JP4396176B2 - Barrier film having pearly luster and laminated packaging material using this barrier film - Google Patents

Description

  The present invention relates to a film having both excellent pearl tone and gas barrier properties and a laminated packaging material thereof.

In order to impart a pearly function to a transparent film or the like, many of those obtained by laminating a printing layer made of a printing ink in which a pearly pigment or the like is dispersed on a base material layer are used, As the pigment, metal oxides such as aluminum oxide and natural mica are used. If there are variations in the particle size, smoothness, purity, dispersion state in the ink, etc., the scattering of light increases and the light interference effect using the refractive index becomes insufficient. there were. Further, sufficient gas barrier properties could not be imparted with the printed layer alone. A structure for transfer in which vapor-deposited thin film layers of metals or metal oxides are laminated in a multilayer structure has been proposed as one having stable high glitter (for example, see Patent Document 1).
JP-A-9-11699

  However, the proposed structure is a transfer material, and is intended to transfer a multilayer vapor-deposited thin film layer to a transfer object to give a bright luster. It could not be packaged and stored.

  The subject of this invention is providing the film which has the outstanding pearl tone and gas-barrier property, and its laminated packaging material.

The invention according to claim 1 of the present invention includes a vapor-deposited thin film layer A made of ferric oxide or titanium oxide, a vapor-deposited thin film layer C made of tin oxide, and aluminum oxide on one surface of a base material layer made of a transparent film. Alternatively, it is a barrier film having a pearly luster characterized by providing a laminate in which thin film layers B made of silicon oxide are sequentially laminated.

In the invention according to claim 2 of the present invention, the vapor-deposited thin film layer A made of ferric oxide or titanium oxide, the vapor-deposited thin film layer C made of tin oxide, aluminum oxide or A pearly luster characterized by providing a laminated body in which a deposited thin film layer B made of silicon oxide, a deposited thin film layer C made of tin oxide, and a deposited thin film layer A made of ferric oxide or titanium oxide are sequentially laminated. It is a barrier film which has .

The invention according to claim 3 of the present invention is a barrier film having pearly luster, characterized in that an overcoat layer is further laminated on the outer surface of the laminate.

In the invention according to claim 4 of the present invention, the overcoat layer comprises a water-soluble polymer and (a) one or more metal alkoxides and hydrolysates thereof or (b) tin chloride. Is a barrier film having a pearly luster characterized by

The invention according to claim 5 of the present invention is a laminated packaging material comprising a laminate in which the printed film is laminated on the outer surface of the laminated body of the barrier film having the pearly gloss described above .

The invention according to claim 6 of the present invention is a laminated packaging material comprising the above-mentioned barrier film having a pearly luster , wherein the adhesive layer and the sealant layer are laminated on the outer surface of the laminate. It is.

The invention according to claim 7 of the present invention is a laminated packaging material comprising the laminate of the barrier film having the pearly gloss described above , wherein an adhesive layer and a sealant layer are laminated on the outer surface of the printed layer. Is

In the laminated packaging material of the present invention, the barrier film having a pearly luster is a vapor-deposited thin film layer A made of ferric oxide or titanium oxide, a vapor-deposited thin film layer made of tin oxide on one surface of a base material layer made of a transparent film. A laminated body obtained by sequentially laminating C and a thin film layer B made of aluminum oxide or silicon oxide , or a deposited thin film layer A made of ferric oxide or titanium oxide on one surface of a base material layer made of a transparent film, oxidized depositing a thin film layer C made of tin, deposited thin layer B made of aluminum oxide or silicon oxide, deposited thin film layer C made of tin oxide, and sequentially stacked laminate deposited thin layer a consisting of ferric oxide or titanium oxide Because it is provided, it has excellent gas barrier properties and pearly luster .

  The pearly barrier film and laminated packaging material of the present invention will be described in detail below along the embodiments.

FIG. 1A is a side sectional view of an embodiment of the pearl-like barrier film of the present invention, and in order of thickness, a base material layer (1), a vapor deposition thin film layer A (2), and a vapor deposition thin film layer B (3 ) Are stacked, (
b) is a cross-sectional side view of another embodiment, in which the base layer (1), the deposited thin film layer A (2), the deposited thin film layer B (3), and the deposited thin film layer A (2) are arranged in order in the thickness direction. (C) is a cross-sectional side view of still another embodiment. In the thickness direction, the base layer (1), the vapor deposition thin film layer A (2), the vapor deposition thin film layer C (4), and the vapor deposition are sequentially formed. Thin film layer B (3), vapor deposition thin film layer C (4), and vapor deposition thin film layer A (2) are laminated.

