JP2020001252A - Laminate film - Google Patents

Abstract

To provide a laminate film which is excellent in adhesion to treated polyolefin, in particular, an untreated polyolefin film, blocking resistance, chemical resistance and heat resistance, and can be advantageously applied to a soft packaging material.SOLUTION: A laminate film 1 has a base material film 2 formed of a resin composition containing a polyolefin resin, an ink layer 3 formed on one surface of the base material film, and a releasable component layer 4 laminated on the ink layer, in which the ink layer is formed of an ink composition composed of a styrenic thermoplastic elastomer (A), a resin (B), a pigment and an organic solvent, the resin (B) is one selected from the group consisting of a terpene-based resin (B1), a styrenic hard resin (B2) and an alicyclic hydrocarbon resin (B3) or a mixture of at least two kinds thereof, and the releasable component layer contains a silicone-based composition (C).SELECTED DRAWING: Figure 1

Description

  The present invention relates to a laminated film provided with an ink layer and a release component layer on the surface of a base film.

  Polyolefin films are excellent in mechanical properties such as tear strength and impact strength, waterproof / moisture proof and chemical resistance, and are extremely light, transparent, breathable and heat-sealing (heat-sealed). Due to its properties such as possessing no toxicity and printing on the surface of the film, it is used in various applications such as light packaging, food packaging, industrial materials and the like.

  In general, polyamide resin, polyurethane resin, acrylic resin, polyolefin resin, cellulose resin and the like have been used as printing inks applicable to polyolefin films. By using corona discharge treatment to improve the adhesion of the ink to the polyolefin film (Patent Document 1), various applications of the film can be developed, and the film can be used not only in soft packaging materials but also in industrial materials. Used in applications.

  However, when printing is performed on a thin film that is difficult to be subjected to corona discharge treatment or a film that cannot be subjected to corona discharge treatment for use (Patent Document 2), the adhesiveness and anti-blocking property are obtained because corona discharge is not performed. In addition, it was difficult to obtain desired performance in terms of chemical resistance (alcohol, fragrance, other chemicals), heat resistance, and the like, and it was difficult to improve the quality to a certain level or more.

  In particular, for printing a polyethylene film that is not subjected to corona discharge treatment, a polyamide resin-based ink is generally used, but in this case, it is very difficult to obtain sufficient adhesiveness of the ink on the film surface, There is a problem that the resistance required for the use of the film cannot be satisfied, and the ink easily falls off.

JP-A-2002-308321 JP 2006-231852 A

  The present invention solves the above-mentioned problems and has excellent adhesiveness to corona discharge-treated polyolefin films and especially to corona discharge-untreated polyolefin films, blocking resistance, chemical resistance (alcohol, fragrance, other chemical liquids), and excellent heat resistance. An object of the present invention is to provide a laminated film that can be advantageously applied to a soft packaging material.

  The laminated film of the present invention is a base film made of a resin composition containing a polyolefin resin, an ink layer formed on one surface of the base film, and a release property laminated on the ink layer. A laminated film having a component layer, wherein the ink layer is formed of an ink composition comprising a styrene-based thermoplastic elastomer (A), a resin (B), a pigment, and an organic solvent. ) Is one selected from the group consisting of a terpene-based resin (B1), a styrene-based hard resin (B2), and an alicyclic hydrocarbon-based resin (B3), or a mixture of at least two kinds; The release component layer contains a silicone composition (C).

  The styrene-based thermoplastic elastomer (A) includes a hydrogenated product of a styrene-ethylene-butylene-styrene block copolymer, a hydrogenated product of a styrene-isoprene-styrene block copolymer, and a styrene-ethylene-propylene-styrene block copolymer. It is one selected from the group consisting of a hydrogenated product of a polymer and a hydrogenated product of a styrene-butadiene-styrene block copolymer, or a mixture of at least two types.

  The styrene-based thermoplastic elastomer (A) is composed of one having an acid value and one having no acid value, and the acid value of the styrene-based thermoplastic elastomer (A) is in the range of 1 to 30 mgKOH / g. .

  The ink composition contains the styrene-based thermoplastic elastomer (A) and the resin (B) in a weight ratio of 9: 1 to 1: 9.

  The organic solvent contains at least one selected from the group consisting of aromatic hydrocarbon solvents and alicyclic hydrocarbon solvents.

  The ink composition contains, as the pigment, 3 to 20% by weight of an organic pigment or 3 to 50% by weight of an inorganic pigment based on the total weight of the ink composition.

  The silicone-based composition (C) includes polyether-modified silicone, polyol-modified silicone, alkyl-modified silicone, aralkyl-modified silicone, fluorine-modified silicone, amino-modified silicone, phenyl-modified silicone, acrylic resin-modified silicone, polyester resin-modified silicone, and fatty acid. Resin-modified silicone, fluoroalkyl-modified silicone, epoxy-modified silicone, carbinol-modified silicone, methacryl-modified silicone, mercapto-modified silicone, carboxyl-modified silicone, methyl hydrogen silicone, dimethyl silicone, and methylphenyl silicone One type or a mixture of at least two types.

  The laminated film of the present invention is a base film made of a resin composition containing a polyolefin resin, an ink layer formed on one surface of the base film, and a release property laminated on the ink layer. A laminated film having a component layer, wherein the ink layer is formed of an ink composition comprising a styrene-based thermoplastic elastomer (A), a resin (B), a pigment, and an organic solvent, and the resin (B) Is one selected from the group consisting of a terpene-based resin (B1), a styrene-based hard resin (B2), and an alicyclic hydrocarbon-based resin (B3), wherein the releasable component layer is a silicone-based composition By containing (C), regardless of the presence or absence of corona discharge treatment, the adhesiveness of the ink layer to a base film made of a resin composition containing a polyolefin-based resin is improved, Blocking resistance, chemical resistance, without providing the laminate layer is excellent in heat resistance, it is possible to realize a laminated film excellent environmental resistance, economical efficiency.

  The resin (B) is a mixture of at least two kinds selected from the group consisting of a terpene-based resin (B1), a styrene-based hard resin (B2), and an alicyclic hydrocarbon-based resin (B3). The laminated film of the invention can exhibit the excellent performance of each resin synergistically.

It is sectional drawing of the laminated film of this invention.

  The laminated film of the present invention will be described in detail below. As shown in the cross-sectional view of FIG. 1, the laminated film 1 of the present invention has a base film 2, an ink layer 3 formed by printing on one surface of the base film 2, and Has a release component layer 4 formed by printing on the substrate.

  The base film 2 is a film made of a resin composition containing a polyolefin resin, and a general polyolefin resin film used for a soft packaging material can be used. The thickness of the base film 2 is not particularly limited, and can be appropriately set according to the use of the laminated film 1 and the like. Since the ink composition used for the ink layer 3 has excellent adhesiveness to a polyolefin resin-based film, as the base film 2, an OPP (biaxially oriented polypropylene) film, a CPP (unoriented polypropylene) film It is preferable to use a polyolefin-based film such as a polyethylene film.

  The base film 2 may have a structure having another layer such as a barrier layer (gas / water vapor barrier property, ultraviolet barrier property, fragrance retention property, etc.). It is also possible to have a biodegradable biomass component that is decomposed into carbon dioxide and carbon dioxide, and it is possible to form films having various structures according to the use and the like.

  The ink layer 3 is formed by applying an ink composition to one surface of the base film 2 by printing or the like, and then drying an organic solvent contained in the ink composition. The printing method is not particularly limited as long as the thickness and density of the ink layer 3 can be controlled, and a letterpress, gravure, screen, gravure offset, roll coater, comma coater, dipping, or the like can be used. Further, the ink layer 3 can be formed by laminating a plurality of layers of different colors.

  The release component layer 4 is formed by applying a silicone composition on the ink layer 3 by a method such as printing and drying an organic solvent or water. The silicone-based composition does not require an organic solvent and water depending on the material to be used. Therefore, when such a material is used, the drying step can be omitted.

  The total thickness of the ink layer 3 and the release component layer 4 in the laminated film 1 of the present invention is appropriately set according to the use of the obtained laminated film 1 and the like. Is preferably in the range of 0.1 to 5.0 μm.

  The ink composition forming the ink layer 3 comprises a styrene-based thermoplastic elastomer (A), a resin (B), a pigment, and an organic solvent. The resin (B) is a terpene-based resin (B1), a styrene-based resin. One type selected from the group consisting of the hard resin (B2) and the alicyclic hydrocarbon-based resin (B3), or a mixture of two or more types is used.

  The styrene-based thermoplastic elastomer (A) preferably has a styrene content in the range of 10 to 50% by weight, and particularly preferably 15 to 45% by weight. The styrene-based thermoplastic elastomer (A) preferably has a weight average molecular weight (polystyrene conversion value by GPC (gel permeation chromatography), hereinafter referred to as Mw) of 5,000 to 700,000, particularly It is preferable to be in the range of 10,000 to 200,000.

  The styrene-based thermoplastic elastomer (A) is modified with various functional groups (hydroxyl group, epoxy group, carboxyl group, etc.), and a monomer having an α, β-monoethylenically unsaturated group (functional group-containing monomer). Monomer and / or another monomer). Examples of the monomer used for the modification include (1) a hydroxyl group-containing monomer such as hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and lactone-modified hydroxyethyl (meth). ) Acrylates, 2-hydroxy-3-phenoxypropyl (meth) acrylates and the like; (2) carboxylic acid (anhydride) group-containing monomers such as (meth) acrylic acid, (anhydride) maleic acid, (anhydride) itaconic acid , (Anhydrous) citraconic acid, ω-carboxy-polycaprolactone mono (meth) acrylate, monohydroxyethyl (meth) acrylate phthalate, etc .; (3) amide group-containing monomers such as (meth) acrylamide, methylol (meth) Acrylamide and the like; (4) an ester group-containing monomer such as (meth) Acrylates (alkyl (C1-C20 or higher)) (meth) acrylates, such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, normal-butyl (meth) acrylate, isobutyl (meth) (5) Epoxy group-containing monomers such as glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate and the like; (6) Isocyanate group-containing monomers such as vinyl isocyanate and isopropenyl isocyanate; (7) Nitrile group-containing monomers, for example, (meth) acrylonitrile and the like can be used, and one or more of these monomers can be used (in the present invention, “(meth) acrylate” refers to acrylate and / Or methacrylate, "( "Maleic anhydride" refers to maleic acid and / or maleic anhydride, with other similar expressions.) The amount of the monomer used for the modification is preferably in the range of 0.5 to 20% by weight, particularly preferably in the range of 1 to 15% by weight, based on the weight of the styrene-based thermoplastic elastomer (A). Examples of the modified styrene-based thermoplastic elastomer (A) include epoxy-modified SBS and hydrogenated SEBS modified with MA (maleic anhydride).

