JP3710909B2 - Laminated body - Google Patents

Description

（以下余白）
【００２９】
【表２】

（以下余白）
【００３０】
【表３】

（以下余白）
【００３１】
【発明の効果】
本発明は、上記のように構成されているので、ＰＰ層に含まれる防曇剤が、浸透阻害層を通過しヒートシーラント層であるＰＥ層に到達するまでの日数を要する。したがって、防曇剤の作用は徐々に全層に均一化するため、持続性がある防曇効果を奏する。また、ＰＰ層に含まれる防曇剤の含有量が少ないのでドライラミネーションのときに、接着剤層の硬化を阻害することもない。
【図面の簡単な説明】
【図１】本発明の積層体の断面を示す概念図である。
【図２】本発明の別態様の積層体の断面を示す概念図である。
【符号の説明】
１ 基材フィルム
２ 接着剤層
３ ＰＰ層
４１ 浸透阻害層
４２ 析出防止層
５ 剥離層
６ ＰＥ層
７、７１ 多層フィルム
１０ 積層体[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a sealing and easy-peeling lid material used in relation to a molded container or a multi-layer seal made of polyethylene as a heat sealant layer, and prevents opacity (fogging) of a film due to water droplets and maintains durability. It belongs to a laminate having both anti-fogging properties, stable heat-sealing properties, easy peelability, and no stringiness when peeled.
[0002]
[Prior art]
The sealing part of the easy-open packaging body, which is configured by heat sealing a molded container with conventional polyethylene on the heat sealant layer side, is blended with one of the heat sealant layers with a different material that controls the heat seal strength. , And the interlaminar strength of the layer becomes brittle and causes cohesive failure in the layer, thereby providing easy-openability.
In addition, some heat seal layers formed in multiple layers are made very thin, and the adhesive strength (peeling strength) between the heat seal layer and the layer in contact with the heat seal layer is adjusted, or there are some which can be easily opened by cohesive failure.
[0003]
However, the heat-sealant layer of the easy-open packaging body in which the heat-seal strength is reduced by mixing different kinds of materials is poorly transparent because it is a blend that is essentially incompatible, and the blended product is made uniform. Since it is difficult to disperse, it was difficult to avoid non-uniform peelability (unevenness of peel strength).
And the peeling part by which the cohesive failure which consists of a mixture of a different substance becomes a rough surface, and was not preferable.
[0004]
There is also disclosed a technique of using a multilayer film in which the heat seal portion of the multilayer film is an ultrathin polyethylene (including linear polyethylene) layer and laminated with a base film with easy opening. However, since the heat sealant layer is made of polyethylene, there is a problem that fogging occurs due to water vapor droplets generated from the packaged contents. This is because the polyolefin resin is a hydrophobic resin. That is, when the package is cooled and the water vapor falls below the dew point, the water vapor inside condenses and fine water droplets uniformly adhere to the surface of the film to cause clouding.
In order to solve this problem, a method of adsorbing moisture by applying a hydrophilic polymer compound layer by coating or pasting, or by adding a surfactant to a polyolefin-based resin for hydrophilic treatment Etc. have been proposed and put to practical use.
[0005]
However, the hydrophilic polymer compound layer is not satisfactory as a heat sealant layer, and in particular, there is nothing that can solve the problems such as foreign matter adhesion heat seal and hot sealability that are indispensable for packaging materials. It is.
In addition, a film obtained by adding a surfactant (antifogging agent) or the like to a polyolefin-based resin and having a hydrophilic treatment can provide antifogging properties as a single-layer film. When the polyolefin film containing is laminated with an adhesive layer, the antifogging agent moves to a curable adhesive layer (hereinafter simply referred to as an adhesive layer) and the adhesive curing agent (isocyanate) and There was a problem that it reacted to reduce its curing action. Further, the antifogging agent (in most cases, a surfactant) contained in the heat sealant layer is deposited on the surface of the PE layer before the storage period of the contents, and loses the antifogging effect during the storage period. There was a problem that the antifogging property could not be maintained for a necessary period.
[0006]
[Problems to be solved by the invention]
Providing a molded container with polyethylene as a heat sealant layer and heat-sealable with multi-layer sheet, and providing durable anti-fogging and easy-open laminates laminated with base film and adhesive It is what.
[0007]
[Means for Solving the Problems]
In order to solve the above problems, the present invention provides at least a base film, a polypropylene resin layer (hereinafter referred to as a PP layer), a resin layer that inhibits penetration of an antifogging agent , a release layer, and a polyethylene resin layer ( hereinafter referred to as PE layer.) the a PP layer of the multilayer film formed by laminating in this order, a multilayer film adhered via an adhesive layer of curable, PP layer and the PE layer are anti-fogging agent Is included.
