Laminate and method for manufacturing the same

Abstract

The objective is to provide a laminate with excellent laminate appearance (no streaky stains, no ink bleeding) and laminate strength, as well as a method for manufacturing the same. [Solution] A laminate comprising a base material 1, a printing layer, an adhesive layer, and a base material 2 in this order, wherein the printing layer comprises an acrylic resin and a compound (A), and the compound (A) comprises at least one selected from the group consisting of acetylene compounds, alcohol alkoxylate compounds, and siloxane compounds, and the acrylic resin content is 5% by mass or more of 100% by mass of the printing layer.

Description

Technical Field

[0001] The present invention relates to a laminate and a method for manufacturing the same.

Background Art

[0002] Gravure printing and flexographic printing are widely used for the purpose of imparting cosmetic properties and functional properties to the printed object. In recent years, however, with the diversification of packaging materials such as packages and the sophistication of packaging technology, as well as efforts to address environmental issues from the perspective of regulations, the performance requirements for printing inks have been diversifying year by year. In order to reduce the environmental impact, the water-based conversion of printing inks has been rapidly progressing, and ensuring performance in an aqueous system has become an issue, and the entire industry has been striving to improve printing suitability and printing effects. In particular, since water-based inks contain a large amount of water, there has been a problem that the laminate strength decreases and the appearance of the laminate laminate deteriorates due to poor drying during printing.

[0003] In Patent Document 1, there is a description of a laminate obtained by printing an ink containing an aqueous acrylic resin on a plastic film and further performing a lamination process. However, since the aqueous acrylic ink does not contain an acetylene-based compound, an alcohol alkoxylate-based compound, and a siloxane-based compound, there is a concern that the laminate appearance may deteriorate. In Patent Document 2, there is a description of a laminate obtained by printing an ink containing an aqueous urethane resin and a water-soluble acrylic resin on a plastic film and further performing a lamination process. However, since the solid content of the water-soluble acrylic resin in the printed layer of the laminate is less than 5% by mass, there is a concern that the laminate strength and the laminate appearance may deteriorate.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

[0005] The objective is to provide a laminate with excellent laminate appearance (no streaky stains, no ink bleeding) and laminate strength, as well as a method for manufacturing the same. [Means for solving the problem]

[0006] As a result of diligent research into the aforementioned problems, the inventors have found that the above problems can be solved by using the packaging material described below, and have thus come to present invention.

[0007] In other words, the present invention is a laminate having a base material 1, a printing layer, an adhesive layer, and a base material 2 in this order. The printed layer comprises an acrylic resin and compound (A), The compound (A) comprises at least one selected from the group consisting of acetylene compounds, alcohol alkoxylate compounds, and siloxane compounds. The present invention relates to a laminate in which the acrylic resin content is 5% by mass or more of 100% by mass of the printed layer.

[0008] In other words, the present invention relates to a laminate in which the glass transition temperature of the adhesive layer is 60°C or lower.

[0009] In other words, the present invention relates to a laminate in which the adhesive layer is a layer formed using a solvent-free adhesive.

[0010] In other words, the present invention relates to a laminate in which the acid value of the acrylic resin is 3 to 250 mgKOH / g.

[0011] In other words, the present invention relates to a laminate in which the glass transition temperature of the acrylic resin is 0 to 110°C.

[0012] In other words, the present invention relates to a laminate in which the acrylic resin has a minimum film-forming temperature, and said minimum film-forming temperature is 50°C or lower.

[0013] That is, the present invention relates to the laminate in which the printing layer further contains a hydrazine derivative.

[0014] That is, the present invention relates to the laminate in which the printing layer further contains an antifoaming agent, and the content of the antifoaming agent is 0.01 to 2% by mass in 100% by mass of the printing layer.

[0015] That is, the present invention relates to the laminate in which the printing layer further contains an extender pigment, and the extender pigment is at least one selected from the group consisting of barium sulfate, calcium carbonate, kaolin clay, and silica.

[0016] That is, the present invention relates to the laminate in which the base material 1 contains an olefin resin.

[0017] That is, the present invention is a method for producing a laminate having a base material 1, a printing layer, an adhesive layer, and a base material 2 in this order. A step of forming the printing layer by printing a printing ink containing an acrylic resin and a compound (A) on the base material 1. And a step of forming the adhesive layer by applying an adhesive on the printing layer. The present invention relates to a method for producing a laminate, wherein the compound (A) contains at least one selected from the group consisting of an acetylene compound, an alcohol alkoxylate compound, and a siloxane compound.

[0018] That is, the present invention relates to a method for producing the laminate, wherein the printing ink further contains an amine compound.

[0019] That is, the present invention relates to a method for producing the laminate, wherein the printing ink further contains an organic solvent having a boiling point of 130 °C or higher.

Advantages of the Invention

[0020] It is possible to provide a laminate excellent in laminate appearance (streaky stains, ink bleeding) and laminate strength, and a method for producing the same.

BEST MODE FOR CARRYING OUT THE INVENTION

[0021] <Laminate> A laminate having a base material 1, a printing layer, an adhesive layer, and a base material 2 in this order, wherein the printing layer contains an acrylic resin and a compound (A), and the compound (A) contains at least one selected from the group consisting of an acetylene-based compound, an alcohol alkoxylate-based compound, and a siloxane-based compound, and the content of the acrylic resin is 5% by mass or more in 100% by mass of the printing layer. The laminate of the present invention is preferably a packaging material.

[0022] When the acrylic resin and the compound (A) are compatible in the printing layer, (1) the leveling property of the printing layer is improved, (2) the film-forming property is improved, and (3) the adhesion between the base material 1 and the printing layer is improved, so that it is excellent in laminate appearance (streaky stains, ink bleeding) and laminate strength. The above effects are based on scientific considerations, and the present invention is not limited to those having only the above effects.

[0023] <Printing layer> The printing layer in the present invention contains an acrylic resin and a compound (A), and the compound (A) contains at least one selected from the group consisting of an acetylene-based compound, an alcohol alkoxylate-based compound, and a siloxane-based compound. The printing layer preferably further contains a hydrazine derivative and / or an antifoaming agent. The printing layer can be formed by printing the following printing ink by a known printing method and removing the volatile components.

[0024] <Acrylic resin> Acrylic resin is a synthetic resin mainly composed of derivatives of acrylic acid or methacrylic acid. There are two methods for synthesizing acrylic resin: solution polymerization and emulsion polymerization. In solution polymerization, acrylic monomers, etc., described later are polymerized in a solvent to obtain a resin with a uniform molecular weight distribution. On the other hand, in emulsion polymerization, acrylic monomers, etc., are emulsified in water, and then polymerized using a surfactant to efficiently produce high molecular weight resins. Preferably, the resin is a styrene-acrylic resin obtained by polymerizing acrylic monomers and styrene monomers, described later. In the above-mentioned styrene-acrylic resin, the acrylic monomers and styrene monomers may be bonded alternately, and acrylic blocks and styrene blocks may be present.

[0025] The acrylic resin used in the present invention is preferably a water-soluble acrylic resin, preferably a water-soluble acrylic resin and / or an emulsion-type acrylic resin, and more preferably an emulsion-type acrylic resin from the viewpoint of lamination strength. A water-soluble acrylic resin is an acrylic resin that dissolves in water, while an emulsion-type acrylic resin is a milky white liquid acrylic resin that disperses without dissolving in water.

