JP2022092305A - Laminate - Google Patents

Abstract

To provide a laminate capable of obtaining high quality printed image free from uneven color and color bleeding and excellent also in adhesion and appearance as the laminate irrespective of before and after a thermal sterilization step by boiling.SOLUTION: A laminate having a transparent substrate 1, an anchor layer 2, an ink layer 3, an overcoat layer 4, an adhesive layer 5, and a base material 6 stacked in this order, in which the anchor layer includes a coagulant (A), the ink layer comprises a drying film of an aqueous ink-jet ink, and the drying film contains a pigment and a pigment dispersion resin (D), the overcoat layer comprises a binder resin (B), and the binder resin (B) and the pigment dispersion resin (D) comprise a structure derived from an ethylenically unsaturated monomer (b1) containing an anion group as a constituent unit, and the adhesive layer comprises a layer made of a cured film of a laminate adhesion composition containing an isocyanate component and a polyol component.SELECTED DRAWING: Figure 1

Description

The present invention relates to a laminate produced using an anchor liquid, a water-based inkjet ink, an overcoat varnish, and a laminate adhesive composition.

The flexible packaging material used for packaging of foods, pharmaceuticals, cosmetics, etc. is a laminated body in which plastic films are bonded to each other and / or a plastic film is bonded to a metal vapor-deposited film or a metal foil. Generally, a separately prepared material such as a plastic film, a metal vapor-deposited film, or a metal foil is bonded to a plastic film on which a print layer is formed in advance to obtain a laminate that can be used as a flexible packaging material or the like. This processing method is called "lamination processing". Further, in order to form a print layer in the laminate, gravure printing or flexographic printing has been conventionally performed on a plastic film (hereinafter, also simply referred to as “film substrate”). Both gravure printing and flexographic printing are printing methods that transfer ink to a plate prepared in advance, and can be said to be suitable for high-speed printing and mass production.

On the other hand, in recent years, in the flexible packaging material market, along with changes and diversification of consumer needs, the variety of products is increasing and the product cycle is shortened. In addition, in consideration of environmental issues and occupational safety, ink is made water-based (see, for example, Patent Document 1), but as long as the above printing method is adopted, a plate for printing is required, so small-quantity production is required. In the case of, it is often unprofitable. In addition, it is difficult to meet short delivery times because it takes time to create a version.

In contrast to the above printing method, digital printing does not require a plate, so cost reduction and quick delivery can be realized, and it is expected that it will be widely used in the future. Inkjet printing, which is a type of digital printing, obtains characters and images by ejecting ink droplets from a very fine nozzle onto a printing substrate and adhering them. Inkjet printing has advantages such as low noise of the equipment used, good operability, and easy colorization, and its use is expanding even in industrial applications. Conventionally, the inks used for inkjet printing in industrial applications have been solvent inkjet inks and UV inkjet inks, but as in the case of gravure printing and flexographic printing, the inks have become water-based in consideration of environmental issues and occupational safety. It is desired.

On the other hand, when inkjet printing is used to manufacture a flexible packaging material, image formation on a film substrate is indispensable as described above. The existing water-based inks used in inkjet printing (hereinafter, also simply referred to as "for inkjet") are images for highly permeable substrates such as plain paper and special paper (for example, photographic glossy paper). It is for forming, and when printed on a non-permeable substrate such as a film substrate, the ink droplets after landing do not penetrate into the substrate at all, so that drying due to penetration occurs. However, there are problems such as color mixture bleeding and color unevenness, impaired print quality, and insufficient adhesion.

In particular, if the adhesion to the film substrate is insufficient, the ink film is peeled off due to rubbing or the like, and the desired printed image cannot be obtained, and further, the adhesive force between the layers constituting the laminated body after the laminating process cannot be obtained. , And so on.

Anchor liquid treatment for a non-permeable substrate is known to solve the problem of impairing print quality. Generally, as an anchor liquid for water-based inkjet ink, a material that forms a layer (ink receiving layer) that absorbs liquid components in the water-based inkjet ink to improve dryness (see Patent Documents 2 and 3), a coloring material, and the like. A layer (ink agglomerated layer) that prevents bleeding between droplets and color unevenness and improves print image quality by intentionally aggregating solid components contained in the water-based inkjet ink such as a resin (Patent Document). 2 types (see 4 to 5) are known. However, regardless of which method is adopted, it is difficult to improve the adhesive strength only by the anchor liquid treatment.

Further, if the adhesion to the film substrate is insufficient, the ink film is peeled off due to rubbing or the like, which causes a problem that the desired printed image cannot be obtained. Furthermore, when the film is bonded to another film via an adhesive (laminate adhesive) (laminate processing), the adhesive force between the layers constituting the laminated body cannot be obtained, and the peeling phenomenon (delamination) between the laminated bodies cannot be obtained. ) May occur. In particular, in the case of flexible packaging materials, after the packaging material is formed, it may undergo a post-heat sterilization process such as boiling or retort, and this heat sterilization process causes water to permeate into the anchor layer, resulting in increased adhesive strength. It deteriorates, causes a peeling phenomenon, and causes a poor appearance.

Patent Document 6 discloses a laminate produced by using a laminate adhesive composition containing an anchor liquid, an aqueous inkjet ink, and an isocyanate component and a polyol component, and has excellent image forming properties on a film substrate. It enables scratch resistance and water resistance. However, when a follow-up experiment was conducted with reference to this patent and a heat sterilization test such as boiling or retort was carried out, the image portion melted due to the moisture absorption of the coagulant component as described above, and the sealant was easily peeled off from the printed matter. It ends up. Therefore, the laminated laminate using the anchor liquid cannot be used for the boil / retort application, and the application of the laminated laminate is greatly limited.

As described above, in printing on a non-penetrating substrate by the water-based inkjet ink printing method, a method for obtaining a laminate having excellent print image quality and a post-processing function including a post-heat sterilization process such as boiling or retort. Was a situation that had not been found so far.

Japanese Unexamined Patent Publication No. 5-171091 Japanese Unexamined Patent Publication No. 2000-238422 Japanese Unexamined Patent Publication No. 2000-335084 Japanese Unexamined Patent Publication No. 2005-74655 Japanese Unexamined Patent Publication No. 2016-168782 International release WO2018 / 221674 Pamphlet

The present invention has been made to solve the above problems, and an object of the present invention is that even when printing on a non-permeable substrate such as a film substrate, there is no color mixing bleeding or color unevenness, and the print image quality is good. Further, it is an object of the present invention to provide a laminated body in which excellent adhesive strength is maintained even after a laminating process, a heat sterilization treatment such as boiling or retort.

As a result of diligent studies by the present inventors in order to solve the above-mentioned problems, it has been found that the above-mentioned problems can be solved by a laminated body having the following structure.

That is, in the present invention, the transparent base material 1, the anchor layer (I), the ink layer (II), the overcoat layer (III), the adhesive layer (IV), and the base material 2 are arranged in this order. It is a laminated body that has
The anchor layer (I) contains the flocculant (A) and contains.
The ink layer (II) is composed of a dry film of two or more different colors of water-based inkjet ink, and the dry film independently contains a pigment and a pigment dispersion resin (D).
The overcoat layer (III) contains a binder resin (B) and contains.
The binder resin (B) and the pigment dispersion resin (D) each independently contain a structure derived from an ethylenically unsaturated monomer (b1) containing an anionic group as a constituent unit.
The present invention relates to a laminated body in which the adhesive layer (IV) is a layer composed of a cured film of a laminated adhesive composition containing an isocyanate component and a polyol component.

The present invention also relates to the above-mentioned laminate in which the flocculant (A) is a polyvalent metal salt and / or a cationic polymer compound.

The present invention also relates to the above-mentioned laminated body in which the thickness of the anchor layer (I) is 0.1 to 2.0 μm.

The present invention also relates to the above-mentioned laminate in which the acid value of the binder resin (B) is 30 to 300 mgKOH / g.

The present invention also relates to the above-mentioned laminate in which the glass transition temperature of the binder resin (B) is −30 ° C. to 50 ° C.

The present invention also relates to the above-mentioned laminate, wherein the overcoat layer (III) is formed of an overcoat varnish (V) containing a composition having a carbodiimide group.

According to the present invention, there is no color mixing bleeding or color unevenness, and the print image quality is good. Even after laminating and heat sterilization such as boiling or retort, good printing image quality and excellent adhesive strength are maintained. You can get a body.

A laminate having a transparent base material 1, an anchor layer (I), an ink layer (II), an overcoat layer (III), an adhesive layer (IV), and a base material 2 in this order.

Hereinafter, the laminated body according to the embodiment of the present invention will be described with reference to preferred embodiments.

The anchor layer (I) included in the laminate of the present invention contains the flocculant (A). Generally, a flocculant that aggregates a resin containing a structure derived from an ethylenically unsaturated monomer (b1) containing an anionic group is soluble in water. Therefore, it is difficult to develop water resistance, and in the case of flexible packaging materials, when the flexible packaging material is in the form of a packaging material and then undergoes a process after heat sterilization treatment such as boiling or retort, water permeates into the anchor layer and the adhesive strength is increased. Will decrease, causing a peeling phenomenon and causing poor appearance.

Therefore, as a result of diligent studies by the present inventors, the transparent base material 1, the anchor layer (I), the ink layer (II), the overcoat layer (III), the adhesive layer (IV), and the base material A laminate having 2 and 2 in this order, in which the anchor layer (I) contains the flocculant (A) and the ink layer (II) dries two or more different color water-based inkjet inks. The dry film is composed of a film, each of which independently contains a pigment and a pigment dispersion resin (D), the overcoat layer (III) contains a binder resin (B), and the binder resin (B) and The pigment dispersion resin (D) independently contains a structure derived from an ethylenically unsaturated monomer (b1) containing an anionic group as a constituent unit, and the adhesive layer (IV) contains an isocyanate component and an isocyanate component. In a laminated body which is a layer made of a cured film of a laminated adhesive composition containing a polyol component, the print quality is good without color bleeding or color unevenness, and after laminating, after heat sterilization such as boiling or retort. Even so, we have found that good print quality and excellent adhesive strength are maintained. The detailed mechanism is not clear, but for example, we are considering the following.

First, the role of each layer in the laminated body of the present invention is as follows.
The role of the anchor layer (I) is to assist the image formation of the water-based inkjet ink and improve the print image quality, and to improve the adhesive strength between the transparent base material 1 and the ink layer (II). The mechanism is that the flocculant (A) contained in the anchor layer (I) has a structure derived from the ethylenically unsaturated monomer (b1) containing an anionic group contained in the water-based inkjet ink (D). ) Is aggregated and deposited to prevent color bleeding and color unevenness caused by mixing water-based inkjet ink droplets with each other.

Further, the role of the overcoat layer (III) in the laminate of the present invention is to prevent direct contact between the anchor layer (I) and the ink layer (II) and the adhesive layer (IV), and the anchor. By trapping the excess coagulant (A) contained in the layer (I), excellent adhesive strength and appearance are realized. Regarding the former, the anchor layer (I) and the ink layer (II) contain a large amount of water and also use a flocculant (A) having a high affinity for water, so that the water content remains even after the drying step. There is a risk of remaining. It is considered that the water content comes into direct contact with the laminated adhesive composition containing the isocyanate component, and prevents the appearance deterioration due to the generation of carbon dioxide gas due to the reaction with the isocyanate component and the deterioration of the adhesive strength due to insufficient cross-linking. Regarding the latter, the flocculant (A) contained in the anchor layer (I) has a high affinity for water due to its characteristics, and by undergoing a post-heat sterilization process such as boiling or retort, it embraces water. , The adhesive strength is reduced, and the appearance is poor due to the peeling phenomenon. However, it is considered that the overcoat layer (III) is provided to trap the excess flocculant (A) and prevent the intrusion of water. Regarding the action of the flocculant (A) and the binder resin (B) having a structure derived from the ethylenically unsaturated monomer (b1) containing the anionic group of the overcoat layer (III), the flocculant (A) is inorganic. In the case of salt, the decrease in water solubility due to chelate formation with cations, in the case of cationic polymer, the decrease in water solubility due to the ionic bond between the cationic polymer and the binder resin (B), and in the case of acid, the anion of the binder resin (B). It is considered that the water solubility is reduced by changing the dissociated state of the group to the non-dissociated state.

Further, when the adhesive layer (IV) in the laminate of the present invention contains an isocyanate component and a polyol component, the adhesive layer (IV) becomes a tough cured film.

As described above, the print image quality is good without color bleeding or color unevenness, and good print image quality and excellent adhesive strength are maintained even after laminating and heat sterilization such as boiling or retort. In order to obtain a laminate, the configuration of the laminate of the present invention is indispensable.

Subsequently, the details of each component constituting the laminated body of the present invention will be described below.

<Anchor layer (I)>
As described above, in the laminate of the present invention, the anchor layer (I) contains the flocculant (A). The anchor layer (I) is formed by applying an anchor liquid containing the flocculant (A) or the like.