Specific examples of the styrene-based thermoplastic elastomer (A) include the following.
1) Epoxy (0.7% by weight) modified SBS (styrene 40% by weight) (Epofriend CT310, manufactured by Daicel Chemical Industries, Ltd.)
2) Epoxy (1.5% by weight) modified SBS (styrene 40% by weight) (Epofriend AT501, manufactured by Daicel Chemical Industries, Ltd.)
3) Hydrogenated SEBS (30% by weight of styrene) (manufactured by Asahi Kasei Chemicals Corporation, Tuftec H1031)
4) Hydrogenated SEBS (Styrene 30% by weight) (Tuftec H1141 manufactured by Asahi Kasei Chemicals Corporation)
5) MA-modified hydrogenated SEBS (styrene 30% by weight, acid value 10) (Tuftec M-1913, manufactured by Asahi Kasei Chemicals Corporation)
6) MA-modified hydrogenated SEBS (styrene 20% by weight, acid value 10) (manufactured by Asahi Kasei Chemicals Corporation, Tuftec M-1943)
7) SIS (16% by weight of styrene) (Quintac 3433N manufactured by Zeon Corporation)
8) SIS (25% by weight of styrene) (Quintac 3460, manufactured by Zeon Corporation)
9) Hydrogenated SIS (styrene 20% by weight) (manufactured by Kuraray Co., Ltd., Hibler 7125)
10) SEPS (30% by weight of styrene) (Septon 2007, manufactured by Kuraray Co., Ltd.)
11) SEPS (styrene 30% by weight) (Septon 4033, manufactured by Kuraray Co., Ltd.)
12) SEEPS (styrene 28% by weight) (Septon HG-252, manufactured by Kuraray Co., Ltd.)

  Examples of the styrene-based thermoplastic elastomer (A) include a block and a random copolymer of styrene and an olefin (especially SEBS, SEPS, SEEPS), and a block and a random copolymer of styrene and a conjugated diene (especially SIS and SBS). , Their hydrogenated products, and mixtures of two or more of these. Among these, hydrogenated products, particularly hydrogenated products of styrene-ethylene-butylene-styrene block copolymer, hydrogenated products of styrene-isoprene-styrene block copolymer, and styrene-ethylene-propylene-styrene block copolymer One or a mixture of two or more selected from the group consisting of a hydrogenated product of a coalesced product and a hydrogenated product of a styrene-butadiene-styrene block copolymer, and has heat resistance, weather resistance, and non-yellowing property. It is preferable from the viewpoint of yellowing resistance. Each of these styrene-based thermoplastic elastomers (A) may be modified as described above.

  As the styrene-based thermoplastic elastomer (A), an elastomer having an acid value (modified elastomer) and an elastomer having no acid value (unmodified elastomer) in various ratios (for example, 9: 1 to 1: 9) (Weight ratio) is preferred for improving various performances such as pigment dispersibility and heat resistance. In particular, the styrene-based thermoplastic elastomer (A) composed of one having an acid value and one having no acid value has an overall (average) acid value within the range of 1 to 30 mgKOH / g, and the pigment dispersibility It is preferable from the point of view.

  As the styrene-based thermoplastic elastomer (A), those having the properties and physical properties shown in Table 1 below are preferable. When two or more styrene-based thermoplastic elastomers (A) are used as a mixture, the average value of the properties and physical properties of the mixture is preferably in the range shown in Table 1.

  The resin (B) in the ink composition used in the present invention is selected from the group consisting of a terpene resin (B1), a styrene hard resin (B2), and an alicyclic hydrocarbon resin (B3). One kind or a mixture of two or more kinds.

  Examples of the terpene resin (B1) include terpene resins, for example, α-pinene resin (manufactured by Eastman Chemical Company, “picolite” (“picolite A-115” or the like)), β-pinene resin (manufactured by Yashara Chemical Co., Ltd.) "YS resin PX"), dipentene resin, and the like, and modified resins of the terpene resins (α-pinene resin, β-pinene resin, etc.), for example, obtained by copolymerizing these resins with aromatic monomers such as styrene. Aromatically modified terpene resins (Yshara Chemical Co., Ltd., "YS Resin TO"), and hydrogenated terpene resins obtained by hydrogenating them (Yashara Chemical Co., Ltd., "Clearon P", "Clearon M", "Clearon K") ), A phenol-modified terpene resin obtained by phenol-modification of these ("YS POLYSTAR T," manufactured by Yasuhara Chemical Co., Ltd.) , "YS Polystar S"), and includes a mixture of two or more thereof.

  The resin (B) is obtained by using the terpene-based resin (B1) in combination with the styrene-based thermoplastic elastomer (A), so that the base film 2 is a corona-discharge-untreated polyolefin film, particularly a corona-discharge-untreated polyethylene film. When the ink is used, the ink layer 3 can exhibit good adhesiveness to the base film 2.

  The styrene hard resin (B2) is a styrene hydrocarbon resin other than the styrene thermoplastic elastomer (A). The styrenic hard resin (B2) generally has a glass transition point (Tg) of 10 to 100 ° C, a softening point (JIS K2207) of 70 to 150 ° C or higher, and usually 500 or more (preferably). Is a styrenic hydrocarbon resin having a Mw of 500 to 7000, particularly preferably 700 to 5000).

  The styrene-based hard resin (B2) includes at least one (co) polymer of a styrene-based monomer, at least one (50% by weight) of a styrene-based monomer, and a hydrocarbon monomer (other aromatic monomer and / or Or an aliphatic monomer), a hydrogenated product of these (co) polymers, and a mixture of two or more thereof.

  Examples of the styrene monomer constituting the styrene hard resin (B2) include styrene and alkyl-substituted styrene, for example, α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methyl. Examples include styrene, vinyl toluene, 2,4-dimethylstyrene, p-ethylstyrene, butylstyrene, and isopropenylstyrene. Examples of the aromatic monomer constituting the styrene-based hard resin (B2) include an aromatic-containing mixture “BTX extraction residue of a C6 to C11 fraction obtained by thermal decomposition of naphtha”, which is generally referred to as a C9 fraction, and other components. Aromatic (including polycyclic aromatic) monomers (aromatic hydrocarbons having an unsaturated bond in the side chain) such as cumarone, indene, methylindene, and vinylnaphthalene. Examples of the aliphatic monomer constituting the styrene hard resin (B2) include olefins such as ethylene and propylene.

  Specific examples of the styrene-based hard resin (B2) include a styrene-based monomer homopolymer, for example, a styrene homopolymer ("Picolastic" manufactured by Eastman Chemical Company) and an α-methylstyrene homopolymer (Mitsui Chemicals) Co., Ltd., "FTR Zero", Eastman Chemical Co., Ltd., "Crystalex"), vinyl toluene homopolymer (Eastman Chemical Co., "Picotex"), and styrene-based monomer (two or more) Such as α-methylstyrene / styrene copolymer (“FTR2000” manufactured by Mitsui Chemicals, Inc.), and aromatic modified products thereof, for example, a copolymer of styrene / aromatic monomers (Mitsui Chemicals, Inc. Co., Ltd., “FMR”).

  Each of the styrene-based hard resins (B2) has an effect of improving oil resistance, heat resistance, and hardness of the ink layer 3, or an effect of improving dryness. Further, the material of the styrene-based hard resin (B2) is appropriately selected according to the use and required performance of the laminated film 1. For example, for a material requiring higher hardness, a material having a large molecular weight and a high softening point is selected. On the other hand, when the adhesiveness is required and the oil resistance is not so required, a modified resin and a styrene homopolymer which emphasize only blocking resistance and drying are used.

  As the styrene-based hard resin (B2), those having the properties and physical properties shown in Table 2 below are preferable.

  The alicyclic hydrocarbon-based resin (B3) includes a hydrogenated petroleum resin (a hydrogenated product of a petroleum resin (a naphthenic petroleum resin, an aromatic petroleum resin, etc.)). Specific examples of the hydrogenated petroleum resin include “Alcon M” and “Alcon P” manufactured by Arakawa Chemical Industries, Ltd. By using the alicyclic hydrocarbon-based resin (B3), when the corona discharge untreated polyolefin film, particularly the corona discharge untreated polyethylene film is used as the base film 2, the ink layer 3 is Good adhesion to the base film 2 can be exhibited.

  The alicyclic hydrocarbon resin (B3) preferably has the properties and physical properties shown in Table 3 below.

  In the present invention, as the resin (B), a mixture of two or more types selected from the group consisting of a terpene-based resin (B1), a styrene-based hard resin (B2), and an alicyclic hydrocarbon-based resin (B3) is used. Thereby, in the laminated film 1, the excellent performance of each of these resins (B) can be synergistically exhibited.

  In the present invention, the ratio between the styrene-based thermoplastic elastomer (A) and the resin (B) can be appropriately set according to the use of the laminated film 1 of the present invention and the required performance. The weight ratio of the styrene-based thermoplastic elastomer (A) to the resin (B) is preferably 9: 1 to 1: 9, more preferably 8: 2 to 2: 8, and particularly preferably 6: 2. : 4 to 3: 7.