[0026] The acid value of the acrylic resin is preferably 3 to 250 mg KOH / g, more preferably 60 to 220 mg KOH / g, and even more preferably 120 to 200 mg KOH / g. When the acid value of the acrylic resin is within the above range, the appearance of the laminate (ink bleed-through) tends to improve. The glass transition temperature (Tg) of the acrylic resin is preferably 0 to 110°C, more preferably 20 to 100°C, and even more preferably 40 to 80°C. When the glass transition temperature is within the above range, the laminate strength tends to improve. Furthermore, emulsion-type acrylic resins have a minimum film-forming temperature. When an acrylic resin has a minimum film-forming temperature, the minimum film-forming temperature is preferably 50°C or lower, more preferably -30 to 30°C, and even more preferably -10 to 20°C. When the minimum film-forming temperature of the acrylic resin is within the above range, the appearance of the laminate (ink bleed-through, streaky stains) and the laminate strength tend to improve. In addition, multiple types of acrylic resin may be used. In this invention, if multiple types of acrylic resin are used, the respective values ​​obtained using the following weighted average calculation formula are treated as the acid value, glass transition temperature, weight-average molecular weight, and minimum film formation temperature of the acrylic resin. (Formula 1) Acid value [mgKOH / g] when n types of acrylic resin are included. TIFF2026113787000001.tif46157(Equation 2) Glass transition temperature [°C] when n types of acrylic resin are included. TIFF2026113787000002.tif42170 (Equation 3) Weight-average molecular weight when n types of acrylic resins are included TIFF2026113787000003.tif38170 (Equation 4) Minimum film-forming temperature when n types of acrylic resins having the lowest film-forming temperature are included TIFF2026113787000004.tif36170

[0027] Acrylic monomers are important when used in inks because their properties improve characteristics such as drying speed, gloss, water resistance, and abrasion resistance. Specific compounds include methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. Each of these monomers has a different alkyl group and has a different effect on the ink's properties. Methyl acrylate is a small molecule and can accelerate the curing speed of the ink. Ethyl acrylate is a slightly larger molecule and imparts flexibility and tackiness to the ink. Butyl acrylate and 2-ethylhexyl acrylate are even larger molecules and can improve the durability and flexibility of the ink.

[0028] Styrene monomers refer to a series of compounds that use styrene as their basic skeleton. Styrene itself has a structure in which an ethylene group is bonded to a benzene ring, and various derivatives are produced when this structure undergoes various chemical modifications. Specific examples include alkyl-substituted styrenes such as methylstyrene, ethylstyrene, and propylstyrene, in which the hydrogen atoms of the benzene ring are replaced with methyl, ethyl, and propyl groups, respectively. There are also halogenated styrenes such as chlorostyrene and bromostyrene, in which the hydrogen atoms of the benzene ring are replaced with chloro or bromo groups. Furthermore, sulfonylstyrene and aminostyrene, which have functional groups containing sulfur or nitrogen, are also known, and these have specific functional groups containing sulfur or nitrogen introduced into them, respectively.

[0029] <Basic compounds that neutralize acrylic resin> It is preferable to neutralize the ionic groups in the acrylic resin with a basic compound. Examples of basic compounds include sodium hydroxide, potassium hydroxide, ammonia, methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, ethanolamine, propanolamine, diethanolamine, N-methyldiethanolamine, dimethylamine, diethylamine, triethylamine, N,N-dimethylethanolamine, 2-dimethylamino-2-methyl-1-propanol, 2-amino-2-methyl-1-propanol, and morpholine. These may be used individually or in combination of two or more. Ammonia is preferred as the basic compound from the viewpoint of water resistance of the printed material and residual odor.

[0030] Commercially available acrylic resins that can be used include BASF's Joncryl 52J, 60J, 63J, 70J, HPD-96J, HPD-196, PDX-7357, PDX-7616A, PDX-7732, and PDX-7164. Examples include the Neocryl A-1092, A-1094, A-2092, A-1127, and A-1125 from COVESTRO, and the Hi-Loss-X YL-1098, GL-2439, and X-2010L from Seikoh PMC.

[0031] The acrylic resin content is 5% by mass or more, preferably 10 to 60% by mass, and more preferably 20 to 50% by mass, based on 100% by mass of the printed layer. When the acrylic resin content is within the above range, the leveling properties of the printed layer are excellent, which tends to improve the appearance of the laminate (streaky stains, ink bleeding).

[0032] <Resins other than acrylic resin> The printing layer used in the present invention may contain resins other than the acrylic resin described above, such as urethane resin, styrene-maleic anhydride resin, polyester resin, rosin-modified maleic acid resin, cellulose resin, and chlorinated polyolefin. The aqueous resin may be used alone or in combination of two or more types. The mass ratio of the acrylic resin to the resin other than the acrylic resin is preferably 50:50 to 100:0, and more preferably 80:20 to 100:0. When the mass ratio of the acrylic resin to the resin other than the acrylic resin is within the above range, the leveling properties of the printing layer are excellent, and the appearance of the laminate (streaky stains), the appearance of the laminate (ink bleeding), and the laminate strength tend to improve.

[0033] <Compound (A)> The compound (A) used in the present invention comprises at least one selected from the group consisting of acetylene compounds, alcohol alkoxylate compounds, and siloxane compounds, with acetylene compounds being preferred. Furthermore, compound (A) is preferably a surfactant. The HLB value of compound (A) is preferably 3 to 14, and more preferably 3 to 9. When the HLB of compound (A) is within the above range, the appearance (ink bleed-through) of the laminate tends to improve. The content of compound (A) is preferably 0.1 to 10% by mass, more preferably 0.2 to 7% by mass, even more preferably 0.3 to 4% by mass, and particularly preferably 0.5 to 2% by mass, per 100% by mass of the printed layer. When the content of compound (A) is within the above range, the appearance (streaky stains, ink bleed-through) and laminate strength of the laminate tend to improve.

[0034] <Acetylene compounds> The acetylene-based compounds used in this invention refer to compounds containing an acetylene group, and specific compound names include 2-butyn-1,4-diol, 3-methyl-1-butyn-3-ol, and 4-pentyn-1,3-diol. In particular, it is preferable to include acetylene glycol-based compounds that have an acetylene group in the center and a bilaterally symmetrical structure. The HLB value of the acetylene-based compound is preferably 3 to 14, and more preferably 3 to 9. When the HLB of the acetylene-based compound is within the above range, the appearance (ink release) of the laminate tends to improve.

[0035] Commercially available acetylene compounds include Olphine E1010, Olphine E1020, Surfinol 104, Surfinol 420, Surfinol 440, Surfinol 465, and Surfinol 485, all manufactured by Nisshin Chemical Industry Co., Ltd.

[0036] <Alcohol alkoxylate compounds> The alcohol alkoxylate compounds used in this invention are compounds formed by the bonding of an alkoxy group to an alcohol.

[0037] Examples of commercially available alcohol alkoxylate compounds that can be used include BYK-DYNWET800 manufactured by BIC Chemie Japan.

[0038] <Siloxane compounds> The siloxane compounds used in this invention have a basic structure of alternating bonds between silicon and oxygen atoms, and are utilized in various industrial fields due to their unique physical and chemical properties. Specifically, they have the effect of reducing surface tension at the interface, thereby providing effects that control emulsification, dispersion, foaming, cleaning, and smoothness. There are many types of siloxane compounds, among which polydimethylsiloxane, amino-modified silicone oil, and methylpolysiloxane are particularly representative.

[0039] Examples of commercially available siloxane compounds include TEGO WET 260 and TEGO TWIN 4000 from EVONIK, and BYK-302 and 333 from BYChemie Japan.

[0040] <Coloring agent> The printed layer may further contain a colorant. Suitable colorants include pigments such as inorganic colorants and organic colorants. Examples of inorganic colorants include titanium dioxide, zinc oxide, zinc sulfide, aluminum hydroxide, chromium oxide, carbon black, and mica. From the viewpoint of coloring power, opacity, chemical resistance, and weather resistance, titanium dioxide is preferred as a white colorant, and more preferably titanium dioxide has a basic pigment surface. Examples of organic colorants include organic pigments and dyes used in general inks, paints, and recording materials. Examples of such organic colorants include azo, phthalocyanine, anthraquinone, perylene, perinone, quinacridone, thioindigo, dioxazine, isoindolinone, quinophthalone, azomethine azo, dicutopyrrolopyrrole, and isoindoline pigments. Any compound listed in the Color Index can be used as a colorant, and copper phthalocyanine is preferred for blue ink, while CIPigment Yellow 83 is preferred for yellow ink due to its lightfastness. The colorant content is preferably 20 to 80% by mass, and more preferably 30 to 70% by mass, of 100% by mass of the printed layer.

