, 5000 ov. Indicates that the value exceeds the upper limit of measurement of 500 g / 15 mm.
[0051]
Boil suitability and retort suitability After making a bag of the laminate obtained by the above method and filling with water, the ends are sealed. In the boil suitability test, 30 minutes in hot water at 90 ° C, and 120 ° C in the retort suitability test. Was immersed in hot water under pressure for 15 minutes, and the suitability for boil and retort were evaluated based on the presence or absence of lami.
A: The one that does not show any lambs.
B: A pinhole shape or a part of which is thin and has a short lami float.
C: A long streaky Lami float is observed on the entire surface.
D: The CPP film is completely peeled off from the printing surface.
[0052]
The above evaluation results are shown in Table 1. In addition, about adhesiveness, boil suitability, and retort suitability, it was judged that the thing of B evaluation or more and a laminate strength 200g / 15mm or more have favorable performance.
[Table 1]
[0053]
【The invention's effect】
As described above in detail with reference to the examples, the ink composition of the present invention has excellent adhesion to the silicon oxide laminated film, and can be applied to boil and retort applications. The obtained laminated product has a high laminate strength.

Claims (4)

A polyurethane resin having a functional group capable of reacting with an isocyanate group in the molecule, a silane coupling agent having a functional group capable of reacting with the isocyanate group in the molecule, and an isocyanate-based curing agent. A printing ink composition for three-component laminating, which is printed on a laminated plastic film. The printing ink composition for a three-component laminate according to claim 1, wherein 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 printing ink composition for three-component laminating according to claim 1 or 2 is printed on a silicon oxide laminated surface of a plastic film in which a silicon oxide is laminated in a thin film, and then anchored on the printed surface as necessary. Laminated product obtained by applying a coating agent and laminating a hot-melt polymer. The printing ink composition for three-component laminating according to claim 1 or 2 is printed on a silicon oxide laminated surface of a plastic film in which silicon oxide is laminated in a thin film, and then an adhesive is applied to the printed surface. Laminated product obtained by laminating polymer films.