JP2017213889A - Resin film, and printing substrate for poster using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a highly glossy resin film, a printing substrate for a poster and the like which have printability on both oil-based ink and ultraviolet curable ink.SOLUTION: A resin film 11 has such a laminated structure that at least a printing layer 21, a gloss-imparting layer 31 and a base layer 41 are laminated in this order. The printing layer 21 contains at least 80-97 mass% of a propylene homopolymer (X), and 3-20 mass% of the total of an olefinic thermoplastic elastomer (Y1) and/or soft polypropylene resin (Y2), with respect to the total amount of the solid content of the printing layer 21. The olefinic thermoplastic elastomer (Y1) and the soft polypropylene resin (Y2) are preferably a metallocene catalyst-based soft polypropylene resin.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a resin film having a predetermined printing layer, and a printing substrate for posters using the same.

  Conventionally, a synthetic paper has been proposed in which a stretched polypropylene film is used as a base material layer, and a stretched polypropylene film containing inorganic fine powder on the front and back surfaces is used as a paper-like layer. Patent Literatures 1 to 3). This type of synthetic paper has a very strong water resistance as compared with pulp paper, and is characterized by, for example, that the paper is not easily swollen or torn by rainwater. An example of the use of synthetic paper that takes advantage of such water resistance is poster paper.

  Also, depending on the production purpose, high gloss multicolor printing may be strongly required. For example, travel posters, movie posters, election posters, and posters for promoting sales of products such as automobiles and soft drinks tend to favor high-gloss offset multicolor printing in order to create a bright and light atmosphere. It is in. Here, there are various types of printing inks, and various high-gloss printing papers have been proposed according to the inks used.

  For example, as a high-gloss printing paper compatible with oil-based inks such as solvent type and oxidative polymerization type, a transparent film layer of a thermoplastic resin not containing inorganic fine powder is provided as a surface layer on a synthetic paper, and further this transparent film layer A resin film having a primer layer provided thereon is known (see Patent Document 4).

  Also, high gloss printing paper for UV curable ink (UV ink) includes 90-100% propylene-based random copolymer and / or polyethylene and 0-10% inorganic fine powder and / or organic filler. A resin film has been proposed in which a printed layer in which the oxygen atom number concentration is adjusted, a predetermined gloss imparting layer, and a synthetic paper (base layer) are provided in this order (see Patent Document 5).

Japanese Patent Publication No. 46-040794 JP 56-141339 A Japanese Patent Laid-Open No. 56-118437 JP-A 61-003748 JP 2007-083714 A

  By the way, in recent years, high-quality printing-compatible or small-lot-compatible printing apparatuses and printing inks such as UV ink have been released one after another. In response to this, equipment introduction and equipment disposal have progressed in each printing company, and as a result, diversification of printing methods among printing companies has progressed. For example, in commercial offset printing, there are printing companies that can handle only oil-based inks such as solvent type and oxidation polymerization type that have been widely used, printing companies that can handle only UV ink, and printing companies that can handle both. You are in a turbulent situation.

  Conventionally, oil-based ink dedicated paper and UV ink dedicated paper have been supplied according to the printing method of each printing company. However, such individual correspondence using dedicated paper can be uneconomical on both the producer side and the printing company side from the viewpoints of quality control, inventory control and logistics.

  In addition, it is well known that the printing quality varies if the type of printing ink and printing paper used are different. For example, in commercial offset printing, print quality using oil-based ink and oil-based ink dedicated paper is generally greatly different from print quality using UV ink and UV ink-specific paper. In order to suppress such fluctuations in print quality and to keep the print quality of the resulting printed matter constant, it is desirable to make common use of printing paper with less burden of equipment change. However, at present, there is no high-gloss printing paper that has the above water resistance and can handle both oil-based inks and UV inks.

  For example, the printing paper described in Patent Document 4 has good adhesion of oil-based inks, but poor transfer properties and adhesion of UV inks. For example, under conditions assuming outdoor use, for example, sunlight or rainwater Due to the influence, there was a problem that the adhesion of the UV ink was lowered in a relatively short period of time, and the UV ink on the printing surface was easily dropped. Further, the printing paper described in Patent Document 5 has a problem that the glossiness is relatively high and the transferability and adhesion of the ink are good, but the drying property of the oil-based ink is poor. Furthermore, there is a problem that sheet blocking in a high temperature environment and cut blocking at the time of cutting are likely to occur, and further, there is a problem that the cost tends to be relatively high.

  The present invention has been made in view of such background art. The object is to provide a high-gloss resin film (printing paper) that is printable for both oil-based inks and ultraviolet curable inks. Another object of the present invention is to provide a high-gloss poster printing substrate that is compatible with both oil-based inks and ultraviolet curable inks.

  Note that the present invention is not limited to the purpose described here, and is an operational effect derived from each configuration shown in the embodiment for carrying out the invention described later, and can also exhibit an operational effect that cannot be obtained by the conventional technology. It can be positioned as another purpose.

  As a result of intensive studies to solve the above problems, the present inventors have found that in a resin film having a laminated structure in which a printing layer, a gloss-imparting layer, and a base layer are laminated in this order, a propylene homopolymer, an olefin-based polymer It has been found that the above-mentioned problems can be solved by employing a novel printing layer containing at least a thermoplastic elastomer and / or a soft polypropylene resin, and the present invention has been completed.

That is, the present invention provides various specific modes shown below.
[1] It has a laminated structure in which a printing layer, a gloss imparting layer, and a base layer are laminated at least in this order, and the printing layer has a propylene single weight of 80 to 97% by mass with respect to the total solid content of the printing layer. A resin film comprising at least the coalescence (X) and a total of 3 to 20% by mass of an olefinic thermoplastic elastomer (Y1) and / or a soft polypropylene resin (Y2).
[2] The resin film according to [1], wherein the olefinic thermoplastic elastomer (Y1) is a metallocene catalyst-based polypropylene-based thermoplastic elastomer.
[3] The resin film according to [1] or [2], wherein the soft polypropylene resin (Y2) is a metallocene catalyst-based soft polypropylene resin.
[4] The gloss-imparting layer comprises 45 to 65% by mass of an olefinic (co) polymer and 35 to 55% by mass of an inorganic fine powder and / or an organic filler, based on the total solid content of the gloss-imparting layer. The resin film according to any one of [1] to [3], containing at least

[5] The above [1] to [1], wherein the olefin thermoplastic elastomer (Y1) and / or the soft polypropylene resin (Y2) has a melt flow rate (JIS K7210-1: 2014) of 3 to 10 g / 10 min. 4] The resin film as described in any one of [4]. [6] The resin film according to any one of [1] to [5], wherein the propylene homopolymer (X) has a melt flow rate (JIS K7210-1: 2014) of 1 to 20 g / 10 min. .
[7] The resin film according to any one of [1] to [6], wherein the printed layer does not substantially contain an inorganic fine powder.
[8] A printing substrate for poster, comprising the resin film according to any one of [1] to [7].

  According to the present invention, it is a high-gloss resin film that can be suitably used for various printing such as offset printing, letterpress printing, flexographic printing, gravure printing, and screen printing, and is suitable for printing on both oil-based inks and UV inks. A highly versatile resin film can be realized, and as a result, a printed matter, a poster, etc. with extremely good weather resistance can be realized.

It is a schematic cross section which shows the resin film (printing substrate for posters) of one Embodiment.

  Hereinafter, each embodiment of the present invention will be described with reference to the drawings. The following embodiments are examples for explaining the present invention, and the present invention is not limited only to the embodiments. In the following, unless otherwise specified, positional relationships such as up, down, left, and right are based on the positional relationships shown in the drawings. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios. In the present specification, for example, the description of a numerical range of “1 to 100” includes both the lower limit value “1” and the upper limit value “100”. This also applies to other numerical range notations.

[Resin film]
FIG. 1 is a schematic cross-sectional view showing a layer structure of a resin film 11 (poster printing substrate 100) according to an embodiment of the present invention. The resin film 11 has a laminated structure in which the printing layer 21, the gloss imparting layer 31, and the base layer 41 are laminated at least in this order.

(1) Print layer The print layer 21 contains at least a propylene homopolymer (X), an olefin-based thermoplastic elastomer (Y1), and / or a soft polypropylene-based resin (Y2). As shown in the figure, the printed layer 21 is located on the outermost layer of the resin film 11 and is printed on the surface thereof.

  The propylene homopolymer (X) is a propylene homopolymer and has the characteristics of high crystallinity and high rigidity. And since the printing layer 21 contains propylene homopolymer (X) as a main component, the printability of oil-based inks, such as a solvent type and an oxidation polymerization type, conventionally used widely can be ensured. Here, the main component means a component contained in the printing layer 21 by 50% by mass or more based on the total solid content of the printing layer 21. In addition, propylene homopolymer (X) can be used individually by 1 type or in combination of 2 or more types. From the viewpoints of improving both compatibility with oil-based inks and UV inks, and improving moldability and glossiness of the resin film 21, the propylene homopolymer (X) is a printing layer based on the total solid content of the printing layer 21. The content of 21 is 80 to 97% by mass, preferably 83 to 96% by mass, and more preferably 85 to 95% by mass.

