JP2015117326A - Film for printing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film for printing that is light in weight and causes no dioxin during incineration.SOLUTION: A film for printing comprises at least comprises a print layer comprising a resin selected from an ethylene-ethyl acrylate copolymer, or an ethylene-vinyl acetate copolymer, or a mixture of them, and calcium carbonate, with a compounding mass ratio of the resin and the calcium carbonate being 30: 70-70: 30.

Description

  The present invention relates to a printing film. The present invention particularly relates to a printing film that is excellent in light weight and does not generate dioxin during incineration.

  Conventionally, a polyvinyl chloride (PVC) film has been used as an indoor and outdoor printing medium. PVC films have been widely used because they are excellent in printability and strength and can be manufactured at low cost. However, in recent years, use has been reconsidered due to environmental considerations that there is a risk of dioxin generation during incineration. Further, the PVC film has a large weight per unit area, and there are problems of workability and conveyance cost.

  As a conventional technique related to a printing film that does not use PVC, a multilayer resin stretched film having a base material layer (A), an amorphous resin-containing layer (B), and a surface layer (C) is known (for example, patents). Reference 1). The multilayer resin stretched film described in Patent Document 1 has a layer structure suitable for general-purpose offset printing inks, and is a technique that requires a multilayer structure and must be manufactured by a stretching method.

JP 2002-36470 A

  However, the invention described in Patent Document 1 is a film having a relatively complicated structure that requires at least a three-layer structure, and requires a plurality of surface treatment steps, resulting in a high manufacturing cost. It was.

  Also, particularly in printing films for inkjet applications, an inkjet receiving layer for absorbing ink is usually required. Even if such a receiving layer is not separately provided, it can be used for inkjet applications. There has been a demand for a printing film having desired characteristics even as a single-layer structure.

  The present invention has been made to solve the above problems. The present inventors use an ethylene-ethyl acrylate copolymer, an ethylene-vinyl acetate copolymer, or a mixture thereof as a resin, and by mixing a predetermined amount of calcium carbonate with such a resin, printing characteristics are improved. It has been found that an excellent film having a single layer structure and exhibiting desired characteristics can be produced, and the present invention has been completed.

  According to one embodiment of the present invention, there is provided a printing film comprising a resin selected from an ethylene-ethyl acrylate copolymer, an ethylene-vinyl acetate copolymer, or a mixture thereof, and calcium carbonate. And a blending mass ratio of the resin and the calcium carbonate is 30:70 to 70:30.

  In the printing film, the resin preferably has a crystallinity of 5 to 40% by mass.

  In the printing film, the resin is preferably an ethylene-ethyl acrylate copolymer, and the ethylene-ethyl acrylate copolymer preferably contains 10 to 30% by mass of ethyl acrylate.

  In the printing film, the calcium carbonate is preferably a surface-treated calcium carbonate having a weight average particle diameter of 0.5 to 4.0 μm.

  In the printing film, it is preferable that the printing layer further contains one or more additives selected from a masking agent, an antioxidant, an ultraviolet absorber, and a light stabilizer.

  In one embodiment, the present invention also provides a printing film composed only of the printing layer.

  In another embodiment, the present invention also provides a printing film further comprising a support layer provided on one surface of the printing layer.

  In the printing film, the support layer includes a single layer or a laminate including at least one selected from the group consisting of a polyethylene film, a polyethylene terephthalate film, a split fiber nonwoven fabric, a flat yarn cloth, a spunbond nonwoven fabric, and a stretched polypropylene. It is preferable that it is a body.

  In the printing film, the support layer is preferably a split fiber nonwoven fabric made of polyolefin resin.

  Moreover, it is preferable that the said film for printing is a film for inkjet printing.

  According to another aspect, the present invention provides a resin compound for producing the printing film, wherein the resin compound is selected from an ethylene-ethyl acrylate copolymer, an ethylene-vinyl acetate copolymer, or a mixture thereof. Resin and calcium carbonate at a blending mass ratio of 30:70 to 70:30.

  In the resin compound, the resin is preferably an ethylene-ethyl acrylate copolymer, and the ethylene-ethyl acrylate copolymer preferably contains 10 to 30% by mass of ethyl acrylate.

  In the resin compound, it is preferable that the resin further contains one or more additives selected from a concealing agent, an antioxidant, an ultraviolet absorber, and a light stabilizer.