As described above, generally, the anchor layer (I) for the water-based inkjet ink includes a layer that forms an ink receiving layer that allows the water-based inkjet ink to permeate inside, and agglomerates and / or increases the components in the water-based inkjet ink. Some form an ink agglomerate layer to be viscous. In the present embodiment, the latter is because the anchor layer (I) is less likely to swell, the color mixing bleeding and color unevenness of the ink layer (II) are suitably suppressed, and a laminate having excellent print quality can be obtained. Select a type.

Specific examples of the flocculant (A) include metal salts, cationic polymer compounds, organic acids and the like. Among them, the metal salt has a particularly strong function as a coagulant, is effective for coagulation and / or thickening of pigments and other components even in a small amount, and reduces bleeding and color unevenness to particularly improve the print quality. It is preferably used because it can be improved. Only one kind of flocculant may be used, or two or more kinds of flocculants may be mixed.

The type of the metal salt is not particularly limited as long as it is composed of a metal ion and an anion bonded to the metal ion. Among them, it is preferable that the metal ion contains a multivalent metal ion from the viewpoint that the color mixing bleeding can be suppressed by causing an instantaneous interaction with the pigment and a clear image without color unevenness can be obtained. Further, the polyvalent metal ion may contain at least one selected from Ca ²⁺ , Mg ²⁺ , Zn ²⁺ , Al ³⁺ , Fe ²⁺ , and Fe ³⁺ , not only with pigments but also with other components such as resins. It is more preferable because it easily causes an interaction, and it is particularly preferable to contain at least one selected from Ca ³⁺ , Mg ³⁺ , and Al ³⁺ . Specific examples of the inorganic metal salt that can be used in the anchor layer (I) include, but are not limited to, calcium ion, magnesium ion, chloride of aluminum ion, sulfate, nitrate and the like. Specific examples of the organic metal salt that can be used in the anchor layer (I) include, but are limited to, calcium salts and magnesium salts of organic acids such as ascorbic acid, formic acid, acetic acid, propionic acid, and lactic acid. It is not something that will be done. In the present invention, it is preferable to select an organic metal salt, a polyvalent metal salt is preferable, and the compound exemplified above is preferable, from the viewpoint of having high compatibility with other components and being effective in maintaining / improving the adhesive strength. Among them, the calcium salt of formic acid and / or acetic acid is more preferable from the viewpoint of solubility in water and interaction with the components in the ink layer (II). Further, the metal salt may be used alone or in combination of two or more.

When the anchor layer (I) used for forming the laminate of the present invention contains a metal salt, the blending amount thereof is preferably 1 to 12% by mass as metal ions with respect to the total amount of the anchor liquid, and 2 to 2 to. It is more preferably 10% by mass, and particularly preferably 3 to 8% by mass. By keeping the content of the metal ion within the above range, the wettability of the pretreatment liquid with respect to the transparent substrate 1 can be ensured and the adhesive strength can be improved while suppressing color mixing bleeding and color unevenness. The content of metal ions with respect to the total amount of anchor liquid is calculated by the following formula (1).
Equation (1):
(Metal ion content) (% by mass) = WC x MM ÷ MC

In the formula (1), WC represents the content of the metal salt with respect to the total amount of the anchor liquid, MM represents the molecular weight of the metal ions constituting the metal salt, and MC represents the molecular weight of the metal salt.

On the other hand, the above-mentioned cationic polymer compound can be arbitrarily used as long as it lowers the dispersion function of the pigment in the ink and has suitable solubility and diffusibility in the anchor liquid. .. Further, one type may be used alone, or two or more types may be used in combination. In the present invention, the "cationic polymer compound" represents a polymer compound having a cationic group exemplified below but no anionic group (a compound having a weight average molecular weight of 1,000 or more).

Examples of the cationic group contained in the cationic polymer compound include, but are not limited to, an amino group, an ammonium group, an amide group, an imino group, a hydrazino group, and -NHCONH ₂ groups. Further, as a material used for introducing the above-mentioned cationic group into a cationic polymer compound,
For example, amine compounds such as vinylamine, allylamine, methyldiallylamine, ethyleneimine;
Amide compounds such as acrylamide and vinylformamide; cyanamide compounds such as dicyandiamide;
Epihalohydrin compounds such as epifluorohydrin, epichlorohydrin, methylepichlorohydrin, epibromohydrin, epiiodohydrin;
Cyclic vinyl compounds such as vinylpyrrolidone, vinylcaprolactam, vinylimidazole;
Amidine compounds; pyridinium salt compounds; imidazolium salt compounds and the like can be mentioned.

Among the above, the cationic polymer compound is preferably a compound containing at least one structural unit selected from a diallylamine structural unit, a diallylammonium structural unit, and an epihalohydrin structural unit, and preferably contains at least a diallylammonium structural unit. Is more preferable. All of the above resins are strong electrolytes, and the dissolution stability of the resin in the anchor liquid is good, and the ability to reduce the dispersion of the pigment in the water-based inkjet ink is excellent.

When the anchor layer (I) used for forming the laminate of the present invention contains a cationic polymer compound, the blending amount thereof may be 1 to 20% by mass in terms of solid content with respect to the total amount of the anchor liquid. It is preferably 3 to 10% by mass, more preferably 3 to 10% by mass. By keeping the blending amount of the cationic polymer compound within the above range, the viscosity of the pretreatment liquid can be kept within a suitable range, the storage stability during long-term storage, and the laminating process and aging. It is possible to obtain a laminated body having excellent adhesive strength later.

When the anchor layer (I) used for forming the laminate of the present invention contains an organic acid as a flocculant, a compound having a carboxyl group is suitable. Specific examples thereof include malonic acid, succinic acid, citric acid, malic acid, tartaric acid, formic acid, acetic acid, propionic acid, and lactic acid. The content of the organic acid is preferably 1 to 12% by mass, more preferably 2 to 10% by mass, and particularly preferably 3 to 8% by mass with respect to the total amount of the anchor liquid.

The anchor liquid preferably contains a resin (however, excluding the above-mentioned cationic polymer compound) from the viewpoint of adhesion to the transparent substrate 1 and the strength of the anchor layer (I). Specifically, (meth) acrylic resin, styrene (meth) acrylic resin, urethane resin, urethane (meth) acrylic resin, polyester resin (polycondensate of polyvalent carboxylic acid and polyhydric alcohol). , Polyester-based resin, styrene-butadiene-based resin, vinyl chloride-based resin and the like. These may be used alone or may be a mixture of two or more kinds of resins. The form of the resin used may be any of a water-soluble resin, a hydrosol which is a water-insoluble resin, and an emulsion. In the present invention, "(meth) acrylic" means acrylic or methacrylic. Further, in the present invention, "emulsion" refers to a form in which an emulsifier is adsorbed on the surface of resin fine particles and dispersed in a dispersion medium, and "hydrosol" refers to acidic and / or basic functionalities present in the resin. It refers to a form in which a group is neutralized and dispersed in a dispersion medium. Further, the hydrosol and the emulsion are generally referred to as "resin fine particles", and refer to those having a 50% volume particle size measured by a method described later having a particle size of 5 to 1000 nm.

When the anchor layer (I) used for forming the laminate of the present invention contains a resin, the blending amount thereof is a solid content with respect to the total amount of the anchor liquid from the viewpoint of coatability and adhesive strength to the transparent substrate 1. In terms of conversion, it is preferably 1 to 20% by mass, and more preferably 3 to 15% by mass.

Further, in order to apply the anchor liquid uniformly on the transparent substrate 1, the anchor liquid can be used with one type or a combination of two or more types of surfactants. Examples of the surfactant include siloxane-based, acrylic-based, fluorine-based, acetylenediol-based, glycol ether-based, and the like. In one preferred embodiment, the surface tension of the pretreatment liquid is controlled to impart excellent wettability on the transparent substrate 1, thereby suppressing color bleeding and color unevenness in the laminate and improving print image quality. From the viewpoint of connection, it is preferable to use a siloxane-based surfactant and / or an acetylene diol-based surfactant, and it is particularly preferable to include an acetylene diol-based surfactant.

When the anchor layer (I) used for forming the laminate of the present invention contains a surfactant, the blending amount thereof is to reduce coating unevenness on the transparent substrate 1 and realize uniform coating. Therefore, from the viewpoint of suppressing color mixing bleeding and color unevenness in the laminated body and improving the print image quality, it is preferably 0.01 to 8% by mass, preferably 0.05 to 5% by mass with respect to the total amount of the anchor liquid. It is more preferably present, and particularly preferably 0.1 to 3% by mass.

Further, the surface tension of the anchor liquid used in the present invention is preferably 20 to 45 mN / m, more preferably 20 to 40 mN / m, and particularly preferably 20 to 40 mN / m from the same viewpoint as described above. It is 35 mN / m. Therefore, it is preferable to adjust the type and blending amount of the surfactant, and further, the type and blending amount of the low surface tension solvent described later so as to obtain the suitable surface tension value. The surface tension in the present embodiment refers to the surface tension measured by the WILLHELMY method (plate method, vertical plate method) in an environment of 25 ° C.

As described above, in the anchor liquid used in the present invention, a low surface tension solvent can also be used in order to set the surface tension to a desired value. Specifically, isopropanol (2-propanol), n-butanol, propylene glycol, 1,2-butanediol, 1,2-hexanediol, 3-ethyl-1,2-hexanediol, diethylene glycol monomethyl ether, diethylene glycol mono Examples thereof include isopropyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monopropyl ether.

In addition, the anchor liquid is used for the purpose of suppressing damage to the members used in the coating device of the anchor liquid, suppressing pH fluctuations over time, and maintaining the above-mentioned performance of the anchor liquid for a long period of time. A pH regulator can be added. In the present embodiment, a material having a pH-adjustable ability can be arbitrarily selected, and in the case of basicization, an alkanol amine such as dimethylethanolamine, diethanolamine, triethanolamine; aqueous ammonia; sodium hydroxide, hydroxide. Hydroxide of alkali metal such as potassium; carbonate of alkali metal such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate and the like can be used. When acidifying, an inorganic acid such as hydrochloric acid, sulfuric acid, or nitric acid may be used, or the above-mentioned organic acid may be used as a material that also serves as a flocculant and a pH adjuster. These pH adjusters may be used alone or in combination of two or more.

Further, in the anchor liquid of the present invention, additives such as a defoaming agent, a thickener and an antiseptic can be appropriately added in order to obtain desired physical property values. When these additives are used, the blending amount thereof is preferably 0.01 to 8% by mass, more preferably 0.01 to 5% by mass, based on the total amount of the anchor liquid.

<Ink layer (II)>
Next, the ink layer (II) constituting the laminate of the present invention will be described. The ink layer (II) is a layer made of a dry film of a water-based inkjet ink (hereinafter, also simply referred to as “water-based ink” or “ink”), and is a layer having two or more different colors. It contains a pigment, a pigment dispersant (D), and a water-soluble organic solvent.

<Pigment>
In the water-based ink used in the present invention, either an inorganic pigment or an organic pigment can be used as the pigment, and the pigment is not particularly limited. Examples of the inorganic pigment include titanium oxide, zinc flower, zinc sulfide, calcium carbonate, precipitated barium sulfate, alumina white and the like as white pigments, and carbon black and iron oxide as black pigments.

Titanium oxide is preferably used as the white pigment. As titanium oxide, either anatase type or rutile type can be used, but it is preferable to use rutile type in order to improve the concealing property of printed matter. Further, it may be produced by any method such as a chlorine method or a sulfuric acid method, but it is preferable to use titanium oxide produced by the chlorine method because the whiteness is high.

It is more preferable that the titanium oxide has a pigment surface treated with an inorganic compound and / or an organic compound. Examples of inorganic compounds include compounds of silicon (SI), aluminum, zirconium, tin, antimony, titanium, and hydrated oxides thereof. Examples of organic compounds include polyhydric alcohols, alkanolamines or derivatives thereof, higher fatty acids or metal salts thereof, organic metal compounds, etc. Among them, polyhydric alcohols or derivatives thereof have a high degree of titanium oxide surface. It can be made hydrophobic and the dispersion stability can be improved, and is more preferably used.

It is also preferable to use hollow resin particles as the white pigment. Hollow resin particles have a smaller specific gravity (apparent density) than titanium oxide and the like, and can easily suppress sedimentation over time, so that ink with excellent storage stability can be obtained. Further, in order to obtain a white ink having both storage stability and concealing property, hollow resin particles and titanium oxide may be used in combination as a pigment.

As the black pigment, carbon black (CI Pigment Black 7) produced by the furnace method or the channel method is preferably used. For example, these carbon blacks have characteristics such as a primary particle diameter of 11 to 40 nm, a specific surface area of 50 to 400 m2 / g by the BET method, a volatile content of 0.5 to 10% by mass, and a pH value of 2 to 10. Those having the above are suitable. As a commercially available product having such characteristics, specifically, No. 33, 40, 45, 52, 900, 2200B, 2300, MA7, MA8, MCF88 (above, manufactured by Mitsubishi Chemical Corporation); RAVEN1080, 1255 (above, manufactured by Bill La Carbon); REGAL330R, 400R, 660R, MOGUL L, ELFTEX415 (above, manufactured by Cabot); NIpex90, 150T, 160IQ, 170IQ, 75, PrInteX85, 95, 90, 35 (above, manufactured by Orion Engineered Carbons) and the like, all of which can be preferably used.