  Various well-known things can be used for the propylene homopolymer (X), and the kind is not specifically limited. Among these, a propylene homopolymer having a melting point of 150 to 170 ° C. is preferable from the viewpoints of moldability, crystallinity, and ink adhesion. In addition, the propylene homopolymer (X) used here has a melt flow rate value (JIS K7210-1) equivalent to (similar to) an olefinic thermoplastic elastomer (Y1) and / or a soft polypropylene resin (Y2) described later. : Measured according to 2014) is preferable. By doing so, when both the propylene homopolymer (X) and the olefinic thermoplastic elastomer (Y1) and / or the soft polypropylene resin (Y2) are kneaded, it becomes easy to knead uniformly, printability and It tends to be easy to obtain the printed layer 21 having both excellent weather resistance. Specifically, the melt flow rate of propylene homopolymer (X) (JIS K7210-1: 2014) is different depending on the olefinic thermoplastic elastomer (Y1) and / or soft polypropylene resin (Y2) used in combination. Is preferably 1 to 20 g / 10 min, more preferably 2 to 15 g / 10 min. In addition, propylene homopolymer (X) can be used individually by 1 type or in combination of 2 or more types. At this time, by blending the propylene homopolymer (X) having a small melt flow rate value (low fluidity) and the propylene homopolymer (X) having a large melt flow rate value (large fluidity), The melt flow rate value of the target olefinic thermoplastic elastomer (Y1) and / or soft polypropylene resin (Y2) can also be adjusted.

  The olefinic thermoplastic elastomer (Y1) has fluidity (plasticity) at high temperatures and rubber-like elasticity (elastomer) at room temperature, and includes a hard segment component made of polyolefin such as polyethylene and polypropylene, Means a polymer material having another polyolefin, α-olefin such as 1-butene, 1-hexene, 1-heptene, 4-methyl-1-pentene, or soft segment component such as ethylene-propylene rubber. As the olefin-based thermoplastic elastomer (Y1), a random copolymer, a block copolymer, a blend, a dynamic cross-linked body, a sea-island dispersion, and the like are known, but the type is not particularly limited. The olefinic thermoplastic elastomer (Y1) may be a binary system or a ternary or higher multi-element system. The olefinic thermoplastic elastomer (Y1) can be used by mixing two or more types having different compositions.

  Various known olefin thermoplastic elastomers (Y1) can be used and are not particularly limited. Among these, a random copolymer and a block copolymer are preferable, an olefin-based thermoplastic elastomer (R-TPO) which is a so-called reactor-made random copolymer and a block copolymer is more preferable, and a so-called metallocene catalyst is used. A metallocene-catalyzed polypropylene thermoplastic elastomer (R-TPO) copolymerized using is particularly preferred.

  The soft polypropylene-based resin (Y2) is mainly composed of propylene, and is copolymerized with α-olefin such as ethylene, 1-butene, 1-hexene, 1-heptene, 4-methyl-1-pentene, and the like. Means a polypropylene-based copolymer having a good stereoregularity. This soft polypropylene resin (Y2) contains propylene in a copolymerization component in excess of 50%. Such a soft polypropylene-based resin (Y2) is easily oxidized, and good UV ink adhesion is easily obtained with the surface treatment. The soft polypropylene resin (Y2) is preferably a random copolymer or a block copolymer, and particularly preferably a metallocene catalyst random copolymer or block copolymer copolymerized using a so-called metallocene catalyst. The soft polypropylene resin (Y2) may be a binary system or a ternary or higher multi-element system. Two or more types of soft polypropylene resins (Y2) having different compositions can be mixed and used.

  When the metallocene catalyst type is used as the olefinic thermoplastic elastomer (Y1) and the soft polypropylene resin (Y2) described above, good kneadability with the propylene homopolymer (X) is easily obtained, which is a cause of blocking. There is a tendency to reduce the adverse effects of stickiness. The reason for this is not clear, but the metallocene catalyst system has a relatively sharp molecular weight distribution and a relatively low content of low molecular weight components compared to those that do not. It is guessed.

  The content of the olefin-based thermoplastic elastomer (Y1) and the soft polypropylene-based resin (Y2) in the printing layer 21 is the solid content of the printing layer 21 from the viewpoint of being compatible with both oil-based inks and ultraviolet curable inks. Based on the total amount, the total is 3 to 20% by mass, preferably 4 to 17% by mass, and more preferably 5 to 15% by mass. These olefinic thermoplastic elastomers (Y1) and soft polypropylene resins (Y2) can be used by mixing two or more types having different compositions and melt flow rates. Moreover, it is preferable that these are 70-160 degreeC of melting | fusing point. If the melting point is 70 ° C. or more, the resin tends to be easier to form because the resin has appropriate fluidity. On the other hand, if the melting point is 160 ° C. or lower, the resin exhibits an appropriate degree of crystallinity, tends to be surface oxidized, and tends to provide good ink adhesion.

  The above olefinic thermoplastic elastomer (Y1) and soft polypropylene resin (Y2) preferably have a melt flow rate (JIS K7210-1: 2014) of 3 to 10 g / 10 min, more preferably 4 to 7 g / 10 min. By using a soft polymer having such a melt freight value, it tends to be easy to form a film with a uniform film thickness and less unevenness. And as stated above, the propylene homopolymer which has a melt flow rate value comparable to the melt freight value of these olefin type thermoplastic elastomers (Y1) and soft polypropylene resin (Y2), for example, 3-10 g / 10min. By using together with (X), it tends to be easy to obtain the printing layer 21 excellent in kneadability, uniformity, blocking property, printability, weather resistance and the like. At this time, the melt flow rate value of the propylene homopolymer (X) can be adjusted by blending a small melt flow rate value and a large melt flow rate value.

  The printing layer 21 may contain other components in addition to the above-described propylene homopolymer (X), olefin-based thermoplastic elastomer (Y1), and soft polypropylene-based resin (Y2). Other components include, for example, polymer components other than the above (X), (Y1) and (Y2), such as ethylene resins (high density polyethylene, medium density polyethylene, low density polyethylene, etc.), polymethyl-1- Polyolefin resins such as pentene and ethylene-cyclic olefin copolymers; metal salts of ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid copolymer ( Ionomers), ethylene-acrylic acid alkyl ester copolymers, ethylene-methacrylic acid alkyl ester copolymers, maleic acid-modified polyethylene, maleic acid-modified polyolefin resins and the like; nylon-6, nylon-6,6 , Nylon-6,10, nylon-6,12, etc. Thermoplastic resins such as aromatic polyesters (polyethylene terephthalate and copolymers thereof, polyethylene naphthalate, polybutylene terephthalate, etc.), aliphatic polyesters (polybutylene succinate, polylactic acid, etc.); aromatic polycarbonates, Polycarbonate resins such as aliphatic polycarbonate; polystyrene resins such as atactic polystyrene, syndiotactic polystyrene, acrylonitrile-styrene (AS) copolymer, acrylonitrile-butadiene-styrene (ABS) copolymer; polyvinyl chloride resin; polyphenylene Examples thereof include, but are not limited to, sulfides, thermoplastic elastomers other than olefins, and the like.

  Moreover, the printing layer 21 may contain the inorganic fine powder and / or the organic filler. However, from the viewpoint of obtaining the printed layer 21 having excellent surface gloss and flatness, the printed layer 21 preferably does not substantially contain the inorganic fine powder and / or the organic filler. Here, in the present specification, “substantially does not contain” means that the total amount of the inorganic fine powder and the organic filler is 0.0 mass% or more and less than 10.0 mass% based on the total solid content of the printing layer 21. More preferably 0.0% by mass to less than 5.0% by mass, further preferably 0.0% by mass to less than 3.0% by mass, and particularly preferably 0.0% by mass or more. It is less than -1.0 mass%. The content of the inorganic fine powder and / or the organic filler is intended to be added intentionally, and so-called contamination is not limited thereto. Since the printing layer 21 does not substantially contain the inorganic fine powder and / or the organic filler, the flat printing layer 21 with less unevenness on the surface can be easily obtained, and inhibition of specular reflection due to irregular reflection tends to be suppressed. Further, if the printing layer 21 is as flat as possible, the printing surface tends to be flat when printing is performed thereon, regular reflection with respect to incident light is likely to be obtained, and glossy gloss tends to be easily obtained. . In addition, about the specific example of the inorganic fine powder and / or organic filler which the printing layer 21 may contain, it is the same as that of the inorganic fine powder and / or organic filler of the gloss providing layer 31 mentioned later, and it overlapped here. Description is omitted.