According to the present invention, by including at least a printing layer having the above-described configuration, it is an environmentally friendly printing film that has excellent printing characteristics, excellent lightness, and does not generate dioxin during incineration even in a single-layer configuration. It becomes possible to provide. Moreover, by setting it as such a structure, it can manufacture comparatively simply using various manufacturing methods, and can provide the film for printing advantageous also in cost. Furthermore, by further providing a support layer, it is also possible to provide a printing film that is further superior in terms of strength and handleability.
In addition, the resin compound according to the present invention is suitably used as a material for the printing layer in the production of the printing film.

  Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to the embodiments described below.

[First embodiment: Single-layer film for printing]
According to the first embodiment, the present invention is a printing single layer film, which is composed of a printing layer mainly containing a resin, calcium carbonate, and optionally various additives.

  As the resin, an ethylene-ethyl acrylate copolymer (EEA) or an ethylene-vinyl acetate copolymer (EVA) can be used. EEA and EVA are not limited to those polymerized by a specific method, and can be synthesized by various methods. For example, those obtained by radical polymerization can be used. In particular, it is preferable to use EEA or EVA having a low crystallinity, more preferably using EEA or EVA having a crystallinity of 5 to 40% by mass, and a crystallinity of 10 to 30% by mass. More preferably, EEA or EVA is used. This is because of excellent mixing characteristics with calcium carbonate.

  When EEA is used as the resin, in particular, EEA having a mass concentration of ethyl acrylate in EEA (hereinafter referred to as EA concentration) of 10 to 30% by mass is preferable. This is because by setting the EA concentration in such a range, the crystallinity can be set in a desired range. When EVA is used, the same crystallinity can be achieved by setting the mass concentration of vinyl acetate in EVA (hereinafter referred to as VA concentration) to 10 to 30 mass%. EEA or EVA preferably has a melt flow rate of 4 to 5. This is from the viewpoint of resin handling.

  Each of EEA and EVA can be used alone, but a mixture thereof may be used as the resin in this embodiment. The mixing mass ratio in that case can be, for example, 1: 9 to 9: 1, but is not limited to a specific mixing ratio.

  Calcium carbonate is mainly contained in the printing layer according to the present embodiment as a medium that absorbs printing ink. As calcium carbonate, those having a weight average particle size of 0.5 to 4.0 μm are preferable, and those having 1 to 2.5 μm are more preferable from the viewpoint of dispersibility. A weight average particle diameter can be calculated | required as the weight average value D50 in the particle size distribution measurement by a laser beam diffraction method. The shape of calcium carbonate is preferably spherical from the viewpoint of dispersibility.

  In addition, it is preferable from the viewpoint of dispersibility that the calcium carbonate is subjected to a surface treatment. The surface treatment may be performed by an ordinary method using an arbitrary surface treatment agent, or a commercially available product may be used. Examples of surface treatment agents that can be used include resin acids, fatty acids, organic acids, sulfate ester type anionic surfactants, sulfonic acid type anionic surfactants, petroleum resin acids, sodium, potassium, and ammonium. Or a fatty acid ester, resin acid ester, wax, paraffin, nonionic surfactant, diene polymer, titanate coupling agent, silane coupling agent, or phosphoric acid coupling. Although a seed | species or 2 or more types is mentioned, it is not limited to these. Examples of sulfate ester type anionic surfactants include long-chain alcohol sulfates, polyoxyethylene alkyl ether sulfates, sulfated oils, and their salts such as sodium and potassium. Examples of the sulfonic acid type anionic surfactant include alkylbenzene sulfonic acid, alkyl naphthalene sulfonic acid, paraffin sulfonic acid, α-olefin sulfonic acid, alkyl sulfosuccinic acid and the like, and salts thereof such as sodium and potassium. Examples of fatty acids include caproic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, hebenic acid, oleic acid, linoleic acid, linolenic acid, and eleostearic acid. Etc. are exemplified. Examples of the organic acid include maleic acid and sorbic acid, and examples of the diene polymer include polybutadiene and isoprene. Examples of nonionic surfactants include polyethylene glycol ester type surfactants.

  The blending mass ratio of the resin that is the main component constituting the printing layer and calcium carbonate is in the range of 30:70 to 70:30. When the amount of calcium carbonate is larger, the printability is better, but when the amount is too large, it is not dispersed and cannot be formed into a film. Preferably, it is 40: 60-60: 40.

  The constituent components of the printing layer according to the present embodiment may be composed of only the resin and calcium carbonate. Alternatively, in addition to these, optional additives may be added to impart desired properties. Preferred additives include, but are not limited to, masking agents, as well as antioxidants, ultraviolet absorbers, light stabilizers and the like. As the additive, any additive can be used as long as the functions of the resin and calcium carbonate are not impaired.