  FIG. 2 (a) is a side sectional view of still another example of the pearl-like barrier film of the present invention. In the thickness direction, the base layer (1), the deposited thin film layer A (2), and the deposited thin film layer B are sequentially arranged. (3) The overcoat layer (5) is laminated, and (b) is a side sectional view of still another example. In the thickness direction, the base layer (1) and the deposited thin film layer A (2) are sequentially arranged. ), A vapor-deposited thin film layer B (3), a vapor-deposited thin film layer A (2), and an overcoat layer (5) are laminated, and (c) is a side cross-sectional view of still another embodiment, and sequentially in the thickness direction. , Substrate layer (1), vapor deposition thin film layer A (2), vapor deposition thin film layer C (4), vapor deposition thin film layer B (3), vapor deposition thin film layer C (4), vapor deposition thin film layer A (2), overcoat Layer (5) is laminated.

  The base material layer (1) is made of a transparent polymer film, and preferably has a high mechanical strength and good dimensional stability such as a polyethylene terephthalate film (PET film) and a nylon film (Ny film). More preferably stretched in the axial direction. Further, in order to improve the adhesion of the deposited thin film layer to the surface of the base material layer (1), corona treatment, low temperature plasma treatment, ion bombardment treatment may be performed as pretreatment, and further chemical treatment, solvent You may give a process etc. A thickness of 5 to 200 μm can be used, and more preferably 12 to 50 μm.

  The deposited thin film layer A (2) is made of ferric oxide or titanium oxide, has an excellent gas barrier property and a high refractive index, and when made of ferric oxide, the red to green interference depends on the film thickness. When it is made of titanium oxide, it has a purple to green interference color depending on the film thickness. The thickness is preferably from 0.01 to 0.7 μm, more preferably from 0.3 to 0.7 μm.

  The vapor-deposited thin film layer B (3) is made of aluminum oxide or silicon oxide, and similarly has excellent gas barrier properties and a low refractive index. In the case of aluminum oxide, the gloss effect is great, and in the case of silicon oxide, interference color. As an iris. The thickness is preferably from 0.01 to 0.7 μm, more preferably from 0.3 to 0.5 μm. .

  The vapor-deposited thin film layer C (4) is made of tin oxide. The tin oxide serves as a nucleus when forming the thin film of the vapor-deposited thin film layer A (2) and the vapor-deposited thin film layer B (3), and acts to make the thin film denser. Have. The thickness is preferably from 0.01 to 0.7 μm, more preferably from 0.3 to 0.5 μm.

  The vapor deposition thin film layer A (2), the vapor deposition thin film layer B (3), and the vapor deposition thin film layer C (4) can be formed by a normal vacuum vapor deposition method. An electron beam heating method, a resistance heating method, an induction heating method, or the like is preferable, and a plasma assist method or an ion beam assist method can be used in order to improve adhesion to the base material layer (1). Further, in order to increase the transparency, it is possible to carry out reactive vapor deposition in which oxygen gas or the like is blown during vapor deposition.

The overcoat layer (5) is laminated to provide high gas barrier properties and to protect the deposited thin film layer, and its constituent components are a water-soluble polymer and (a) one or more metal alkoxides. And a hydrolyzate or (b) an aqueous solution containing at least one of tin chloride or a water / alcohol mixed solution is applied to form a coating agent. Evaporation thin film layer: A solution in which water-soluble polymer and tin chloride are dissolved in an aqueous (water or water / alcohol mixed) solvent, or a solution in which metal alkoxide is directly or previously hydrolyzed is mixed. It was formed by coating and heating and drying.

  Examples of the water-soluble polymer used in the overcoat layer (5) include polyvinyl alcohol, polyvinyl pyrrolidone, starch, methyl cellulose, carboxymethyl cellulose, and sodium alginate. In particular, when polyvinyl alcohol (hereinafter referred to as PVA) is used, gas barrier properties are most excellent. PVA as used herein is generally obtained by saponifying polyvinyl acetate, from a so-called partially saponified PVA in which several tens percent of acetic acid groups remain to completely saponified PVA in which only several percent of acetic acid groups remain. Including, but not limited to.

The tin chloride may be stannous chloride (SnCl ₂ ), stannic chloride (SnCl ₄ ), or a mixture thereof, and may be an anhydride or a hydrate.

  Further, the metal alkoxide is preferably tetraethoxysilane, triisopropoxyaluminum or a mixture thereof.

As a specific composition of the coating agent, for example, 89.6 g of 0.1N hydrochloric acid was added to 10.4 g of tetraethoxysilane, and the mixture was stirred for 30 minutes to hydrolyze with a solid content of 3 wt% (in terms of SiO ₂ ). A decomposition solution and a 3% by weight water / isopropyl alcohol solution of polyvinyl alcohol resin (water / isopropyl alcohol is 90/10 in a weight% ratio) blended in a 60% by weight ratio are used.