  The total content of the styrene-based thermoplastic elastomer (A) and the resin (B) is 10 to 40% by weight, particularly 12 to 35% by weight, based on the total weight of the ink composition. Is preferably from 15 to 95% by weight, particularly preferably from 30 to 90% by weight, based on the weight of

  As the pigment of the ink composition, an inorganic, organic or extender pigment used in a solvent-based gravure ink can be used. As the inorganic pigment, titanium oxide, red iron oxide, molybdenum, carbon black, navy blue, ultramarine, metal powder (aluminum, brass, etc.) and the like can be used. As the organic pigment, a soluble azo pigment, an insoluble azo pigment, Azo lake pigments, condensed azo pigments, copper phthalocyanine pigments, condensed polycyclic pigments, functional pigments (fluorescent pigments, luminous pigments) and the like can be used. Further, as the extender, calcium carbonate, kaolin clay, barium sulfate, aluminum hydroxide, talc and the like can be used, and a mixture of two or more of these can be used. The content of the pigment can be appropriately changed. However, in the case of an inorganic pigment, it is preferably 1 to 50% by weight, particularly preferably 5 to 40% by weight, based on the total weight of the ink composition. In this case, the content is preferably 1 to 20% by weight, particularly preferably 3 to 15% by weight.

  The silicone composition (C) used for the release component layer has various properties such as oil, resin, liquid rubber, and rubber, but is suitable for printing and coating methods to form the release component layer. Must be selected and adjusted. In particular, the silicone composition (C) is preferably an oil or resinous material in terms of mixability and coatability, and includes polyether-modified silicone, polyol-modified silicone, alkyl-modified silicone, and aralkyl. Modified silicone, fluorine-modified silicone, amino-modified silicone, phenyl-modified silicone, acrylic resin-modified silicone, polyester resin-modified silicone, fatty acid resin-modified silicone, fluoroalkyl-modified silicone, epoxy-modified silicone, carbinol-modified silicone, methacryl-modified silicone, mercapto-modified silicone Silicone, carboxyl-modified silicone, methyl hydrogen silicone, dimethyl silicone, methyl phenyl silicone and the like can be used. Silicone composition as (C), 1 species of these silicone, or the use of two or more thereof are possible and can thereby adjust the release performance. As the silicone composition (C), there are a solvent type which can be mixed with an organic solvent and a water soluble type which can be used by mixing with water.

  The content of the silicone component in the silicone composition (C) can be appropriately changed, but is preferably 1 to 60% by weight, particularly preferably 3 to 30% by weight based on the total weight of the silicone composition (C). In particular, the content is preferably 5 to 15% by weight.

Specific examples of the silicone composition (C) include the following.
1) Polyether-modified silicone (KP-109, manufactured by Shin-Etsu Chemical Co., Ltd.)
2) Acrylic resin-modified silicone (Cymac US-270, manufactured by Toa Gosei Co., Ltd.)
3) Silicone resin (WACKER TPR, manufactured by Asahi Kasei Wacker Silicone Corp.)
4) Fluorine-modified silicone (KP-625, manufactured by Shin-Etsu Chemical Co., Ltd.)
5) Dimethyl silicone (KP-310, manufactured by Shin-Etsu Chemical Co., Ltd.)

  Examples of the organic solvent used in the ink composition and the silicone composition (C) include aromatic hydrocarbons such as toluene, xylene, and ethylbenzene, and alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, and ethylcyclohexane. , Aliphatic hydrocarbons such as hexane and heptane, esters such as ethyl acetate, normal propyl acetate, isopropyl acetate, normal butyl acetate and isobutyl acetate, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, propylene glycol Glycol derivatives such as monomethyl ether and propylene glycol monomethyl ether acetate; alcohols such as methanol, ethanol, normal propanol, isopropanol, normal butanol and isobutanol S, and it is possible to use a mixture of two or more thereof.

  Among these organic solvents, aromatic hydrocarbon solvents, alicyclic hydrocarbon solvents, and the like are preferable in that they are good solvents as materials for the ink composition. The content of the organic solvent in the ink composition is preferably such that the concentration of nonvolatile components in the ink composition is 5 to 60% by weight, particularly 15 to 50% by weight. The solvent of the silicone composition is not particularly limited, but it is necessary to select a solvent according to the silicone component to be used in consideration of solubility, compatibility and the like. For example, it is preferable to use the non-volatile content in the silicone composition in the range of 0.5 to 20% by weight, particularly 1 to 15% by weight.

  The ink composition and the silicone composition (C) may contain, if necessary, one or more kinds of other resins, oligomers, fats and oils, various stabilizers, and other additives. Can be contained.

  Other resins that can be used in the ink composition and the silicone composition (C) include acrylic resins, polystyrene resins, polyurethane resins, polyvinyl chloride-vinyl acetate copolymer resins, and polyvinyl chloride. Resin, polyethylene-vinyl alcohol resin, polyamide resin, polyester resin, cellulose resin, polyolefin resin, polyvinyl butyral resin, polycarbonate resin, epoxy resin, rosin S resin, melamine resin, phenol Resins, ketone resins, and mixed resins of two or more of these resins.

As the oligomer used in the ink composition, a liquid atactic butadiene oligomer (1,2-PB) obtained by polymerizing butadiene, a hydrogenated product thereof, a modified product thereof (acid or acid anhydride ( Such as maleic anhydride) or modified with glycol (ethylene glycol) to introduce a reactive group or a hydrophilic group such as a carboxyl group or a hydroxyl group). These oligomers can be used as a tackifier or for adjusting properties such as water resistance, chemical resistance, electrical properties, heat resistance, etc., and impart these properties to the thermoplastic elastomer (A). Used for purposes.
1) 1,2-PB (Nisso-PB B-1000, manufactured by Nippon Soda Co., Ltd.)
2) Glycol modified (NISSO-PB G-1000, manufactured by Nippon Soda Co., Ltd.)
3) Hydrogenation denaturation (NISSO-PB BI-2000, manufactured by Nippon Soda Co., Ltd.)
4) Maleic anhydride modification (acid value 29) (Ricon131MA5, manufactured by Clay Valley)
5) Epoxy modification (Ricon 657, manufactured by Clay Valley)

  The stabilizer includes an antioxidant (such as a hindered phenol), a weathering stabilizer, a heat resistance inhibitor, a rubber aging inhibitor, a preservative, a fungicide, an antibacterial agent, and the like. Are other colorants (dyes such as azo dyes and anthraquinone dyes), defoamers, thickeners, dispersants, surfactants, catalysts, fillers, waxes, antiblocking agents, plasticizers, leveling agents, Crosslinking agents, antisettling agents and the like are included.

  Although the content of the stabilizer can be appropriately changed, the content of the stabilizer is 5% by weight or less, particularly 0.1 to 2% by weight, based on the total weight of the ink composition and the silicone composition (C). The other additives are preferably 15% by weight or less, particularly preferably 0.1 to 10% by weight.

  The ink composition is prepared by dispersing and dissolving the styrene-based thermoplastic elastomer (A), the resin (B), the pigment, and if necessary, other components in the organic solvent. For the dispersion, a known dispersing / mixing device can be used, and for example, a ball mill, a sand mill, a bead mill, a three-roll, a paint shaker, a kneader, a two-roll, a high-speed dissolver, or the like can be used.

  In the laminated film 1 of the present invention, the adhesiveness of the ink layer 3 to the base film 2 is improved by providing the release component layer 4 on the ink layer 3 without performing corona discharge treatment. In addition, it is possible to realize a film having excellent blocking resistance, chemical resistance, and heat resistance, which can be used in various applications, and since there is no need to provide a laminate layer, environmental friendliness and economy can be achieved. A film with excellent properties can be realized.

  In addition, since the ink composition of the ink layer 3 has high compatibility with the base film 2, the laminated film 1 of the present invention can realize a film having excellent recyclability.

  Hereinafter, the laminated film 1 of the present invention will be described using examples, but the laminated film 1 of the present invention is not limited to the following examples.

  First, the styrene thermoplastic elastomer (A), resin (B), pigment, wax, and additives of the ink composition used in the examples will be described.

The styrene thermoplastic elastomer (A) is as follows.
Elastomer [1]: Acid-modified hydrogenated styrene-based (SEBS type) thermoplastic elastomer (Toughtec M1943, manufactured by Asahi Kasei Chemicals Corporation)
Elastomer [2]: Hydrogenated styrene-based (SIS type) thermoplastic elastomer (HIBRA 7125, manufactured by Kuraray Co., Ltd.)
Elastomer [3]: Epoxy-modified styrene-based (SBS type) thermoplastic elastomer (Epofriend CT310, manufactured by Daicel Chemical Industries, Ltd.)
Elastomer [4]: hydrogenated styrene (SEPS type) thermoplastic elastomer (Septon 2007, manufactured by Kuraray Co., Ltd.)
Elastomer [5]: Hydroxy-modified styrene (SEEPS type) thermoplastic elastomer (Septon HG-252, manufactured by Kuraray Co., Ltd.)

The resin (B) is as follows.
Resin [1]: Alicyclic saturated hydrocarbon resin (Arukawa Chemical Industries, Ltd., Archon M-135)
Resin [2]: α-methylstyrene resin (FTR-0120, manufactured by Mitsui Chemicals, Inc.)
Resin [3]: Terpene resin (Picolite A-115, manufactured by Eastman Chemical Company)
Resin [4]: alicyclic saturated hydrocarbon resin (Arukawa Chemical Industries, Ltd., Alcon P-140)

The pigment is as follows.
Pigment [1]: Titanium oxide (manufactured by Teica Co., Ltd., titanium oxide JR-603)
Pigment [2]: Copper phthalocyanine blue (Cyanine Blue 4976EP, manufactured by Dainichi Seika Co., Ltd.)

The wax is as follows.
Wax [1]: Polymerized fatty acid amide-based wax (Amide Polymer EX-1 manufactured by Tenka Polymer Co., Ltd.)
Wax [2]: polytetrafluoroethylene / polyethylene wax (Lanco wax TF1778, manufactured by Japan Lubrizol Co., Ltd.)
Wax [3]: polyethylene wax (manufactured by South Africa Sazol Company, Sazol wax SPN-3)
Wax [4]: erucic acid amide wax (manufactured by Kao Corporation, fatty acid amide E)

The plasticizers and additives are as follows.
Plasticizer [1]: N-butylbenzenesulfonamide (BM-4, manufactured by Daihachi Chemical Industry Co., Ltd.)
Additive [1]: diisopropoxytitanium bis (acetylacetonate) (T-50, manufactured by Nippon Soda Co., Ltd.)