A concealing agent, which is an example of an additive, can be used for improving the concealing property of the printed layer and preventing see-through. Examples of the masking agent include anatase type titanium white (TiO ₂ ), rutile type titanium white (TiO ₂ ), zinc oxide, antimony oxide, zinc sulfide, calcium silicate, basic calcium carbonate and the like. It is not limited. The amount of the masking agent added can be, for example, 0.1 to 10 parts by mass when the total mass of the resin and calcium carbonate is 100 parts by mass.

  An antioxidant, which is an example of an additive, can be used for the purpose of improving the weather resistance of the printed layer. The antioxidant can be used as a phosphorus antioxidant, a phenol antioxidant, or a combination thereof, but is not limited thereto. Examples of phosphorus antioxidants include tridecyl phosphite, diphenyl decyl phosphite, tetrakis (2,4-di-tert-butylphenyl) [1,1-biphenyl] -4,4′-diylbisphosphonite, Illustrate bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester phosphorous acid, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, etc. Can do. Examples of phenolic antioxidants include 2,6-di-t-butyl-4-methylphenol (dibutylhydroxytoluene), n-octadecyl-3- (4-hydroxy-3,5-di-t-butyl). Phenyl) propionate, tetrakis (methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)) methane and the like can be exemplified.

  The addition amount of the antioxidant can be, for example, 0.1 to 10 parts by mass, when the total mass of the resin and calcium carbonate is 100 parts by mass. In addition, when using 2 or more types of antioxidant, total amount can be made into the said mass part.

  An ultraviolet absorber, which is an example of an additive, can also be used for the purpose of improving the weather resistance of the printed layer. As the ultraviolet absorber, a triazine-based or benzotriazole-based ultraviolet absorber can be used. The addition amount of the ultraviolet absorber can be, for example, 0.1 to 10 parts by mass when the total mass of the resin and calcium carbonate is 100 parts by mass.

  The light stabilizer which is an example of an additive can also be used for the purpose of improving the weather resistance of the printed layer. A hindered amine stabilizer can be used as the light stabilizer. Examples of hindered amine stabilizers include Tinuvin 326 and Kimasorb 944LD manufactured by BASF. The addition amount of the light stabilizer can be, for example, 0.1 to 10 parts by mass when the total mass of the resin and calcium carbonate is 100 parts by mass.

  These additives can be used alone or in combination of two or more.

  The thickness (thickness) of the single-layer film for printing according to the present embodiment is determined by a person skilled in the art according to the purpose and application from the viewpoint of printing characteristics (ink absorption characteristics), handling properties, etc. can do. For example, the thickness can be 5 to 200 μm, and preferably 5 to 80 μm, but is not limited to a specific thickness.

  The printing surface of the film printing layer can be subjected to a surface treatment such as a corona treatment, but the printing layer according to the present embodiment has desired printing characteristics even without a special surface treatment. .

  Next, the single layer film for printing which concerns on 1st Embodiment is demonstrated from a viewpoint of a manufacturing method. The printing single layer film according to the first embodiment may be manufactured by a manufacturing method including a step of obtaining a film material composed of components constituting the printing layer, and a step of forming the obtained film material into a film shape. it can. Both the step of obtaining the film material and the step of forming can be performed by various methods. For example, after performing a step of obtaining a film material by mixing a resin as a material, calcium carbonate, and optionally an additive, then performing a step of forming into a film shape without a time interval, A single-layer film for printing can be produced by a one-step method. Alternatively, after carrying out the step of obtaining a film material by mixing resin, calcium carbonate and optionally additives as materials, melt extrusion, cooling and preparing a pellet-shaped resin compound, any After the time interval, the resin compound can be melted again, and can be manufactured by a two-stage method in which a step of forming into a film shape is performed. The former method is advantageous in that the process is simple and the manufacturing cost can be suppressed. On the other hand, the latter method has an advantage that the resin compound can be produced independently of the film production, so that it is stable in terms of quality such as dispersibility of calcium carbonate.

  In both the one-step method and the two-step method, the step of forming into a film shape can be performed by a melt extrusion method such as an inflation method or a T-die method.

  The single-layer film for printing according to the first embodiment is particularly advantageous in that it has excellent printing characteristics even in a single-layer configuration, is easy to manufacture, and is excellent in lightness. The printing film according to the prior art requires a coating process of the receiving layer and a special surface treatment in order to optimize the printing characteristics, and has a relatively complicated structure. However, according to the present invention, it was possible to achieve desired characteristics with a single layer configuration by selecting the combination of the main components. Such a printing film can be suitably used particularly for inkjet printing applications.