  Furthermore, in addition to the above components, the printing layer 21 includes a heat stabilizer (antioxidant), a light stabilizer, an ultraviolet absorber, a dispersant, a lubricant, a slip agent such as a fatty acid amide, an anti-blocking agent, and a kneading-type charge. It may contain known additives such as inhibitors, dyes, pigments, plasticizers, crystal nucleating agents, mold release agents, flame retardants and the like. When the resin film 11 is used outdoors, such as poster paper, for example, it is preferable to add an antioxidant or a light stabilizer from the viewpoint of enhancing durability. Examples of the heat stabilizer include heat stabilizers such as sterically hindered phenolic antioxidants, phosphorus antioxidants, and amine antioxidants. Although the addition amount of a heat stabilizer is not specifically limited, 0.001-1 mass% is preferable in conversion of solid content with respect to the thermoplastic resin mentioned above. Examples of the light stabilizer include sterically hindered amine light stabilizers, benzotriazole light stabilizers, benzophenone light stabilizers, sulfur light stabilizers, and the like. Although the addition amount of a light stabilizer is not specifically limited, 0.001-1 mass% is preferable in conversion of solid content with respect to the thermoplastic resin mentioned above. The dispersant is used, for example, for the purpose of highly dispersing the inorganic fine powder in the film layer containing the above-described thermoplastic resin. Examples of the dispersant include silane coupling agents, higher fatty acids such as oleic acid and stearic acid, metal soap, polyacrylic acid or polymethacrylic acid, or salts thereof. Although the addition amount of a dispersing agent is not specifically limited, 0.01-4 mass% is preferable in conversion of solid content with respect to the thermoplastic resin mentioned above.

  The print layer 21 may be an unstretched layer or a stretched layer. From the viewpoint of obtaining a flatter surface and interface, the printing layer 21 is preferably a uniaxially stretched or biaxially stretched layer.

(2) Gloss imparting layer The gloss imparting layer 31 is laminated on the inner side of the printing layer 21 that is the outermost layer of the resin film 11, and is for improving the glossiness of the resin film 11. In the resin film 11 of the present embodiment, a glossy gloss is obtained by providing a relatively smooth and transparent printing layer 21 in the outermost layer. However, the light incident on the resin film 11 also gives gloss to the printing layer 21. Glossiness is further enhanced by regular reflection at the interface with the layer 31 or irregular reflection within the gloss imparting layer 31.

  As long as the glossiness imparting layer 31 improves the glossiness of the resin film 11, those known in the art can be used, and the blending composition is not particularly limited. One preferred form of the gloss imparting layer 31 is a transparent or translucent resin film layer. Typically, a material containing 45 to 65% by mass of a thermoplastic resin and 35 to 55% by mass of an inorganic fine powder and / or an organic filler based on the total solid content of the gloss imparting layer 31 may be mentioned. Hereinafter, the gloss-imparting layer 31 of this preferred form will be described in detail.

  Examples of the thermoplastic resin for the gloss imparting layer 31 include ethylene resins such as ethylene copolymers and ethylene copolymers obtained by copolymerizing ethylene and other copolymerization components (high density polyethylene, medium density). Polyethylene, low density polyethylene, etc.), polypropylene homopolymer, polypropylene block copolymer, polypropylene random copolymer and other propylene resins, polymethyl-1-pentene, cyclopentadiene-α-olefin copolymer, ethylene-cyclic olefin copolymer Polyolefin resins such as polymers; ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, metal salt of ethylene-methacrylic acid copolymer (ionomer), ethylene-acrylic acid Alkyl ester copolymer, ethylene-alkyl methacrylate Functional group-containing polyolefin resins such as polyester copolymer, maleic acid-modified polyethylene and maleic acid-modified polypropylene; polyamide resins such as nylon-6, nylon-6,6, nylon-6,10, nylon-6,12; Thermoplastic polyester resins such as aromatic polyesters (polyethylene terephthalate and copolymers thereof, polyethylene naphthalate, polybutylene terephthalate, etc.), aliphatic polyesters (polybutylene succinate, polylactic acid, etc.); aromatic polycarbonates, aliphatic polycarbonates Polycarbonate resins such as: atactic polystyrene, syndiotactic polystyrene, acrylonitrile-styrene (AS) copolymer, acrylonitrile-butadiene-styrene (ABS) copolymer, etc. Examples thereof include, but are not particularly limited to, resin based on polymethyl methacrylate, polyvinyl alcohol, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride resin, polyvinylidene chloride, polyphenylene sulfide, and the like. These can be used alone or in combination of two or more. Further, these copolymers may be binary systems or multi-element systems of ternary systems or higher. Moreover, a random copolymer, a block copolymer, or a graft copolymer may be used.

  Among these, from the viewpoints of mechanical strength, physical properties, chemical properties, productivity, and the like, polyolefin resins such as high-density polyethylene and propylene resins, functional group-containing polyolefin resins, and polyester resins such as polyethylene terephthalate Is preferred. In particular, high-density polyethylene, propylene-based resin, propylene-based resin and high-density or low-density polyethylene are more preferable, and propylene-based resin, propylene-based resin and high-density or low-density polyethylene from the viewpoint of excellent balance of various properties described above. Further preferred is a mixture with polyethylene having a density, a propylene homopolymer having a melting point of 150 to 170 ° C, a propylene copolymer having a melting point of 70 to 160 ° C, an ethylene homopolymer having a melting point of 50 to 140 ° C, or Ethylene copolymers are particularly preferred.

  The content of the thermoplastic resin in the gloss imparting layer 31 is more preferably 47 to 63% by mass, still more preferably 50 to 60% by mass based on the total solid content of the gloss imparting layer 31.

  Examples of the inorganic fine powder include heavy calcium carbonate, light calcium carbonate, calcined clay, talc, diatomaceous earth, titanium oxide, barium sulfate, alumina, silica, zinc oxide, magnesium oxide, white clay, zeolite, mica, sericite, bentonite. , Sepiolite, vermiculite, dolomite, wollastonite, glass fiber, hollow glass beads and the like, but not limited thereto. Among these, heavy calcium carbonate, light calcium carbonate, silica, aluminosilicate, diatomaceous earth, baked clay, talc, titanium dioxide, barium sulfate, alumina, and the like are preferable from the viewpoint of improving gloss and cost. Heavy calcium carbonate and titanium dioxide are preferred. The inorganic fine powder may be subjected to surface treatment as necessary.

  As the organic filler, it is preferable to select a different type of resin from the constituent base material (matrix resin, here, the thermoplastic resin of the gloss imparting layer 31). For example, when a polyolefin resin is used as a constituent base material, preferable organic fillers include polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyamide, polycarbonate, polystyrene, nylon-6, nylon-6,6, and cyclic olefin homopolymer. , Ethylene-cycloolefin copolymer, polyethylene sulfide, polyimide, polymethacrylate, polyethyl ether ketone, polyethylene sulfide, polyphenylene sulfide, melamine resin particles having a melting point higher than the melting point of the thermoplastic resin of the constituent matrix (for example, 120 -300 degreeC) or a glass transition temperature (for example, 120-280 degreeC), and a thing incompatible with the thermoplastic resin of a structural base material is illustrated.

  The average particle size of the inorganic fine powder and the average dispersed particle size of the organic filler may be appropriately selected according to the desired performance, and are not particularly limited. From the viewpoint of mechanical strength and stable film formation, 0.01 to 15 μm is preferable, 0.02 to 8 μm is more preferable, and 0.03 to 4 μm is still more preferable.

  In the present specification, the average particle diameter of the inorganic fine powder means a value measured by a laser diffraction particle measuring apparatus “Microtrack”. Further, in this specification, the average dispersed particle size of the organic filler is determined by observing the cut surface of the resin film 11 with an electron microscope and measuring the dispersed particle size of 100 randomly extracted organic fillers. Mean value calculated based on The dispersed particle diameter is determined from the maximum value (maximum diameter) of the distance between two points on the particle outline.

  The gloss imparting layer 31 may contain one kind of inorganic fine powder alone or in combination of two or more kinds. The gloss imparting layer 31 may contain one kind of organic filler alone or in combination of two or more kinds. Further, the gloss imparting layer 31 may contain a combination of one or more inorganic fine powders and one or more organic fillers. In addition, the content of the inorganic fine powder and the organic filler in the gloss imparting layer 31 is more preferably 37 to 53% by mass in total based on the total solid content of the gloss imparting layer 31, and more preferably 40 to 50 in total. % By mass.

  Further, the gloss-imparting layer 31 is composed of a heat stabilizer (antioxidant), a light stabilizer, an ultraviolet absorber, a dispersant, a lubricant, a slip agent such as a fatty acid amide, an anti-blocking agent, and a kneading type in addition to the above components. It may contain known additives such as antistatic agents, dyes, pigments, plasticizers, crystal nucleating agents, mold release agents, flame retardants and the like. Since these are the same as those of the printing layer 21 described above, a duplicate description here is omitted.

  The gloss imparting layer 31 may be an unstretched layer or a stretched layer. From the viewpoint of obtaining a flatter surface and interface, the gloss imparting layer 31 is preferably a uniaxially stretched or biaxially stretched layer. Here, when the gloss imparting layer 31 contains an inorganic fine powder and / or an organic filler and is stretched, pores having these as a core may be formed inside the gloss imparting layer 31. In this case, the light incident on the inside of the gloss imparting layer 31 can be efficiently reflected at the resin / air interface of the pores, and higher glossiness tends to be obtained. For example, when the gloss-imparting layer 31 is a uniaxially stretched layer, the holes are easily formed in a rugby ball shape, and the light reflection at the layer is so-called irregular reflection with poor directivity with respect to incident light, and the appearance is matte. The impression tends to be a strong gloss. On the other hand, when the gloss imparting layer 31 is a biaxially stretched layer, the pores are easily formed in a flattened disk shape, the ratio of regular reflection in light reflection in the layer increases, and the appearance has a pearl-like impression. It tends to be strong gloss.