[0041] <Body pigments> The printed layer preferably contains an extender pigment from the viewpoint of laminate strength and laminate appearance (streaky stains, ink bleeding). Examples of extender pigments include barium sulfate, calcium carbonate, magnesium carbonate, kaolin clay, mica, and silica, which are used individually or in combination of two or more. In particular, from the viewpoint of laminate appearance (streaky stains), it is preferable that at least one is selected from the group consisting of barium sulfate, calcium carbonate, kaolin clay, and silica, and more preferably at least one is selected from the group consisting of barium sulfate, calcium carbonate, and kaolin clay. From the viewpoint of laminate strength, the content of the extender pigment is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 8% by mass or less, based on 100% by mass of the solid content of the printed layer.

[0042] <Additives> The printed layer may contain additives as needed. These additives may be known additives used in printing inks, such as crosslinking agents (curing agents), defoaming agents, waxes, plasticizers, and preservatives. It is preferable that the printed layer contains a crosslinking agent and / or a defoaming agent. The crosslinking agent is preferably a hydrazine derivative, a silane coupling agent, or a carbodiimide, with a hydrazine derivative being particularly preferred.

[0043] <Hydrazine derivatives> Hydrazine derivatives generally refer to compounds in which the amide bond of a carboxylic acid is replaced with hydrazine (NH2-NH2). Specific examples of hydrazine derivatives include adipic acid dihydrazide, sebacate acid dihydrazide, phthalate dihydrazide, isophthalate dihydrazide, and terephthalate dihydrazide, with adipic acid dihydrazide being preferred. The hydrazine derivative content is preferably 0.1 to 2.0% by mass, and more preferably 0.2 to 0.8% by mass, based on 100% by mass of the printed layer. When the hydrazine derivative content is within the above range, the laminate strength tends to improve.

[0044] <Antifoaming agent> The defoaming agent used in the present invention has a foam-breaking effect by acting on the interface and reducing surface tension. Therefore, it tends to improve the smoothness of the printed layer surface and improve the laminate strength and laminate appearance (streaky stains, ink bleeding). Specifically, examples include siloxane-based defoaming agents, alcohol-based defoaming agents, mineral oil-based defoaming agents, aliphatic derivative-based defoaming agents, and hydrocarbon-based defoaming agents. Among these, it is preferable to include at least one selected from the group consisting of siloxane-based defoaming agents, hydrocarbon-based defoaming agents, and aliphatic derivative-based defoaming agents, and it is more preferable to include a siloxane-based defoaming agent. The amount of defoaming agent is preferably 0.01 to 3% by mass, more preferably 0.02 to 2% by mass, and even more preferably 0.03 to 1% by mass, based on 100% by mass of the printed layer. When the amount of defoaming agent is 0.01% by mass or more, the printed appearance tends to improve by suppressing foam in the ink solution during printing. When the amount of defoaming agent is 3% by mass or less, the occurrence of adhesive repulsion during lamination is suppressed, and the laminate appearance (no streaks, no ink bleeding) and laminate strength tend to improve.

[0045] <Siloxane-based antifoaming agent> Siloxane-based defoamers are preferably defoamers whose main component is silicone oil, whose basic structure consists of alternating bonds between silicon and oxygen atoms. Silicone oil has high surface activity, which can reduce the surface tension of a liquid and prevent the formation of bubbles. Specifically, these include polydimethylsiloxane (PDMS), amino-modified silicone oil, and epoxy-modified silicone oil. Each of these compounds has different properties and is selected according to the usage environment and purpose.

[0046] Examples of commercially available siloxane-based defoamers include TEGO FOAMEX 1488, 3062, 852, 810, 840, and 835 from EVONIK, and BYK-017, 1707, 024, and 094 from BYChemie Japan.

[0047] <Hydroxide-based defoaming agent> Hydrocarbon-based defoamers are compounds generally used to suppress or remove foam generated in oily systems. These defoamers primarily have hydrocarbons as their basic structure and exert their defoaming effect by reducing foam stability through their surfactant properties. Specific examples of such compounds include polyalkylene glycols, alkylbenzenes, and mineral oils.

[0048] Commercially available hydrocarbon-based defoamers include EVONIK's TEGO FOAMEX K3 and K7, and BYK-038, 039, and 1690SD from BICH CHEMI Japan.

[0049] <Aliphatic derivative-based defoaming agent> Aliphatic derivative-based defoamers contain specific aliphatic derivatives as their main component, thereby exhibiting excellent defoaming effects. Specifically, these defoamers generally contain aliphatic derivatives such as fatty acid amides, fatty acid esters, and fatty acid ethers. These compounds have surface-active properties, reducing the surface tension of bubbles and promoting their bursting, thereby exerting an antifoaming effect.

[0050] One commercially available product that can be used as an aliphatic derivative-based defoaming agent is BYK-014 manufactured by BIC Chemie Japan.

[0051] The mass ratio of the total acrylic resin to the total defoaming agent is preferably 99.9:0.1 to 90:10, and more preferably 99.8 to 95:5. This tends to improve the laminate appearance (ink bleed-through) and laminate strength.

[0052] <Printing Ink> The printing ink used in the present invention is preferably an aqueous printing ink. The printing ink comprises the acrylic resin, compound (A), and medium described above, and may further contain various materials, amine compounds, etc., as described in the <printing layer> section above.

[0053] <medium> The printing ink used in the present invention preferably contains water as a medium, and more preferably contains an organic solvent with a boiling point of 130°C or higher, and more preferably contains an organic solvent with a boiling point of 130 to 280°C. Examples of organic solvents with a boiling point of 130°C or higher include ethylene glycol (boiling point 197°C), propylene glycol (boiling point 188°C), butylene glycol (boiling point 230°C), hexylene glycol (boiling point 250°C), dipropylene glycol (boiling point 230°C), diethylene glycol (boiling point 244°C), tripropylene glycol (boiling point 271°C), triethylene glycol (boiling point 285°C), propylene glycol monoethyl ether (boiling point 133°C), and propylene glycol monopropyl ether. Examples include ether (boiling point 150°C), propylene glycol monobutyl ether (boiling point 170°C), dipropylene glycol monomethyl ether (boiling point 190°C), dipropylene glycol monoethyl ether (boiling point 132°C), tripylene glycol monomethyl ether (boiling point 243°C), diethylene glycol monomethyl ether (boiling point 193°C), diethylene glycol monoethyl ether (boiling point 196°C), and diethylene glycol monobutyl ether (boiling point 231°C). Furthermore, the organic solvent may also include, for example, methanol (boiling point 64°C), ethanol (boiling point 78°C), 1-propanol (boiling point 97°C), 2-propanol (boiling point 82°C), 1-butanol (boiling point 117°C), 2-butanol (boiling point 99°C), isobutanol (boiling point 108°C), etc., as an organic solvent with a boiling point of less than 130°C. The total amount of media contained in the printing ink used in this invention is preferably 20 to 80% by mass, and more preferably 30 to 70% by mass, of 100% by mass of the printing ink. The water content is preferably 30 to 70% by mass, and more preferably 35 to 65% by mass, based on 100% by mass of the printing ink. The content of organic solvents with a boiling point of 130°C or higher is preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 5% by mass or less, based on 100% by mass of the printing ink. The preferred content of the above organic solvent includes 0% by mass, but is preferably 0.2% by mass or more, and more preferably 0.5% by mass or more.

[0054] <Amine compounds> The printing ink preferably contains an amine compound from the viewpoint of the laminate appearance (streaky stains). The amine compound can be the same as the basic compound for neutralizing the acrylic resin described above. The boiling point of the amine compound is preferably -40 to 180°C, and more preferably -40 to 100°C. When the boiling point of the amine compound is within the above range, the laminate appearance (streaky stains) and laminate strength tend to improve.

[0055] The method for manufacturing printing ink is not particularly limited, and the above raw materials can be manufactured by dispersing and mixing them using known dispersers such as roller mills, ball mills, pebble mills, attritors, and sand mills. If the printing ink contains air bubbles or unexpectedly large particles, it is preferable to remove them by filtration or the like, as this will degrade the quality of the printed material. Conventional known filters can be used.