In addition to carbon black, for example, aniline black, lumogen black, azomethine azo black and the like can be used as the black pigment. Further, a plurality of chromatic pigments such as cyan pigment, magenta pigment, yellow pigment, brown pigment, and orange pigment, which will be described later, may be used to obtain a black pigment.

Examples of the organic pigment include azo pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, isoindolinone pigments, quinophthalone pigments, dye lake pigments, fluorescent pigments and the like.

Specifically, the color index is used as a cyan pigment as C.I. I. PIgment Blue 1, 2, 3, 15: 1, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64 and the like can be mentioned.

Further, as a magenta pigment, C.I. I. PIgment Red 5, 7, 12, 31, 48, 49, 52, 53, 57, 112, 120, 122, 146, 147, 149, 150, 168, 170, 184, 185, 188, 202, 209, 238, 242, 254, 255, 264, 269, 282; C.I. I. Pigment Violet 19, 23, 29, 30, 37, 40, 50 and the like.

The yellow pigment is C.I. I. Pigment Yellow 10,11,12,13,14,16,17,20,24,74,83,86,93,94,95,109,110,117,120,125,128,137,138,139, 147, 148, 150, 151, 154, 155, 166, 168, 180, 185, 213 and the like can be mentioned.

In addition to the above, special colors such as orange pigment, green pigment, and brown pigment can also be used. Specifically, C.I. I. PIgment Orange 16, 36, 38, 40, 43, 62, 63, 64, 71, C.I. I. Pigment Green 7, 10, 36, Pigment Brown 23, 25, 26 and the like can be mentioned.

In the water-based ink used for producing the laminate of the present invention, a plurality of the above pigments can be mixed and used in order to keep the hue and color development property of the printed matter within a suitable range. For example, in order to improve the tint at a low printing rate, a small amount of one or more pigments selected from cyan pigments, magenta pigments, orange pigments, and brown pigments can be added to black inks using carbon black. ..

Except for the case of white ink, these pigments are preferably contained in the range of 2% by mass or more and 20% by mass or less, and preferably in the range of 2.5% by mass or more and 15% by mass or less with respect to the total amount of ink. Is more preferable, and it is particularly preferable that it is contained in the range of 3% by mass or more and 10% by mass or less. Further, in the case of white ink, the content of the pigment is preferably 5% by mass or more and 40% by mass or less, and more preferably 8% by mass or more and 30% by mass or less with respect to the total amount of white ink. By setting the pigment content to 2% by mass or more (5% by mass or more in the case of white ink), sufficient color development (concealment in the case of white ink) can be obtained even in 1-pass printing. .. Further, by setting the pigment content to 20% by mass or less (40% by mass or less in the case of white ink), the viscosity of the ink can be kept within a range suitable for inkjet printing, and the storage stability of the ink is also improved. It can be maintained in good condition, and as a result, long-term discharge stability can be ensured.

<Pigment dispersion resin (D)>
As a method for stably dispersing and holding the pigment in the water-based ink, (1) a method of adsorbing and dispersing the pigment-dispersed resin on the pigment surface, and (2) a water-soluble and / or water-dispersible surfactant are applied to the pigment surface. A method of adsorbing and dispersing, (3) a method of chemically and physically introducing a hydrophilic functional group on the pigment surface and dispersing it in an ink without a dispersion resin or a surfactant (self-dispersing pigment), (4) water. Examples thereof include a method of coating a pigment with an insoluble resin and, if necessary, using another pigment-dispersing resin or a surfactant to disperse the pigment in the ink.

In the water-based ink used in the present invention, the method (1) or (4) above, that is, the method using a pigment-dispersed resin is selected, and the pigment-dispersed resin (D) is an anion as a constituent unit. By including the structure derived from the ethylenically unsaturated monomer (b1) containing a group, in addition to being able to secure solubility in water and a water-soluble organic solvent, the flocculant instantly aggregates and / or thickens the viscosity. It is possible to reduce color mixture bleeding and color unevenness and to improve the print image quality in particular. Further, it is also preferable from the viewpoint that the viscosity of the pigment dispersion liquid can be suppressed by making the pigment dispersion state suitable. Further, since the above effects are more preferably exhibited, the acid value of the pigment dispersion resin (D) is preferably 30 to 375 mgKOH / g, more preferably 65 to 350 mgKOH / g, and further preferably 100 to 300 mgKOH / g. g.

The type of the pigment dispersion resin is not particularly limited, and for example, (meth) acrylic resin, styrene (meth) acrylic resin, (anhydrous) maleic acid resin, styrene (anhydrous) maleic acid resin, and olefin (anhydrous). Maleic acid-based resin, polyurethane-based resin, polyester-based resin and the like can be used. Above all, it is particularly preferable to use a (meth) acrylic resin, a styrene (meth) acrylic resin, a polyurethane resin, or a polyester resin in terms of the size of material selectivity and the ease of synthesis. Further, the pigment dispersion resin described above can be synthesized by a known method or a commercially available product can be used. In the present invention, "(anhydrous) maleic acid" means maleic acid or maleic anhydride.

Further, the pigment dispersion resin (D) preferably contains a structural unit derived from a monomer containing an aromatic ring structure. This is an improvement in adhesive strength using the π-cation interaction formed by the aromatic ring structure contained in the pigment dispersion resin (D) and the nitrogen atom in the urethane bond contained in the adhesive layer (IV). When combined with the anchor layer (I) in the form of forming an ink cohesive layer, which secures and improves the dispersion stability of the pigment in the water-based ink containing a water-soluble organic solvent and the dispersion stability is secured and improved. The purpose is to suppress excessive aggregation and prevent omission in solid images and the like. The amount of the structural unit derived from the monomer containing the aromatic ring structure is preferably 10 to 80% by mass, more preferably 15 to 75% by mass, based on the total amount of the pigment dispersion resin (D). , 20-70% by mass is particularly preferable. By keeping the amount of the structural unit derived from the monomer containing the aromatic ring structure within the above range, the effect of improving the adhesive strength by utilizing the π-cation interaction and the pigment in the water-based ink containing the water-soluble organic solvent can be obtained. The effect of ensuring / improving the dispersion stability of the above is preferable.

Further, the pigment dispersion resin (D) preferably contains an alkyl group having 10 to 36 carbon atoms in addition to the aromatic ring structure. This is because by setting the number of carbon atoms of the alkyl group to 10 to 36, it is possible to reduce the viscosity of the pigment dispersion liquid, further improve the print image quality, stabilize the dispersion, and stabilize the viscosity at the same time. The number of carbon atoms of the alkyl group is preferably 12 to 30, and more preferably 18 to 24 carbon atoms. The alkyl group may be linear or branched as long as it has 10 to 36 carbon atoms, but a linear group is preferable.

Further, in one embodiment, it is also preferable that the pigment dispersion resin (D) contains an alkylene oxide group in addition to the aromatic ring structure. By introducing an alkylene oxide group, the hydrophilicity and hydrophobicity of the pigment dispersion resin (D) can be arbitrarily adjusted, and the dispersion stability of the water-based ink can be improved. When a water-soluble pigment-dispersed resin is used as the pigment-dispersed resin (D), it is preferable to select an ethylene oxide group as the alkylene oxide group in order to preferably exhibit the above functions. Similarly, when a water-insoluble resin is used as the pigment dispersion resin (D), it is preferable to select a propylene oxide group as the alkylene oxide group.

When a water-soluble pigment-dispersed resin is used as the pigment-dispersed resin (D) as a method for stably dispersing and holding the pigment in the water-based ink, the pigment-dispersed resin (D) is contained in order to increase the solubility in the ink. It is preferable to neutralize the acid group with a base. However, if an excessive amount of base is added, if the anchor layer (I) contains a flocculant, the flocculant is neutralized and a sufficient effect cannot be exerted. Therefore, the addition thereof is not possible. You need to pay attention to the amount. Whether or not the amount of the base added is excessive can be confirmed, for example, by preparing a 10% by mass aqueous solution of the pigment dispersion resin (D) and measuring the pH of the aqueous solution. Above all, in order to fully exhibit the function of the anchor liquid, the pH of the aqueous solution is preferably 7 to 11, and more preferably 7.5 to 10.5.

Examples of the base for neutralizing the pigment dispersion resin (D) include alkanolamines such as diethanolamine, triethanolamine and N-methyldiethanolamine; aqueous ammonia; alkalis such as lithium hydroxide, sodium hydroxide and potassium hydroxide. Metal hydroxides; alkali metal carbonates such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate and the like can be mentioned.

The molecular weight of the pigment-dispersed resin (D) is preferably in the range of 1,000 or more and 200,000 or less, and more preferably in the range of 5,000 or more and 100,000 or less. When the weight average molecular weight is in the above range, the pigment is stably dispersed in water, and it is easy to adjust the viscosity when applied to a water-based ink. In particular, when the weight average molecular weight is 1,000 or more, the pigment dispersion resin (D) is difficult to dissolve in the solvent added to the water-based ink. Therefore, the pigment dispersion resin (D) for the pigment is difficult to dissolve. ) Is strong and the dispersion stability is excellent. Further, when the weight average molecular weight is 200,000 or less, the viscosity at the time of dispersion is suppressed to a low level, the ejection stability from the inkjet head is excellent, and stable printing over a long period of time becomes possible.

In the present invention, the blending amount of the pigment dispersion resin (D) is preferably 1 to 50% by mass with respect to the pigment. By setting the blending amount of the pigment dispersion resin (D) to 1 to 50% by mass with respect to the pigment, the viscosity of the pigment dispersion liquid can be suppressed, and the viscosity stability and dispersion stability of the pigment dispersion liquid and the water-based ink (A) can be suppressed. It is preferable because the property is improved and the dispersion function can be rapidly deteriorated when mixed with the anchor liquid. The blending amount of the pigment dispersion resin (D) with respect to the pigment is more preferably 2 to 45% by mass, further preferably 3 to 40% by mass, and most preferably 4 to 35% by mass.

<Ethylene unsaturated monomer containing anionic group (b1)>
The pigment dispersion resin (D) used in the present invention contains a structure derived from an ethylenically unsaturated monomer (b1) containing an anionic group as a structural unit. The "anionic group" includes a carboxylic acid (carboxyl) group, a sulfonic acid group, a phosphonic acid group, and the like, and any of them may be selected in the present invention. Above all, in addition to being able to secure solubility in water and water-soluble organic solvents and having excellent dispersion stability, the flocculant instantly aggregates and / or thickens, reduces color bleeding and color unevenness, and particularly improves print image quality. It is preferable to select a carboxyl group from the viewpoint that it can be improved.

As the ethylenically unsaturated monomer (b1) containing an anionic group, a known one can be used. Specifically, acrylic acid, methacrylic acid, carboxymethyl (meth) acrylate, carboxyethyl (meth) acrylate, acryloyloxyethyl succinic acid, methacryloyloxyethyl succinic acid, acryloyloxyethyl phthalic acid, methacryloyloxyethyl phthalic acid, acryloyl. Oxyisobutyric acid, methacryloyloxyisobutyric acid, 2-sulfoethyl (meth) acrylate, acryloyloxyethylphosphonic acid, methacryloyloxyethylphosphonic acid, 2- (phosphonooxy) ethyl (meth) acrylate, vinylsulfonic acid, styrenecarboxylic acid, styrenesulfone Examples thereof include acid and styrene-phosphonic acid, but the present invention is not particularly limited thereto. The ethylenically unsaturated monomer (b1) containing these anionic groups can be used alone or in combination of two or more. In the present invention, "(meth) acrylate" represents at least one selected from "acrylate" and "methacrylate".

<Water-soluble organic solvent>
The water-based ink used in the present invention preferably contains a water-soluble organic solvent. By containing the water-soluble organic solvent, the wettability of the water-based ink on the printing substrate is ensured, and a printed image without omission in the solid portion or the like can be obtained.

The water-soluble organic solvent is not particularly limited, and known ones can be arbitrarily used, but materials such as a pigment dispersion resin (D), a binder resin added as needed, and a surfactant are used. From the viewpoint of compatibility and affinity with the components, it is preferable to contain a glycol ether solvent and / or an alkyl polyol solvent. In particular, it is preferable that the molecular structure contains one or more hydroxyl groups. This is because the hydroxyl group of the water-soluble organic solvent reacts with the polyisocyanate component of the laminating adhesive composition to improve the adhesive strength after the laminating process. Further, it is preferable that the boiling point of the water-soluble organic solvent under 1 atm is 100 ° C. or higher and lower than 240 ° C. When the temperature is 100 ° C or higher, the ejection property, dispersion stability, and moisture retention of the water-based ink are improved, and when the temperature is lower than 240 ° C, the drying property, color mixing bleeding, blocking resistance, and lamination of the printed matter are improved. The adhesive strength of the body is improved.