(3) Base layer The base layer 41 is a layer that supports the printing layer 21 and the gloss-imparting layer 31 described above, and is laminated on the surface of the gloss-imparting layer 31 opposite to the surface on which the printing layer (A) is formed. Has been. Thereby, the resin film 11 of this embodiment includes the laminated structure which laminated | stacked in order of the printing layer 21 / gloss provision layer 31 / base layer 41. FIG. Providing such a base layer 41 tends to facilitate stable stretch molding.

  As long as the base layer 41 can support the printing layer 21 and the gloss imparting layer 31, those known in the art can be used, and the blending composition is not particularly limited. One preferred form of the base layer 41 is a transparent or opaque resin film layer containing a thermoplastic resin. Typically, based on the total solid content of the base layer 41, a material containing 30 to 100% by mass of a thermoplastic resin and 0 to 70% by mass of an inorganic fine powder and / or an organic filler may be mentioned. More preferably, what contains 50-100 mass% thermoplastic resin and 0-50 mass% inorganic fine powder and / or an organic filler on the basis of the total solid content of the base layer 41 is mentioned. The details of these components and blending compositions, as well as optional blending components, are the same as those described for the gloss-imparting layer 31 described above, and redundant descriptions are omitted here.

  The base layer 41 may be an unstretched layer or a stretched layer. From the viewpoint of obtaining a flatter surface and interface, the base layer 41 is preferably a uniaxially stretched or biaxially stretched layer.

(4) Layer Configuration The resin film 11 of the present embodiment has a multilayer structure in which the printing layer 21, the gloss imparting layer 31, and the base layer 41 are laminated at least in this order. In this specification, “laminated in this order” means that they are arranged in this order, and between the printed layer 21 and the gloss imparting layer 31 and / or the gloss imparted layer 31. This includes a mode in which an arbitrary layer such as an adhesive layer or an intermediate layer is interposed between the base layer 41 and the base layer 41. Hereinafter, various specific modes will be described while representing the print layer 21 as A, the gloss imparting layer 31 as B, and the base layer 41 as C as necessary.

  For example, the resin film 11 of this embodiment is symmetrical with the printing layer 21 (A) and the gloss-imparting layer 31 (B) on both sides of the base layer 41 (C), in addition to the three-layer structure of A to C described above. It can be set as the structure (for example, A / B / C / B / A) provided automatically. Further, a structure in which another resin film layer (D) or the like is provided on at least one surface of the base layer 41 (C) (for example, A / B / C / D, A / B / D / C, A / B / D / C / D). Whatever the multi-layer structure, it is sufficient that the printed layer 21 (A) of the resin film 11 is disposed so as to be the outermost layer. At this time, the base layer 41 (C) also functions as the core material of the resin film 11 of each aspect.

  Furthermore, the resin film 11 of the present embodiment may be a laminate provided with another resin film, pulp papermaking, plain woven fabric, or non-woven fabric. Furthermore, it may be one containing an adhesive layer and release paper (for example, A / B / C / adhesive / release paper) as necessary.

  Moreover, after printing on the printing surface (printing layer 21 (A)) of the resin film 11 of this embodiment, the obtained printed matter can also be used as an in-mold label (in-mold label). Then, by inserting the label into a mold and producing a resin molded product by a method such as injection molding or blow molding, a resin molded product in which the label is integrated can be obtained. The in-mold label is suitable as a form in which a layer of a known heat seal resin is laminated on the surface opposite to the printed layer 21 (A) of the resin film (for example, A / B / C / heat seal resin layer). Can be used.

  As illustrated above, the molded body having a structure in which the resin film 11 of the present embodiment is the outermost layer and the resin film 11 is laminated on another resin film or a resin molded product is one of the preferred aspects of the present embodiment. is there. The printed matter obtained by printing on the printing surface (printing layer 21 (A)) of the resin film 11 of the present embodiment is not only used as a poster or label, but also used as a resin film having high rigidity (rigidity) It is because it can be utilized as a standing signboard (signboard), an electric decoration signboard, etc. by laminating.

  In order to increase the rigidity of the resin film, a laminate of the resin film 11 of the present embodiment and another resin film is preferable. Here, other resin films for increasing the rigidity include not only the resin used in each layer of the resin film 11 of the present embodiment, but also an epoxy resin, an unsaturated polyester resin, a phenol resin, a urea resin, a melamine resin, and a polyurethane. Thermosetting resins such as resins, silicone resins and diallyl phthalate resins can also be suitably used. These may contain inorganic fine powders such as calcium carbonate, aluminosilicate, alumina, calcined clay, silica, diatomaceous earth, talc, titanium oxide and barium sulfate.

(5) Molding method The molding method of the resin film 11 of this embodiment can apply a well-known method suitably, The kind is not specifically limited. For example, using a single-layer or multi-layer T-die or I-die connected to a screw-type extruder, cast molding for extruding molten resin into a sheet, using an O-die connected to a screw-type extruder, Inflation molding, extruding molten resin into a cylinder, calendering, rolling molding, molding using a method of removing a solvent or oil after casting or calendering a mixture of a thermoplastic resin and an organic solvent or oil, etc. it can.

(6) Lamination A known method can be appropriately applied to the method for laminating the resin film 11 of the present embodiment, and the type thereof is not particularly limited. For example, a multilayer die method using a feed block and a multi-manifold, an extrusion lamination method using a plurality of dies, and the like can be applied. A multilayer die method and an extrusion lamination method can also be used in combination. In addition, any known laminating method such as dry lamination using an adhesive, wet lamination, or hot melt lamination can be used.

  Specifically, in molding the resin film 11 of the present embodiment, a laminated structure in which the printing layer 21 / gloss imparting layer 31 / base layer 41 are laminated in this order is integrally extruded by coextrusion using a multilayer die method. Can do. Further, after the base layer 41 is once formed into a sheet shape by the cast molding described above, the printing layer 21 and the gloss imparting layer 31 can be laminated by a laminating method. At this time, the printing layer 21 and the gloss imparting layer 31 may be individually laminated in order using a plurality of dies, or the printing layer 21 and the gloss imparting layer 31 may be coextruded and laminated simultaneously using a multilayer die. Good.

(7) Stretching In addition, the resin film 11 of the present embodiment is preferably stretched at least in the uniaxial direction. By stretching, it is easy to obtain a thickness and stiffness excellent in various printability as a printing paper, and it is easy to obtain a uniform thickness by reducing variations in the thickness of the resin film 11, and further, a flat surface or There is a tendency that an interlayer interface is easily obtained.

  The number of stretching axes in each layer is not particularly limited. For example, in the three-layer structure, A / B / C = 1 axis / 1 axis / 1 axis, 1 axis / 1 axis / 2 axis, 1 axis / 2 axis / 1 axis, 2 axis / 1 axis / 1 axis, 1 axis / 2 axis / 2 axis, 2 axis / 2 axis / 1 axis, 2 axis / 2 axis / 2 axis, and the like. Even in the case of a layer structure of four or more layers, the number of stretching axes can be arbitrarily combined as in these cases.

  The stretching method is not particularly limited, and can be appropriately selected from known methods. For example, it is possible to use longitudinal stretching utilizing the peripheral speed difference of the roll group, transverse stretching using a tenter oven, rolling, simultaneous biaxial stretching using a combination of a tenter oven and a linear motor, and the like.

  The temperature at the time of stretching is not particularly limited, and may be appropriately set in consideration of the blending composition of each layer, for example, the melting point of the thermoplastic resin. In general, it is preferably not higher than the melting point of the thermoplastic resin, more preferably within a temperature range of 2 to 20 ° C. lower than the melting point. Also, the stretching speed is not particularly limited, but it is preferably performed within a range of 20 to 350 m / min.

  The draw ratio may be appropriately set in consideration of the blend composition of each layer, and is not particularly limited. In the case of uniaxial stretching, usually 2 to 12 times are preferable, more preferably 3 to 10 times, and further preferably 4 to 8 times. In the case of biaxial stretching, usually 4 to 80 times are preferable in terms of area magnification. More preferably, it is 10-65 times, More preferably, it is 20-50 times.

(8) Thickness The thickness (total thickness) of the resin film 11 of the present embodiment may be appropriately set according to the application and required performance, and is not particularly limited. Usually, 20 micrometers-1000 micrometers are preferable, More preferably, they are 30 micrometers-500 micrometers, More preferably, they are 40 micrometers-300 micrometers. If the thickness of the resin film 11 is 20 μm to 1000 μm, it is difficult to cause problems when performing offset printing, and the utility value as printing paper tends to increase.