The silicone components, synthetic resins and additives of the silicone composition (C) used in the examples are as follows.
Silicone [1]: Polyether-modified silicone (KP-109, manufactured by Shin-Etsu Chemical Co., Ltd.)
Silicone [2]: Acrylic resin-modified silicone (Cymac US-270 manufactured by Toa Gosei Co., Ltd.)
Silicone [3]: Silicone resin (WACKER TPR, manufactured by Asahi Kasei Wacker Silicone Corp.)
Wax [2]: polytetrafluoroethylene / polyethylene wax (Lanco wax TF1778, manufactured by Japan Lubrizol Co., Ltd.)
Resin [5]: vinyl chloride-vinyl acetate copolymer resin (Solvine C, manufactured by Nissin Chemical Industry Co., Ltd.)

  Next, the ink composition (ink white I / II, ink blue I / II) and the silicone composition (varnish I / II) used in the examples will be described.

・ Ink White I
(1) Preparation of Pigment Dispersion Resin Solution [I] In a container equipped with a stirrer, 3.5 parts by weight of elastomer [1], 1 part by weight of elastomer [2], 1.5 parts by weight of elastomer [3], resin [1] 2 parts by weight, 3 parts by weight of resin [2], 6 parts by weight of resin [3], 29.5 parts by weight of methylcyclohexane, 10 parts by weight of ethylcyclohexane, and 7 parts by weight of normal propyl acetate are mixed and dissolved to disperse pigment. 63.5 parts by weight of a resin solution [I] was obtained.
(2) Preparation of Pigment Dispersion White [I] A mixture of 63.5 parts by weight of the pigment dispersing resin solution [I] and 23 parts by weight of the pigment [1] was dispersed in a sand mill, and the pigment dispersion white [I] was dispersed. ] 86.5 parts by weight.
(3) Preparation of Ink White for Polyolefin [I] 86.5 parts by weight of Pigment Dispersion Liquid White [I], 3 parts by weight of wax [1], 1.5 parts by weight of wax [2], plasticizer [1] 1 Then, 6.5 parts by weight of isopropyl alcohol and 6.5 parts by weight of isopropyl alcohol were added, and after mixing and dissolution, 1.5 parts by weight of the additive [1] were mixed to obtain 100 parts by weight of an ink white for polyolefin [I].

・ Ink Indigo I
(1) Preparation of Pigment Dispersion Liquid Indigo [I] To 63.5 parts by weight of the pigment dispersion resin solution [I] prepared with Ink White I, 7 parts by weight of pigment [2], 13 parts by weight of methylcyclohexane, normal propyl acetate A mixture of 3 parts by weight was dispersed by a sand mill to obtain 86.5 parts by weight of a pigment dispersion liquid [I].
(2) Preparation of Ink Indigo [I] for Polyolefin To 86.5 parts by weight of pigment dispersion indigo [I], 3 parts by weight of wax [1], 1.5 parts by weight of wax [2], plasticizer [1] 1 After mixing and dissolving, 2 parts by weight of the additive [1] was mixed to obtain 100 parts by weight of a polyolefin ink indigo [I].

・ Ink White II
(1) Preparation of Pigment Dispersion Resin Solution [II] In a vessel equipped with a stirrer, 3.5 parts by weight of elastomer [1], 1.5 parts by weight of elastomer [4], 1 part by weight of elastomer [5], resin [4] ] 5.5 parts by weight, 4 parts by weight of resin [2], 4 parts by weight of resin [3], 37 parts by weight of toluene, and 7 parts by weight of normal propyl acetate are mixed and dissolved, and a resin solution for pigment dispersion [II] 63. 5 parts by weight were obtained.
(2) Preparation of Pigment Dispersion Liquid White [II] A mixture of 63.5 parts by weight of the pigment dispersing resin solution [II] and 23 parts by weight of the pigment [1] was dispersed by a sand mill, and the pigment dispersion white [II] was dispersed. II] 86.5 parts by weight.
(3) Preparation of Ink White for Polyolefin [II] To 86.5 parts by weight of Pigment Dispersion Liquid White [II], 3 parts by weight of wax [1], 1.5 parts by weight of wax [2], and plasticizer [1] 1 Then, 6.5 parts by weight of isopropyl alcohol and 6.5 parts by weight of isopropyl alcohol were added, and after mixing and dissolution, 1.5 parts by weight of the additive [1] were mixed to obtain 100 parts by weight of an ink white for polyolefin [II].

・ Ink Indigo II
(1) Preparation of Pigment Dispersion Liquid Indigo [II] To 63.5 parts by weight of the pigment dispersion resin solution [II] prepared with Ink White II, 7 parts by weight of pigment [2], 13 parts by weight of toluene, and normal propyl acetate 3 The resulting mixture was dispersed in a sand mill to obtain 86.5 parts by weight of a pigment dispersion liquid [II].
(2) Preparation of Ink Indigo [II] for Polyolefin In 86.5 parts by weight of pigment dispersion indigo [II], 3 parts by weight of wax [1], 1.5 parts by weight of wax [2], plasticizer [1] 1 After mixing and dissolving, 2 parts by weight of the additive [1] was mixed to obtain 100 parts by weight of a polyolefin ink indigo [II].

Preparation of Silicone Varnish [I] In a container equipped with a stirrer, 10.5 parts by weight of silicone [1], 0.5 parts by weight of wax [2], 19 parts by weight of water, and 30 parts by weight of propylene glycol monomethyl ether And 40 parts by weight of isopropyl alcohol, were mixed and dissolved to obtain 100 parts by weight of a silicone varnish [I].

Preparation of Silicone Varnish [II] In a container equipped with a stirrer, 20 parts by weight of silicone [2], 5 parts by weight of silicone [3], 1 part by weight of wax [2], and 5 parts by weight of resin [5]. Parts by weight of methyl ethyl ketone and 20 parts by weight of toluene were mixed and dissolved to obtain 100 parts by weight of a silicone varnish [II].

  The ink compositions used in the comparative examples are as follows. As a comparative example ink, a polyamide-cellulosic resin type ink "POC 620 primary color indigo" is used for untreated polyolefin film, manufactured by Osaka Printing Ink Manufacturing Co., Ltd. A polyamide-cellulosic resin-type ink “POC 665 White”, which was used by Ink Manufacturing Co., Ltd. for untreated polyolefin film, was used. A chlorinated polyolefin type ink “PEL-SNW CM-90 indigo” manufactured by Osaka Printing Ink Mfg. Co., Ltd. for untreated polyolefin film was used as Ink Indigo II for Comparative Example. A chlorinated polyolefin type ink "PEL-SNW Holder White" was used for untreated and treated polyolefin film manufactured by Printing Ink Manufacturing Co., Ltd.

  The laminated films of Examples 1 to 24 were prepared using the ink and the varnish as described above, and the laminated films of Comparative Examples 1 to 24 were prepared using the ink composition for the comparative example, and tested. Hereinafter, the laminated films of Examples 1 to 24 and the laminated films of Comparative Examples 1 to 24 will be described.

  Ink Indigo I was diluted with a mixed solvent of MCH / ECH / ethyl acetate / isopropyl alcohol = 40/35/20/5, and the printing viscosity was measured using Zancup # 3 manufactured by Rigo Co., Ltd. It was adjusted to 17 seconds under the condition of 25 ° C. Using the gravure calibrator (a direct gravure plate of 175 lines / inch, using a depth of 30 μm), the ink indigo I whose viscosity has been adjusted in this way is used for corona discharge treated OPP (biaxially oriented polypropylene) film for packaging ( Gravure printing is performed on a film base material having a thickness of 38 μm) to form an ink layer which is a monochromatic blue print, and a silicone varnish I is gravure-corrected on the ink layer without adjusting the viscosity. A releasable component layer was formed by gravure printing using a machine, and a laminated film of Example 1 was prepared.

  Ink Indigo II was diluted with a mixed solvent of MCH / ECH / ethyl acetate / isopropyl alcohol = 40/35/20/5, and the printing viscosity was measured using an ink temperature of Zancup # 3 manufactured by Rigo Co., Ltd. It was adjusted to 17 seconds under the condition of 25 ° C. Using the gravure calibrator (a direct gravure plate of 175 lines / inch, using a depth of 30 μm), the ink indigo II whose viscosity was adjusted in this manner was applied onto a corona discharge treated OPP film (thickness: 38 μm) on a film substrate. Gravure printing to form an ink layer, which is a monochromatic monochromatic print, and a silicone-based varnish II is gravure-printed on the ink layer with a gravure proofing machine without adjusting the viscosity, and the releasable component is formed. The layers were formed, and the laminated film of Example 2 was prepared.

-Comparative example 1
The comparative Ink Indigo I was diluted with a mixed solvent of toluene / isopropyl alcohol / ethyl acetate = 50/35/15, and the printing viscosity was adjusted using a Zaan Cup # 3 manufactured by Rigo Co., Ltd. to an ink temperature of 25. The temperature was adjusted to 17 seconds under the condition of ° C. Using a gravure calibrator (a 175 line / inch direct gravure plate, using a depth of 30 μm), the film base which is a corona discharge treated OPP film (thickness: 38 μm) was used for the comparative example ink indigo I thus adjusted in viscosity. Gravure printing was performed on the material to form an ink layer that was a monochromatic blue print, and a laminated film of Comparative Example 1 was produced.

-Comparative example 2
Comparative Ink Indigo II was diluted with a mixed solvent of methyl ethyl ketone / toluene / isopropyl alcohol = 40/55/5, and the printing viscosity was adjusted to 25 ° C. using a Zaan cup # 3 manufactured by Rigo Co., Ltd. Was adjusted to 17 seconds under the above conditions. A film substrate which is a corona discharge-treated OPP film (thickness: 38 μm) using the gravure calibrator (a direct gravure plate of 175 lines / inch, using a depth of 30 μm) of the ink blue for comparative example II whose viscosity has been adjusted in this way. Gravure printing was performed thereon to form an ink layer, which was a monochromatic blue print, and a laminated film of Comparative Example 2 was produced.

