JPH039863B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to metallic glossy paper with improved rigidity and adhesiveness, which is used as a forming material for carrying bags and cylindrical packaging bags. Conventionally, metallic gloss paper has been produced using so-called aluminum foil paper or aluminum foil, which is made by laminating aluminum foil with a thickness of 6 to 20 microns to a paper, polyethylene terephthalate film, or stretched polypropylene film (OPP) support via an adhesive layer. Film used to be the mainstream, but recently, from the perspective of resource saving, the aluminum foil has been replaced with an aluminum vacuum-deposited layer (thickness is approx.
0.025 to 0.2 micron) is used instead. Those whose support is a resin film are used as strings and agricultural mulching films, and those whose support is made of paper are used as vapor-deposited paper for cigarette packaging, printing paper, and labels. Such vapor-deposited paper is produced by (A) directly applying a solvent-based or water-based anchor coating agent 4 to a base paper such as high-quality paper, pure white roll, or art paper, which is the support 1, and then vapor-depositing aluminum 3 to coat the vapor-deposited surface. Direct metallized paper with 3 as the skin (see Figure 1)
(B) A polyethylene terephthalate film or stretched polypropylene film (OPP) is used as the release film 5, and a release agent 6 is applied onto the release film to form a release layer. A transfer foil having an aluminum vapor-deposited layer on its surface is dry-laminated on a base paper 1 having an adhesive layer 7 on its surface, and then the release film is peeled off to obtain a vapor-deposited layer as a release agent layer. (Fig. 2) and (C) aluminum vapor-deposited OPP film or polyethylene terephthalate film bonded to a pure white roll [``Paper to Plastic'', November 1982 issue] , pp. 30-35]. The surface of these vapor-deposited papers is further coated with varnish containing 1% by weight of yellow pigment, and is also used as golden glossy paper (Utility Model Publication No. 58-520, No. 58-521).
Publication No.). When printing on direct vapor deposited paper, a polyester anchor coating agent is applied to the surface of the aluminum vapor deposited layer and gravure printing is performed. Carrying bags made from these conventional metallic glossy papers,
When forming a bag for liquid filling, the material must meet the following performance requirements. (1) Water resistance (2) Printability (3) Good adhesion since it is made into a bag shape (4) Excellent metallic luster (5) Mechanical strength that can withstand practical use (6) Must have excellent rigidity. Anchor-coated direct metallized paper is superior to transfer metallized paper in terms of printability and adhesion, but is inferior in terms of water resistance. Therefore, polyethylene film containing a large amount of white extender pigment is sometimes used as a base paper instead of coated paper (wood-free paper, art paper, coated paper) to impart water resistance. There are disadvantages in that the metallic luster is slightly lowered, and due to the low rigidity of the polyethylene film, the bag is less easy to open and packaging suitability is lowered (repulsion force is weak). Although the laminated product is superior to direct metallized paper in which the aluminum-deposited surface is anchor-coated in terms of price and water resistance, it has the disadvantage that it is inferior to direct metallized paper in which bag opening, packaging suitability, and printability are treated with anchor coating. The present invention solves the drawbacks of the direct metallized paper and laminated paper, and has the advantages of both metallic glossy papers, such as rigidity and
A metallic glossy paper with excellent water resistance, that is, a synthetic paper having at least a stretched film layer of a thermoplastic resin selected from polypropylene and polyethylene terephthalate with a melting point of 145 to 268°C containing 8 to 65% by weight of inorganic fine powder. A support 1 is formed on the surface of the support 1 in order: an adhesive layer 7, a layer 2 made of a polypropylene or polyethylene terephthalate film that does not substantially contain inorganic fine powder, and an aluminum vapor deposition layer deposited on the anchor coating agent. 3. A metallic glossy paper is provided with an outermost layer 4 made of a transparent coating film made of an anchor coating agent (see FIG. 3). In the present invention, as the synthetic paper serving as the first support, one having a biaxially stretched film layer of a thermoplastic resin such as polyethylene terephthalate or polypropylene is used. Its simplest structure consists of 8 to 65 inorganic fine powders.