(9) Glossiness The resin film 11 of this embodiment preferably has a glossiness (JIS P-8142) on the surface side of the printing layer 21 of 70% to 110%, more preferably 80 to 108%, and even more preferably. Is 85 to 105%. When the glossiness is 70% or more, when printing is performed on the printing layer 21 of the resin film 11, a high glossy and bright printed material texture and a light atmosphere tend to be easily obtained. The glossiness can be adjusted, for example, by selecting the material of each layer of the resin film 11 and stretching conditions (temperature, magnification, etc.) during production.

(10) Opacity The opacity (JIS P-8138) of the resin film 11 of the present embodiment is not particularly limited as long as it is appropriately set according to the application, required performance, and the like. Such opacity can be adjusted by the concentration of the inorganic fine powder and / or organic filler in each layer of the resin film 11, the stretch ratio of the resin film, the stretch temperature of the resin film, and the like. When transparent or translucent layers are used for the print layer 21 and the gloss imparting layer 31, the opacity can be easily adjusted by the opacity of the base layer 41 in particular.

  For example, a resin film having an opacity of 80 to 100% is opaque and has little light penetration. For this reason, it is often used for various applications that require a transparent backing such as a base paper for adhesive processing such as labels and stickers, a base paper for commercial printing such as a poster or pamphlet, and a base paper for packaging paper. . And if it prints on the resin film which is the above-mentioned opacity, the printed pattern will not be influenced by the back surface, the outline becomes clear and it exists in the tendency which is easy to obtain printed matter with favorable recognition property. On the other hand, a resin film having an opacity of 30% or more and less than 80% is translucent and is often used for book covers, electric signboards, and the like. Here, an electric signboard is a character, photograph, or design drawn on a film for customers and passersby by applying multicolor printing on one or both sides and irradiating light from a light bulb, fluorescent light, LED, etc. from the back. It is possible to draw attention to a design such as the above or a notice. These are often used for menus of fast food restaurants such as hamburgers and sushi, and for advertising in department stores, museums, on the streets, and underpasses. A resin film having an opacity of 1% or more and less than 30% is transparent and is often used for applications such as a see-through adhesive label.

(11) Surface Treatment (11a) Oxidation Treatment The resin film 11 of the present embodiment is preferably subjected to an oxidation treatment on its surface, particularly the surface on the printed layer 21 side. Thus, by subjecting the surface of the printing layer 21 to an oxidation treatment, the presence ratio of polar groups can be adjusted, and the oxygen atom number concentration on the surface of the printing layer 21 of the resin film 11 can be adjusted. Then, the surface of the resin film 11 is oxidized, and the oxygen atom number concentration on the surface of the printed layer 21 of the resin film 11 is adjusted, whereby a chemical bonding force with the ink component can be easily obtained. The adhesion between the resin film 11 and the ultraviolet curable ink or oil-based ink tends to be improved.

As the oxidation treatment method, methods such as corona discharge treatment, flame treatment, plasma treatment, glow discharge treatment, and ozone treatment that are generally used for films can be used alone or in combination, and the type is not particularly limited. . Among these, corona discharge treatment and flame treatment are preferable, and corona discharge treatment is more preferable from the viewpoint of ease of equipment and operation. What is necessary is just to set suitably according to oxidation treatment amount (energy amount), required performance, etc., and it does not specifically limit. For example, in the case of corona discharge treatment, the applied energy used is usually preferably 600 to 12,000 J / m ² (10 to 200 W · min / m ² ), and preferably 720 to 9,000 J / m ² (12 to 150 W · m). Min / m ² ), more preferably in the range of 900 to 7,800 J / m ² (15 to 130 W · min / m ² ). In the case of frame processing, the applied energy to be used is usually preferably from 5,000 to 200,000 J / m ² , more preferably from 10,000 to 100,000 J / m ² .

(11b) Oxygen atom number concentration In this specification, the oxygen atom number concentration on the (printing layer 21) surface of the resin film 11 is determined within one week after the above oxidation treatment by an X-ray photoelectron spectrometer (Shimadzu Corporation). Manufactured under the trade name ESCA-3200) under a vacuum degree of 1 × 10 ⁶ Torr or less, a Mg Kd line (1254.0 eV) as an X-ray source, and a value measured under a photoelectron emission angle of 90 °. And The O1s peak (533 eV) was used as the oxygen atom peak measured here.

  The oxygen atom number concentration on the surface of the (printing layer 21) of the resin film 11 of the present embodiment is preferably 3.8 to 20%, more preferably 4.0 to 10%. When the oxygen atom number concentration is within a preferable range, the adhesion of the ultraviolet curable ink tends to be improved while suppressing the roughening of the surface of the printing layer 21 and the accompanying decrease in glossiness. The oxygen atom number concentration can be adjusted by the processing range, processing energy amount, etc. of the above-described oxidation processing method.

(11c) Anchor agent The effect of improving the good adhesion to the ultraviolet curable ink by performing the oxidation treatment tends to attenuate with the lapse of time after the treatment. Therefore, in order to provide more stable adhesion with ink, it is preferable to apply an anchor agent to the surface of the print layer 21 after the oxidation treatment. As such an anchoring agent, those known in the art can be appropriately used, and the kind thereof is not particularly limited. Examples include, but are not particularly limited to, a polyimine polymer or an ethyleneimine adduct of polyamine polyamide alone or mixed, or a compound obtained by adding a crosslinking agent to these. Examples of the ethyleneimine adduct of polyimine polymer or polyamine polyamide include polyethyleneimine, poly (ethyleneimine-urea) and polyimine polyamide ethyleneimine adduct, or alkyl-modified products, cycloalkyl-modified products, aryl-modified products thereof. Examples include allyl-modified products, aralkyl-modified products, alchiral-modified products, benzyl-modified products, cyclopentyl-modified products, or aliphatic cyclic hydrocarbon-modified products, hydroxides thereof, and compounds obtained by combining several of these compounds. However, it is not particularly limited to these.

(11d) Antistatic agent By adding a polymer type antistatic agent to the anchor agent, dust on the resin film 11 due to static electricity or troubles on the printing press during multi-feed printing can be reduced. . As the polymer type antistatic agent, cationic type, anionic type, amphoteric type, nonionic type and the like are known, and any of them can be used. Specifically, examples of the cationic type include those having an ammonium salt structure or a phosphonium salt structure, but are not particularly limited thereto. Anionic types include alkali metal salts such as sulfonic acid, phosphoric acid, and carboxylic acid, for example, alkali metal salts such as acrylic acid, methacrylic acid, and (anhydrous) maleic acid (for example, lithium salt, sodium salt, potassium salt) structure Is included in the molecular structure, but is not particularly limited thereto. Examples of the amphoteric type include those containing both the cationic and anionic structures in the same molecule, specifically, betaine type. Nonionic types include, but are not limited to, ethylene oxide polymers having an alkylene oxide structure, polymers having an ethylene oxide polymerization component in the molecular chain, and the like. In addition, a polymer type antistatic agent having boron in the molecular structure can be given as an example. Among these, a cationic polymer antistatic agent is preferable, and a nitrogen-containing polymer antistatic agent is more preferable. Examples thereof include tertiary nitrogen or quaternary nitrogen (ammonium salt structure) -containing acrylic polymer.

(11e) Amount ratio of anchor agent and antistatic agent When the above-described anchor agent and antistatic agent are used in combination, these amount ratios can be appropriately set according to the required performance, and are not particularly limited. From the viewpoint of sufficiently exerting, the antistatic agent is preferably 0 to 400 parts by mass, more preferably 20 to 300 parts by mass, and further preferably 30 to 150 parts by mass with respect to 100 parts by mass of the anchor agent in terms of solid content.

(11f) Form of anchor agent The above-mentioned anchor agent is generally used in a solution state after being dissolved in water or a solvent such as methyl alcohol, ethyl alcohol, isopropyl alcohol, acetone, methyl ethyl ketone, ethyl acetate, toluene, xylene. is there. Among these, it is preferable to use in the form of an aqueous solution. From the viewpoint of handling properties at the time of application, etc., the anchor agent solution concentration is preferably about 0.5 to 40%, more preferably about 1 to 20%.

(11 g) Amount of anchor agent applied The amount of anchor agent applied to the resin film 11 is not particularly limited, but is usually in terms of solid content from the viewpoints of production cost, stickiness suppression, ink adhesion improvement effect, and the like. preferably 0.01 to 3 g / m ² in, more preferably 0.01 to 1 g / m ^2, more preferably from 0.02 to 0.5 g / m ^2.

(11h) Anchor Agent Application Device The application device for the anchor agent to the resin film 11 can be any of various application devices known in the art, and is not particularly limited. For example, coating apparatuses such as a die coater, bar coater, lip coater, roll coater, gravure coater, spray coater, blade coater, air knife coater, and size press coater can be used.