-Comparative Example 1 '
The laminated film of Comparative Example 1 'was obtained by removing the release component layer of Varnish I from the laminated film of Example 1. For this purpose, as in Example 1, the ink indigo I was diluted with a mixed solvent of MCH / ECH / ethyl acetate / isopropyl alcohol = 40/35/20/5, and the printing viscosity was adjusted by Zaansha, Zahn. Using cup # 3, the ink temperature was adjusted to 17 seconds at 25 ° C. Using the gravure calibrator (a direct gravure plate of 175 lines / inch, using a depth of 30 μm), the ink indigo I whose viscosity has been adjusted in this way is used for corona discharge treated OPP (biaxially oriented polypropylene) film for packaging ( Gravure printing was performed on a film substrate having a thickness of 38 μm) to form an ink layer that was a monochromatic blue print, thereby producing a laminated film of Comparative Example 1 ′.

  Ink Indigo I was diluted with a mixed solvent of MCH / ECH / ethyl acetate / isopropyl alcohol = 40/35/20/5, and the printing viscosity was measured using Zancup # 3 manufactured by Rigo Co., Ltd. It was adjusted to 17 seconds under the condition of 25 ° C. Using a gravure calibrator (a 175 line / inch direct gravure plate, using a depth of 30 μm), the ink indigo I whose viscosity was adjusted in this manner was subjected to corona discharge treated LDPE (low density polyethylene) film (thickness) for packaging. Gravure printing on a film substrate having a thickness of 40 μm) to form an ink layer that is a monochromatic blue print, and a silicone varnish I on the ink layer without adjusting the viscosity. To form a release component layer, and a laminated film of Example 3 was prepared.

  Ink Indigo II was diluted with a mixed solvent of MCH / ECH / ethyl acetate / isopropyl alcohol = 40/35/20/5, and the printing viscosity was measured using an ink temperature of Zancup # 3 manufactured by Rigo Co., Ltd. It was adjusted to 17 seconds under the condition of 25 ° C. Using a gravure calibrator (a 175 line / inch direct gravure plate, using a depth of 30 μm), the ink indigo II whose viscosity has been adjusted in this manner was used to prepare a corona discharge-treated LDPE film (thickness: 40 μm). A gravure printing is performed thereon to form an ink layer, which is a blue monochromatic printed matter, and a silicone varnish II is gravure printed on the ink layer with a gravure proofing machine without adjusting the viscosity, and the mold is released. An ionic component layer was formed, and a laminated film of Example 4 was produced.

-Comparative example 3
The comparative Ink Indigo I was diluted with a mixed solvent of toluene / isopropyl alcohol / ethyl acetate = 50/35/15, and the printing viscosity was adjusted using a Zaan Cup # 3 manufactured by Rigo Co., Ltd. to an ink temperature of 25. The temperature was adjusted to 17 seconds under the condition of ° C. Using the gravure calibrator (a 175 line / inch direct gravure plate, using a depth of 30 μm), the ink indigo I for comparative example whose viscosity was adjusted in this manner was used as a film base which was a corona discharge treated LDPE film (thickness: 40 μm). Gravure printing was performed on the material to form an ink layer that was a monochromatic blue print, and a laminated film of Comparative Example 3 was produced.

-Comparative example 4
Comparative Ink Indigo II was diluted with a mixed solvent of methyl ethyl ketone / toluene / isopropyl alcohol = 40/55/5, and the printing viscosity was adjusted to 25 ° C. using a Zaan cup # 3 manufactured by Rigo Co., Ltd. Was adjusted to 17 seconds under the above conditions. Using the gravure calibrator (a 175 line / inch direct gravure plate, using a depth of 30 μm), a film base that is a corona discharge-treated LDPE film (thickness: 40 μm) was used for the comparative example Ink Blue II whose viscosity was adjusted in this manner. Gravure printing was performed on the material to form an ink layer that was a monochromatic blue print, and a laminated film of Comparative Example 4 was produced.

-Comparative Example 3 '
The laminated film of Comparative Example 3 'was obtained by removing the release component layer of Varnish I from the laminated film of Example 3. For this purpose, in the same manner as in Example 3, the ink indigo I was diluted with a mixed solvent of MCH / ECH / ethyl acetate / isopropyl alcohol = 40/35/20/5, and the printing viscosity was adjusted by Zango Co., Ltd., Zahn. Using cup # 3, the ink temperature was adjusted to 17 seconds at 25 ° C. Using a gravure calibrator (a 175 line / inch direct gravure plate, using a depth of 30 μm), the ink indigo I whose viscosity was adjusted in this manner was subjected to corona discharge treated LDPE (low density polyethylene) film (thickness) for packaging. (40 μm) was gravure-printed on a film substrate to form an ink layer, which was a monochromatic blue print, to produce a laminated film of Comparative Example 3 ′.

The following tests were performed on the laminated films of Examples 1 to 4 and Comparative Examples 1 to 4, 1 ', and 3', and the results were indicated by a 5-level relative evaluation of 1 to 5 (5 is the best). The results are shown in Tables 4 and 5.
Tape adhesion: Peel off the same portion five times with cellophane tape (Nichiban Co., Ltd.), and observe the state of the ink film falling off. Depending on the degree, 5 was determined if no drop was found, 2 to 4 if partially dropped, and 1 if dropped entirely. (The same applies to the following.)
Rubbing resistance: The printed matter left for 24 hours in an environment of 25 ° C. and 0 ° C. is rubbed by hand massage 10 times, and the falling off of the ink film is observed.
Abrasion resistance: Using a Gakushin type abrasion resistance tester, the printed matter was rubbed 100 times with a load of 2N against No. 3, and the state of the ink film falling off was observed.
Blocking resistance: The printed surface and the back surface are overlapped, and the printed surface and the back surface are left standing at 50 ° C. for 24 hours under a load of 500 g / cm ² , after which the printed surface and the back surface are peeled off, and the state of the ink film falling off is observed.
Alcohol resistance: The ink film is rubbed five times with a cotton cloth immersed in a 70% by weight ethanol solution (weight ratio, water: ethanol = 30: 70), and the state of the ink film falling off is observed.
Fragrance resistance: Fine paper immersed in a fragrance (deodorant: import sales agency: Konan Shoji Co., Ltd.-LIFELEX, deodorant liquid type in the room) is superimposed on the ink film, and a load of 25 g / cm ² is applied from above. , And left at 60 ° C. for 1 hour. Thereafter, the printed surface and the back surface are peeled off, and the state of the ink film falling off is observed.
Heat resistance: A Teflon (registered trademark) sheet is superimposed on the printed surface, and a heat sealer is used to perform a heat resistance test on the printed surface under the following conditions to observe the adhesion state of the ink film to the Teflon (registered trademark) sheet. Test conditions: 0.3 MPa, 1 second, testing at 100 ° C., 120 ° C., 140 ° C., 160 ° C.

  A corona discharge untreated CPP (unstretched polypropylene) film (thickness: 30 μm) for packaging was used in place of the treated OPP (biaxially stretched polypropylene) film of the laminated film of Example 1, and all others were the same as in Example 1. Under the conditions, a laminated film of Example 5 was produced.

  A corona discharge untreated CPP (unstretched polypropylene) film (thickness: 30 μm) for packaging was used in place of the treated OPP (biaxially stretched polypropylene) film of the laminated film of Example 2, and all others were the same as in Example 2. Under the conditions, a laminated film of Example 6 was produced.

-Comparative example 5
Instead of the treated OPP (biaxially oriented polypropylene) film of the laminated film of Comparative Example 1, a corona discharge untreated CPP (unstretched polypropylene) film (thickness of 30 μm) for packaging was used, and all others were the same as Comparative Example 1. Under the conditions, a laminated film of Comparative Example 5 was produced.

Comparative Example 6
Instead of the treated OPP (biaxially oriented polypropylene) film of the laminated film of Comparative Example 2, a corona discharge untreated CPP (non-oriented polypropylene) film (thickness of 30 μm) for packaging was used, and all others were the same as Comparative Example 2. Under the conditions, a laminated film of Comparative Example 6 was produced.

-Comparative Example 5 '
Instead of the treated OPP (biaxially oriented polypropylene) film of the laminated film of Comparative Example 1 ', a corona discharge untreated CPP (unoriented polypropylene) film (thickness: 30 µm) for packaging was used, and all others were Comparative Example 1' Under the same conditions as described above, a laminated film of Comparative Example 5 ′ was prepared. The laminated film of Comparative Example 5 ′ thus prepared corresponds to a structure in which the release component layer made of the varnish I was removed from the laminated film of Example 5.

  Instead of the treated LDPE (low-density polyethylene) film (thickness 40 μm) of the laminated film of Example 3, a corona discharge-untreated LDPE (low-density polyethylene) film (thickness 40 μm) for packaging was used, and all other examples were used. Under the same conditions as in Example 3, a laminated film of Example 7 was produced.

  Instead of the treated LDPE (low-density polyethylene) film (thickness 40 μm) of the laminated film of Example 4, a corona discharge-untreated LDPE (low-density polyethylene) film (thickness 40 μm) for packaging was used. Under the same conditions as in Example 4, a laminated film of Example 8 was produced.

-Comparative example 7
Instead of the treated LDPE (low-density polyethylene) film (thickness 40 μm) of the laminated film of Comparative Example 3, an untreated LDPE (low-density polyethylene) film for packaging (thickness 40 μm) was used, and all others were comparative examples. Under the same conditions as in Example 3, a laminated film of Comparative Example 7 was produced.

Comparative Example 8
Instead of the treated LDPE (low-density polyethylene) film (thickness 40 μm) of the laminated film of Comparative Example 4, an untreated LDPE (low-density polyethylene) film (thickness 40 μm) for packaging was used, and all others were comparative examples. Under the same conditions as in Example 4, a laminated film of Comparative Example 8 was produced.

-Comparative Example 7 '
Instead of the corona discharge treated LDPE (low density polyethylene) film of the laminated film of Comparative Example 3 ′, a corona discharge untreated LDPE (low density polyethylene) film (40 μm thick) for packaging was used, and all others were Comparative Example 3. Under the same conditions as in ', a laminated film of Comparative Example 7' was prepared. The laminated film of Comparative Example 7 ′ thus prepared corresponds to a structure in which the release component layer made of the varnish I was removed from the laminated film of Example 7.

  With respect to the laminated films of Examples 5 to 8 and Comparative Examples 5 to 8, 5 ', and 7', the same tests as those of Examples 1 to 4 and Comparative Examples 1 to 4 were performed. The results are indicated by evaluation (5 is the best) and are shown in Tables 6 and 7.