% by weight of the above thermoplastic resin film in the machine direction (MD) and 3.5 to 7 times in the transverse direction (LD).
It consists only of a biaxially stretched film that is oriented in the biaxial direction and has pearlescent luster on the surface obtained by stretching the film at a temperature 10 times lower than the melting point of the resin. As shown in FIG. 3, a preferred label structure is such that a uniaxially stretched film of polypropylene 2 containing 8 to 65% by weight of inorganic fine powder 1 is used as the paper-like layer 1b, and a biaxially stretched polypropylene film 1a is used as the base layer. It is a multilayer film. In this case, the base material layer can also contain 3 to 50% by weight of inorganic fine powder such as titanium oxide or calcium carbonate. The structure of this composite film is that on one side of the base layer,
A two-layer film with a structure in which paper-like layers are laminated together,
Even if it is a three-layer film with a structure in which paper-like layers are integrally laminated on both sides of the base layer, three or more layers in which another type of film is further integrally laminated on the back side of the two-layer film. It may be film. This composite film is obtained by T-die molding the resin composition forming the base layer 1a, and then stretches the film 3 to 7 times in the uniaxial direction in advance, and then forms a paper-like layer on the stretched film. 8~ fine powder forming 1b
A resin composition film containing 65% by weight is melt-laminated and then laminated in a direction perpendicular to the stretching direction.
It is produced by stretching 3.5 to 10 times (Japanese Patent Publication No. 40794/1983, Japanese Patent Publication No. 118437/1983). By stretching, many fine holes are formed inside the paper-like layer, giving the laminated film a paper-like texture.
Moreover, surface cracks mainly caused by fine powder are also formed on the surface of the paper-like layer, and transfer of not only gravure printing ink but also offset printing ink is good.
A synthetic paper with a multi-layer structure having this uniaxially stretched film as a paper-like layer provides a metallic luster paper with superior metallic luster than a synthetic paper made of a single layer of biaxially stretched film. In addition, paper feeding performance is also better. The thickness of the support 1 is suitably 50 to 300 microns. Polypropylene includes propylene homopolymer, a propylene copolymer obtained by copolymerizing propylene with one or more olefins such as ethylene, butene-1, hexene-1, etc., and polyethylene terephthalate includes terephthalic acid and copolymer. Polyethylene terephthalate obtained by condensing ethylene glycol, in addition to both raw materials, adipic acid, azelaic acid, propylene glycol, bisphenol A
Examples include co-condensates obtained by co-condensing a third component such as . Other resins such as polyamide and polyethylene may be used, but these are not preferred from the viewpoint of cost or heat resistance. Polypropylene is preferred from the standpoint of chemical resistance, and polyethylene terephthalate is preferred from the standpoint of gas barrier properties. These synthetic papers containing inorganic fine powders cannot be directly deposited with aluminum due to the presence of inorganic fine powders on their surfaces. Therefore, a polypropylene film that does not substantially contain inorganic fine powders is used between the synthetic paper and the aluminum deposited layer. Or interpose a polyethylene terephthalate film. Next, for aluminum vapor deposition on polypropylene film (OPP) and polyethylene terephthalate film, a polyester or polyurethane anchor coating agent is applied to the surface of these films, such as "Underlatscar RL" manufactured by Toyo Ink Manufacturing Co., Ltd.
(Product name), “Adcoat” manufactured by Toyo Morton Co., Ltd.
AD506F” (product name), etc.
After coating at a rate of 0.03 to 5 g/m ² , aluminum is deposited on the anchor coating surface.
The thickness of the film generally used is 8 to 20 microns. Also, the thickness of the aluminum vapor deposition layer is
0.025-0.2 micron, preferably 0.03-0.05 micron. The aluminum-deposited polypropylene or polyethylene terephthalate film and the synthetic paper support are bonded using a solvent-based urethane adhesive, such as BLS-
Mixture of 2080A and BLS-2080B (trade name), adhesive hot melt adhesive, e.g. manufactured by Nitta Gelatin Co., Ltd.
This is done by applying an adhesive such as HT-381 (trade name) and dry laminating the synthetic paper surface and the OPP film or polyethylene terephthalate film surface. An anchor coating agent is applied to the aluminum-deposited surface of this laminate of synthetic paper and aluminum-deposited film in order to provide printability and increase gloss.