[0056] <Formation of the printed layer> The printed layer can be formed by printing the above-mentioned printing ink onto a substrate, which will be described later. Suitable printing methods include known flexographic printing and gravure printing. The printed layer is obtained by applying the ink using these methods and then drying and fixing it using an oven or the like. The drying temperature is typically around 40 to 100°C. The thickness of the printed layer is preferably 0.1 to 5 μm, more preferably 0.1 to 2.5 μm. The printing speed is preferably 100 to 300 m / min, more preferably 150 to 280 m / min, and even more preferably 200 to 250 m / min.

[0057] <Flexographic printing method> Flexographic printing is more preferably used as the printing method described above. For flexographic printing, cell-engraved ceramic anilox rolls, chrome-plated anilox rolls, etc., can be used as anilox. To obtain printed materials with excellent dot reproducibility, an anilox roll with a line screen count of 5 times or more, preferably 6 times or more, the line screen count used during printing is preferred. For example, if the line screen count used is 75 lpi, an anilox with a line screen count of 375 lpi or higher is preferred. The anilox capacity is preferably 1 to 10 cc / m² from the viewpoint of printing ink drying properties and blocking properties. 2 , more preferably 2-8 cc / m 2 That is the case.

[0058] Examples of printing plates used in flexographic printing include photosensitive resin plates that utilize UV ​​curing with a UV light source, or elastomer material plates that use a direct laser engraving method. Regardless of the method of forming the image portion of the flexographic plate, a screen ruling of 75 lpi or higher is preferred. Any type of sleeve or cushioning tape can be used to attach the plate.

[0059] Flexographic printing presses include CI-type multi-color flexographic printing presses and unit-type multi-color flexographic printing presses. Ink supply methods include chamber type and two-roll type, and the appropriate printing press can be used.

[0060] <Adhesive layer> The adhesive layer in the present invention is not particularly limited as long as it can bond each layer, but it is preferably at least one selected from the group consisting of olefin resins such as polypropylene resin and polyethylene resin, acrylic resins, ethylene-vinyl acetate copolymer resins, cured products of polyol and isocyanate curing agents, imine resins, isocyanate resins, polybutadiene resins, and titanium resins, and more preferably a cured product of polyol and isocyanate curing agent. The adhesive layer may be a single layer or composed of multiple layers, and if composed of multiple layers, it is preferable that the adhesive layer (first layer) contains an imine resin and / or an isocyanate resin, and the adhesive layer (second layer) contains an olefin resin. The adhesive layer can be formed using the above resins, and the method of forming the adhesive layer is not particularly limited, but known processing methods such as solvent-free lamination, dry lamination, and extrusion lamination can be used, but solvent-free lamination is preferred. The solvent-free lamination method is a method of forming an adhesive layer using a solvent-free adhesive whose raw material is at least one selected from the group consisting of the resins described above. The glass transition temperature of the adhesive layer is preferably 60°C or lower, more preferably -10 to 60°C, and even more preferably 0 to 40°C. When the glass transition temperature of the adhesive is within the above range, the leveling properties of the adhesive layer are improved, and in addition, the adhesive layer relaxes stress appropriately, so the laminate appearance (streaky stains, ink bleeding) and laminate strength tend to improve. The glass transition temperature is measured after the glass transition of the adhesive layer has been cured. If the adhesive layer is formed by multiple layers with different glass transition temperatures, the glass transition temperature is calculated by the weighted average of the glass transition temperatures of each layer.

[0061] The resin contained in the adhesive layer used in the present invention can be synthesized by the method described in Japanese Patent Application Publication No. 2006-306931, etc. The method for controlling the glass transition temperature of the adhesive layer is not particularly limited, but for example, a resin synthesized by the above method or a commercially available product from Toyo Morton Co., Ltd., such as product names EA-N373A / B, EA-N373A / EA-N6173, EA-N6001 / EA-N5510, EA-N6802 / EA-N5802, EA-N6008 / EA-N5618, TM-320 / CAT-13B, TM-340V / CAT-29B, TM-2314 / CAT-RT37, TM-569 / CAT-RT37, TM-250HV / CAT-RT86L-60, can be used after measuring the glass transition temperature using the following method.

[0062] <Glass transition temperature of adhesive layer> After applying each adhesive solution to a release-treated release sheet and drying it, the sheet was cured (aged) by heating in a 40°C atmosphere for 24 hours or 96 hours, forming an adhesive layer with a thickness of approximately 50 μm. The adhesive layer was cut into 1.5 cm x 0.5 cm pieces and peeled off the release sheet. The glass transition temperature was measured using a dynamic viscoelasticity tester (IT Measurement Control Co., Ltd., DVA-200). The temperature range for measurement was -150 to 250°C, and the heating rate was 10°C / min. The glass transition temperature was calculated from the peak top temperature of the obtained tanδ waveform.

[0063] Preferred combinations of the components of the printing layer and the adhesive layer include a combination in which the printing layer contains an acrylic resin and compound (A), and the adhesive layer contains at least one selected from the group consisting of olefin resins, acrylic resins, ethylene-vinyl acetate copolymer resins, and cured products of polyols and isocyanate curing agents, and a combination in which the printing layer contains an acrylic resin and compound (A), and the glass transition temperature of the adhesive layer is 60°C or lower. In the case of the above combinations, (1) the adhesion between the printing layer and the adhesive layer is improved, (2) the leveling properties of the adhesive layer are improved, and (3) the dissolution of the printing layer is suppressed, so the laminate appearance (streaky stains, ink bleeding) and laminate strength tend to be further improved. It should be noted that the above effects are based on scientific considerations, and the present invention is not limited to those that exhibit these effects.

[0064] <Polyol> The polyol used in the adhesive layer can be any compound having two or more hydroxyl groups, and can be selected from known polyols. Examples of polyols include polyester polyols, polycarbonate polyols, polycaprolactone polyols, polyether polyols, and polyolefin polyols. These polyols may be used individually or in combination of two or more. The polyol preferably includes polyether polyols and / or polyester polyols from the viewpoint of laminate appearance and laminate strength.

[0065] <Polyether polyol> A polyether polyol can be any compound having two or more hydroxyl groups and two or more ether bonds in its molecule, and may be a bifunctional polyether polyol or a polyether polyol with three or more functions. Alternatively, it may be a polyether polyol obtained by reacting an isocyanate compound with the hydroxyl groups to introduce urethane bonds. These polyether polyols may be used individually or in combination of two or more.

[0066] Examples of bifunctional polyether polyols include polyalkylene glycols such as polyethylene glycol, polytrimethylene glycol, polypropylene glycol, polytetramethylene glycol, and polybutylene glycol; polyethylene glycol / polypropylene glycol block copolymers; and propylene oxide-ethylene oxide random polyethers. Alternatively, addition polymers obtained by addition polymerization of oxirane compounds such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran to a low molecular weight polyol initiator such as water, ethylene glycol, or propylene glycol may be used as polyether polyols. Examples of such addition polymers include propylene glycol-propylene oxide adducts.

[0067] Examples of polyether polyols with three or more functions include modified polyether polyols obtained by ring-opening polymerization of various cyclic ether bond-containing compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether, using low molecular weight polyols such as trimethylolethane, trimethylolpropane, glycerin, hexanetriol, pentaerythritol, sorbitol, and sucrose as initiators; and lactone-based polyester polyols obtained by polycondensation reactions of the aliphatic polyol with various lactones such as ε-caprolactone.

[0068] <Polyester Polyol> Examples of polyester polyols include polyester polyols obtained by reacting a carboxyl group component with a hydroxyl group component; and polyester polyols obtained by ring-opening polymerization of lactones such as polycaprolactone, polyvalerolactone, and poly(β-methyl-γ-valerolactone). Alternatively, some hydroxyl groups may be modified by reacting an isocyanate compound to introduce a urethane bond, or by reacting an acid anhydride to introduce a carboxyl group. Preferably, the carboxyl group component of the polyester polyol obtained by reacting a carboxyl group component with a hydroxyl group component is a polyvalent carboxylic acid having carboxyl groups at both ends, such as acyclic aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, and fumaric acid; alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, and 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid; anhydrides or ester-forming derivatives of these aliphatic or aromatic dicarboxylic acids; and polybasic acids such as p-hydroxybenzoic acid, p-(2-hydroxyethoxy)benzoic acid, ester-forming derivatives of these dihydroxycarboxylic acids, and dimer acids.