(12) Adhesive label form (12a) Adhesive The resin film 11 of this embodiment can be used as an adhesive label by further laminating an adhesive. As the pressure-sensitive adhesive used for the pressure-sensitive adhesive label, generally, a rubber-based pressure-sensitive adhesive, an acrylic pressure-sensitive adhesive, and a silicone-based pressure-sensitive adhesive are known, and the kind thereof is not particularly limited, and any one can be used. Specific examples of rubber-based adhesives include polyisobutylene rubber, butyl rubber and mixtures thereof, or tackifiers such as rosin esters of abietic acid, terpene / phenol copolymers, terpene / indene copolymers, etc. However, it is not particularly limited to these. As specific examples of the acrylic pressure-sensitive adhesive, the glass transition point of 2-ethylhexyl acrylate / n-butyl acrylate copolymer, 2-ethylhexyl acrylate / ethyl acrylate / methyl methacrylate copolymer, etc. is −20 ° C. Although the following are mentioned, it does not specifically limit to these. In addition, these pressure-sensitive adhesives include a solvent type, an emulsion type, and a hot melt type, and any of them can be used. In general, a solvent type or an emulsion type is preferable from the viewpoint of productivity.

  The application of the pressure-sensitive adhesive is not particularly limited, and various coating apparatuses known in the art can be used. For example, coating apparatuses such as a die coater, bar coater, comma coater, lip coater, roll coater, gravure coater, spray coater, blade coater, reverse coater, and air knife coater can be used. In general, after coating, a pressure-sensitive adhesive layer is formed through a drying process by performing a smoothing treatment or the like as necessary.

  In forming the pressure-sensitive adhesive layer, it is possible to employ a method in which a pressure-sensitive adhesive layer formed by applying a pressure-sensitive adhesive to a release paper described below and laminating it is laminated on the resin film 11. In some cases, the adhesive may be directly applied to the resin film 11 and dried.

The coating amount of the pressure-sensitive adhesive is not particularly limited, but is usually preferably 3 to 60 g / m ² , more preferably 10 to 40 g / m ^{2 in} terms of solid content. Further, the delamination strength of the pressure-sensitive adhesive layer is not particularly limited, but it is usually preferably 200 to 3,000 g / 20 mm. In addition, when the adhesive force between the resin film 11 and the adhesive is small, an anchor is previously provided on the surface on which the adhesive on the side opposite to the printed layer 21 side of the resin film 11 is provided before the adhesive is applied. It is preferable to apply a coating agent. The anchor coating agent is not particularly limited, and known anchor coating materials such as polyurethane, polyisocyanate / polyether polyol, polyisocyanate / polyester polyol / polyethyleneimine, and alkyl titanate can be used. These are generally used by being dissolved in an organic solvent such as methanol, ethyl acetate, toluene, hexane, or water. The coating amount of the anchor coating agent is not particularly limited, is preferably 0.01-5 g / m ² on a solid basis after coating and drying, and more preferably 0.02~2g / m ² .

(12b) Release paper Moreover, the resin film 11 of this embodiment can also be used as a base paper for adhesive labels by providing a release paper further through the above-mentioned adhesive. As the release paper, those known in the art can be used without particular limitation, and the type thereof is not particularly limited. For example, high-quality paper or kraft paper as it is, or calendered on high-quality paper or kraft paper, coated with resin, laminated with film, glassine paper, coated paper, plastic film, etc., and silicone The thing etc. which gave the process can be used. In order to improve the peelability from the pressure-sensitive adhesive layer, a release paper having a silicone treatment applied to the surface in contact with the pressure-sensitive adhesive layer is preferably used.

(13) Printing (13a) Types of ink The resin film 11 of this embodiment is excellent in printing not only for oil-based inks such as solvent type and oxidation polymerization type that have been widely used in the past, but also for ultraviolet curable inks. Have aptitude. The ultraviolet curable ink is an ink that forms a film by causing a photochemical reaction with ultraviolet energy and solidifying from a liquid to a solid in seconds. Various types of UV curable inks are known, and the main components are generally a photopolymerizable prepolymer or monomer vehicle, a photopolymerization initiator, a colorant and an auxiliary agent. Many of them do not contain organic solvents. One of the characteristics is that the ink containing no organic solvent is a solventless ink having a solid content of 100%. The advantages of using UV-curable inks compared to solvent-based inks are that drying is fast, film strength is high, solvent removal in the printing process can be realized, and the ink does not dry on the printing plate, making it a stable printing operation for a long time. It is easy to contribute. The development of an ultraviolet curable drying system has solved the problem of drying, which has been a major obstacle particularly when printing is applied to plastics, and many ultraviolet curable inks have already been put into practical use.

  As the resin film 11 of the present embodiment, various types of materials can be used as long as they are oil-based ink and ultraviolet curable ink, regardless of printing methods such as offset printing, letterpress printing, flexographic printing, and screen printing. It is. That is, the oil-based ink and the ultraviolet curable ink in the present specification include various inks such as offset printing ink, relief printing ink, flexographic printing ink, and screen printing ink.

  The viscosity of the ink varies depending on the type of ink and the printing method, and is not particularly limited. For example, in an ultraviolet curable ink, the offset printing is greatly different from 300 to 800 dPa · s, and the flexographic printing is greatly different from 1 to 2 dPa · s. What is necessary is just to select suitably according to a use or required performance.

(13b) Applicable printing apparatus As described in detail above, the resin film 11 of this embodiment can cope with various printing methods such as letterpress printing, flexographic printing, gravure printing, screen printing as well as offset printing. It is.

(13c) Application The resin film 11 (printing substrate 100 for posters) of the present embodiment can obtain a printed matter with high gloss and excellent weather resistance by performing various kinds of printing as described above. Therefore, it is useful as, for example, a commercial printed matter such as a poster, a pamphlet, a catalog or a signboard, a publication such as a book, a map, a book cover, a bookmark, or a wrapping paper. Moreover, the resin film 11 of this embodiment can be utilized for uses, such as a label, a sticker, pop, a seal, by laminating | stacking an adhesive layer and making it an adhesive label form. Furthermore, the resin film 11 of this embodiment can also be made into an in-mold label form by laminating a heat seal layer. The resin film 11 (printing substrate 100 for posters) of the present embodiment is intended for outdoor use that is affected by sunlight or rainwater, for example (for example, for posters for elections and signboards) because of its high basic performance. It is particularly useful for posters, various stickers, and various labels) and applications (posters, various stickers, and various labels) that are exposed to water such as saunas, public baths, and bathrooms. In addition, it is compatible with both oil-based inks and UV-curable inks, and in many printing companies throughout Japan where the printing methods are diversifying, even if the printing methods are different, relatively uniform printed matter can be obtained. Since each company can be manufactured in large quantities in a relatively short time at the same time, it is particularly useful in such applications (campaign use, Olympic use, World Cup use, election use, etc.).

  Hereinafter, the features of the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these. That is, the materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention.

Example 1
(1) 85 parts by mass of a propylene homopolymer (manufactured by Nippon Polypro Co., Ltd., trade name “NOVATEC PP MA3U”), and heavy calcium carbonate having an average particle size of 1.25 μm (manufactured by Bihoku Flour Industry Co., Ltd.) The resin composition (C) mixed with 15 parts by mass of “Softon 1800”) was melt-kneaded with an extruder set at 270 ° C. Then, this was extruded to the sheet form, and this was further cooled with the cooling roll, and the unstretched sheet was obtained. Next, the non-stretched sheet was heated again to 150 ° C., and then stretched 5 times in the sheet flow direction using a speed difference between rolls to obtain a longitudinally stretched resin film.

  (2) In addition, 52 parts by mass of a propylene homopolymer (manufactured by Nippon Polypro Co., Ltd., trade name “Novatech PP MA3U”), high density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., trade name “Novatech HD HJ360”) 3 masses Parts, 44 parts by mass of heavy calcium carbonate having an average particle size of 1.25 μm (trade name “Softon 1800”, manufactured by Bihoku Flour Industry Co., Ltd.) ] 1 part by mass of resin composition (B) mixed with propylene homopolymer (Nippon Polypro Co., Ltd., trade name “NOVATEC PP MA3U”), propylene homopolymer (Nippon Polypro Co., Ltd.) 45 parts by mass, product name “NOVATEC PP EA6A”, and polyolefin thermoplastic elastomer (manufactured by Mitsui Chemicals, Inc., product name “Toughma”) PN0040 ") resin composition prepared by mixing 10 parts by weight of (A), were melt-kneaded each in a separate extruder set at 270 ° C.. Next, after supplying these to one multilayer die and laminating inside the die, the obtained laminate is coextruded into a sheet form from the die, and this is a longitudinally stretched resin obtained in the step (1) above. On one surface of the film, the laminate was laminated so that the layer (A) was on the outside, and a laminated sheet having a three-layer structure was obtained.