It is applied at a rate of 0.05 to 5 g/m ² to produce the metallic gloss paper of the present invention. Since the metallic glossy paper of the present invention uses a stretched film having excellent water resistance and rigidity as a support, it is useful as carrier bags and liquid packaging materials that require water resistance and ease of opening. Curling is also prevented by using a stretched film. Furthermore, compared to conventional vapor-deposited paper that uses unstretched white polyethylene balls containing inorganic fine powder as a support, it is lighter because many fine pores are formed in the film by stretching, with the inorganic fine powder as the core. , and looks more paper-like. In addition, many fine cracks are formed on the surface of the film due to stretching, making the surface rough, and this roughness and stretching impart directionality to the film, making it easy to feed metallic glossy paper. Become. Furthermore, the metallic glossy surface has a very high gloss due to the coating film formed by the anchor coating agent. In another embodiment of the present invention, 0.3 to 5% by weight of pigments such as marine blue, malachite green, salmon pink, wine red, yellow lead, and zinc yellow are blended into the anchor coating agent forming the outermost coating film. This allows you to obtain blue, green, pink, wine-colored, and golden metallic luster. Hereinafter, the present invention will be explained in more detail with reference to Examples. Note that parts and percentages in the examples are based on weight. Example of manufacturing synthetic paper 1 Mitsubishi Yuka Co., Ltd. polypropylene “Noblen MA-”
6” (product name) 90 parts, high-density polyethylene “Yukalon Hard EY-40” manufactured by Mitsubishi Yuka Co., Ltd. (product name) 100
part, 0.8 part of titanium oxide with an average particle size of 1μ as a light resistance improver, and Bis(2,2,6,6-
Tetramethyl-4-piperidyl) sebacate “Sanol LS-770” (trade name) 0.06 parts, clay 15 parts,
Yosinotsucus manufactured by Yoshitomi Pharmaceutical Co., Ltd. as an antioxidant
BHT" (trade name), Adeka Argus Chemical Co., Ltd.'s "Mark-329" (trade name) and Ciba Geigy Co., Ltd.'s "Irganox-1076" (trade name) at 0.1 part each, and Kao soap ( A composition consisting of 0.1 part of oleic acid "Lunatsuku" (trade name) manufactured by Co., Ltd. was melted and kneaded using an extruder, then extruded into a sheet from a die at a temperature of 200°C, and the sheet was heated to about 50°C. The sheet was then heated to about 135°C, and then stretched four times in the longitudinal direction using the difference in peripheral speed between the rolls.Separately, polypropylene (Mitsubishi Noblen
6) 100 parts, 80 parts of clay with an average particle size of 1.5μ, 10 parts of titanium oxide with an average particle size of 1μ, bis(2,2,6,6
-tetramethyl-4-piperidyl) sebacate
0.4 parts each of Yoshinox BHT, Mark 329 and Irganox-1076 as antioxidants.
A composition containing 0.1 part of oleic acid and 0.1 part of oleic acid was melt-kneaded using two other extruders, and then extruded from the die.
The longitudinally stretched sheet is laminated on both sides of the sheet at a temperature of 200°C, and once heated at 20°C from room temperature.
After cooling to a higher temperature, it was reheated to about 155°C, stretched 8 times in the transverse direction using a tenter, and then stretched to 160°C.
The biaxially stretched film of the intermediate layer (base material layer) was heated to a thickness of 70μ by passing it through an oven at ℃.