The boiling point under 1 atm can be measured by using a thermal analyzer such as DSC (Differential Scanning Calorimetry).

The total amount of the water-soluble organic solvent in the water-based ink used in the present invention is preferably 3% by mass or more and 40% by mass or less with respect to the total amount of the water-based ink. Further, from the viewpoint of ejection stability from the inkjet head and sufficient adhesive strength when the anchor layer (I) and the adhesive layer (IV) are combined, the content should be 5% by mass or more and 35% by mass. Is more preferable, and it is particularly preferable that it is 8% by mass or more and 30% by mass or less. By setting the total amount of the water-soluble organic solvent to 3% by mass or more, the moisturizing property of the ink, the ejection stability, and the wettability of the water-based ink on the printing substrate are improved. Further, by setting the total content of the water-soluble organic solvent to 40% by mass or less, a printed matter having good drying property and color mixing bleeding and good blocking resistance can be obtained.

Preferred alkyl polyol-based solvents include, for example, 1,2-ethanediol (ethylene glycol), 1,2-propanediol (propylene glycol), 1,3-propanediol, 1,2-butanediol, 1, 3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 2,2-dimethyl-1,3-propanediol, 2-methyl- 1,3-Propylenediol, 2-ethyl-2-methyl-1,3-propanediol, 3-methyl-1,3-butanediol, 3-methyl-1,5-pentanediol, 2-methyl-2- Examples thereof include propyl-1,3-propanediol, 2-methylpentane-2,4-diol, 2-ethyl-1,3-hexanediol, diethylene glycol, and dipropylene glycol.

Preferred glycol ether-based solvents include, for example, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and triethylene. Glycol monobutyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol mono Glycol monoalkyl ethers such as butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monobutyl ether; diethylene glycol diethyl ether, diethylene glycol isopropylmethyl ether, diethylene glycol butylmethyl ether, triethylene glycol dimethyl ether, triethylene glycol butylmethyl ether, tetraethylene glycol Examples thereof include glycol dialkyl ethers such as dimethyl ether.

Above all, 1,2-propanediol, 1,2-butanediol, and 1,3-butanediol can be achieved at the same time as excellent discharge stability, moisturizing property, and drying property, and adhesiveness after laminating. , 1,2-Pentanediol, 1,5-Pentanediol, 1,2-hexanediol, Diethylene glycol monopropyl ether, Propylene glycol monoethyl ether, Propylene glycol monopropyl ether, Dipropylene glycol monopropyl ether, and Dipropylene. It is preferable to select one or more selected from the group consisting of glycol monobutyl ether.

<Binder resin>
The water-based inkjet ink of the present invention preferably contains a binder resin. Generally, as the form of the resin, a water-soluble resin, a hydrosol which is a water-insoluble resin, and an emulsion are known, and any form can be used as the binder resin. In the present invention, the "emulsion" refers to a form in which an emulsifier or a water-soluble polymer compound is adsorbed on the surface of resin fine particles and dispersed in a dispersion medium, and the "hydrosol" refers to the acidity and acidity present in the resin. / Or refers to a form in which a basic functional group is neutralized and dispersed in a dispersion medium. Further, the hydrosol and the emulsion are generally referred to as "resin fine particles", and refer to those having a 50% volume particle size measured by a method described later having a particle size of 5 to 1000 nm.

Of the above, the emulsion can contain a resin having a large weight average molecular weight, can lower the viscosity of the water-based ink, and can contain a larger amount of resin, so that the printed matter has scratch resistance and blocking resistance. Suitable for enhancing the properties and adhesive strength of the laminate.

When a hydrosol and a water-soluble resin are used, the weight average molecular weight is preferably in the range of 10,000 or more and 80,000 or less, and more preferably 20,000 or more and 50,000 or less. When the weight average molecular weight is 10,000 or more, the scratch resistance of the printed matter can be made suitable, which is preferable. When the weight average molecular weight is 80,000 or less, the ejection stability from the inkjet head can be maintained in a suitable state, which is preferable. The weight average molecular weight and the number average molecular weight in the present specification can be measured by the methods described in Examples described later.

The type of resin used as the binder resin is not particularly limited, but is (meth) acrylic resin, styrene (meth) acrylic resin, urethane resin, urethane (meth) acrylic resin, vinyl chloride resin, and polyolefin. Examples include based resin and polyester based resin.

From the viewpoint of preferably exhibiting the above effects, the content of the binder resin is in the range of 1% by mass or more and 20% by mass or less, and more preferably 2% by mass or more and 15% by mass or less in terms of solid content. The range is as follows, and particularly preferably the range of 3% by mass or more and 10% by mass or less. The acid value of the binder resin is preferably 0 mgKOH / g or more and less than 65 mgKOH / g.

<Surfactant>
The water-based inkjet ink used in the present invention uses a surfactant for the purpose of adjusting the surface tension, ensuring the wettability on the transparent substrate 1 and the anchor layer (I), and improving the print quality. Is preferable. On the other hand, if the surface tension is too low, the nozzle surface of the inkjet head gets wet with the water-based ink and the ejection stability is impaired. Therefore, it is important to select the type and amount of the surfactant. From the viewpoint of ensuring optimum wettability and realizing stable ejection from the inkjet head, it is preferable to use a surfactant such as a siloxane-based, acetylene-based, acrylic-based, fluorine-based, or polyoxyalkylene alkyl ether-based surfactant. It is particularly preferred to use siloxane-based and / or acetylene-based surfactants. The amount of the surfactant added is preferably 0.05% by mass or more and 5.0% by mass or less, more preferably 0.1% by mass or more and 3.0% by mass or less, based on the total amount of the water-based ink (A). When the content is 0.05% by mass or more, the function of the surfactant can be fully exerted, and when the content is 5.0% by mass or less, the storage stability and ejection stability of the water-based ink are suitable. Can be maintained at the level.

<Other ingredients>
In addition to the above components, the water-based inkjet ink used in the present invention contains additives such as a pH adjuster, an antifoaming agent, a preservative, an infrared absorber, an ultraviolet absorber, and a thickener, if necessary. It can be added as appropriate. As an example of the addition amount of these additives, 0.01% by mass or more and 10% by mass or less is preferable with respect to the total mass of the water-based ink.

<Overcoat layer (III)>
Next, the overcoat layer (III) constituting the laminate of the present invention will be described. The overcoat layer (III) is a layer made of a dry film of an overcoat varnish, and as a constituent unit, a binder resin (B) having a structure derived from an ethylenically unsaturated monomer (b1) containing an anionic group is used. include.

<Binder resin (B)>
Generally, as the form of the resin, a water-soluble resin, a hydrosol which is a water-insoluble resin, and an emulsion are known, and any form can be used as the binder resin (B). In the present invention, the "emulsion" refers to a form in which an emulsifier or a water-soluble polymer compound is adsorbed on the surface of resin fine particles and dispersed in a dispersion medium, and the "hydrosol" refers to the acidity and acidity present in the resin. / Or refers to a form in which a basic functional group is neutralized and dispersed in a dispersion medium.

When a water-soluble polymer compound is used as the binder resin (B), it is preferable to contain an aromatic ethylenically unsaturated monomer in addition to the ethylenically unsaturated monomer (b1) containing an anionic group. As the polymerization method, known polymerization methods such as solution polymerization, emulsion polymerization, suspension polymerization and bulk polymerization can be used. In the present invention, solution polymerization and bulk polymerization, which facilitate reaction control and molecular weight control, are preferable.

When the water-soluble polymer compound is used in the shell portion of an emulsion, it has the role of a polymer surfactant that copolymerizes the monomer used in the core portion. Therefore, an ethylenically unsaturated monomer (b1) containing an anionic group having appropriate hydrophilicity and an ethylenically unsaturated monomer containing an aromatic ethylenically unsaturated monomer having appropriate hydrophobicity are used. Is preferable.

As the aromatic ethylenically unsaturated monomer, known ones can be used. Specifically, styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, vinylnaphthalene, benzyl acrylate, benzyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, phenoxydiethylene glycol acrylate, phenoxydiethylene glycol. Examples thereof include, but are not limited to, methacrylate, phenoxytetraethylene glycol acrylate, phenoxytetraethylene glycol methacrylate, phenoxyhexaethylene glycol acrylate, phenoxyhexaethylene glycol methacrylate, phenylacrylate, and phenylmethacrylate.

As the ethylenically unsaturated monomer (b1) containing an anionic group, a known one can be used. Specifically, acrylic acid, methacrylic acid, carboxymethyl (meth) acrylate, carboxyethyl (meth) acrylate, acryloyloxyethyl succinic acid, methacryloyloxyethyl succinic acid, acryloyloxyethyl phthalic acid, methacryloyloxyethyl phthalic acid, acryloyl. Oxyisobutyric acid, methacryloyloxyisobutyric acid, 2-sulfoethyl (meth) acrylate, acryloyloxyethylphosphonic acid, methacryloyloxyethylphosphonic acid, 2- (phosphonooxy) ethyl (meth) acrylate, vinylsulfonic acid, styrenecarboxylic acid, styrenesulfone Acids, styrene phosphonic acid and the like can be mentioned. The ethylenically unsaturated monomer (b1) containing these anionic groups can be used alone or in combination of two or more.

Further, other ethylenically unsaturated monomers can be used for the synthesis of the water-soluble polymer compound.

As the other ethylenically unsaturated monomer, known ones can be used. Specifically, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, pentyl (meth) acrylate, heptyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Contains linear or branched alkyl groups such as octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, and tetradecyl (meth) acrylate. Acrylate unsaturated monomer;
Alicyclic alkyl group-containing ethylenically unsaturated monomers such as cyclohexyl (meth) acrylates and isobonyl (meth) acrylates;
(Meta) acrylamide, N-methoxymethyl- (meth) acrylamide, N-ethoxymethyl- (meth) acrylamide, N-propoxymethyl- (meth) acrylamide, N-butoxymethyl- (meth) acrylamide, N-pentoxymethyl -(Meta) acrylamide, N, N-di (methoxymethyl) acrylamide, N-ethoxymethyl-N-methoxymethylmethacrylamide, N, N-di (ethoxymethyl) acrylamide, N-ethoxymethyl-N-propoxymethylmetha Acrylamide, N, N-di (propoxymethyl) acrylamide, N-butoxymethyl-N- (propoxymethyl) metaacrylamide, N, N-di (butoxymethyl) acrylamide, N-butoxymethyl-N- (methoxymethyl) meta Acrylamide, N, N-di (pentoxymethyl) acrylamide, N-methoxymethyl-N- (pentoxymethyl) metaacrylamide, N, N-dimethylaminopropylacrylamide, N, N-diethylaminopropylacrylamide, N, N- Amid group-containing ethylenically unsaturated monomers such as dimethylacrylamide and N, N-diethylacrylamide;
2-Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyvinylbenzene, 1-ethynyl-1-cyclohexanol, allyl Examples thereof include, but are not limited to, hydroxyl group-containing ethylenically unsaturated monomers such as alcohols;

The water-soluble polymer compound is an ethylenically unsaturated monomer containing 10% by mass to 70% by mass of an aromatic ethylenically unsaturated monomer and an anionic group in 100% by mass of the ethylenically unsaturated monomer (1% by mass). It is preferable to copolymerize b1) with an ethylenically unsaturated monomer containing 3% by mass to 40% by mass. By using an ethylenically unsaturated monomer in these ranges, the adhesive strength between the anchor layer (I), the ink layer (II), and the adhesive layer (IV) can be further improved, and the heat sterilization treatment is performed. It is possible to prevent water from seeping into the anchor layer.

A known polymerization initiator can be used for the synthesis of the water-soluble polymer compound. It is preferable to use 0.1 to 10 parts by mass of the polymerization initiator with respect to 100 parts by mass of the ethylenically unsaturated monomer. When synthesizing by bulk polymerization, if the reaction temperature is raised to a high temperature, copolymerization may be possible without using a polymerization initiator.

The polymerization initiator is preferably an organic peroxide or an azo compound. The organic peroxide may be, for example, benzoyl peroxide, tert-butylperoxybenzoate, tert-butylhydroperoxide, tert-butylperoxy (2-ethylhexanoate), tert-butylperoxy-3,5. , 5-trimethylhexanoate, di-tert-butyl peroxide and the like. The azo compound is, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, 2,2'-azobis (4-methoxy-2,4-dimethyl). Valeronitrile), 1,1'-azobis-cyclohexane-1-carbonitrile, and the like, but are not particularly limited thereto.

The water-soluble polymer compound preferably has a weight average molecular weight of 5,000 to 30,000, more preferably 7,000 to 20,000. When the weight average molecular weight is in the range of 5000 to 30,000, the adhesive strength between the anchor layer (I), the ink layer (II), and the adhesive layer (IV) can be further improved, and the anchor layer is formed by heat sterilization treatment. It is possible to prevent the infiltration of water. Furthermore, the copolymerizability of the core portion can be improved. The weight average molecular weight is a polystyrene-equivalent value measured by GPC (gel permeation chromatography).