  Or, the overcoat layer (5) is a resin used as a binder for ordinary printing inks, for example, any one of cellulose resin, vinyl chloride / vinyl acetate copolymer resin, polyester resin, polyurethane resin, etc. You may form using the coating liquid which has resin as a main component.

  As the method for laminating the overcoat layer (5), known means such as a commonly used gravure coating method and roll coating method can be used. The film thickness after drying may be 0.01 μm or more, but if the thickness exceeds 50 μm, cracks are likely to occur in the film, and therefore the range of 0.01 to 50 μm is preferable.

  FIG. 3 (a) is a side sectional view of an embodiment of the laminated packaging material of the present invention, and the base material layer (1), the deposited thin film layer A (2), and the deposited thin film layer B (3) are sequentially arranged in the thickness direction. The printing layer (6) is laminated, and (b) is a side sectional view of another embodiment, in which the substrate layer (1), the vapor deposition thin film layer A (2), and the vapor deposition thin film layer are sequentially arranged in the thickness direction. B (3), the vapor deposition thin film layer A (2), and the printing layer (6) are laminated | stacked, (c) is a sectional side view of another Example, and is a base material layer (1 in order in the thickness direction). ), Vapor deposition thin film layer A (2), vapor deposition thin film layer C (4), vapor deposition thin film layer B (3), vapor deposition thin film layer C (4), vapor deposition thin film layer A (2), and printing layer (6) are laminated. (D) is a side sectional view of still another embodiment, and in order of thickness, a base material layer (1), a deposited thin film layer A (2), a deposited thin film layer B (3), and an overcoat layer (5), printing layer (6) (E) is a cross-sectional side view of still another embodiment, and the base material layer (1), the vapor deposition thin film layer A (2), the vapor deposition thin film layer B (3), and the vapor deposition are sequentially arranged in the thickness direction. The thin film layer A (2), the overcoat layer (5), and the printing layer (6) are laminated, and (f) is a side sectional view of still another example. 1), vapor deposition thin film layer A (2), vapor deposition thin film layer C (4), vapor deposition thin film layer B (3), vapor deposition thin film layer C (4), vapor deposition thin film layer A (2), overcoat layer (5), A printing layer (6) is laminated.

  The printing layer (6) may be of a single color configuration or a multicolor configuration. In the case of a multicolor configuration, by providing a printing layer made of black ink at the end of printing, a pearly effect when viewed from the substrate layer side. Is strengthened.

  FIG. 4A is a side sectional view of still another embodiment of the laminated packaging material of the present invention. In the thickness direction, the base layer (1), the deposited thin film layer A (2), and the deposited thin film layer B ( 3) The adhesive layer (7) and the sealant layer (8) are laminated, and (b) is a side sectional view of still another embodiment, and the base material layer (1) and the vapor deposition are sequentially arranged in the thickness direction. The thin film layer A (2), the vapor deposition thin film layer B (3), the vapor deposition thin film layer A (2), the adhesive layer (7), and the sealant layer (8) are laminated, and (c) is still another embodiment. It is side sectional drawing of this and is a base material layer (1), vapor deposition thin film layer A (2), vapor deposition thin film layer C (4), vapor deposition thin film layer B (3), vapor deposition thin film layer C (4) in order of thickness direction. Further, the vapor-deposited thin film layer A (2), the adhesive layer (7), and the sealant layer (8) are laminated, and (d) is a side sectional view of still another example. Layer (1 , Vapor deposition thin film layer A (2), vapor deposition thin film layer B (3), overcoat layer (5), adhesive layer (7), sealant layer (8) are laminated, (e) is still another implementation It is side sectional drawing of an example, and is a base material layer (1), vapor deposition thin film layer A (2), vapor deposition thin film layer B (3), vapor deposition thin film layer A (2), overcoat layer (5) in order of the thickness direction. The adhesive layer (7) and the sealant layer (8) are laminated, and (f) is a side cross-sectional view of still another embodiment. The base material layer (1) and the deposited thin film layer are sequentially arranged in the thickness direction. A (2), vapor deposition thin film layer C (4), vapor deposition thin film layer B (3), vapor deposition thin film layer C (4), vapor deposition thin film layer A (2), overcoat layer (5), adhesive layer (7) The sealant layer (8) is laminated, and (g) is a sectional side view of each of the other examples. The base material layer (1) and the deposited thin film layer A (2) are sequentially arranged in the thickness direction. , The deposited thin film layer B (3), the printed layer (6), the adhesive layer (7), and the sealant layer (8) are laminated, and (h) is a side sectional view of still another example, Base material layer (1), vapor deposition thin film layer A (2), vapor deposition thin film layer B (3), vapor deposition thin film layer A (2), printing layer (6), adhesive layer (7), sealant layer in order (8) is laminated | stacked, (i) is a sectional side view of another Example, The base material layer (1), vapor deposition thin film layer A (2), vapor deposition thin film layer C (in order of the thickness direction) 4) Vapor deposition thin film layer B (3), Vapor deposition thin film layer C (4), Vapor deposition thin film layer A (2), Print layer (6), Adhesive layer (7), Sealant layer (8) are laminated , (J) is a side sectional view of still another embodiment, and in order of thickness, a base material layer (1), a deposited thin film layer A (2), a deposited thin film layer B (3), and an overcoat layer (5 ), Printing layer (6), adhesive layer (7), sealant layer (8) are laminated, (k) is a side cross-sectional view of still another example, the base material layer (1), in order in the thickness direction, Deposition thin film layer A (2), Deposition thin film layer B (3), Deposition thin film layer A (2), Overcoat layer (5), Print layer (6), Adhesive layer (7), Sealant layer (8) (L) is a side sectional view of still another embodiment, and in order of thickness, a base material layer (1), a vapor deposition thin film layer A (2), a vapor deposition thin film layer C (4), and a vapor deposition Thin film layer B (3), vapor deposition thin film layer C (4), vapor deposition thin film layer A (2), overcoat layer (5), printing layer (6), adhesive layer (7), sealant layer (8) are laminated. Has been.