  Ink White I was diluted with a mixed solvent of MCH / ECH / ethyl acetate / isopropyl alcohol = 40/35/20/5, and the printing viscosity was measured using a Zaan Cup # 3 manufactured by Rigo Co., Ltd. It was adjusted to 17 seconds under the condition of 25 ° C. Using a gravure calibrator (a 175 line / inch direct gravure plate, using a depth of 30 μm), the ink white I thus adjusted in viscosity was treated with an OPP (biaxially oriented polypropylene) film for packaging (38 μm thick). ) Is gravure-printed on a film substrate to form an ink layer which is a white monochrome print, and a silicone-based varnish I is gravure printed on the ink layer with a gravure calibrator without adjusting the viscosity. Printing was performed to form a release component layer, and a laminated film of Example 9 was produced.

  Ink White II was diluted with a mixed solvent of MCH / ECH / ethyl acetate / isopropyl alcohol = 40/35/20/5, and the printing viscosity was measured using Zancup # 3 manufactured by Rigo Co., Ltd. It was adjusted to 17 seconds under the condition of 25 ° C. The ink white II thus adjusted in viscosity is gravure on a film substrate which is a processed OPP film (thickness: 38 μm) using a gravure calibrator (a direct gravure plate of 175 lines / inch, using a depth of 30 μm). Printing is performed to form an ink layer that is a white monochrome print, and a silicone-based varnish II is gravure-printed on the ink layer with a gravure proofing machine without adjusting the viscosity to form a release component layer. Then, a laminated film of Example 10 was produced.

Comparative Example 9
Comparative Ink White I was diluted with a mixed solvent of toluene / isopropyl alcohol / ethyl acetate = 50/35/15, and the printing viscosity was adjusted using a Zaan Cup # 3 manufactured by Rigo Co., Ltd. to an ink temperature of 25. The temperature was adjusted to 17 seconds under the condition of ° C. Using the gravure calibrator (a 175 line / inch direct gravure plate, using a depth of 30 μm), the ink white I for comparative example whose viscosity was adjusted as described above was used to prepare a film substrate as a processed OPP film (thickness: 38 μm). Gravure printing was performed thereon to form an ink layer which was a white monochrome print, and a laminated film of Comparative Example 9 was produced.

Comparative Example 10
Comparative Ink White II was diluted with a mixed solvent of methyl ethyl ketone / toluene / isopropyl alcohol = 40/55/5, and the printing viscosity was adjusted to 25 ° C. using Zancup # 3 manufactured by Rigo Co., Ltd. Was adjusted to 17 seconds under the above conditions. The ink white II for comparative example whose viscosity was adjusted in this manner was applied to a processed OPP film (thickness: 38 μm) using a gravure calibrator (a direct gravure plate of 175 lines / inch, using a depth of 30 μm). Was subjected to gravure printing to form an ink layer which was a white monochrome print, thereby producing a laminated film of Comparative Example 10.

-Comparative Example 9 '
A laminated film of Comparative Example 9 ′ was obtained by removing the release component layer formed of the varnish I from the laminated film of Example 9. For this purpose, as in Example 9, Ink White I was diluted with a mixed solvent of MCH / ECH / ethyl acetate / isopropyl alcohol = 40/35/20/5, and the printing viscosity was measured by Zango Co., Ltd., Zahn. Using cup # 3, the ink temperature was adjusted to 17 seconds at 25 ° C. Using a gravure calibrator (a 175-line / inch direct gravure plate, using a depth of 30 μm), the ink white I thus adjusted in viscosity was used for corona discharge treated OPP (biaxially oriented polypropylene) film for packaging ( Gravure printing was performed on a film base material having a thickness of 38 μm) to form an ink layer as a white monochromatic print, whereby a laminated film of Comparative Example 9 ′ was prepared.

  Ink White I was diluted with a mixed solvent of MCH / ECH / ethyl acetate / isopropyl alcohol = 40/35/20/5, and the printing viscosity was measured using a Zaan Cup # 3 manufactured by Rigo Co., Ltd. It was adjusted to 17 seconds under the condition of 25 ° C. Using a gravure calibrator (a 175 line / inch direct gravure plate, using a depth of 30 μm), the ink white I thus adjusted in viscosity is treated with a processed LDPE (low density polyethylene) film (40 μm in thickness) for packaging. Gravure printing on a film base material to form an ink layer which is a white monochromatic print, and further, on the ink layer, gravure printing of a silicone varnish I with a gravure proofing machine without performing viscosity adjustment. Thus, a release component layer was formed, and a laminated film of Example 11 was produced.

  Ink White II was diluted with a mixed solvent of MCH / ECH / ethyl acetate / isopropyl alcohol = 40/35/20/5, and the printing viscosity was measured using Zancup # 3 manufactured by Rigo Co., Ltd. It was adjusted to 17 seconds under the condition of 25 ° C. Using a gravure calibrator (a direct gravure plate of 175 lines / inch, using a depth of 30 μm), the ink white II thus adjusted in viscosity is coated on a film substrate which is a treated LDPE film (thickness: 40 μm). Gravure printing is performed to form an ink layer that is a white monochrome print, and a silicone-based varnish II is gravure-printed on the ink layer with a gravure proofing machine without adjusting the viscosity. Was formed to prepare a laminated film of Example 12.

Comparative Example 11
Comparative Ink White I was diluted with a mixed solvent of toluene / isopropyl alcohol / ethyl acetate = 50/35/15, and the printing viscosity was adjusted using a Zaan Cup # 3 manufactured by Rigo Co., Ltd. to an ink temperature of 25. The temperature was adjusted to 17 seconds under the condition of ° C. Using the gravure calibrator (a 175 line / inch direct gravure plate, using a depth of 30 μm), the ink white I for comparative example whose viscosity was adjusted as described above was used to process a film substrate that was a processed LDPE film (thickness: 40 μm). Gravure printing was performed thereon to form an ink layer as a white monochromatic print, and a laminated film of Comparative Example 11 was produced.

Comparative Example 12
Comparative Ink White II was diluted with a mixed solvent of methyl ethyl ketone / toluene / isopropyl alcohol = 40/55/5, and the printing viscosity was adjusted to 25 ° C. using Zancup # 3 manufactured by Rigo Co., Ltd. Was adjusted to 17 seconds under the above conditions. Using the gravure calibrator (a 175 line / inch direct gravure plate, using a depth of 30 μm), the ink white II for comparative example whose viscosity was adjusted in this manner was used to prepare a treated LDPE film (thickness: 40 μm). Gravure printing was performed thereon to form an ink layer that was a white monochrome print, and a laminated film of Comparative Example 12 was produced.

-Comparative Example 11 '
A laminated film of Comparative Example 11 ′ was obtained by removing the release component layer of Varnish I from the laminated film of Example 11. For this purpose, as in Example 11, Ink White I was diluted with a mixed solvent of MCH / ECH / ethyl acetate / isopropyl alcohol = 40/35/20/5, and the printing viscosity was adjusted to Using cup # 3, the ink temperature was adjusted to 17 seconds at 25 ° C. Using a gravure calibrator (a 175 line / inch direct gravure plate, using a depth of 30 μm), the ink white I whose viscosity was adjusted in this manner was used for corona discharge treated LDPE (low-density polyethylene) film (thickness) for packaging. 40 μm) was formed by gravure printing on a film substrate to form an ink layer as a white monochromatic print, thereby producing a laminated film of Comparative Example 11 ′.

  For the laminated films of Examples 9 to 12 and Comparative Examples 9 to 12, 9 ', and 11', the same tests as in Examples 1 to 4 and Comparative Examples 1 to 4 were performed. The results are indicated by evaluation (5 is the best) and are shown in Tables 8 and 9.

  Instead of the treated OPP (biaxially oriented polypropylene) film of the laminated film of Example 9, an untreated CPP (unoriented polypropylene) film (thickness of 30 μm) for packaging was used, and all other conditions were the same as in Example 9. The laminated film of Example 13 was produced.

  Instead of the treated OPP (biaxially oriented polypropylene) film of the laminated film of Example 10, an untreated CPP (unoriented polypropylene) film (thickness of 30 μm) for packaging was used, and all other conditions were the same as in Example 10. The laminated film of Example 6 was produced.

Comparative Example 13
Instead of the treated OPP (biaxially oriented polypropylene) film of the laminated film of Comparative Example 9, an untreated CPP (unoriented polypropylene) film (thickness: 30 μm) for packaging was used, and all other conditions were the same as in Comparative Example 9. A laminated film of Comparative Example 13 was produced.

Comparative Example 14
Instead of the treated OPP (biaxially oriented polypropylene) film of the laminated film of Comparative Example 10, an untreated CPP (unoriented polypropylene) film (thickness: 30 μm) for packaging was used, and all other conditions were the same as in Comparative Example 10. A laminated film of Comparative Example 14 was produced.

-Comparative Example 13 '
Instead of the treated OPP (biaxially oriented polypropylene) film of the laminated film of Comparative Example 9 ′, a corona discharge untreated CPP (unoriented polypropylene) film (thickness of 30 μm) for packaging was used, and all others were Comparative Example 9 ′ Under the same conditions as described above, a laminated film of Comparative Example 13 'was prepared. The laminated film of Comparative Example 13 ′ thus prepared corresponds to a structure in which the release component layer made of the varnish I is removed from the laminated film of Example 13.

  Instead of the treated LDPE (low-density polyethylene) film (thickness 40 μm) of the laminated film of Example 11, an untreated LDPE (low-density polyethylene) film (thickness 40 μm) for packaging was used. Under the same conditions, a laminated film of Example 15 was produced.

  Instead of the treated LDPE (low-density polyethylene) film (thickness 40 μm) of the laminated film of Example 12, an untreated LDPE (low-density polyethylene) film (thickness 40 μm) for packaging was used. Under the same conditions, a laminated film of Example 16 was produced.

Comparative Example 15
Instead of the treated LDPE (low density polyethylene) film (thickness 40 μm) of the laminated film of Comparative Example 11, an untreated LDPE (low density polyethylene) film (thickness 40 μm) for packaging was used. Under the same conditions, a laminated film of Comparative Example 15 was produced.