[0069] The hydroxyl group component is not particularly limited as long as it is a known component, but examples include diols and polyols with three or more functionalities, and diols are preferred. Diols are preferred because they suppress excessive crosslinking when mixed with polyisocyanates, thereby improving pot life. Examples of the diols include aliphatic diols such as ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3,3'-dimethylolheptane, and 1,4-bis(hydroxymethyl)cyclohesane; ether glycols such as polytetramethylene ether glycol and polyoxyethylene glycol; modified polyetherdiols obtained by ring-opening polymerization of the aliphatic diol with various cyclic ether bond-containing compounds such as ethylene oxide and tetrahydrofuran; lactone-based polyester polyols obtained by polycondensation reactions of the aliphatic diol with various lactones such as lactanoides and ε-caprolactone; and alkylene oxide adducts of bisphenols obtained by adding ethylene oxide or the like to bisphenols such as bisphenol A and bisphenol F. The diol is preferably an aliphatic diol, and more preferably at least one selected from the group consisting of ethylene glycol, diethylene glycol, neopentyl glycol, and 1,6-hexanediol.

[0070] Examples of the three- or more functional polyols include aliphatic polyols such as trimethylolethane, trimethylolpropane, glycerin, hexanetriol, and pentaerythritol; modified polyether polyols obtained by ring-opening polymerization of the aliphatic polyol with various cyclic ether bond-containing compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether; and lactone-based polyester polyols obtained by polycondensation reaction of the aliphatic polyol with various lactones such as ε-caprolactone. The three- or more functional polyol is preferably an aliphatic polyol, and more preferably trimethylolpropane.

[0071] The polyol may be obtained by reacting an isocyanate compound with some of the hydroxyl groups to introduce a urethane bond. Examples of the isocyanate compound include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, hexamethylene diisocyanate, and hydrogenated diphenylmethane diisocyanate.

[0072] Furthermore, the polyol may be obtained by reacting an acid anhydride with some of the hydroxyl groups to introduce carboxyl groups (hereinafter sometimes abbreviated as acid modification). Examples of the acid anhydride include pyromellitic anhydride, mellitic anhydride, trimellitic anhydride, and trimellitic anhydride esters. Examples of trimellitic anhydrides include ester compounds obtained by esterifying an alkylene glycol or alkanetriol having 2 to 30 carbon atoms with trimellitic anhydride, and specifically, ethylene glycol bisanehydrotrimellitate, propylene glycol bisanehydrotrimellitate, etc. can be used.

[0073] The weight-average molecular weight (Mw) of the polyol is preferably 500 to 80,000, and more preferably 1,000 to 50,000. When used as a solvent-free adhesive, it is preferably 500 to 10,000, and more preferably 1,000 to 8,000, from the viewpoint of improving adhesive strength, heat seal strength, and handling properties. A weight-average molecular weight of 500 or more is preferable because it improves the cohesive force of the polyurethane polyol, thereby improving adhesive strength and heat seal strength. A weight-average molecular weight of 10,000 or less is preferable because it reduces viscosity, improving appearance and handling properties.

[0074] The acid value of the polyol is not particularly limited, but is preferably 0 to 50 mg KOH / g, more preferably 0 to 40 mg KOH / g. The hydroxyl value of the polyol is not particularly limited, but is preferably 1 to 200 mg KOH / g, more preferably 10 to 150 mg KOH / g, even more preferably 20 to 120 mg KOH / g, and more preferably 50 to 120 mg KOH / g.

[0075] <Isocyanate-based curing agent> Isocyanate-based curing agents function as curing agents in reactive adhesives. By having isocyanate groups that are reactive with hydroxyl groups, they increase the adhesive strength and cohesive force of the adhesive, and also enable curing at low temperatures around room temperature.

[0076] As the isocyanate curing agent, diisocyanates or urethane prepolymers which are reaction products of diisocyanates and polyols are preferred, and as such diisocyanates, various known aromatic, aliphatic, or alicyclic diisocyanates can be used. For example, 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzylu isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylenediisocyanate, 1,4-phenylenediisocyanate, tolylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropyl diisocyanate, methylene diisocyanate, 2,2,4-tri Representative examples include methylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanate-methyl)cyclohexane, methylcyclohexane diisocyanate, m-tetramethylxylylene diisocyanate, and dimer isocyanates obtained by converting the carboxyl groups of dimer acids to isocyanate groups. They can also be used as polyisocyanate compounds with three or more functions, such as adducts, isocyanurates, and biuret compounds of trimethylolpropane. These can be used individually or in combination of two or more.

[0077] In the embodiments, the polyol and isocyanate curing agent are preferably used such that the molar equivalent ratio NCO / OH of the functional groups (hydroxyl groups derived from the polyol and isocyanate groups derived from the isocyanate resin) is 1.5 to 8.0, and more preferably 2.0 to 5.0. A molar equivalent ratio NCO / OH of 2.0 or higher is preferable because it reduces the viscosity of the derived polyisocyanate and improves appearance performance and pot life. A molar equivalent ratio NCO / OH of 5.0 or lower is preferable because it improves the cohesive force of the derived polyisocyanate and suppresses residual tack.

[0078] <Adhesive> The adhesive used in the present invention may contain the materials described in the <adhesive layer> above, and in addition, reaction catalysts, silane coupling agents, phosphoric acid or phosphoric acid derivatives, leveling agents, defoaming agents, and the following additives may be added, to the extent that they do not impair the effects of the present invention. Examples of additives include inorganic fillers such as silica, alumina, mica, talc, aluminum flakes, and glass flakes, layered inorganic compounds, stabilizers (antioxidants, heat stabilizers, UV absorbers, hydrolysis inhibitors, etc.), rust inhibitors, thickeners, plasticizers, antistatic agents, lubricants, antiblocking agents, colorants, fillers, crystal nucleating agents, and catalysts for adjusting the curing reaction. Furthermore, the medium contained in the adhesive described below may also be included.

[0079] <Media contained in adhesives> The medium contained in the adhesive can be described using the same information as the <medium> described in the <printing layer> section above. Furthermore, if the adhesive is oil-based, it is preferable to use an organic solvent.

[0080] <Formation of adhesive layer> The adhesive layer is formed by curing it for about 1 day to 1 week under conditions of 20 to 60°C, for example, after a known lamination process such as a solvent-free lamination method. The lamination method is not limited, but examples include solvent-free lamination, dry lamination, and extrusion lamination, with solvent-free lamination being preferred. The thickness of the adhesive layer is not particularly limited and can be appropriately selected depending on the application, but is preferably in the range of 1.0 to 3.0 μm for solvent-free lamination, 1.0 to 5.0 μm for dry lamination, and 10 to 50 μm for extrusion lamination. When the thickness of the adhesive layer is within the above range, physical properties such as laminate strength and heat seal strength, as well as the appearance of the laminate, are improved.

[0081] <Base material> Substrates 1 and 2 are not particularly limited and include, for example, conventionally known plastic films, paper, metal foil, etc., with plastic films being preferred. Substrates 1 and 2 may be of the same type or different types. As the plastic film, a thermoplastic resin or a thermosetting resin film can be used, and a thermoplastic resin film is preferred. Examples of thermoplastic resins include polyolefins, polyesters, polyamides, polystyrenes, vinyl chloride resins, vinyl acetate resins, ABS resins, acrylic resins, acetal resins, polycarbonate resins, and cellulose-based plastics. Substrates 1 and 2 may have a barrier layer consisting of a vapor-deposited film of one or more inorganic substances or inorganic oxides such as silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), and yttrium (Y). The vapor-deposited film can consist of two or more layers, and may be composed of the same material or different materials. Among the above, from the viewpoint of adhesion and gas barrier properties, the barrier layer is preferably composed of aluminum, aluminum oxide (alumina), or silicon oxide (silica).