The adhesive layer (7) is made of an adhesive such as polyester / polyurethane or polyether / polyurethane, and the coating amount is 1 to 5 g / m ² (dry state).

  The sealant layer (8) is made of ethylene resin such as low density polyethylene resin, medium density polyethylene resin, linear low density polyethylene resin, ethylene / vinyl acetate copolymer resin, homopolypropylene resin, propylene-ethylene random copolymer. It consists of polyolefin resin, such as polypropylene resin, such as a polymer, a propylene-ethylene block copolymer, a polypropylene-alpha-olefin copolymer, and laminates | stacks by a well-known melt extrusion method. In addition, you may use resin which added additives, such as carbon black, to the said polyolefin resin, In that case, since the sealant layer (8) becomes black, the effect of a pearl tone becomes better.

(A)-(c) is a sectional side view of each Example of the barrier film which has pearl tone glossiness . (A)-(c) is a sectional side view of each other Example of the barrier film which has a pearly luster . (A)-(f) is a sectional side view of each Example of the laminated packaging material using the barrier film which has pearly luster . (A)-(l) is side sectional drawing of each other Example of the laminated packaging material using the barrier film which has pearl-like glossiness .

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Base material layer 2 ... Deposition thin film layer A
3. Evaporated thin film layer B
4 ... Evaporated thin film layer C
5 ... Overcoat layer 6 ... Print layer 7 ... Adhesive layer 8 ... Sealant layer

Claims (7)

On one surface of a base material layer made of a transparent film, a deposited thin film layer A made of ferric oxide or titanium oxide, a deposited thin film layer C made of tin oxide, and a thin film layer B made of aluminum oxide or silicon oxide are sequentially laminated. A barrier film having a pearly luster, characterized in that a laminated body is provided . On one surface of the base material layer made of a transparent film, a deposited thin film layer A made of ferric oxide or titanium oxide, a deposited thin film layer C made of tin oxide , a deposited thin film layer B made of aluminum oxide or silicon oxide, and tin oxide A barrier film having a pearly luster, characterized in that a laminated body in which a vapor-deposited thin film layer C made of and a vapor-deposited thin film layer A made of ferric oxide or titanium oxide are sequentially laminated is provided . The overcoat layer is further laminated | stacked on the outer surface of the said laminated body, The Claim 1 or 2 characterized by the above-mentioned.
Barrier film with pearly luster . 4. The pearl according to claim 3 , wherein the overcoat layer comprises a water-soluble polymer and at least one of (a) one or more metal alkoxides and hydrolysates thereof or (b) tin chloride. Barrier film with glossiness . A laminated packaging material comprising a laminate of the barrier film having pearly luster according to any one of claims 1 to 4 , wherein a printed layer is laminated on an outer surface of the laminate. 5. A laminated packaging material comprising a laminate of the barrier film having a pearly luster according to any one of claims 1 to 4 , wherein an adhesive layer and a sealant layer are laminated on an outer surface of the laminate. . 6. A laminated packaging material comprising a laminate of the barrier film having pearly luster according to claim 5 , wherein an adhesive layer and a sealant layer are laminated on the outer surface of the printed layer .

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