Comparative Example 16
Instead of the treated LDPE (low-density polyethylene) film (thickness: 40 μm) of the laminated film of Comparative Example 12, an untreated LDPE (low-density polyethylene) film (thickness: 40 μm) for packaging was used. Under the same conditions, a laminated film of Comparative Example 16 was produced.

-Comparative Example 15 '
Instead of the corona discharge treated LDPE (low density polyethylene) film of the laminated film of Comparative Example 11 ′, a corona discharge untreated LDPE (low density polyethylene) film for packaging (40 μm thickness) was used, and all others were Comparative Example 11 Under the same conditions as in ', a laminated film of Comparative Example 15' was prepared. The laminated film of Comparative Example 15 ′ thus prepared corresponds to a structure in which the release component layer made of the varnish I was removed from the laminated film of Example 15.

  For the laminated films of Examples 13 to 16 and Comparative Examples 13 to 16, 13 ', and 15', the same tests as in Examples 1 to 4 and Comparative Examples 1 to 4 were performed. The results are indicated by evaluation (5 is the best) and are shown in Tables 10 and 11.

  Ink Indigo I was diluted with a mixed solvent of MCH / ECH / ethyl acetate / isopropyl alcohol = 40/35/20/5, and the printing viscosity was measured using Zancup # 3 manufactured by Rigo Co., Ltd. It was adjusted to 17 seconds under the condition of 25 ° C. Ink White I was similarly diluted using a mixed solvent of MCH / ECH / ethyl acetate / isopropyl alcohol = 40/35/20/5, and the printing viscosity was measured using Zaan Cup # 3 manufactured by Rigo Co., Ltd. The temperature was adjusted to 17 seconds at an ink temperature of 25 ° C. Using a gravure calibrator (a 175 line / inch direct gravure plate, using a depth of 30 μm), the ink indigo I whose viscosity has been adjusted in this way is treated with an OPP (biaxially oriented polypropylene) film for packaging (38 μm thick). ), A gravure printing on a film substrate, a gravure printing of an ink white I using a gravure proofing machine, and a white ink layer overprinted with a blue ink layer. Further, on the white ink layer, a silicone-based varnish I was gravure-printed with a gravure calibrator without performing viscosity adjustment to form a release component layer, and a laminated film of Example 17 was formed. did.

  Ink Indigo II was diluted with a mixed solvent of MCH / ECH / ethyl acetate / isopropyl alcohol = 40/35/20/5, and the printing viscosity was measured using an ink temperature of Zancup # 3 manufactured by Rigo Co., Ltd. It was adjusted to 17 seconds under the condition of 25 ° C. Ink White II was similarly diluted with a mixed solvent of MCH / ECH / ethyl acetate / isopropyl alcohol = 40/35/20/5, and the printing viscosity was measured using Zaan Cup # 3 manufactured by Rigo Co., Ltd. The temperature was adjusted to 17 seconds at an ink temperature of 25 ° C. Using the gravure calibrator (a 175 line / inch direct gravure plate, using a depth of 30 μm), the ink indigo II whose viscosity has been adjusted as described above is gravure coated on a film substrate which is a processed OPP film (thickness: 38 μm). Printing, and gravure printing of Ink White II thereon using a gravure proofing machine to form two ink layers in which a white ink layer is overprinted on a blue ink layer. On top of this, a silicone-based varnish II was gravure-printed with a gravure calibrator without adjusting the viscosity to form a release component layer, whereby a laminated film of Example 18 was produced.

Comparative Example 17
The comparative Ink Indigo I was diluted with a mixed solvent of toluene / isopropyl alcohol / ethyl acetate = 50/35/15, and the printing viscosity was adjusted using a Zaan Cup # 3 manufactured by Rigo Co., Ltd. to an ink temperature of 25. The temperature was adjusted to 17 seconds under the condition of ° C. Similarly, Comparative Ink White I was diluted with a mixed solvent of toluene / isopropyl alcohol / ethyl acetate = 50/35/15, and the printing viscosity was determined using Zaan Cup # 3 manufactured by Rigo Co., Ltd. It was adjusted to 17 seconds under the condition of an ink temperature of 25 ° C. Using the gravure calibrator (a direct gravure plate of 175 lines / inch, using a depth of 30 μm), the ink base I for comparative example having the viscosity adjusted as described above was used to prepare a film substrate as a treated OPP film (thickness: 38 μm). Gravure printing on the top, gravure printing of Comparative Example Ink White I thereon using a gravure proofing machine, to form two ink layers of a white ink layer overprinted on the blue ink layer, A laminated film of Comparative Example 17 was produced.

Comparative Example 18
Comparative Ink Indigo II was diluted with a mixed solvent of methyl ethyl ketone / toluene / isopropyl alcohol = 40/55/5, and the printing viscosity was adjusted to 25 ° C. using a Zaan cup # 3 manufactured by Rigo Co., Ltd. Was adjusted to 17 seconds under the above conditions. Similarly, Comparative Example Ink White II was diluted with a mixed solvent of methyl ethyl ketone / toluene / isopropyl alcohol = 40/55/5, and the printing viscosity was adjusted using Zahn Cup # 3 manufactured by Rigo Co., Ltd. The temperature was adjusted to 17 seconds at a temperature of 25 ° C. The indigo dye for comparative example II whose viscosity was adjusted in this way was processed using a gravure calibrator (a direct gravure plate of 175 lines / inch, using a depth of 30 μm) on a film substrate which was an OPP film (thickness: 38 μm). Gravure printing, and gravure printing of Comparative Example Ink White II thereon using a gravure proofing machine to form two ink layers in which a white ink layer is overprinted on a blue ink layer. A laminated film of Example 18 was made.

-Comparative Example 17 '
A laminated film of Comparative Example 17 'was obtained by removing the release component layer of Varnish I from the laminated film of Example 17. For this purpose, as in Example 17, the ink indigo I was diluted with a mixed solvent of MCH / ECH / ethyl acetate / isopropyl alcohol = 40/35/20/5, and the printing viscosity was reduced by Zango Co., Ltd., Zahn. Using cup # 3, the ink temperature was adjusted to 17 seconds at 25 ° C. Ink White I was similarly diluted using a mixed solvent of MCH / ECH / ethyl acetate / isopropyl alcohol = 40/35/20/5, and the printing viscosity was measured using Zaan Cup # 3 manufactured by Rigo Co., Ltd. The ink temperature was adjusted to 17 seconds at 25 ° C. Using the gravure calibrator (a direct gravure plate of 175 lines / inch, using a depth of 30 μm), the ink indigo I whose viscosity has been adjusted in this way is used for corona discharge treated OPP (biaxially oriented polypropylene) film for packaging ( Gravure printing on a film substrate having a thickness of 38 μm), gravure printing of Ink White I thereon using a gravure proofing machine, and overprinting a white ink layer on an indigo ink layer. An ink layer was formed to prepare a laminated film of Comparative Example 17 '.

  Ink Indigo I was diluted with a mixed solvent of MCH / ECH / ethyl acetate / isopropyl alcohol = 40/35/20/5, and the printing viscosity was measured using Zancup # 3 manufactured by Rigo Co., Ltd. It was adjusted to 17 seconds under the condition of 25 ° C. Ink White I was similarly diluted using a mixed solvent of MCH / ECH / ethyl acetate / isopropyl alcohol = 40/35/20/5, and the printing viscosity was measured using Zaan Cup # 3 manufactured by Rigo Co., Ltd. The temperature was adjusted to 17 seconds at an ink temperature of 25 ° C. Using the gravure calibrator (a direct gravure plate of 175 lines / inch, using a depth of 30 μm), the ink indigo I whose viscosity has been adjusted in this way is processed LDPE (low density polyethylene) film for packaging (thickness: 40 μm). Gravure printing on a film substrate, and gravure printing of Ink White I on the film base using a gravure proofing machine, and overprinting a white ink layer on a blue ink layer to form two ink layers Then, on the white ink layer, a silicone-based varnish I was gravure-printed with a gravure proofer without adjusting the viscosity to form a release component layer, and a laminated film of Example 19 was formed. .

  Ink Indigo II was diluted with a mixed solvent of MCH / ECH / ethyl acetate / isopropyl alcohol = 40/35/20/5, and the printing viscosity was measured using an ink temperature of Zancup # 3 manufactured by Rigo Co., Ltd. It was adjusted to 17 seconds under the condition of 25 ° C. Ink White II was similarly diluted with a mixed solvent of MCH / ECH / ethyl acetate / isopropyl alcohol = 40/35/20/5, and the printing viscosity was measured using Zaan Cup # 3 manufactured by Rigo Co., Ltd. The temperature was adjusted to 17 seconds at an ink temperature of 25 ° C. Using the gravure calibrator (a 175 line / inch direct gravure plate, using a depth of 30 μm), the ink indigo II whose viscosity has been adjusted in this manner is coated on a film substrate that is a treated LDPE film (thickness: 40 μm). Gravure printing, and gravure printing of Ink White II thereon using a gravure proofing machine to form two ink layers in which a white ink layer is overprinted on a blue ink layer; A silicone-based varnish II was gravure-printed on the layer with a gravure calibrator without adjusting the viscosity to form a release component layer, and a laminated film of Example 20 was produced.

Comparative Example 19
The comparative Ink Indigo I was diluted with a mixed solvent of toluene / isopropyl alcohol / ethyl acetate = 50/35/15, and the printing viscosity was adjusted using a Zaan Cup # 3 manufactured by Rigo Co., Ltd. to an ink temperature of 25. The temperature was adjusted to 17 seconds under the condition of ° C. Similarly, Comparative Ink White I was diluted with a mixed solvent of toluene / isopropyl alcohol / ethyl acetate = 50/35/15, and the printing viscosity was determined using Zaan Cup # 3 manufactured by Rigo Co., Ltd. It was adjusted to 17 seconds under the condition of an ink temperature of 25 ° C. Using the gravure calibrator (a 175 line / inch direct gravure plate, using a depth of 30 μm), the ink base I for comparative example having the viscosity adjusted as described above was treated with a LDPE film (thickness: 40 μm). Gravure printing on the top, gravure printing of Comparative Example Ink White I thereon using a gravure proofing machine, to form two ink layers of a white ink layer overprinted on the blue ink layer, A laminated film of Comparative Example 19 was produced.