The emulsion is a resin obtained by emulsion polymerization of an ethylenically unsaturated monomer in the presence of a water-soluble polymer compound or a surfactant which is a shell portion of a core-shell emulsion. In particular, it may contain an ethylenically unsaturated monomer containing an alkyl group-containing ethylenically unsaturated monomer having 1 to 8 carbon atoms and an ethylenically unsaturated monomer containing an aromatic ethylenically unsaturated monomer. Preferably, the adhesive force between the anchor layer (I), the ink layer (II), and the adhesive layer (IV) can be improved, and water can be prevented from seeping into the anchor layer due to the heat sterilization treatment.

The alkyl group-containing ethylenically unsaturated monomer having 1 to 8 carbon atoms is, for example, methyl methacrylate, methyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl methacrylate, n-butyl acrylate, t. -Butyl methacrylate, pentyl (meth) acrylate, heptyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate and the like can be mentioned, but the present invention is not particularly limited thereto. ..

Ethylene unsaturated monomers containing aromatic ethylenically unsaturated monomers include, for example, styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, vinylnaphthalene, benzylacrylate, and the like. Benzyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, phenoxydiethylene glycol methacrylate, phenoxydiethylene glycol methacrylate, phenoxytetraethylene glycol acrylate, phenoxytetraethylene glycol methacrylate, phenoxyhexaethylene glycol acrylate, phenoxyhexaethylene glycol methacrylate, phenylacrylate, phenylmethacrylate, etc. However, it is not particularly limited to these.

Further, by using another ethylenically unsaturated monomer as described above for the synthesis of the emulsion, the balance between hydrophilicity and hydrophobicity can be adjusted, or the stability of the emulsion can be improved.

The other ethylenically unsaturated monomer is, for example, an alicyclic alkyl group-containing ethylenically unsaturated monomer such as cyclohexyl (meth) acrylate and isobonyl (meth) acrylate;
(Meta) acrylamide, N-methoxymethyl- (meth) acrylamide, N-ethoxymethyl- (meth) acrylamide, N-propoxymethyl- (meth) acrylamide, N-butoxymethyl- (meth) acrylamide, N-pentoxymethyl -(Meta) acrylamide, N, N-di (methoxymethyl) acrylamide, N-ethoxymethyl-N-methoxymethylmethacrylamide, N, N-di (ethoxymethyl) acrylamide, N-ethoxymethyl-N-propoxymethylmetha Acrylamide, N, N-di (propoxymethyl) acrylamide, N-butoxymethyl-N- (propoxymethyl) metaacrylamide, N, N-di (butoxymethyl) acrylamide, N-butoxymethyl-N- (methoxymethyl) meta Acrylamide, N, N-di (pentoxymethyl) acrylamide, N-methoxymethyl-N- (pentoxymethyl) metaacrylamide, N, N-dimethylaminopropylacrylamide, N, N-diethylaminopropylacrylamide, N, N- Amid group-containing ethylenically unsaturated monomers such as dimethylacrylamide and N, N-diethylacrylamide;
2-Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyvinylbenzene, 1-ethynyl-1-cyclohexanol, allyl Hydroxy unsaturated monomer containing hydroxyl group such as alcohol;
Allyl (meth) acrylate, 1-methylallyl (meth) acrylate, 2-methylallyl (meth) acrylate, 1-butenyl (meth) acrylate, 2-butenyl (meth) acrylate, 3-butenyl (meth) acrylate, 1,3- Methyl-3-butenyl (meth) acrylate, 2-chloroallyl (meth) acrylate, 3-chloroallyl (meth) acrylate, o-allylphenyl (meth) acrylate, 2- (allyloxy) ethyl (meth) acrylate, allyllactyl (meth) Acrylate, citroneryl (meth) acrylate, geranyl (meth) acrylate, loginyl (meth) acrylate, cinnamyl (meth) acrylate, diallyl maleate, diallyl itaconic acid, vinyl (meth) acrylate, vinyl crotonate, vinyl oleate, linolenic acid Vinyl, 2- (2'-vinyloxyethoxy) ethyl (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol (meth) acrylate, tetraethylene glycol (meth) acrylate, trimethyl propantri (meth) acrylate , Pentaerythritol tri (meth) acrylate, 1,1,1-trishydroxymethylethanediacrylate, 1,1,1-trishydroxymethylethanetriacrylate, 1,1,1-trishydroxymethylpropanetriacrylate, divinylbenzene , Ethyl unsaturated monomer having two or more ethylenically unsaturated groups such as divinyl adipate, diallyl isophthalate, diallyl phthalate, diallylate maleate;
Epoxy group-containing ethylenically unsaturated monomers such as glycidyl (meth) acrylate and 3,4-epoxycyclohexyl (meth) acrylate;
γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyltributoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-acryloxy Propyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-methacryloxymethyltrimethoxysilane, γ-acryloxymethyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane , Vinyl tributoxysilane, vinylmethyldimethoxysilane and other alkoxysilyl group-containing ethylenically unsaturated monomers; and the like, but are not particularly limited thereto. Among these, when a hydroxyl group-containing ethylenically unsaturated monomer is used, the stability of the core-shell type emulsion can be further improved. These can be used alone or in combination of two or more.

The emulsion contains 10% by mass to 70% by mass of an aromatic ethylenically unsaturated monomer and an alkyl group-containing ethylenically unsaturated monomer having 1 to 8 carbon atoms in 100% by mass of an ethylenically unsaturated monomer. It is preferable to copolymerize (emulsify polymerize) 100% by mass of the ethylenically unsaturated monomer containing 10% by mass to 90% by mass of. By using the ethylenically unsaturated monomer in these ranges, the adhesive strength between the anchor layer (I), the ink layer (II), and the adhesive layer (IV) can be further improved, and the heat sterilization treatment is performed. It is possible to prevent water from seeping into the anchor layer.

For the synthesis of the emulsion, a persulfate, a peroxide, and an azo compound of a water-soluble polymerization initiator can be used. Specifically, for example, ammonium persulfate (APS), potassium persulfate (KPS), hydrogen peroxide, 2,2'-azobis (2-methylpropionamidine) dihydrochloride and the like are preferable. It is preferable to use 0.1 to 10 parts by mass of the water-soluble polymerization initiator with respect to 100 parts by mass of the ethylenically unsaturated monomer.

Further, by using a reducing agent in combination with the water-soluble polymerization initiator, the polymerization rate can be increased or the polymerization can be carried out at a low reaction temperature. Examples of the reducing agent include reducing inorganic compounds such as scorbic acid, elsorbic acid, tartrate acid, citric acid, glucose, sodium sulfite, sodium bisulfite, and sodium metabisulfite. The reducing agent is an ethylenically unsaturated single amount. It is preferable to use 0.05 to 5 parts by mass with respect to 100 parts by mass of the body.

In the present invention, a water-soluble polymer compound can be neutralized and used when synthesizing an emulsion. The water-soluble polymer compound can be solubilized by the neutralization. A basic compound can be used for the neutralization.
Specifically, for example, amines such as ammonia, trimethylamine, triethylamine, butylamine, 2-dimethylaminoethanol, 2-diethylaminoethanol, diethanolamine, triethanolamine, aminomethylpropanol, and morpholin;
Hydroxide salts such as potassium hydroxide and sodium hydroxide; and the like. Of these, ammonia, which is easy to remove by drying after coating, is preferable.

Buffers and chain transfer agents can be used as appropriate in the synthesis of the emulsion. Examples of the buffer include sodium acetate, sodium citrate, sodium bicarbonate and the like. Examples of the chain transfer agent include octyl mercaptan, 2-ethylhexyl thioglycolate, octyl thioglycolate, stearyl mercaptan, lauryl mercaptan, and mercaptan such as t-dodecyl mercaptan.

Surfactants can be used in the synthesis of emulsions. Examples of the surfactant include higher fatty acid salts such as sodium oleate, alkylaryl sulfonates such as sodium dodecylbenzene sulfonate, alkyl sulfate ester salts such as sodium lauryl sulfate, and poly such as polyoxyethylene lauryl ether sodium sulfate. Oxyethylene alkyl ether sulfates, polyoxyethylene alkylaryl ether sulfates such as polyoxyethylene nonylphenyl ether sulfate, alkyl sulfosuccinates such as monooctyl sulfosuccinate, sodium dioctyl sulfosuccinate, and sodium polyoxyethylene lauryl sulfosuccinate. Anionic non-reactive emulsifiers such as acid ester salts and their derivatives, polyoxyethylene distyrene phenyl ether sulfate ester salts;
Polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene stearyl ether, polyoxyethylene alkylphenyl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether, sorbitan monolaurate, sorbitan mono Solbitan higher fatty acid esters such as stearate and sorbitan trioleate, polyoxyethylene sorbitan higher fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene such as polyoxyethylene monolaurate and polyoxyethylene monostearate. Nonionic non-reactive emulsifiers such as higher fatty acid esters, glycerin higher fatty acid esters such as oleic acid monoglyceride and stearate monoglyceride, polyoxyethylene polyoxypropylene block copolymers and polyoxyethylene distyrene phenyl ethers;
Anionic reactive emulsifiers such as polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate;
Nonionic nonionic reactive emulsifiers such as polyoxyethylene-1- (allyloxymethyl) alkyl ethers; and the like.

The emulsion preferably has a weight average molecular weight of 200,000 to 1,000,000, more preferably 300,000 to 500,000. When the weight average molecular weight is in the range of 200,000 to 1,000,000, the adhesive strength between the anchor layer (I), the ink layer (II), and the adhesive layer (IV) can be further improved, and the heat sterilization treatment can be applied to the anchor layer. It is possible to prevent water from seeping in.

When the binder resin (B) contained in the overcoat varnish is a core-shell type emulsion, it is preferable that the core portion is 150 parts by mass to 400 parts by mass with respect to 100 parts by mass of the shell portion. By setting the core-shell ratio of the core-shell type emulsion within the above range, emulsion polymerization can be facilitated and a uniform emulsion can be obtained. In addition, the anchor layer (I), the ink layer (II), and the adhesive can be obtained. The adhesive strength with the layer (IV) can be improved, and water can be prevented from seeping into the anchor layer due to the heat sterilization treatment.

The content of the binder resin (B) is in the range of 5% by mass or more and 40% by mass or less, and more preferably 10% by mass or more and 35% by mass or less in the total amount of overcoat varnish in terms of solid content. Particularly preferably, it is in the range of 15% by mass or more and 30% by mass or less. By keeping the content of the binder resin (B) within the above range, the adhesive strength between the anchor layer (I), the ink layer (II), and the adhesive layer (IV) can be further improved, and the heat sterilization treatment can be performed. It is possible to prevent water from seeping into the anchor layer.

The acid value of the binder resin (B) is preferably 30 mgKOH / g or more and less than 300 mgKOH / g, and more preferably 100 mgKOH / g or more and less than 300 mgKOH / g. By setting the acid value of the binder resin (B) within the above range, the flocculant contained in the anchor layer (I) can be more trapped and water can be prevented from seeping into the anchor layer due to the heat sterilization treatment. The acid value of the binder resin (B) may be either an emulsion or a water-soluble polymer compound contained in the binder resin (B).

The glass transition temperature (Tg) of the binder resin (B) is preferably −30 ° C. or higher and lower than 50 ° C., more preferably −20 ° C. or higher and lower than 40 ° C. By keeping the glass transition temperature of the binder resin (B) within the above range, the adhesive strength between the anchor layer (I), the ink layer (II), and the adhesive layer (IV) can be further improved, and heat sterilization can be performed. It is possible to prevent water from seeping into the anchor layer due to the treatment. When the binder resin (B) is a core-shell emulsion, the calculation is performed with the total value of the core composition and the shell composition as 100% by mass.

The above glass transition temperature refers to a theoretical value calculated from the following FOX equation.
<FOX type>
1 / Tg = W1 / Tg1 + W2 / Tg2 + ... + WI / TgI + ... Wn / Tgn
[In the above FOX formula, the glass transition temperature of the homopolymer of each monomer constituting the polymer composed of n kinds of monomers is TgI (K), and the mass fraction of each monomer is WI. (W1 + W2 + ... WI + ... Wn = 1). ]

When the binder resin (B) is a core shell emulsion, commercially available products such as BASF's JONCRYL67, JONCRYL678, JONCRYL586, JONCRYL611, JONCRYL683, JONCRYL690, JONCRYL57J, JONCRYL60J, JONCRYL60J, JONCRYL60J ９６Ｊ、ＪＯＮＣＲＹＬ５０１Ｊ、ＪＯＮＣＲＹＬＰＤＸ－６１０２Ｂ、ビックケミー社製ＤＩＳＰＥＲＢＹＫ、ＤＩＳＰＥＲＢＹＫ１８０、ＤＩＳＰＥＲＢＹＫ１８７、ＤＩＳＰＥＲＢＹＫ１９０、ＤＩＳＰＥＲＢＹＫ１９１、ＤＩＳＰＥＲＢＹＫ１９４、ＤＩＳＰＥＲＢＹＫ２０１０、ＤＩＳＰＥＲＢＹＫ２０１５、ＤＩＳＰＥＲＢＹＫ２０９０、ＤＩＳＰＥＲＢＹＫ２０９１、ＤＩＳＰＥＲＢＹＫ２０９５、ＤＩＳＰＥＲＢＹＫ２１５５、ゼネカ社製ＳＯＬＳＰＥＲＳ４１０００、サートマー社製、ＳＭＡ１０００Ｈ、ＳＭＡ１４４０Ｈ、ＳＭＡ２０００Ｈ、 SMA3000H, SMA17352H and the like can be mentioned.