[0082] The base material 1 is preferably a plastic film. Examples of plastic films commonly used in packaging materials include polyester resin films such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polylactic acid (PLA); polyolefin resin films such as polyethylene (PE) and polypropylene (PP); polystyrene resin films; polyamide resin films such as nylon 6 and poly-p-xylylene adipamide (MXD6 nylon); polycarbonate resin films; polyacrylonitrile resin films; polyimide resin films; and composites of these (e.g., nylon 6 / MXD6 / nylon 6, nylon 6 / ethylene-vinyl alcohol copolymer (EVOH) / nylon 6) or mixtures thereof. Among the above, polyolefin resin films such as polyethylene (PE) and polypropylene (PP) are preferred from the viewpoint of lamination strength.

[0083] When the base material 2 is the outermost layer of the laminate, it is preferable that the base material 2 is a sealant base material among plastic films. Examples of sealant substrates include polyethylene such as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and high-density polyethylene (HDPE), acid-modified polyethylene, polypropylene (PP), acid-modified polypropylene, copolymerized polypropylene, ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid ester copolymer, ethylene-(meth)acrylic acid copolymer, and ionomer. Furthermore, by creating bumps and dips with height differences of several micrometers on the sealant substrate, slipperiness and tearability of the packaging bag can be enhanced.

[0084] The thickness of the base material 1 can be arbitrarily selected, but from the viewpoint of moldability and transparency, it is preferably 5 μm to 50 μm, and more preferably 10 μm to 40 μm. A film thickness of 5 μm or more of the base material 1 is preferable because it increases the rigidity of the laminate and improves the strength of the laminate, suppressing delamination and wrinkles that tend to occur when the laminate and packaging bag of the present invention are subjected to impact. A thickness of 50 μm or less of the base material 1 is preferable because it increases the flexibility of the laminate, making it easier to process, for example, when filling the packaging bag with contents.

[0085] The thickness of the base material 2 can be arbitrarily selected, but from the viewpoint of strength as a packaging material, it is preferably 5 μm to 500 μm, more preferably 10 μm to 250 μm, and even more preferably 15 μm to 200 μm. A thickness of 5 μm or more of the base material 2 is preferable because it increases the heat seal strength, allowing heavier contents to be filled into the packaging bag of the present invention, thereby expanding the applications of the packaging bag. Furthermore, a thickness of 500 μm or less of the base material 2 is preferable because it leads to cost reduction and increases the flexibility of the laminate, for example, improving the processability of the contents filling as described above.

[0086] The laminate of the present invention can be manufactured, for example, by printing printing ink onto a substrate 1, drying it, applying an adhesive, stacking substrate 2 on top, and then curing the adhesive by an aging process. Multiple printing layers and substrates 2 may be provided. For example, the printing layers may have configurations such as a color printing layer / white printing layer, a color printing layer / white printing layer / white printing layer, or a color printing layer / color printing layer / white printing layer / white printing layer.

[0087] Examples of the configuration of the laminate of the present invention are given below, but are not limited to these. If the laminate comprises multiple adhesive layers, at least one of the adhesive layers may be formed from the solvent-free adhesive of the present invention. In the following, transparent deposition means a silica or alumina deposition layer. Biaxially oriented polypropylene (OPP) / Printed layer / Adhesive layer / Unoriented polypropylene (CPP) OPP / Printed layer / Adhesive layer / AL vapor-deposited CPP, OPP / Printed layer / Adhesive layer / AL vapor-deposited CPP, OPP / Printed layer / Adhesive layer / AL-deposited polyethylene terephthalate (AL-deposited PET) OPP / Printed layer / Adhesive layer / Linear low-density polyethylene (LLDPE) OPP / printing layer / adhesive layer / EVOH / LLDPE PET / printing layer / adhesive layer / CPP, PET / Printing layer / Adhesive layer / AL vapor-deposited CPP, PET / Printing layer / Adhesive layer / AL vapor-deposited PET, PET / printing layer / adhesive layer / LLDPE, PET / printing layer / adhesive layer / EVOH / LLDPE PET / Printing layer / Adhesive layer / Nylon (NY) / CPP, PET / printing layer / adhesive layer / AL / CPP, PET / printing layer / adhesive layer / NY / AL / CPP, MDOPE / printing layer / adhesive layer / LLDPE, NY / printing layer / adhesive layer / CPP, NY / Printing layer / Adhesive layer / AL vapor deposition CPP, NY / Printing layer / Adhesive layer / AL vapor-deposited PET, NY / printing layer / adhesive layer / LLDPE,

[0088] <Manufacturing of laminates> The laminate of the present invention comprises a base material 1, a printed layer, an adhesive layer, and a base material 2 in this order, and is preferably manufactured by a manufacturing method having the following steps (1) and (2). Step (1): A basic step of forming the printed layer by flexographic printing a printing ink containing an acrylic resin and at least one selected from the group consisting of acetylene compounds, alcohol alkoxylate compounds, and siloxane compounds onto a substrate 1. Step (2): A step of applying an adhesive containing a polyol and an isocyanate-based curing agent onto the printed layer to form the adhesive layer. [Examples]

[0089] The present invention will be specifically described below with reference to examples and comparative examples. In the examples and comparative examples, "parts" and "%" refer to "parts by mass" and "% by mass" respectively, unless otherwise specified.

[0090] [Methods for measuring number-average molecular weight (Mn) and weight-average molecular weight (Mw)] The number-average molecular weight and weight-average molecular weight were measured using the Showa Denko GPC (gel permeation chromatography) system "Shodex GPC System-21". GPC is a liquid chromatography method that separates and quantifies substances dissolved in a solvent based on differences in their molecular size. Tetrahydrofuran was used as the solvent, and the molecular weight was determined in terms of polystyrene equivalents.

[0091] [Method for measuring acid value (AV)] The acid value is the number of milligrams of potassium hydroxide required to neutralize the acidic components contained in 1 gram of resin, and was calculated by potentiometric titration with a potassium hydroxide-ethanol solution in accordance with JIS K2501.

[0092] <Manufacturing of water-based inks> (Preparation of water-based ink (C-1)) 18.0 parts copper phthalocyanine (LIONOL BLUE FG7400-G, manufactured by Toyo Color Co., Ltd.), 2.0 parts calcium carbonate, 48.0 parts water-soluble acrylic resin AC1 (acid value 210 mg KOH / g, Tg 70℃, molecular weight 12000, solids content 30%), 10.0 parts water, and 1.0 part 1-propanol are stirred and mixed, then kneaded in a sand mill. Then, 5.0 parts aqueous acrylic emulsion resin (AE1), 8.25 parts water, 3.0 parts propylene glycol, 0.5 parts acetylene compound (acetylene glycol compound, HLB value: 4, solids content: 100%), 2.0 parts polyethylene wax (particle size: 3 μm, penetration: <1, solids content: 40%, solvent: water), and siloxane-based defoamer (solids content: 100%) are added. 0.05 parts of [unclear], 0.2 parts of dihydrazide adipic acid (100% solids), and 2 parts of N,N-dimethylaminoethanol were stirred and mixed to prepare an aqueous ink (C-1).

[0093] (Preparation of water-based inks (C-2 to C-30, CC-1 to CC-3)) Water-based inks C-2 to C-30 and CC-1 to CC-3 were prepared using the same method as C-1, except that the raw materials and ratios shown in Tables 1-1 to 1-3 were used. The ingredients used are as follows: • Water-soluble acrylic resin AC2 (acid value 270 mg KOH / g, Tg 130℃, molecular weight 6000, solids content 30%) • Acrylic emulsion resin AE1 (acid value 20 mg KOH / g, Tg 5℃, minimum film formation temperature 5℃, solids content 45%) • Acrylic emulsion resin AE2 (acid value 60 mg KOH / g, Tg -5℃, minimum film formation temperature 0℃, solids content 45%) • Acrylic emulsion resin AE3 (acid value 60 mg KOH / g, Tg 75℃, minimum film formation temperature 55℃, solids content 45%) • Water-soluble urethane resin (acid value 35 mg KOH / g, Tg -10℃, solids content 30%) • Alcohol alkoxylate compounds (100% solids) • Siloxane compounds (100% solids) • Fluorine-based compounds (100% solids) • Hydrocarbon-based defoaming agent (100% solids) • Aliphatic derivative-based defoaming agent (100% solids content)

[0094] (Preparation of water-based ink (W-1)) 38.0 parts titanium dioxide (Titanics JR-805, manufactured by Teika Co., Ltd.), 2.0 parts calcium carbonate, 33.0 parts aqueous acrylic resin AC1, 3.25 parts water, and 1.0 part 1-propanol were stirred and mixed, then kneaded in a sand mill. After that, 15.0 parts aqueous acrylic emulsion resin (AE1), 3.25 parts water, 3.0 parts propylene glycol, 0.5 parts acetylene glycol compound (acetylene glycol compound, HLB value: 4, solids content: 100%), 2.0 parts polyethylene wax (particle size: 3 μm, penetration: <1, solids content: 40%, solvent: water), 0.05 parts silicone-based defoamer (solids content: 100%), 0.2 parts adipic acid dihydrazide, and 2 parts N,N-dimethylaminoethanol were stirred and mixed to prepare aqueous ink (W-1).