  (3) Further, 52 parts by mass of a propylene homopolymer (manufactured by Nippon Polypro Co., Ltd., trade name “Novatech PP MA3U”), high density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., trade name “Novatech HD HJ360”) 3 masses Parts, 44 parts by mass of heavy calcium carbonate having an average particle size of 1.25 μm (trade name “Softon 1800”, manufactured by Bihoku Flour Industry Co., Ltd.) )) 1 part by mass of resin composition (D), propylene homopolymer (Nippon Polypro Co., Ltd., trade name “Novatech PP MA3U”) 49 parts by mass, high density polyethylene (Nippon Polyethylene Co., Ltd.) , Trade name “Novatec HD HJ360”), 5 parts by weight, heavy calcium carbonate with an average particle diameter of 1.25 μm (manufactured by Bihoku Powder Chemical Co., Ltd., trade name “Softon 1800”) 45 parts by mass and a resin composition (E) in which 1 part by mass of maleic acid-modified polypropylene (manufactured by Sanyo Chemical Industries, Ltd., trade name “Yumex 1001”) was mixed was set at 270 ° C. Each was melt-kneaded in each of the extruders. Then, after supplying these to a multilayer die different from (2) and laminating inside the die, the obtained laminate is co-extruded from the die into a sheet, which is obtained in the step (2) above. On the surface of the longitudinally stretched resin film side (the layer side of (C) above) of the laminated sheet having a three-layer structure, the layer (E) is laminated so as to be the outside, and A / B / C / D / E A laminated sheet having a five-layer structure was obtained. The resulting laminated sheet having a five-layer structure was cooled to 60 ° C., reheated to 155 ° C. again, stretched 8.5 times in the sheet width direction using a tenter, and then annealed at 165 ° C. . Then, after cooling again to 60 degreeC, the ear | edge part is slit and the thickness of 110 micrometers (A / B / C / D) of a five-layer structure (uniaxial stretching / uniaxial stretching / biaxial stretching / uniaxial stretching / uniaxial stretching) is carried out. / E = 9 μm / 16 μm / 66 μm / 15 μm / 4 μm).

(4) A high-frequency power source (manufactured by Kasuga Electric Co., Ltd., trade name “AGF-B10”), an aluminum electrode having a length of 0.8 m, and a silicone film roll as a treater roll, and a gap between the electrode and the roll. (A) layer side of the film under the condition of applied energy density of 2,040 J / m ² (34 W · min / m ² ) while passing the obtained resin film at a line processing speed of 15 m / min. The surface of this was subjected to corona discharge treatment.

(5) Next, on the (A) layer side surface of the resin film after the corona discharge treatment, 100 parts by mass of the coating agent (i) component of Synthesis Example 1 described later and the coating agent (ii) component 100 of Synthesis Example 2 described later. The coating agent containing a mass part was apply | coated so that the solid content of the coating film after drying might be 0.05 g / m < ² > using a roll coater, it was made to dry-solidify, and the resin film of Example 1 was obtained.

  (6) The obtained resin film has a glossy appearance on the printed layer ((A) layer) side surface and a matte appearance on the back coat layer ((E) layer) side surface. Met. Further, the glossiness of the (A) layer side surface measured in accordance with JIS P8142 was 89%, and the glossiness of the (E) layer side surface measured by the same method was 17%. On the other hand, the oxygen atom number concentration measured by X-ray photoelectron analysis from the (A) layer side surface was 5.0%. Moreover, when the transfer property of UV ink mentioned later, the adhesiveness of UV ink, the drying property of oil-based ink, and blocking property were evaluated, all were good results.

(Synthesis Example 1)
A glycidol-modified polyethyleneimine was synthesized as a coating agent (i) component by the following procedure. This is used as an anchor agent. In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen gas inlet, polyethyleneimine (manufactured by Nippon Shokubai Co., Ltd., trade name “Epomin P-1000 (degree of polymerization 1600)”) 25 A 100% by mass aqueous solution, 10 parts by mass of glycidol, and 10 parts by mass of propylene glycol monomethyl ether were added and stirred under a nitrogen stream, and a denaturation reaction was carried out at 80 ° C. for 16 hours to obtain a glycidol-modified polyethyleneimine aqueous solution. After drying this, the epoxy group of glycidol was converted to polyethyleneimine by infrared spectroscopic analysis, ¹ H-nuclear magnetic resonance spectroscopic analysis ( ¹ H-NMR), and ¹³ C-nuclear magnetic resonance spectroscopic analysis ( ¹³ C-NMR). It was confirmed that the structure formed by adding to nitrogen and that 23% of polyethyleneimine nitrogen reacted with glycidol.

(Synthesis Example 2)
A cationic methacrylate copolymer was synthesized as a coating agent (ii) component by the following procedure. This is used as an antistatic agent. A four-necked flask equipped with a reflux condenser, a thermometer, a glass tube for nitrogen substitution, and a stirrer, 35 parts by mass of dimethylaminoethyl methacrylate, 20 parts by mass of ethyl methacrylate, 20 parts by mass of cyclohexyl methacrylate, stearyl methacrylate 25 parts by mass, 150 parts by mass of ethyl alcohol and 1 part by mass of azobisisobutyronitrile were added, and a polymerization reaction was performed at 80 ° C. for 6 hours under a nitrogen stream. Next, 70 parts by mass of a 60% by mass ethyl alcohol solution of 3-chloro-2-hydroxypropylammonium chloride was added and further reacted at 80 ° C. for 15 hours, and then the ethyl alcohol was distilled off while adding water dropwise. A quaternary ammonium salt copolymer having a solid content of 30% was obtained. This copolymer is a cationic methacrylate ester copolymer containing a structure represented by the following formula in the molecular chain.

(Examples 2-8, Comparative Examples 1-4)
Instead of the resin composition (A) of Example 1 described above, the same procedure as in Example 1 was performed except that the resin composition mixed in the raw materials described in Table 1 and the blending ratio described in Table 2 was used. The resin films of Examples 2 to 8 and Comparative Examples 1 to 4 were obtained. About each obtained resin film, glossiness, oxygen atom number density | concentration, UV ink transferability, UV ink adhesion, oil-based ink drying property, and blocking property were evaluated by the methods described above. The evaluation results are summarized in Table 2.

<Measurement conditions and evaluation method>
(A) Glossiness The glossiness of the printed layer ((A) layer) side surface and the back coat layer ((E) layer) side surface of the obtained resin film is a variable gloss according to JIS P8142: 2005. Using a meter (trade name “UGV-6P”, manufactured by Suga Test Instruments Co., Ltd.), the incidence angle / light reception angle were measured at 75 °.

(B) Oxygen atom concentration of the printed layer ((A) layer) High frequency power source (trade name “AGF-B10” manufactured by Kasuga Electric Co., Ltd.), 0.8 m long aluminum electrode, and silicone coating as a treater roll A roll was used, the gap between the electrode and the roll was set to 5 mm, and a voltage was applied while the obtained resin film was passed at a line processing speed of 15 m / min to apply an applied energy density of 2,040 J / m ² (34 W · min / m ² ) Was subjected to corona discharge treatment on the surface of the film on the layer side (A). The resin film immediately after the corona discharge treatment was cut into a 5 mm × 10 mm rectangle to prepare a test piece for XPS (X-ray photoelectron spectrometer) measurement. Using an XPS measurement device (Thermo Fisher Scientific, trade name “K-ALPHA”), with an aperture diameter of 400 μm and a scan of 10 times, the carbon atom weight, oxygen atom weight, nitrogen atom weight for one test piece, Measurement of sodium atomic weight and chlorine atomic weight was performed three times. The ratio of oxygen atoms when the total of the measurement results of each element was taken as 100% was determined, and the average of three times was defined as the oxygen atom concentration.

(C) Appropriate evaluation of printed matter The surface of the obtained resin film on the printed layer ((A) layer) side is printed by the following method, and the obtained printed matter is evaluated for suitability by the following method and criteria. did.

(C1) UV printing printer (made by Kokubo Seimitsu Co., Ltd., trade name “RI-3 type printing aptitude test machine”) and ultraviolet curable printing ink (made by T & K TOKA Co., Ltd., trade name “Best Cure UV161 (ink) ) ") And UV printing was performed. Note that an ultraviolet irradiator (trade name “ECS-401GX” manufactured by Eye Graphics Co., Ltd.) was used for ultraviolet irradiation for solidifying the ink after printing.

Here, the resin film is first punched into A4 size, adjusted for 3 days in an atmosphere of 23 ° C. and 50% relative humidity, and then the surface of the printed layer (A) of the resin film using the above-mentioned printing machine. Was solid-printed to a thickness of 1.5 g / m ² . After printing, the printed surface of the resin film was irradiated with ultraviolet rays under the condition of 100 mJ / cm ² using the above-described ultraviolet irradiation machine, and the ultraviolet curable ink was dried to obtain a printed matter.

(C2) UV ink transferability evaluation The print surface of the obtained printed matter was measured for 9 print densities per sample using a portable spectral densitometer (trade name “508” manufactured by X-Rite Co., Ltd.) The average value was obtained. In this test, whether the transfer density was 1.4 or higher was evaluated as good (◯), and when it was less than 1.4, the transferability was determined as poor (x).

(C3) UV ink adhesion evaluation Weathering acceleration treatment (exposure test)
In applications such as posters, the ink of UV ink printed matter may be peeled off when used outdoors, which may be a problem. However, in the evaluation of weather resistance, when an exposure test is actually performed outdoors, the results tend to fluctuate due to various variation factors such as climate and weather. In this specification, the printed matter was subjected to a weather resistance promotion treatment (exposure test) under uniform conditions in accordance with JIS K-7350-4, and then evaluated for UV ink adhesion. More specifically, the promotion treatment was performed under the following conditions.