The overcoat varnish can contain additives such as a water-soluble organic solvent, a defoaming agent, a surfactant, a preservative, and a wax as optional components. The optional component preferably has no deliquescent property.

The water-soluble organic solvent is not particularly limited, and any known solvent can be used, but from the viewpoint of compatibility and compatibility with material components such as the binder resin (B) and the surfactant, the water-soluble organic solvent is not particularly limited. It is preferable to contain a glycol ether solvent and / or an alkyl alcohol solvent / or an alkyl polyol solvent.

The total amount of the water-soluble organic solvent in the overcoat varnish used for producing the laminate of the present invention is preferably 3% by mass or more and 40% by mass or less, preferably 3% by mass or more and 20% by mass, based on the total amount of the overcoat varnish. % Or less is more preferable. By keeping the total amount of the water-soluble organic solvent within the above range, the wettability to the anchor layer (I) and the ink layer (II) is improved, the drying property is improved, and the adhesive strength can be improved.

Examples of the wax include carnauba wax, mitsuro, paraffin wax, microcrystallin wax, polyethylene wax, polyethylene oxide wax, fatty acid amide, polypropylene wax, polypropylene oxide wax, Fisher Tropushwax, polytetrafluoroethylene and the like.

Further, for the overcoat varnish, a commercially available wax fine particle dispersion can be used for the purpose of improving the friction resistance of the coating film. Examples of the wax resin fine particle dispersion include the Chemipearl series manufactured by Mitsui Chemicals, the Aquacer series manufactured by Big Chemy Japan, the Hi-Tech series manufactured by Toho Chemical Industry Co., Ltd., and the polyethylene wax fine particle dispersion is particularly preferable. ..

The amount of the wax fine particle dispersion added is about 1 to 10% by mass in terms of solid content in 100% by mass of the overcoat varnish in consideration of the balance between the improvement of the friction resistance in the physical characteristics of the coating film and the adverse effect on the hue. Is preferable.

Further, in the overcoat varnish, various surfactants can be used for the purpose of adjusting the leveling property to the anchor layer (I) and the ink layer (II). A product synthesized by a known method may be used, or a commercially available product may be used.
As the commercially available product of the acetylene-based surfactant, for example, Surfinol 61, 104E, 104H, 104A, 104BC, 104DPM, 104PA, 104PG-50, 420, 440, 465, 485, SE, SE-F, Dynol 604, 607 (manufactured by Air Products Co., Ltd.), Orfin E1004, E1010, E1020, PD-001, PD-002W, PD-004, PD-005, EXP. 4001, EXP. 4200, EXP. 4123, EXP. 4300 (manufactured by Nissin Chemical Industry Co., Ltd.) and the like can be mentioned.
Examples of the commercially available siloxane-based surfactants include BY16-201, FZ-77, FZ-2104, FZ-2110, FZ-2162, F-2123, L-7001, L-7002, SF8427, SF8428, SH3749. 、ＳＨ８４００、８０３２ＡＤＤＩＴＩＶＥ、ＳＨ３７７３Ｍ（東レ・ダウコーニング社製）、ＴｅｇｏｇｌＩｄｅ４１０、ＴｅｇｏｇｌＩｄｅ４３２、ＴｅｇｏｇｌＩｄｅ４３５、ＴｅｇｏｇｌＩｄｅ４４０、ＴｅｇｏｇｌＩｄｅ４５０、ＴｅｇｏｔｗＩｎ４０００、ＴｅｇｏｔｗＩｎ４１００、Ｔｅｇｏｗｅｔ２５０、Ｔｅｇｏｗｅｔ２６０、Ｔｅｇｏｗｅｔ２７０、Ｔｅｇｏｗｅｔ２８０（エボニックデグサ社製）、ＳＡＧ－００２、ＳＡＧ－５０３Ａ (Manufactured by Shin-Etsu Chemical Co., Ltd.), BYK-331, BYK-333, BYK-345, BYK-346, BYK-347, BYK-348, BYK-349, BYKUV3500, BYK-UV3510 (manufactured by Big Chemie), KF- 351A, KF-352A, KF-353, KF-354L, KF355A, KF-615A, KF-640, KF-642, KF-643 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like can be mentioned.

The amount of the surface conditioner added is preferably about 0 to 3.0% by mass in terms of solid content in 100% by mass of the overcoat varnish in consideration of the balance of adverse effects on the physical characteristics of the coating film.

Further, in the overcoat varnish, a hydrazide-based additive can be used for the purpose of improving the adhesion to the base material, cross-linking the resin at room temperature (in the case of containing a keto group), and the like. Examples of the hydrazide-based additive include adipic acid hydrazide and the like.

Further, the overcoat varnish may be used in combination with a resin fine particle dispersion containing a carbodiimide group for the purpose of preventing water from seeping into the anchor layer due to the heat sterilization treatment and further improving the adhesive force. The binder resin (B) and the pigment dispersion resin (D) contain a structure derived from an ethylenically unsaturated monomer (b1) containing an anionic group and react with the carbodiimide group of the carbodiimide group-containing resin fine particle dispersion. , Water resistance is improved.

As the carbodiimide group-containing resin fine particle dispersion, water dispersion in which a hydrophilic group is denatured in polycarbodiimide produced from dicyclohexylmethane-4,4'-diisocyanate or 1,3-bis (2-isocyanato-2-propyl) benzene. The body etc. can be mentioned. Examples of commercially available products include Carbodilite E-02, E-03A, SV-02, V-02, V-02, L-2, V-04, E-04 and the like manufactured by Nisshinbo.

The amount of the carbodiimide group-containing resin fine particle dispersion added is preferably about 0.5 to 10% by mass in terms of solid content in 100% by mass of the overcoat varnish. If the amount added is less than 0.5% by mass, the above effect may not be confirmed. On the other hand, if it exceeds 10% by mass, the storage stability may deteriorate.

A known coating method can be used for coating the overcoat varnish, but a flexographic method and a gravure method are preferable. The flexographic method is a method in which a paint is once transferred from an intaglio plate called anilox roll to a resin plate or a rubber plate, and the coating agent on the resin plate or the rubber plate is transferred to the original fabric. It is also possible to pattern a resin plate or a rubber plate. The gravure method includes a method of transferring the coating agent directly from the intaglio plate to the original fabric, and a so-called gravure offset method of transferring the coating agent from the intaglio plate to the planographic plate and then transferring it to the original fabric. It is also possible to pattern the intaglio. In the case of the gravure method, it is preferable to perform a pressing process with a smoothing roll after coating.

<Adhesive layer (IV)>
In order to bond the transparent base material 1, the anchor layer (I), the ink layer (II), the overcoat layer (III) and the base material 2, a laminating process using a laminating adhesive composition is required. .. Examples of the laminating method include an extrusion laminating method, a dry laminating method, and a non-solvent laminating method.
The adhesive layer (IV) constituting the laminated body of the present invention is a layer made of a cured film of a laminated adhesive composition containing a polyisocyanate component and a polyol component, and does not limit the laminating processing method. The laminated adhesive composition is applied onto the ink layer (II) or the overcoat layer (III) and / or onto the substrate 2, to prepare a precursor of the adhesive layer, and then the adhesive. The laminate of the present invention is formed by superimposing the ink layer (II) and the base material 2 via the precursor of the layer and further curing the precursor of the adhesive layer to form the adhesive layer (IV). Will be. Specific laminating adhesive compositions (polyol component / isocyanate component) include TM-250HV / CAT-RT86L-60, TM-550 / CAT-RT37, TM-314 / CAT-14B manufactured by Toyo Morton Co., Ltd. , TM-265L / CAT-RT37, EA-N373A / B and the like.

<Transparent base material 1>
In the present invention, the "transparent base material" means that the base material transmits visible light, and specifically, black characters (characters consisting of 8-point MS Mincho characters) through the base material. Indicates that is visible. As the transparent base material 1 constituting the laminate of the present invention, a polyolefin resin such as polyethylene and polypropylene; a polyester resin such as polyethylene terephthalate (hereinafter, also referred to as PET), polycarbonate and polylactic acid; and a polystyrene, AS resin and ABS resin. Polypropylene resin such as; Polyethylene resin such as Nylon 6 and Nylon 12; Chlorine-containing resin such as polyvinyl chloride and polyvinylidene chloride; Cellophane; can. The base material used for these transparent base materials 1 may be coated with polyvinyl alcohol or the like, or may be subjected to surface treatment such as corona treatment or plasma treatment.

<Base material 2>
Specific examples of the base material 2 constituting the laminate of the present invention include polyolefin resins such as polyethylene and polypropylene; polyester resins such as polyethylene terephthalate, polyethylene naphthalate, polycarbonate and polylactic acid; nylon 6, nylon 12 and the like. Polyethylene resin; Polyethylene resin such as polystyrene, AS resin, ABS resin, Chlorine-containing resin such as polyvinyl chloride and vinylidene chloride; Ethylene-vinyl alcohol copolymer resin; Cellophane; Paper; Aluminum, Stainless steel, A metal foil such as iron; or a film or sheet made of a composite material thereof can be used. Further, in order to enhance the durability, heat resistance, water resistance, light resistance, and gas barrier property of the laminated body, a composite material may be used, and for example, it has an aluminum vapor deposition layer, an alumina vapor deposition layer, a silica vapor deposition layer, and the like. There are polyolefin-based resin films, polyester-based resin films, polyamide-based resin films, and the like. At that time, it is preferable that the vapor-filmed layer is in contact with the adhesive layer (III) in the laminated body. Further, as the base material 2, a material obtained by stacking a plurality of the base materials exemplified above to form a laminated body may be used. As a result, the heat resistance, gas barrier property, etc. of the laminated body are further improved, and a more suitable flexible packaging material for food packaging can be obtained.

The base material used for the base material 2 may be coated with polyvinyl alcohol or the like, or may be surface-treated such as corona treatment or plasma treatment.

The base material 2 constituting the laminate of the present invention preferably has an oxygen permeability of 100 cc / ^m 2.24 hrs · atm or less at 25 ° C. Among the above-exemplified base materials, those having high oxygen permeability per 1 μm (for example, polyamide-based resin) can be kept within the above oxygen permeability range by increasing the thickness of the base material at the time of use. It becomes. Further, since the composite material having a vapor-filmed layer does not easily allow oxygen to permeate regardless of the thickness of the base material, it can be suitably used in the laminate of the present invention.

The oxygen permeability can be measured by using an oxygen permeability measuring device (for example, a MOCON oxygen permeability measuring device manufactured by Hitachi High-Technologies Corporation) according to the method of JIS K 7126.

Hereinafter, the laminated body according to the embodiment of the present invention will be described in more detail with reference to Examples and Comparative Examples. In the following description, "parts" and "%" represent "parts by mass" and "% by mass", respectively, unless otherwise specified.

<Production example of anchor liquid 1>
The following materials were put into a mixing container equipped with a stirrer, mixed at room temperature (25 ° C.) for 1 hour, and then filtered through a membrane filter having a pore size of 1 μm to obtain an anchor liquid 1.
Supercron 480T (solid content 30%) 16.7 parts Calcium acetate 5.0 parts Surfinol 465 1.0 parts Proxel GXL 0.1 parts 2-propanol 5.0 parts Ion-exchanged water 72.3 parts

<Production example of anchor liquids 2 to 4>
Anchor liquids 2 to 4 were obtained in the same operation as the anchor liquid 1 except that the materials shown in Table 1 were used.

The details of the materials used in the production of the anchor liquids 1 to 4 are as follows.
-Calcium acetate; PAS-H-1L manufactured by Kishida Chemical Co., Ltd .; Diallyldimethylammonium chloride polymer manufactured by Nittobo Medical Co., Ltd.-Apple acid; Kishida Chemical Co., Ltd. Calcium glycol-based IPA manufactured by Air Products; Isopropanol / Proxel GXL; manufactured by Arch Chemicals

<Manufacturing of water-based inkjet ink>
<Synthesis example of pigment dispersion resin 1>
95 parts of butanol was charged in a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, and replaced with nitrogen gas. The inside of the reaction vessel was heated to 110 ° C., and 35 parts of styrene, 35 parts of acrylic acid, 30 parts of behenyl acrylate as a polymerizable monomer, and V-601 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a polymerization initiator. A mixture of 6 parts was added dropwise over 2 hours to carry out a polymerization reaction. After completion of the dropping, the reaction was further carried out at 110 ° C. for 3 hours, 0.6 part of V-601 was added, and the reaction was further continued at 110 ° C. for 1 hour to obtain a solution of the pigment dispersion resin 1. Further, after cooling to room temperature, dimethylaminoethanol was added to completely neutralize the mixture, and then 100 parts of water was added to make the product aqueous. Then, the mixture was heated to 100 ° C. or higher, and butanol was azeotropically boiled with water to distill off butanol, and the solid content concentration was adjusted to 30%. From this, an aqueous solution having a solid content concentration of 30% for the pigment dispersion resin 1 was obtained. The weight average molecular weight of the pigment-dispersed resin 1 was 28,000, and the acid value was 273 mgKOH / g.