[0095] [Table 1-1]

[0096] [Table 1-2]

[0097] [Table 1-3]

[0098] (Preparation of adhesives (AD-1~AD-3)) The following raw materials were mixed and stirred to obtain adhesives AD-1 to AD-3. (AD-1) • Polyol A-1 (polyether compound, 100% solids content) • Isocyanate-based curing agent B-1 (aliphatic compound, 100% solids content) Polyol A-1 and isocyanate-based curing agent B-1 were mixed in a mass ratio of 100:50. (AD-2) • Polyol A-2 (combination of polyether-based and polyester-based compounds, 100% solids content) • Isocyanate-based curing agent B-2 (aromatic compound, 100% solids content) Polyol A-2 and isocyanate-based curing agent B-2 were mixed in a mass ratio of 80:100. (AD-3) • Polyol A-3 (polyether compound, 70% solids content) • Isocyanate-based curing agent B-3 (aromatic compound, solid content 60%) Polyol A-3 and isocyanate-based curing agent B-3 were mixed in a mass ratio of 100:50.

[0099] <Evaluation of adhesives> <Glass transition temperature of adhesive layer> After applying each adhesive solution to a release-treated release sheet and drying it, the sheet was cured (aged) by heating in a 40°C atmosphere for 24 hours or 96 hours, forming an adhesive layer with a thickness of approximately 50 μm. The adhesive layer was peeled from the release sheet, and the glass transition temperature was measured using a dynamic viscoelasticity tester. The heating rate during the measurement was 10°C / min. The glass transition temperature was calculated from the peak top temperature of the obtained tanδ waveform.

[0100] [Example 1] Laminate P-1 Water-based ink (C-1) was diluted with water to a 12-second exposure time using a Zaan cup #4. Under normal temperature conditions, a flexographic plate (photosensitive resin plate, KODAK FLEXCELNXH digital flexographic plate, 1.14 mm thick, 150 lpi) and an anilox roll (900 lpi, 3 cc / m²) were applied to the corona-treated surface of a corona-treated polypropylene substrate (Futamura Chemical Co., Ltd. "FOR", 20 μm thick, hereinafter referred to as OPP) as substrate 1. 2 Using a flexographic printing press (MIRAFLEXCM) equipped with the above, diluted aqueous ink (C-1) was printed at a printing speed of 200 m / min, with an inter-color dryer at 100°C and a tunnel dryer at 100°C to form a printed layer (first layer) with a thickness of 1 μm, and an intermediate laminate p-1 consisting of "substrate 1 / printed layer (first layer)" was obtained. Next, at room temperature, solvent-free adhesive AD-1 was applied to the printed layer (first layer) using a laminator in a solvent-free lamination method (hereinafter referred to as NS) to form an adhesive layer (first layer). Then, this adhesive layer (first layer) and the corona-treated surface of an unstretched polypropylene film (FCMN, manufactured by Futamura Chemical Co., Ltd., hereinafter referred to as CPP) with a thickness of 30 μm were bonded together to obtain a laminate with a length of 1000 m. The lamination speed was 250 m / min, and the thickness of the adhesive layer (first layer) was 2 μm. For the purpose of determining the evaluation position in the laminate appearance evaluation described below, a mark was made at the end of lamination at a lamination speed of 250 m / min. The laminated material was wound onto a paper tube and stored in a 40°C, 65% RH environment. After 48 hours, it was removed to obtain laminate P-1, which has the configuration of "substrate 1 / printed layer (first layer) / adhesive layer (first layer) / substrate 2".

[0101] [Examples 2-29, 31, 41, 42, and Comparative Examples 1-3] Laminates P-2-P-29, P-31, P-41, P-42, and PP-1-PP-3 Laminates P-2 to P-29, P-31, P-41, P-42, and PP-1 to PP-3 were obtained in the same manner as in Example 1, except that the water-based ink and adhesive were changed according to Tables 2-1 to 2-4.

[0102] [Example 30] Laminate P-30 Water-based ink (C-1) was diluted with water to a 12-second interval using a Zaan cup #4, and water-based ink (W-1) was diluted with water to a 12-second interval using a Zaan cup #4. Under normal temperature conditions, a flexographic plate (photosensitive resin plate, KODAK FLEXCELNXH digital flexographic plate, 1.14 mm thick, 150 lpi) and an anilox roll (900 lpi, 3 cc / m²) were applied to the corona-treated surface of a corona-treated polypropylene substrate (Futamura Chemical Co., Ltd. "FOR", 20 μm thick, hereinafter referred to as OPP) as substrate 1. 2Using a flexographic printing press (MIRAFLEXCM) equipped with ), diluted water-based ink (C-1) was printed under the conditions of a printing speed of 200 m / min, a color-inter-color dryer of 100°C, and a tunnel dryer of 100°C to form a printed layer (first layer) with a thickness of 1 μm. Next, under normal temperature conditions, an aqueous ink (W-1) was printed onto the printed layer (first layer) to form a printed layer (second layer) with a thickness of 1 μm. The printing press and printing conditions used were the same as those used to form the printed layer (first layer). Next, at room temperature, solvent-free adhesive AD-1 was applied to the printed layer (second layer) using a laminator in a solvent-free lamination method (hereinafter referred to as NS) to form an adhesive layer (first layer). Then, this adhesive layer (first layer) and the corona-treated surface of an unstretched polypropylene film (FCMN, manufactured by Futamura Chemical Co., Ltd., hereinafter referred to as CPP) with a thickness of 30 μm were bonded together to obtain a laminate with a length of 1000 m. The lamination speed was 250 m / min, and the thickness of the adhesive layer (first layer) was 2 μm. For the purpose of determining the evaluation position in the laminate appearance evaluation described below, a mark was made at the end of lamination at a lamination speed of 250 m / min. The laminated material was wound onto a paper tube and stored in a 40°C, 65% RH environment. After 48 hours, it was removed to obtain laminate P-30, which has the configuration of "substrate 1 / printed layer (first layer) / printed layer (second layer) / adhesive layer (first layer) / substrate 2".

[0103] [Example 32] Laminate P-32 Under normal temperature conditions, a solvent-type adhesive AD-3, whose solid content was adjusted to 30% with ethyl acetate, was applied to the printed layer (first layer) of the intermediate laminate p-1 using a dry lamination method (hereinafter DL) to form an adhesive layer (first layer). This adhesive layer (first layer) was then bonded to a 30 μm thick unstretched polypropylene film (Futamura Chemical Co., Ltd.'s "FCMN", hereinafter CPP) as the substrate 2, with the corona-treated surface in contact, to obtain a laminate with a length of 1000 m. The lamination speed was 200 m / min, and the thickness of the adhesive layer (first layer) was 2.95 μm. For the purpose of determining the evaluation position in the laminate appearance evaluation described below, a mark was made at the end of lamination at a lamination speed of 200 m / min. The laminated material was wound onto a paper tube and stored in a 40°C, 65% RH environment. After 48 hours, it was removed to obtain laminate P-32, which has the configuration of "substrate 1 / printed layer (first layer) / adhesive layer (first layer) / substrate 2".