[Second Embodiment: Resin Compound]
According to a second embodiment of the present invention, there is provided a resin compound used as a printing film material, wherein the resin is selected from an ethylene-ethyl acrylate copolymer, an ethylene-vinyl acetate copolymer, or a mixture thereof. And calcium carbonate at a blending mass ratio of 30:70 to 70:30.

  The resin compound according to the second embodiment is preferably obtained by mixing the components that are the material of the single-layer film composed of only the printing layer described in the first embodiment, and melt-extrusion without directly forming into a film shape. Is a granular material formed into a pellet and cooled. Therefore, the constituent components are as described in detail in the first embodiment, and the description thereof is omitted here.

  According to the resin compound according to the second embodiment, there are obtained advantages such as good dispersibility of calcium carbonate and uniform concentration.

[Third embodiment: multilayer film for printing]
According to the third embodiment of the present invention, there is provided a printing multilayer film substantially comprising a printing layer mainly comprising a resin, calcium carbonate, and optionally various additives, and a support layer. Configured.

  The printed layer may be the same as the aspect described in the first embodiment in terms of the constituent components and the manufacturing method, and the description thereof is omitted here. The thickness of the print layer can be the same as that in the first embodiment, but can be reduced by providing a support layer. By providing the support layer, the strength of the entire film is increased, so that the strength specification of the printing layer can be reduced. Such an embodiment is advantageous in that the amount of expensive calcium carbonate and EEA used can be reduced.

  The support layer is provided on one surface of the print layer mainly for the purpose of reinforcing the print layer. The support layer may be made of a general-purpose member having a certain strength, and having desired characteristics according to the purpose, such as flexibility and lightness, and cost reduction due to thin print layer. Examples of the member constituting the support layer include, but are not limited to, a polyethylene film, a polyethylene terephthalate (PET) film, a split fiber nonwoven fabric, a flat yarn cloth, a spunbond nonwoven fabric, and a stretched polypropylene. The support layer may be a single layer support layer made of one kind of material, or a laminate support layer made of a plurality of kinds of materials. Therefore, it may be a support layer formed by laminating a plurality of different members described above, or may be a support layer of a laminate including a layer formed of another member not illustrated.

  In particular, it is preferable to include a support layer comprising at least a split fiber nonwoven fabric made of a polyolefin-based resin such as Warif (registered trademark) or CLAF (registered trademark). This is because it is stretch-strengthened and has high strength and can maintain good printability without impairing the smoothness of the printed layer.

  The thickness (wall thickness) of the support layer can also be appropriately determined by those skilled in the art according to the desired purpose, and is not limited to a specific thickness. As an example, the thickness in the case of a support layer made of a single layer of split fiber nonwoven fabric made of polyolefin resin can be 10 to 200 μm.

  The manufacturing method of the printing multilayer film substantially composed of the printing layer and the support layer includes the step of manufacturing the printing layer according to the manufacturing method described in the first embodiment, and the printing layer and the supporting layer are bonded together. It can be carried out by a two-stage process.

  Various methods are known as the step of laminating the printed layer and the support layer, and examples thereof include, but are not limited to, extrusion lamination and thermocompression bonding. Under the present circumstances, you may further provide the contact bonding layer which consists of a general purpose polyethylene resin between a printing layer and a support layer. The thickness of the adhesive layer can be set to 10 to 50 μm, for example.

  Or the multilayer film for printing can also be manufactured according to the one-step process by fuse | melting the resin compound demonstrated in 2nd Embodiment, and shape | molding directly on a support layer, without using an contact bonding layer. Alternatively, when the constituent component of the support layer is a resin, the print layer and one or more support layers are formed by a multi-layer inflation molding method, and the multi-layer film for printing is formed in a single step. It can also be manufactured.

  According to the multilayer film for printing by 3rd Embodiment, it has the printing characteristics similar to the single layer film of 1st Embodiment, and has the advantage of light weight and low cost.

  Hereinafter, the present invention will be described in more detail with reference to examples. The following examples are intended to illustrate the present invention and are not intended to limit the present invention.

[Example 1]
The raw materials listed in Tables 1 to 4 below were preliminarily friended with a Henschel mixer and charged into an extruder maintained at 200 ° C. After melt extrusion with an extruder, the mixture was cooled and pelletized to obtain a resin compound as a film material. The resin compound was put into an inflation film molding machine maintained at 200 ° C. to produce a calcium carbonate / EAA single layer film according to the first embodiment of the present invention. The thickness of the film was 70 μm.