The acid value was calculated from the composition of the monomers constituting the pigment dispersion resin by the method shown below. The weight average molecular weight and the number average molecular weight described later were measured using a TSKgel column (manufactured by Tosoh Corporation) and a GPC equipped with an RI detector (manufactured by Tosoh Corporation, HLC-8120GPC) and using THF as a developing solvent. These are polystyrene-equivalent values.

The method of calculating the acid value of the pigment dispersion resin 1 is specifically shown. The number of moles (referred to as MCOOH) of the acid group (carboxyl group derived from acrylic acid) present in 1 g of the pigment dispersion resin 1 is {35 ÷ (35 + 35 + 30)} ÷ 72.06 ≈ 0.004857 (mol). Therefore, the mass (unit: mg) of potassium hydroxide required to neutralize 1 g of the pigment-dispersed resin 1 is MCOOH × 56.11 ≈ 0.273 (g) = 273 (mg), and therefore the pigment. The acid value of the dispersed resin 1 is about 273 (mgKOH / g). However, 72.06 and 56.11 in the above formula are the molecular weights of acrylic acid and potassium hydroxide, respectively.

<Synthesis example of pigment dispersion resin 2>
Aqueous with a solid content concentration of 30% of the pigment dispersion resin 2 by the same operation as the pigment dispersion resin 1 except that the monomers shown in Table 2 are used as the polymerizable monomer and amine neutralization is not required. A chemical solution was obtained.

The abbreviations listed in Table 2 are as follows.
St: Styrene AA: Acrylic acid VA: Behenyl acrylate PME-400 (Methoxypolyethylene glycol methacrylate manufactured by NOF CORPORATION)

<Production example of pigment dispersion liquid 1 (C, M, Y, K)>
Mix 20 parts of Lionol Blue 7358G (CI Pigment Blue 15: 3) manufactured by Toyo Color Co., Ltd., 15 parts of an aqueous solution of pigment dispersion resin 1 (solid content concentration 30%), and 65 parts of water, and use a disper. After pre-dispersion, the main dispersion was carried out using a dynomill having a volume of 0.6 L filled with 1800 g of zirconia beads having a diameter of 0.5 mm to obtain a pigment dispersion liquid 1C (cyan). In addition, the above C.I. I. Pigment dispersion 1M (magenta), 1Y (yellow), and 1K (black) were obtained in the same manner as the pigment dispersion 1C except that Pigment Blue 15: 3 was replaced with the pigments shown below.
-Magenta: DIC's FASTGEN SUPER MAGENTA RGT
(CI Pigment Red 122)
・ Yellow: LIONOL YELLOW TT-1405G manufactured by Toyo Color Co., Ltd.
(CI Pigment Yellow 14)
-Black: PrInteX85 manufactured by Orion Engineered Carbons
(CI Pigment Black 7)

<Production example of pigment dispersion liquid 1W>
40 parts of CR-90-2 (titanium oxide) manufactured by Ishihara Sangyo Co., Ltd., 30 parts of an aqueous solution of pigment dispersion resin 1 (solid content concentration 30%) and 30 parts of water were mixed, and the same as the pigment dispersion liquid 1C. Dispersion was carried out by the method to obtain 1 W of a pigment dispersion liquid.

<Production example of pigment dispersion liquid 2 (C, M, Y, K, W)>
The pigment dispersion liquid 2 (C, M, Y, K, W, respectively) was obtained by using the same method as the pigment dispersion liquid 1 except that the pigment dispersion resin 2 was used as the pigment dispersion resin.

Table 3 shows the configurations of the pigment dispersions 1 and 2.

<Synthesis example of binder resin 1>
93.4 parts of butanol was charged in a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, and replaced with nitrogen gas. The inside of the reaction vessel was heated to 110 ° C., and 25 parts of styrene, 5 parts of methacrylic acid, 70 parts of methyl methacrylate as a polymerizable monomer and 6 parts of V-601 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a polymerization initiator. The mixture was added dropwise over 2 hours to carry out a polymerization reaction. After completion of the dropping, the reaction was further carried out at 110 ° C. for 3 hours, 0.6 part of V-601 was added, and the reaction was further continued at 110 ° C. for 1 hour to obtain a solution of the dispersed resin 1. Further, after cooling to room temperature, 37.1 parts of dimethylaminoethanol was added for neutralization, and 100 parts of water was added to make it aqueous. Then, the mixture was heated to 100 ° C. or higher, and butanol was azeotropically boiled with water to distill off butanol, and the solid content was adjusted to 30%. From this, an aqueous solution having a solid content of 30% of the binder resin 1 was obtained. The weight average molecular weight of the binder resin 1 measured in the same manner as in the case of the pigment dispersion resin 1 was 18,000. The acid value of the binder resin 1 was calculated to be 32 mgKOH / g.

<Manufacturing example of inkjet ink 1>
The materials described in 1C below were sequentially added to the mixing vessel while stirring with a disper, and the mixture was stirred until it became sufficiently uniform. Then, filtration was performed with a membrane filter having a pore size of 1 μm to obtain 1C. Further, by using the pigment dispersion liquids 1M, 1Y, and 1K instead of the pigment dispersion liquid 1C, ink 1M, ink 1Y, and ink 1K were obtained. Further, 1 W of ink was obtained from the material described in 1 W below. Inkjet inks consisting of 5 colors in total were obtained.
Inkjet ink 1C
Pigment dispersion 1C 25.0 parts Binder resin (solid content concentration 30%) 25.0 parts 1,2-propanediol 20.0 parts Surfinol 465 1.0 parts TEGO WET 280 1.0 parts Proxel GXL 0.05 Part Ion exchange water 27.95 parts

Inkjet ink 1W
Pigment dispersion 1W 40.0 parts Binder resin (solid content concentration 30%) 25.0 parts 1,2-propanediol 20.0 parts Surfinol 465 1.0 parts TEGO WET 280 1.0 parts Proxel GXL 0.05 Part Ion exchange water 12.95 parts

<Manufacturing example of inkjet ink 2>
Inkjet ink 2 having five colors of C, M, Y, K, and W was obtained by the same method as that of inkjet ink 1 except that the materials shown in Table 4 were used.

The details of the materials shown in Table 4 are as follows.
-PG: 1,2-propanediol-TegoWet280: siloxane-based surfactant manufactured by Evonik Japan-Surfinol 465: acetylenediol-based surfactant manufactured by Air Products Co., Ltd.

<Manufacturing example of overcoat varnish>
Binder resins 1 to 19, which are binder resins (B), were produced by the following procedure.
<Synthesis example of binder resin 1>
60.7 parts of isopropyl alcohol was charged in a reaction vessel equipped with a stirrer, a thermometer, two dropping funnels, and a reflux device, and the temperature was raised to 80 ° C. under reflux with nitrogen while stirring. Next, two dropping funnels were prepared, one of which was 30.0 parts of styrene (St), 47.0 parts of methyl methacrylate (MMA), 3.0 parts of acrylic acid (AA), and PME-400 20.0. The portion was charged and dropped over 3 hours. On the other hand, 10.0 parts of azobisisobutyronitrile (AIBN) was dissolved in 6.0 parts of isopropyl alcohol, charged, and added dropwise over 4 hours. After the dropping was completed, the reaction was continued for 10 hours at the reflux temperature, and then the reaction was completed. Further, after cooling to room temperature, ammonia water having a concentration of 25% was added to completely neutralize the mixture, and then 150 parts of water was added to make the water aqueous. Then, the mixture was heated to 100 ° C., isopropyl alcohol was azeotropically boiled with water to distill off the isopropyl alcohol, and the solid content concentration was adjusted to 30%. From this, a binder resin 1 which is a water-soluble polymer compound having a solid content concentration of 30% was obtained. The weight average molecular weight of the binder resin 1 was 9000, the acid value was 23.4 mgKOH / g, and the glass transition temperature was 53.2 ° C.

<Synthesis Examples of Binder Resins 2 to 13; Water-Soluble Polymer Compounds>
Binder resins 2 to 13 were obtained by reacting in the same manner as the binder resin 1 except that the raw materials and compounding ratios shown in Table 5 were changed. Since the binder resin 13 does not have an acid value, amine neutralization is not performed.
BA is butyl acrylate.

The weight average molecular weight referred to here is a polystyrene-equivalent value measured by GPC (gel permeation chromatography). The dried shell portion (A) was dissolved in tetrahydrofuran to prepare a 0.1% solution, and the weight average molecular weight was measured by the following equipment and measurement conditions. Equipment: HLC-8320-GPC system (manufactured by Tosoh Corporation) Column; TSKgel-SuperMultiIporeHZ-M0021488
4.6 mm I. D. × 15 cm × 3 (molecular weight measurement range 20 to about 2 million)
Elution solvent; Tetrahydrofuran standard substance; Polystyrene (manufactured by Tosoh Corporation)
Flow rate; 0.6 mL / min, sample solution usage; 10 μL, column temperature; 40 ° C.

<Synthesis example of binder resin 14; core shell emulsion>
142.9 parts of binder resin and 50.0 parts of ion-exchanged water were charged in a reaction vessel equipped with a stirrer, a thermometer, two dropping funnels, and a refluxer, and the temperature was raised to 80 ° C. under nitrogen reflux. Next, two dropping funnels were prepared, one of which was charged with 100 parts of butyl methacrylate and dropped over 2 hours. On the other hand, 5.0 parts of an aqueous solution of ammonium persulfate (APS) having a concentration of 20% was charged and added dropwise over 2 hours. After the dropping was completed, the reaction was continued at 80 ° C. for 2 hours, and then the reaction was completed. Next, the non-volatile content of the solution was adjusted to 30% by mass with ion-exchanged water to obtain a cobinder resin 14. The weight average molecular weight of the core portion of the core-shell emulsion was 420000. The weight average molecular weight of the core portion of the core-shell emulsion was calculated by measuring the weight average molecular weight of the entire core-shell emulsion and subtracting the weight average molecular weight of the shell portion.

<Synthesis example of binder resin 15-19; core shell emulsion>
Binder resins 15 to 19 were obtained by reacting in the same manner as the binder resin 14 except that the raw materials and compounding ratios shown in Table 6 were changed. Further, the weight average molecular weight of the binder resins 15 to 19 was calculated in the same manner as described above.

<Manufacturing example of overcoat varnish 1>
The following materials were sequentially added to the mixing vessel while stirring with a disper, and stirred until sufficiently uniform. Then, filter cloth filtration having a pore size of 50 μm was performed.
Binder resin 1 (solid content concentration 30%) 66.67 parts PG 7.0 parts Surfinol 465 1.0 parts TEGO WET 280 1.0 parts ADH (azipic acid dihydrazide) 0.5 parts Aquacer 515 8.57 parts Proxel GXL 0.05 part Ion-exchanged water 15.21 parts

<Manufacturing example of overcoat varnish 2-21>
Overcoat varnishes 2 to 21 were obtained by the same method as overcoat varnish 1 except that the materials shown in Table 6 were used.

<Example of Fabrication of Anchor Layer (I)>
K control coater K202 manufactured by Matsuo Sangyo Co., Ltd., wire bar No. After applying the anchor liquid prepared above to each of the transparent base materials 1 shown below using 0, the transparent base material 1 coated with the anchor liquid is dried in an air oven at 70 ° C. for 3 minutes. As a result, a printed substrate in which the anchor layer (I) was added to the transparent substrate 1 was produced.
・ Unitika nylon film "Emblem ON"
(Thickness 15 μm, described as “Ny” in Table 10 described later)
・ Toyobo's polyethylene terephthalate film "E5100"
(Thickness 12 μm, described as “PET” in Table 10 described later)

When applying the anchor liquid, in addition to the K control coater K202 manufactured by Matsuo Sangyo Co., Ltd., a wire bar manufactured by Kobayashi Seisakusho Co., Ltd. and a D bar manufactured by OSG System Products Co., Ltd. are used so that the desired layer thickness is obtained. I selected the bar as appropriate. Further, an inkjet method may be used for applying the anchor liquid.

The thickness of the anchor layer (I) was calculated from the mass change of the printed substrate 20 cm square before and after the application of the anchor liquid.