Comparative Example 20
Comparative Ink Indigo II was diluted with a mixed solvent of methyl ethyl ketone / toluene / isopropyl alcohol = 40/55/5, and the printing viscosity was adjusted to 25 ° C. using a Zaan cup # 3 manufactured by Rigo Co., Ltd. Was adjusted to 17 seconds under the above conditions. Similarly, Comparative Example Ink White II was diluted with a mixed solvent of methyl ethyl ketone / toluene / isopropyl alcohol = 40/55/5, and the printing viscosity was adjusted using Zahn Cup # 3 manufactured by Rigo Co., Ltd. The temperature was adjusted to 17 seconds at a temperature of 25 ° C. Using the gravure calibrator (a 175-line / inch direct gravure plate, using a depth of 30 μm), the ink substrate for comparative example II whose viscosity was adjusted in this way was treated with a LDPE film (thickness: 40 μm). Gravure printing on the top, gravure printing of Comparative Example Ink White II thereon using a gravure proofing machine, to form two ink layers by overprinting a white ink layer on the blue ink layer, A laminated film of Comparative Example 20 was made.

-Comparative Example 19 '
A laminated film of Comparative Example 19 ′ was obtained by removing the release component layer of Varnish I from the laminated film of Example 19. For this purpose, in the same manner as in Example 19, the ink indigo I was diluted with a mixed solvent of MCH / ECH / ethyl acetate / isopropyl alcohol / = 40/35/20/5, and the printing viscosity was adjusted by Rigosha Co., Ltd. Using Zahn Cup # 3, the ink temperature was adjusted to 17 seconds at 25 ° C. Ink White I was similarly diluted using a mixed solvent of MCH / ECH / ethyl acetate / isopropyl alcohol / = 40/35/20/5, and the printing viscosity was measured using Zaan Cup # 3 manufactured by Rigo Co., Ltd. The ink temperature was adjusted to 17 seconds at 25 ° C. Using a gravure calibrator (a 175 line / inch direct gravure plate, using a depth of 30 μm), the ink indigo I whose viscosity was adjusted in this manner was subjected to corona discharge treated LDPE (low density polyethylene) film (thickness) for packaging. Gravure printing on a film substrate of 40 μm), gravure printing of Ink White I thereon using a gravure proofing machine, and double printing of a white ink layer on a blue ink layer. A layer was formed, and a laminated film of Comparative Example 19 ′ was prepared.

  With respect to the laminated films of Examples 17 to 20 and Comparative Examples 17 to 20, 17 ', and 19', the same tests as in Examples 1 to 4 and Comparative Examples 1 to 4 were performed. The results are indicated by evaluation (5 is the best) and are shown in Tables 12 and 13.

  Instead of the treated OPP (biaxially oriented polypropylene) film of the laminated film of Example 17, an untreated CPP (unoriented polypropylene) film (thickness of 30 μm) for packaging was used, and all other conditions were the same as in Example 17. The laminated film of Example 21 was produced.

  Using an untreated CPP (unstretched polypropylene) film (thickness: 30 μm) for packaging instead of the treated OPP (biaxially stretched polypropylene) film of the laminated film of Example 18, all other conditions were the same as in Example 18. The laminated film of Example 21 was produced.

Comparative Example 21
Instead of the treated OPP (biaxially oriented polypropylene) film of the laminated film of Comparative Example 17, an untreated CPP (non-oriented polypropylene) film (thickness: 30 μm) for packaging was used, and all other conditions were the same as those of Comparative Example 17. The laminated film of Comparative Example 21 was produced.

Comparative Example 22
Instead of the treated OPP (biaxially oriented polypropylene) film of the laminated film of Comparative Example 18, an untreated CPP (unoriented polypropylene) film (thickness: 30 μm) for packaging was used, and all other conditions were the same as in Comparative Example 18. A laminated film of Comparative Example 22 was produced.

-Comparative Example 21 '
Instead of the treated OPP (biaxially oriented polypropylene) film of the laminated film of Comparative Example 17 ', a corona discharge untreated CPP (unoriented polypropylene) film (thickness of 30 µm) for packaging was used, and all others were Comparative Example 17' Under the same conditions as described above, a laminated film of Comparative Example 21 ′ was prepared. The laminated film of Comparative Example 21 ′ thus prepared corresponds to a structure obtained by removing the release component layer formed of the varnish I from the laminated film of Example 21.

  Instead of the treated LDPE (low-density polyethylene) film (thickness 40 μm) of the laminated film of Example 19, an untreated LDPE (low-density polyethylene) film (thickness 40 μm) for packaging was used. Under the same conditions, a laminated film of Example 23 was produced.

  Instead of the treated LDPE (low density polyethylene) film (thickness 40 μm) of the laminated film of Example 20, an untreated LDPE (low density polyethylene) film (thickness 40 μm) for packaging was used. Under the same conditions, a laminated film of Example 24 was produced.

Comparative Example 23
Instead of the treated LDPE (low-density polyethylene) film (thickness 40 μm) of the laminated film of Comparative Example 19, an untreated LDPE (low-density polyethylene) film (thickness 40 μm) for packaging was used. Under the same conditions, a laminated film of Comparative Example 23 was produced.

Comparative Example 24
Instead of the treated LDPE (low-density polyethylene) film (thickness 40 μm) of the laminated film of Comparative Example 20, an untreated LDPE (low-density polyethylene) film (thickness 40 μm) for packaging was used. Under the same conditions, a laminated film of Comparative Example 24 was prepared.

-Comparative Example 23 '
Instead of the corona discharge treated LDPE (low density polyethylene) film of the laminated film of Comparative Example 19 ′, a corona discharge untreated LDPE (low density polyethylene) film (40 μm thickness) for packaging was used, and all others were Comparative Example 19 Under the same conditions as in ', a laminated film of Comparative Example 23' was made. The laminated film of Comparative Example 23 ′ thus prepared corresponds to a structure in which the release component layer made of the varnish I was removed from the laminated film of Example 23.

  For the laminated films of Examples 21 to 24 and Comparative Examples 21 to 24, 21 ', and 23', the same tests as in Examples 1 to 4 and Comparative Examples 1 to 4 were performed. The results are indicated by evaluation (5 is the best) and are shown in Tables 6 and 7.

  Comparing the test results of Examples 1 to 24 and Comparative Examples 1 to 24, the laminated film of the present invention is superior to the laminated film of Comparative Example in adhesiveness, blocking resistance, chemical resistance, and heat resistance. You can see that there is. In addition, the laminated film of the present invention was tested using a treated film (Examples 1 to 4, 9 to 12 and 17 to 20), and using a non-treated film (Example 5). -8, 13-16, 21-24), almost the same results can be obtained, whereas the laminated film of the comparative example uses a treated film ( Comparing the test results of Comparative Examples 1 to 4, 9 to 12 and 17 to 20) with the test results when using untreated films (Comparative Examples 5 to 8, 13 to 16 and 21 to 24) It can be seen that the test result of the laminated film using the untreated film was clearly inferior. Further, it can be seen that the laminated film of the present invention has excellent effects in adhesiveness, blocking resistance, chemical resistance, and heat resistance by providing a release component layer using a varnish.

  From the above test results, the laminated film of the present invention, with respect to the conventional laminated film, adhesion, blocking resistance, chemical resistance, in the heat resistance, has an excellent effect, especially, has not been treated When a film is used, effects superior to those of the related art can be obtained.

DESCRIPTION OF SYMBOLS 1 Laminated film 2 Base film 3 Ink layer 4 Release component layer

Claims (7)

A base film comprising a resin composition containing a polyolefin resin,
An ink layer formed on one surface of the base film, and
A laminated film having a release component layer laminated on the ink layer,
The ink layer is formed of an ink composition comprising a styrene-based thermoplastic elastomer (A), a resin (B), a pigment, and an organic solvent,
The resin (B) is one or at least two selected from the group consisting of a terpene resin (B1), a styrene hard resin (B2), and an alicyclic hydrocarbon resin (B3). A mixture,
The laminated film, wherein the release component layer contains a silicone composition (C).   The styrene-based thermoplastic elastomer (A) includes a hydrogenated product of a styrene-ethylene-butylene-styrene block copolymer, a hydrogenated product of a styrene-isoprene-styrene block copolymer, and a styrene-ethylene-propylene-styrene block copolymer. The polymer according to claim 1, which is one selected from the group consisting of a hydrogenated product of a polymer and a hydrogenated product of a styrene-butadiene-styrene block copolymer, or a mixture of at least two types. Laminated film.   The styrene-based thermoplastic elastomer (A) is composed of one having an acid value and one having no acid value, and the acid value of the styrene-based thermoplastic elastomer (A) is in the range of 1 to 30 mgKOH / g. The laminated film according to claim 1 or 2, wherein:   The ink composition according to any one of claims 1 to 3, wherein the styrene-based thermoplastic elastomer (A) and the resin (B) are contained in a weight ratio of 9: 1 to 1: 9. 3. The laminated film according to item 1.   The laminate according to any one of claims 1 to 4, wherein the organic solvent contains at least one selected from the group consisting of an aromatic hydrocarbon solvent and an alicyclic hydrocarbon solvent. the film.   The ink composition according to claim 1, wherein the pigment comprises, as the pigment, 3 to 20 wt% of an organic pigment or 3 to 50 wt% of an inorganic pigment based on the total weight of the ink composition. The laminated film according to any one of claims 1 to 5.   The silicone composition (C) includes polyether-modified silicone, polyol-modified silicone, alkyl-modified silicone, aralkyl-modified silicone, fluorine-modified silicone, amino-modified silicone, phenyl-modified silicone, acrylic resin-modified silicone, polyester resin-modified silicone, and fatty acid. Resin-modified silicone, fluoroalkyl-modified silicone, epoxy-modified silicone, carbinol-modified silicone, methacryl-modified silicone, mercapto-modified silicone, carboxyl-modified silicone, methyl hydrogen silicone, dimethyl silicone, and methylphenyl silicone The laminated film according to any one of claims 1 to 6, wherein the laminated film is one kind or a mixture of at least two kinds.