[Example 2]
The resin compound made of the raw material of Example 1-1 and polyethylene (LE541H manufactured by Nippon Polyethylene Co., Ltd.) were introduced into an inflation film molding machine maintained at 200 ° C., and the two-layer inflation film formation method was used. A calcium carbonate / EEA + PE multilayer film according to the third embodiment was prepared (Example 2-1). The thickness of the entire film was 90 μm, of which the thickness of the calcium carbonate / EAA layer was 60 μm and the thickness of the PE layer was 30 μm.

  CLAF (registered trademark, brand: LX (F)) manufactured by JX Nippon Mining & Energy Co., Ltd. is extruded and laminated with a general-purpose polyethylene resin (the thickness of the polyethylene resin adhesive layer) on the calcium carbonate / EAA film obtained in Example 1 above. 40 μm) to obtain a calcium carbonate / EAA multilayer film reinforced with CLAF according to the third embodiment of the present invention (Example 2-2). Similarly, CLX (registered trademark, brand: LX (F)) manufactured by JX Nippon Mining & Energy Co., Ltd. is extruded and laminated with a general-purpose polyethylene resin on the calcium carbonate · EEA + PE multilayer film obtained in Example 2-1 above. Bonding was performed by the method (polyethylene resin adhesive layer thickness 40 μm) to obtain a calcium carbonate / EEA + PE multilayer film reinforced by CLAF according to the third embodiment of the present invention (Example 2-3). The thickness of each layer was the same as in Examples 2-1 and 2-2.

  The single-layer films produced in Examples 1-1 and 1-2 and the multilayer films produced in Examples 2-1 to 2-3 were respectively used as inkjet printers (solvent inks) manufactured by Mimaki Engineering Co., Ltd. and Japan. Printing was performed using an inkjet printer (UV ink) manufactured by Ose, and an inkjet printer (latex ink) manufactured by Hewlett-Packard. As a result, all had good color development, no bleeding, no ink peeling due to friction, and good printability. On the other hand, in the composition of Comparative Example 1-1, film formation was impossible, and in the single-layer film produced in Comparative Example 1-2, ink peeling occurred and printability was poor.

  About the film manufactured by said Example 1-1, Example 2-1, 2-2, 2-3, based on JISL1096, tensile strength and elongation are each measured about the vertical direction and the horizontal direction of a film. did. The results are shown in Table 5 below. In particular, it was confirmed that the tensile strength was greatly improved in both the longitudinal direction and the transverse direction by adopting a multilayer structure laminated with CLAF. Such a characteristic is particularly advantageous in applications such as a hanging advertisement in which a load of tension due to its own weight is large.

  The printing film according to the present invention can be usefully used as an indoor / outdoor printing medium.

Claims (13)

A resin selected from an ethylene-ethyl acrylate copolymer, an ethylene-vinyl acetate copolymer, or a mixture thereof;
Comprising at least a printing layer containing calcium carbonate,
The film for printing whose compounding mass ratio of the said resin and the said calcium carbonate is 30: 70-70: 30.   The printing film according to claim 1, wherein the resin has a crystallinity of 5 to 40% by mass.   The printing film according to claim 1 or 2, wherein the resin is an ethylene-ethyl acrylate copolymer, and the ethylene-ethyl acrylate copolymer contains 10 to 30% by mass of ethyl acrylate.   The printing film according to claim 1, wherein the calcium carbonate is a surface-treated calcium carbonate having a weight average particle diameter of 0.5 to 4.0 μm.   The printing film according to claim 1, wherein the printing layer further contains one or more additives selected from a masking agent, an antioxidant, an ultraviolet absorber, and a light stabilizer.   The film for printing in any one of Claims 1-5 comprised only from the said printing layer.   The printing film according to claim 1, further comprising a support layer provided on one surface of the printing layer.   The support layer is a monolayer or laminate comprising at least one selected from the group consisting of a polyethylene film, a polyethylene terephthalate film, a split fiber nonwoven fabric, a flat yarn cloth, a spunbond nonwoven fabric, and a stretched polypropylene. 8. The printing film according to 7.   The printing film according to claim 7 or 8, wherein the support layer is a split fiber nonwoven fabric made of a polyolefin resin.   The film for printing in any one of Claims 1-9 for inkjet printing. A resin selected from an ethylene-ethyl acrylate copolymer, an ethylene-vinyl acetate copolymer, or a mixture thereof;
A resin compound for use as a film material for printing, comprising calcium carbonate at a blending mass ratio of 30:70 to 70:30.   The resin compound according to claim 11, wherein the resin is an ethylene-ethyl acrylate copolymer, and the ethylene-ethyl acrylate copolymer contains 10 to 30% by mass of ethyl acrylate.   The resin compound according to claim 11 or 12, further comprising one or more additives selected from a masking agent, an antioxidant, an ultraviolet absorber, and a light stabilizer.