<Example of manufacturing ink layer (II)>
An inkjet head KJ4B-1200 (manufactured by Kyocera, resolution 1200 dpi, maximum drive frequency 64 kHz) is installed on the top of a conveyor capable of transporting a printing substrate, and the water-based inkjet ink produced above is applied from the upstream side to K (black) and C. (Cyan), M (magenta), Y (yellow), W (white) were filled in this order. Next, after fixing the transparent base material 1 provided with the anchor layer (I) produced above on the conveyor, the conveyor is driven at 50 m / min and passed through the installation portion of the inkjet head. , Water-based inkjet ink was ejected and printing was performed. The drop volume at the time of printing was adjusted in the range of 1.5 pL to 5 pL so as to have a desired layer thickness. Then, the printed matter was promptly put into an air oven at 70 ° C. and dried for 3 minutes to prepare a printed matter to which the ink layer (II) was applied.

<Printed image used for evaluation>
A solid image was printed with a gradation pattern having a different printing rate using all the filled inks. The gradation pattern was performed in the non-printed portion, 50 to 100%, 50 to 160%, 50 to 220%, 50 to 280%, and 50 to 340%.

<Production example of overcoat layer (III)>
K control coater K202 manufactured by Matsuo Sangyo Co., Ltd., wire bar No. Overcoat varnish is applied to the transparent substrate 1 provided with the anchor layer (I) and / or the ink layer (II) using 2, and then dried in an air oven at 70 ° C. for 3 minutes to overcoat. A printed substrate provided with the layer (III) was prepared.

When applying the overcoat varnish, in addition to the K control coater K202 manufactured by Matsuo Sangyo Co., Ltd., a wire bar manufactured by Kobayashi Seisakusho Co., Ltd. and a D bar manufactured by OSG System Products Co., Ltd. are used so that the desired layer thickness is obtained. The bar was selected as appropriate. In addition, an inkjet method may be used for applying the overcoat varnish.

<Example of laminated body. Laminates 1-12>
Laminate adhesive (TM-265L / CAT-RT37 manufactured by Toyo Morton Co., Ltd., or EA) on the upper surface of the overcoat layer of the transparent substrate 1 provided with the anchor layer (I), the ink layer (II) and the overcoat layer (III). -N373A / B) was applied so that the adhesive layer was 3.0 g / m ² , and then the base material 2 was laminated on the adhesive layer surface to obtain a laminated body.
When TM-265L / CAT-RT37 manufactured by Toyo Morton Co., Ltd. was used, the solid content was adjusted to 30% with ethyl acetate, and after coating, drying was performed. Then, the laminated adhesive composition was cured by aging for one day in an environment of 25 ° C. and 80% RH to prepare a laminated body.
The laminated adhesive TM-265L / CAT-RT37 manufactured by Toyo Morton Co., Ltd. (described as "adhesive 1" in Table 8 described later) is a solvent type, and is EA-N373A / B (in Table 8 described later, "Adhesive 1"). Adhesive 2 ”) is a solvent-free type.
・ Mitsui Chemicals Tohcello Co., Ltd. linear low-density polyethylene film "TUX-FC-D"
(Thickness 40 μm, described as “LLDPE” in Table 8 below and below)
・ Futamura Chemical Co., Ltd. unstretched polypropylene film "FHK2"
(Thickness 25 μm, described as “CPP” in Table 8 below and below)

The combinations of the transparent base material 1, the anchor liquid, the ink, the overcoat varnish, the laminated adhesive composition, and the base material 2 used for producing each laminated body are as shown in Table 8.

[Examples 1 to 30, Comparative Examples 1 to 4]
Evaluations 1 to 6 shown below were performed on each of the above-mentioned laminates.

<Evaluation 1: Evaluation of color unevenness>
Printing and drying were performed under the above conditions, and all the inks filled in the film substrate coated with the anchor liquid were used to print a solid image with gradation patterns having different printing rates. The gradation pattern was performed in the non-printed portion, 50 to 100%, 50 to 160%, 50 to 220%, 50 to 280%, and 50 to 340%. The color unevenness was evaluated by visually observing the degree of color unevenness from the transparent substrate 1 side of the laminate prepared by using the completely solid printed matter as the printed image. The evaluation criteria were as follows, and 3 to 5 points were set as the practically usable area.
5 points: No color unevenness was seen in the gradation pattern with a printing rate of 50 to 340% 4 points: No color unevenness was seen in the gradation pattern with a printing rate of 50 to 280% 3 points: Printing rate 50 to 220 No color unevenness was seen in the% gradation pattern 2 points: No color unevenness was seen in the gradation pattern with a printing rate of 50 to 160% 1 point: Color unevenness was not seen in the gradation pattern with a printing rate of 50 to 100% Was not seen

<Evaluation 2: Evaluation of mixed color bleeding>
Printing and drying were performed under the above conditions, and all the inks filled in each were used on the film substrate coated with the anchor liquid, and solid images were printed with gradation patterns having different printing rates. The gradation pattern was performed in the non-printed portion, 50 to 100%, 50 to 160%, 50 to 220%, 50 to 280%, and 50 to 340%. A laminate prepared using a completely solid printed matter as a printed image was observed at 200 times with an optical microscope for the dot shape of the printed portion, and the color mixing bleeding was evaluated. The evaluation criteria were as follows, and 3 to 5 points were set as the practically usable area.
5 points: Dots are independent in the gradation pattern with a printing rate of 50 to 340%, and no color mixing bleeding is seen. 4 points: Dots are independent in the gradation pattern with a printing rate of 50 to 280%, and the colors are mixed. No bleeding was seen. 3 points: Dots were independent in the gradation pattern with a printing rate of 50 to 220%, and no color mixing bleeding was seen. 2 points: Dots were found in the gradation pattern with a printing rate of 50 to 160%. Independent, no color mixing bleeding 1 point: Dots were independent in a gradation pattern with a printing rate of 50 to 100%, and no color mixing bleeding was seen.

<Evaluation 3: Evaluation of adhesive strength>
A laminate prepared by using two parts, a completely solid printed matter (printing rate 340%) and a non-printing portion, as a printed image was cut into a length of 300 mm and a width of 15 mm to obtain a test piece. Using an Instron type tensile tester, the T-type peel strength (N) between the transparent base material 1 and the base material 2 was measured by pulling at a peeling speed of 300 mm / min in an environment of 25 ° C. This test was performed 5 times, and the adhesive strength was evaluated by calculating the average value of each. The evaluation criteria were as follows, and 3 to 5 points were set as the practically usable area.
5 points: The adhesive strength of each of the 2 parts is 1.5N / 15mm or more 4 points: The adhesive strength of each of the 2 parts is 1.0 or more and less than 1.5N / 15mm 3 points: The adhesive strength of each of the 2 parts 2 points: the adhesive strength of each of the 2 parts is 0.3 or more and less than 0.6N / 15 mm 1 point: the adhesive strength of each of the 2 parts is 0.3N / Less than 15 mm

<Evaluation 4: Evaluation of adhesive strength after boiling test>
A laminate prepared by using two parts, a completely solid printed matter (printing rate 340%) and a non-printing portion, as a printed image was cut into a length of 300 mm and a width of 15 mm to obtain a test piece. Then, the test piece was boiled with hot water at 85 ° C. for 30 minutes. Using an Instron type tensile tester, the T-type peel strength (N) between the transparent base material 1 and the base material 2 was measured by pulling at a peeling speed of 300 mm / min in an environment of 25 ° C. This test was performed 5 times, and the adhesive strength was evaluated by calculating the average value of each, and the result of the part having the lower score was adopted. The evaluation criteria were as follows, and 3 to 5 points were set as the practically usable area.
5 points: Adhesive strength is 1.5N / 15mm or more 4 points: Adhesive strength is 1.0 or more and less than 1.5N / 15mm 3 points: Adhesive strength is 0.6 or more and less than 1.0N / 15mm 2 points: Adhesive strength is 0.3 or more and less than 0.6N / 15mm 1st point: Adhesive strength is less than 0.3N / 15mm

<Evaluation 5: Evaluation of the appearance of the laminated body>
A laminate prepared by using two parts, a completely solid printed matter (printing rate 340%) and a non-printing part, as a printed image is cut into a length of 200 mm and a width of 100 mm, observed from the film surface, and the appearance is evaluated and graded. The result of the lower part was adopted. The evaluation criteria were as follows, and 3 to 5 points were set as the practically usable area.
5 points: No delamination and foaming in the laminate, or delamination and foaming in an area of less than 1% 4 points: Delamination and foaming in an area of 1% or more and less than 3% in the laminate There are 3 points: Delamination and foaming in an area of 3% or more and less than 20% in the laminate 2 points: Delamination and foaming in an area of 20% or more and less than 50% in the laminate 1 point: Laminates have delamination and foaming over 50% area

<Evaluation 6: Evaluation of the appearance of the laminated body after the boil test>
A laminate prepared by using a completely solid printed matter (printing rate 340%) and a non-printing portion as a printed image was cut into a length of 200 mm and a width of 100 mm, and then hot water boiled at 85 ° C. for 30 minutes. The appearance was evaluated by observing from the film surface, and the result of the part having the lower score was adopted. The evaluation criteria were as follows, and 3 to 5 points were set as the practically usable area.
5 points: No delamination and foaming in the laminate, or delamination and foaming in an area of less than 1% 4 points: Delamination and foaming in an area of 1% or more and less than 3% in the laminate There are 3 points: Delamination and foaming in an area of 3% or more and less than 20% in the laminate 2 points: Delamination and foaming in an area of 20% or more and less than 50% in the laminate 1 point: Laminates have delamination and foaming over 50% area

The evaluation results of Examples and Comparative Examples are shown in Tables 9 and 10.

In Comparative Example 1, since the binder resin (B) contained in the overcoat layer does not contain the structure derived from the ethylenically unsaturated monomer (b1) containing an anionic group as a constituent unit, the flocculant contained in the anchor layer. The trap of (A) could not be performed, and the heat sterilization treatment step of the boil resulted in water permeating into the anchor layer, resulting in a decrease in adhesive strength and a poor appearance. In Comparative Example 2, since the pigment dispersion resin (D) contained in the ink layer does not contain the structure derived from the ethylenically unsaturated monomer (b1) containing an anionic group as a constituent unit, the flocculant by the anchor layer (in Comparative Example 2). In A), the pigment-dispersed resin (D) did not aggregate, resulting in color unevenness and color bleeding. Comparative Example 3 is a laminate not containing the overcoat layer (III), and the heat sterilization treatment step of the boil resulted in water permeating into the anchor layer, resulting in a decrease in adhesive strength and a poor appearance. ..
In Comparative Example 4, the anchor layer (I) was a laminated body containing no flocculant (A), resulting in color unevenness and color mixing bleeding.

On the other hand, Examples 1 to 30 are systems using a suitable anchor liquid, water-based ink, and overcoat varnish, and have a transparent base material 1, an anchor layer (I), an ink layer (II), and an overcoat layer (III). The adhesive layer (IV) and the base material 2 have a suitable layer structure, and high-quality print image quality without color unevenness or color mixing bleeding can be obtained. It was excellent regardless of before and after the sterilization process, and everything was in the practical range.

The laminated bodies 1 to 12 have a laminated adhesive (TM-265L / CAT-RT37 or EA-N373A / B manufactured by Toyo Morton Co., Ltd.) on the upper surface of the base material 2, and the adhesive layer is 3.0 g / m ² . After coating so as to be, the overcoat layer of the transparent base material 1 provided with the anchor layer (I), the ink layer (II) and the overcoat layer (III) is laminated on the adhesive layer surface and laminated. You can also get it. The evaluation was the same as in Table 9.

1: Transparent substrate 1
2: Anchor layer 3: Ink layer 4: Overcoat layer 5: Adhesive layer 6: Base material 2

Claims (6)

A laminate having a transparent base material 1, an anchor layer (I), an ink layer (II), an overcoat layer (III), an adhesive layer (IV), and a base material 2 in this order. hand,
The anchor layer (I) contains the flocculant (A) and contains.
The ink layer (II) is composed of a dry film of two or more different colors of water-based inkjet ink, and the dry film independently contains a pigment and a pigment dispersion resin (D).
The overcoat layer (III) contains a binder resin (B) and contains.
The binder resin (B) and the pigment dispersion resin (D) each independently contain a structure derived from an ethylenically unsaturated monomer (b1) containing an anionic group as a constituent unit.
A laminated body in which the adhesive layer (IV) is a layer composed of a cured film of a laminated adhesive composition containing an isocyanate component and a polyol component. The laminate according to claim 1, wherein the flocculant (A) is a polyvalent metal salt and / or a cationic polymer compound. The laminate according to claim 1 or 2, wherein the anchor layer (I) has a thickness of 0.1 to 2.0 μm. The laminate according to any one of claims 1 to 3, wherein the binder resin (B) has an acid value of 30 to 300 mgKOH / g. The laminate according to any one of claims 1 to 4, wherein the binder resin (B) has a glass transition temperature of −30 ° C. to 50 ° C. The laminate according to any one of claims 1 to 5, wherein the overcoat layer (III) is formed of an overcoat varnish (V) containing a composition having a carbodiimide group.

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