Super accelerated weathering tester (Daipura Wintes Co., Ltd., trade name “Metal Weather KU-R5N-A”, metal halide lamp type) and glass filter “KF-2 Filter” that transmits ultraviolet light of 295 to 450 nm ( Product name). The test piece obtained by cutting out the obtained printed material into a size of 90 mm × 150 mm has an aluminum foil tape “AL-T” (trade name, manufactured by Takeuchi Kogyo Co., Ltd.) so that the printed surface side becomes an exposed surface. And affixed to a stainless steel plate (100 mm × 200 mm) and fixed in a tester. The irradiance on the surface of the test piece was 90 W / m ² , and the black panel temperature was 63 ° C. The accelerated treatment was carried out for 2 cycles, with 5 cycles of exposure at 63 ° C. and 50% relative humidity and 3 hours of exposure at 30 ° C. and 98% relative humidity as one cycle. Therefore, the radiation exposure amount on the printed surface was 5.18 × 10 ⁶ J / m ² .

UV Ink Adhesion Evaluation Next, the test piece subjected to the weather resistance promotion treatment was treated with JAPAN TAPPI paper pulp test method No. 18-2 paper and paperboard-Internal bond strength test method-Part 2: In consideration of the internal bond tester method, using "Internal bond tester" (trade name, manufactured by Kumagaya Riki Kogyo Co., Ltd.) The test which peels off the ink layer on a printing surface was done. The load (loss energy) required for peeling was obtained from the scale, and this was used as the adhesion of UV ink. More specifically, the evaluation was performed under the following conditions.

  After the test piece subjected to the weather resistance promotion treatment was stored for 3 days in an atmosphere of 23 ° C. and 50% relative humidity, three test pieces each having a width of 25 mm and a length of 45 mm were collected from the test piece. Subsequently, the test piece was affixed on the sample holder through a double-sided adhesive tape so that the printing surface of the test piece faced up. Next, cellophane tape (manufactured by Nichiban Co., Ltd., trade name “Cellotape LP-18”) was carefully affixed by hand on the printed surface of the test piece so that no bubbles would enter. Next, place the aluminum angle on the test piece at the base position of the sample holder and the cellophane tape, fold back one end of the cellophane tape and adhere and fix it to the inside of the aluminum angle with double-sided adhesive tape. did. Next, the sample block is fixed between the aluminum angle mounting base and the holder, and a load is applied by the pressure lever. The printed surface of the test piece is bonded to the cello tape and the non-printed surface of the test piece is bonded to the sample holder with a constant pressure. I let you. The press load was 98 N (10 kgf) for one sample block, and the press time was 30 seconds.

  Next, a set of sample blocks (a sample bonded to the aluminum angle and the holder) was taken out and fixed to the mounting base of the measurement unit in such a direction that the pendulum hits the inside of the aluminum angle. The pendulum was swung up 90 degrees to the right (counterclockwise) and fixed on the stopper device clasp. Align the pointer with the starting point, remove the clasp, swing the pendulum down and hit the aluminum angle. The loss energy was read from the position of the pointer on the dial plate and recorded. The above measurement was performed with three test pieces per printed matter, and the average value of these was calculated as the adhesion strength of the ink. In this test, whether the adhesion strength of the ink was 0.5 kgf · cm or more was judged good or bad, and if the same value was less than 0.5 kgf · cm, the possibility of poor adhesion (x) was judged.

(C4) Oil-based printing Printing press (manufactured by Kokubo Seimitsu Co., Ltd., trade name "RI-3 type printing aptitude tester") and oxidation polymerization type synthetic paper ink "Best SP" (manufactured by T & K TOKA) , Product name). The resin film is punched into A4 size, adjusted for 3 days in an atmosphere of 23 ° C. and 50% relative humidity, and then oxidized polymerization type synthetic paper on the surface of the printed layer (A) of the resin film using the above-mentioned printer. The printing ink was solid-printed to a thickness of 1.5 g / m ² to obtain a printed matter.

(C5) Evaluation of oil-based ink drying property The obtained printed matter is left still in an atmosphere of 23 ° C. and a relative humidity of 50% with the printed surface facing upward (so as to come into contact with the atmosphere). Every other hour, after 6 hours had passed and 24 hours had passed, the ink dried state was evaluated in the following manner. First, the index finger's belly was pushed into the solid print portion of the printed material to the extent that the index finger was warped, and the print surface was touched and the printing ink was transferred to the index finger's belly. Subsequently, the belly of the index finger was again pressed into the surface of the printing layer (A) of the unprinted resin film prepared separately, and the transfer condition of the printing ink onto the surface was evaluated according to the following criteria. In this test, the propriety was determined from the evaluation results after 24 hours had passed since printing.
5 (possible): There is no tack on the printed surface, and no ink is transferred to the finger and the resin film. 4 (possible): There is a tack on the printed surface, and the ink is thinly transferred to the shape of the fingertip. 3 (impossible): There is tack on the printed surface, and the ink is transferred thinly along the outline of the finger pad 2 (impossible): There is tack on the printed surface, and the ink is transferred thinly on the entire shape of the finger pad 1 (not possible) : There is a feeling of fluidity on the printed surface, and the ink is darkly transferred to the entire shape of the belly of the finger.

(D) Evaluation of anti-blocking property In this specification, when the resin film sheets are overlapped and a load is applied, the resin films stick to each other is called blocking. When the resin film is blocked, not only the handling property during printing is lowered, but also a problem such as causing a paper jam on the machine by simultaneously transporting a plurality of sheets at the time of sheet-fed offset printing is not preferable. Therefore, the antiblocking property was evaluated by the following procedure.

  The obtained resin film was cut into a size of 20 mm wide × 80 mm long to obtain a test piece. Two test pieces were taken as one set, shifted by 10 mm in the length direction, and overlapped so that one A layer and one E layer were in contact with each other to prepare 15 sets of laminates. A PET film “Mylar” (trade name, manufactured by Teijin DuPont Films Co., Ltd.) was sandwiched between each pair of the laminate so that the pairs did not stick to each other.

Next, 15 sets of test pieces were sandwiched between two iron plates (thickness 5 mm, width 50 mm, length 80 mm), and a pressure jack “J-15” (manufactured by Masada Seisakusho Co., Ltd.) was used. Then, pressurization was performed at a pressure of 10.3 MPa for 5 minutes in an environment where the temperature was 23 ° C. and the relative humidity was 50%. Take out 15 sets of test pieces after pressurization so as not to peel off, and each set is attached to a Tensilon universal testing machine (Orientec Co., Ltd., trade name “RTM-250”), a 5 kg dedicated chuck (Toyo Baldwin Co., Ltd.) 2) 10 mm parts which are shifted from each other are fixed to the gripping part, and the two sheets are pulled in a sliding direction at a pulling speed of 50 mm / min, and the peel adhesive strength (gf) between the two test pieces is measured. It was measured. The average value of peel adhesion strength is read using an automatic balance recorder (manufactured by Toyo Baldwin Co., Ltd., product Sakae “AR-6000”), and the average value of 15 sets of measured values is obtained to obtain anti-blocking properties. Evaluation was made according to the following criteria.
○: 0 gf / 20 mm to 150 gf / 20 mm
Blocking does not occur.
X: More than 150 gf / 20 mm Blocking is likely to occur.

  The resin film of the present invention is a base paper for adhesive processed paper such as labels and stickers, base paper for in-mold labels, base paper for commercial printing such as posters, brochures, catalogs and signboards, base paper for wrapping paper, maps and books. It is useful as a raw material for publishing paper such as covers and bookmarks.

DESCRIPTION OF SYMBOLS 11 Resin film 21 Print layer 31 Gloss imparting layer 41 Base layer 100 Print substrate for poster

Claims (8)

Having a laminated structure in which a printed layer, a gloss-imparting layer, and a base layer are laminated at least in this order;
The printing layer is 80 to 97% by mass of propylene homopolymer (X), 3 to 20% by mass of olefinic thermoplastic elastomer (Y1) and / or soft, based on the total solid content of the printing layer. A resin film comprising at least a polypropylene resin (Y2). The resin film according to claim 1, wherein the olefin-based thermoplastic elastomer (Y1) is a metallocene catalyst-based polypropylene-based thermoplastic elastomer. The resin film according to claim 1 or 2, wherein the soft polypropylene resin (Y2) is a metallocene catalyst-based soft polypropylene resin. The gloss-imparting layer contains at least 45 to 65% by mass of an olefinic (co) polymer and 35 to 55% by mass of an inorganic fine powder and / or an organic filler with respect to the total solid content of the gloss-imparting layer. The resin film according to any one of claims 1 to 3. The olefin-based thermoplastic elastomer (Y1) and / or the soft polypropylene-based resin (Y2) have a melt flow rate (JIS K7210-1: 2014) of 3 to 10 g / 10 min. The resin film as described in the item. The resin film according to any one of claims 1 to 5, wherein the propylene homopolymer (X) has a melt flow rate (JIS K7210-1: 2014) of 1 to 20 g / 10 min. The resin film as described in any one of Claims 1-6 in which the said printing layer does not contain an inorganic fine powder substantially. A printing substrate for a poster comprising the resin film according to claim 1.

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