A white film having a three-layer structure with the front and back uniaxially stretched films each having a thickness of 10 μm and excellent printing and writing properties was obtained. The apparent density of this three-layer film is 0.78
g/cc, and many fine voids were formed in both the base layer and the front and back layers. In addition, many fine cracks were observed on the surfaces of the front and back layers. Example 2 100 parts of the above polypropylene, 35 parts of calcium carbonate with an average particle size of 1.5μ, 5 parts of rutile titanium oxide,
2,6 di-tert-butyl-4-methylphenol 0.1
part, octadecyl 3,5-di-tert-butyl-4-
0.1 part of hydroxyphenyl) propionate,
0.1 part of distearyl pentaerythritol diphosphite, 0.5 part of oleic acid and bis(2,2,
A composition consisting of 0.4 part of 6,6-tetramethyl-4-piperidyl) sebacate was kneaded using an extruder,
It was extruded into a sheet at 230°C and cooled to 90°C. The obtained sheet was heated again to 140°C and then stretched 4 times in the machine direction. Then, after reheating to 155℃, crosswise 5.5
The film was stretched twice to obtain a biaxially stretched film with a pearlescent surface. Many fine voids were observed inside this biaxially stretched film with a wall thickness of 70 μm. Manufacturing example of vapor deposited film Polypropylene film (OPP) with a wall thickness of 12μ
Polyurethane anchor coating agent “Underlatscar RL” (product name) manufactured by Toyo Ink Manufacturing Co., Ltd. is applied to the surface of
After applying it to a concentration of 2g/m ² and semi-drying it,
A deposited film was obtained by depositing aluminum to a thickness of 500 angstroms (Å). Comparative Example of Production of Metallic Glossy Paper 1 Solvent-based urethane adhesive “BLS-” manufactured by Toyo Morton Co., Ltd. was applied to the surface layer side of the three-layer synthetic paper obtained in Example 1.
2080A" (resin) and BLS-2080B (curing agent) at a concentration of 3 g/ ^m2 , dry lamination was performed so that the OPP side of the aluminum vapor-deposited film adhered to the surface layer side of the synthetic paper. A metallic glossy paper was obtained. Example 1 2 g/m 2 of an anchor coating agent “Under Luxur RL (trade name)” manufactured by Toyo Ink Mfg. Co., Ltd. was applied to the aluminum vapor-deposited surface of the metallic glossy paper obtained in Comparative Example ¹ . Example 2 The surface was prepared in the same manner as in Example 1, except that the biaxially stretched film synthetic paper obtained in Example 2 was used instead of the three-layer synthetic paper. Metal gloss paper having a coating film of an anchor coating agent was obtained.Pure white rolled paper laminated products of commercially available direct vapor deposition paper, transfer vapor deposition paper, and vapor deposition film shown in Examples 1 to 2, Comparative Example 1, and Table 1 above were obtained. Water resistance, moisture permeability, metallic luster, bag opening properties, packaging suitability (repulsion force), gravure printability, curl prevention properties, and paper feeding properties were evaluated.The results are shown in the same table.

[Table] * Solvent ethylene/vinyl acetate copolymer solution

[Brief explanation of the drawing]

Figure 1 shows a cross-sectional view of conventional direct metallized paper.
FIG. 2 shows a cross-sectional view of a conventional transfer vapor deposited paper, and FIG. 3 shows a cross-sectional view of a metallic glossy paper showing an embodiment of the present invention. In the figure, 1 is a support, 1a is a biaxially stretched film,
2 is a film, 3 is an aluminum vapor deposited layer, and 4 is a transparent coating film formed from an anchor coating agent.

Claims (1)

[Scope of Claims] 1. Melting point containing 8 to 65% by weight of inorganic fine powder
The support 1 is an opaque synthetic paper having at least a stretched film layer of a thermoplastic resin selected from polypropylene and polyethylene terephthalate at a temperature of 145 to 268°C, and an adhesive layer 7 and an inorganic fine powder are sequentially applied to the surface of the support 1. A layer 2 made of a film of polypropylene or polyethylene terephthalate that does not substantially contain any of Structured metallic glossy paper. 2 The support 1 is a biaxially stretched polypropylene film 1a containing 3 to 50% by weight of inorganic fine powder as a base layer, and a paper-like layer is a uniaxially stretched polypropylene film 1b containing 16 to 65% by weight of inorganic fine powder. The metallic glossy paper according to claim 1, which is a synthetic paper with a multilayer structure. 3 The outermost layer 4 of the coating film contains 0.3 of a pigment selected from malachide green, amber, salmon pink, marine blue, wine red, zinc yellow or yellow lead.
The metallic gloss paper according to claim 1, characterized in that it is a colored coating film containing ~5% by weight.