[0104] [Example 33] Laminate P-33 Under normal temperature conditions, adhesive AD-5 (Toyo Morton Co., Ltd., EL-420, imine-based adhesive) was printed onto the printed layer (first layer) of the intermediate laminate p1 using an extrusion laminator equipped with a gravure plate with a plate depth of 15 μm at a printing speed of 150 m / min and an in-line oven at 50°C to form an adhesive layer (first layer). Subsequently, polyethylene resin (AD-4), melted at a resin temperature of 315°C, was coated onto the adhesive layer (first layer) using the same laminator in an extrusion lamination method (hereinafter referred to as EL) to form an adhesive layer (second layer). This adhesive layer (second layer) was then bonded to the corona-treated surface of an unstretched polypropylene film (Futamura Chemical Co., Ltd., "FCMN", hereinafter referred to as CPP) with a thickness of 30 μm as the substrate 2, to obtain a laminate with a length of 1000 m. The lamination speed was 250 m / min, the thickness of the adhesive layer (1st layer) was 0.5 μm, and the thickness of the adhesive layer (2nd layer) was 15 μm. The formation of the adhesive layer (1st layer) and adhesive layer (2nd layer) was performed in-line. In addition, a mark was made at the end of lamination at a lamination speed of 250 m / min to determine the evaluation position in the laminate appearance evaluation described below. The laminated material was wound onto a paper tube and stored in a 40°C, 65% RH environment. After 48 hours, it was removed to obtain laminate P-33, which has the configuration of "substrate 1 / printed layer (first layer) / adhesive layer (first layer) / adhesive layer (second layer) / substrate 2".

[0105] [Examples 34 and 35] Laminates P-34 and P-35 Laminates P-34 and P-35 were obtained in the same manner as in Example 33, except that the adhesive was changed according to Table 2. The adhesives used are as follows: AD-6:EL-530A / EL-530B (isocyanate-based adhesive) was used. • AD-7: EL-451 (butadiene-based adhesive) manufactured by Toyo Morton Co., Ltd.

[0106] [Examples 36-40] Laminates P-36-P-40 Laminates P-36 to P-40 were obtained in the same manner as in Example 1, except that base materials 1 and 2 were changed according to Table 2-4. The materials used are as follows: • PET: Corona-treated polyester (PET) substrate (Toyobo Co., Ltd. "E5102", 12 μm thickness) • NY: Corona-treated nylon substrate (Unitika Corporation's "Emblem ON-RT", 15 μm thickness) • MDOPE: Corona-treated uniaxially oriented polyethylene (MDOPE) substrate (Futamura Chemical Co., Ltd. "PE3K-H", 25 μm thickness) • LLDPE: 50μm thick polyethylene film (TUX-FCD, manufactured by Mitsui Chemicals Tohcello Co., Ltd.) • VMCPP: 25μm thick aluminum-coated unoriented polypropylene film (Toray Industries "2703")

[0107] <Evaluation of laminates> The following evaluations were performed on the obtained laminates. The results are shown in Tables 2-1 to 2-4.

[0108] <Appearance of the laminate (streaky stains)> The resulting laminate was unrolled from the paper tube and its appearance was evaluated at a point 10m from the lamination end point toward the lamination start point (evaluation range: the entire range from 10m to 11m) according to the following criteria. Note that A through C represent the range within which there are no practical problems. A: No streaky stains (very good condition) B: Streaky stains occurred, but the stained area was less than 5% of the total area (good). C: Streaky stains occurred, and the stained area was between 5% and 10% of the total area (usable). D: Streaky stains occur, and the stained area exceeds 10% of the total area (unusable).

[0109] <Appearance of laminated material (ink loss)> The resulting laminate was unrolled from the paper tube and its appearance was evaluated at a point 10m from the lamination end point toward the lamination start point (evaluation range: the entire range from 10m to 11m) according to the following criteria. Note that A through C represent the range within which there are no practical problems. A: No ink bleeding, and the overall color is uniform (very good) B: Ink loss occurred, but the area affected was less than 5% (good). C: Ink loss occurred, and the area affected was 5% or more but less than 10% (usable). D: Ink leakage occurred, and the area affected by ink leakage was 10% or more (unusable).

[0110] <Lamination Strength> The resulting laminate was cut into 15 mm wide and 300 mm long specimens to serve as test pieces. In accordance with JIS K6854, an Instron tensile testing machine was used to measure the T-type peel strength [N / 15 mm] between substrate 1 and substrate 2 at a peel rate of 300 mm / min under conditions of 20°C and 65% relative humidity. Five measurements were taken, and the average value was used for evaluation according to the following criteria. Furthermore, because the resulting laminate was printed at a high speed of 200 m / min using printing ink, the time the printed layer spends in the in-line oven is shortened, and if the film-forming ability of the printed layer is low, the laminate strength tends to decrease. Therefore, compared to creating a laminate with low-speed printing, this represents an excessive condition. Note that A through C represent the range within which there are no practical problems. A: 1.5 [N / 15mm] or better (Very good) B: 1.0 [N / 15mm] or higher, less than 1.5 [N / 15mm] (good) C: 0.5 [N / 15mm] or more, less than 1.0 [N / 15mm] (usable) D: Less than 0.5 [N / 15mm] (Not usable)

[0111] [Table 2-1]

[0112] [Table 2-2]

[0113] [Table 2-3]

[0114] [Table 2-4]

[0115] According to the evaluation results, in Comparative Example 1, the printed layer did not contain at least one selected from the group consisting of acetylene compounds, alcohol alkoxylate compounds, and siloxane compounds, but instead contained a fluorine compound, resulting in an unevenly formed adhesive layer and insufficient laminate strength. In Comparative Example 2, the printed layer did not contain at least one selected from the group consisting of acetylene compounds, alcohol alkoxylate compounds, and siloxane compounds, resulting in an unevenly formed printed layer, ink bleeding in the laminate, and a poor laminate appearance. In Comparative Example 3, the acrylic resin content in 100% by mass of the printed layer was less than 5% by mass, resulting in streaky stains on the laminate, a poor laminate appearance, and insufficient laminate strength. On the other hand, in all of the examples, streaky stains and ink bleeding in the laminate did not occur, meaning that both excellent laminate appearance and high laminate strength were achieved.

Claims

1. A laminate comprising base material 1, a printing layer, an adhesive layer, and base material 2 in this order. The printed layer comprises an acrylic resin and compound (A), The compound (A) comprises at least one selected from the group consisting of acetylene compounds, alcohol alkoxylate compounds, and siloxane compounds. A laminate in which the acrylic resin content is 5% by mass or more of the printed layer by 100% by mass.

2. The laminate according to claim 1, wherein the glass transition temperature of the adhesive layer is 60°C or lower.

3. The laminate according to claim 1 or 2, wherein the adhesive layer is a layer formed using a solvent-free adhesive.

4. The laminate according to claim 1 or 2, wherein the acid value of the acrylic resin is 3 to 250 mg KOH / g.

5. The laminate according to claim 1 or 2, wherein the glass transition temperature of the acrylic resin is 0 to 110°C.

6. The laminate according to claim 1 or 2, wherein the acrylic resin has a minimum film-forming temperature, and the minimum film-forming temperature is 50°C or less.

7. The laminate according to claim 1 or 2, wherein the printed layer further comprises a hydrazine derivative.

8. The laminate according to claim 1 or 2, wherein the printed layer further contains an antifoaming agent, and the amount of the antifoaming agent is 0.01 to 2% by mass of 100% by mass of the printed layer.

9. The laminate according to claim 1 or 2, wherein the printing layer further comprises an extender pigment, the extender pigment being at least one selected from the group consisting of barium sulfate, calcium carbonate, kaolin clay, and silica.

10. The laminate according to claim 1 or 2, wherein the base material 1 includes an olefin resin.

11. A method for manufacturing a laminate having a base material 1, a printing layer, an adhesive layer, and a base material 2 in this order. The process involves printing a printing ink containing an acrylic resin and compound (A) onto the substrate 1 to form the printed layer, The process includes the step of applying an adhesive to the printed layer to form the adhesive layer, A method for producing a laminate, wherein the compound (A) comprises at least one selected from the group consisting of acetylene compounds, alcohol alkoxylate compounds, and siloxane compounds.

12. The method for producing a laminate according to claim 11, wherein the printing ink further comprises an amine compound.

13. The method for producing a laminate according to claim 11, wherein the printing ink further contains an organic solvent with a boiling point of 130°C or higher.

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