Moreover, the anti-fogging agent of the multilayer film formed by laminating | stacking the base film, the resin layer which prevents precipitation of an anti-fogging agent , PP layer, the resin layer which inhibits penetration of an anti-fogging agent , a peeling layer, and PE layer in this order a laminate for bonding the layer resin for preventing the precipitation through the adhesive layer of the curable, a laminate including only anti-fogging agent to the PP layer and the PE layer.
And the antifogging agent contained in PP layer of the said multilayer film is 0.01-0.06 weight% , and the antifogging agent contained in PE layer is 0.03-0.2 weight%. It was prepared in the range.
Further, the resin layer for preventing the precipitation of the resin layer or anti-fogging agent that inhibits the penetration of the anti-fogging agent of the multilayer film, PP layer not containing an anti-fogging agent or an ethylene-vinyl acetate copolymer saponified layer, It is a layer selected from polyamide layers .
[0008]
DETAILED DESCRIPTION OF THE INVENTION
As shown in FIG. 1, the laminate of the present invention is a multilayer film 7 (PP layer 3) composed of (base film 1) and “PP layer 3, permeation inhibition layer 41, release layer 5 and PE layer 6”. In the laminate 10 in which the PP layer 3 and the PE layer 6 include an antifogging agent in the laminate 10 that is bonded and configured via the adhesive layer 2.
Further, as shown in FIG. 2, (PP layer 3) of multilayer film 71 including (base film 1) and “precipitation preventing layer 42, PP layer 3, permeation inhibition layer 41, release layer 5 and PE layer 6”. ) Are bonded and configured via the adhesive layer 2, and the PP layer 3 and the PE layer 6 include a defogging agent.
The amount of the antifogging agent contained in the PP layer 3 of the multilayer film 7 or 71 is 0.01 to 0.06% by weight, and the amount of the antifogging agent contained in the PE layer 6 is 0.00. It was prepared in the range of 03 to 0.2% by weight.
The permeation inhibiting layer 41 and the precipitation preventing layer 42 of the multilayer film 7 or 71 are layers selected from a PP layer not containing an antifogging agent, a saponified ethylene / vinyl acetate copolymer, or a polyamide.
[0009]
The base film of the present invention defines the surface shape and physical properties of the laminate, and can be processed with a multilayer film and an adhesive layer by applying an adhesive, as well as a printed pattern layer and packaging A film having various barrier properties (light, oxygen, water vapor, aroma, etc.) is selected.
[0010]
The base film is preferably obtained in a winding shape suitable for multilayer film and adhesion processing, and a stretched or unstretched film of thermoplastic resin or a processed one of those films is preferably used.
For example, polyester, polypropylene, polyethylene, polystyrene, polycarbonate, saponified ethylene / vinyl acetate copolymer, acrylic resin, polyamide, polyvinyl chloride, cellulose acetate film, cellophane, aluminum foil, paper, etc. Those laminated by the above lamination method are used.
[0011]
The base film can be made by coating a material with barrier properties such as polyvinylidene chloride and polyvinyl alcohol, or by depositing a metal-aluminum-deposited film that has been subjected to window opening processing, ITO, ZnO ₂ or other metal or metal oxide. There is a processed film provided by sputtering.
And these base film is 10-100 micrometers in thickness, and can provide a pattern layer by normal gravure printing, flexographic printing, etc.
[0012]
The lamination process of the present invention is carried out by ordinary dry lamination, and the adhesive is a general polyester, polyester polyurethane, polyether, polyether polyurethane, vinyl chloride / vinyl acetate copolymer and polyisocyanate. Two-component reactive adhesives, polyether polyurethane polyisocyanate-based, polyester polyurethane polyisocyanate-based one-component reactive adhesives are used.
[0013]
The PP layer constituting the multilayer film is a polypropylene that serves as a base when a multilayer film that imparts easy peelability is formed. And from the grade which can perform a cast sheet | seat, melt extrusion coating, or an inflation process, the homopolymer of a polypropylene and the copolymer with ethylene and other olefins are used by the thickness of 20-60 micrometers.
And the pulverized product of the scrap (the surplus film generated when it cuts to the use width | variety) when manufacturing a multilayer film can be added suitably, and can be used.
[0014]
The addition amount of the antifogging agent contained in the PP layer is 0.01 to 0.06% by weight, and at 0.06% or more, it reacts with isocyanate contained in the dry lamination adhesive to cure the adhesive. May cause inhibition. On the other hand, if it is 0.01% by weight or less, the antifogging retention period of the laminate cannot be maintained.
[0015]
The permeation inhibiting layer 41 may be of a level that allows the antifogging agent to permeate the PE layer continuously, and can be selected from polypropylene homopolymers, polyamides, saponified ethylene / vinyl acetate copolymers, etc. It is preferable that a polypropylene homopolymer having a thickness of 2 to 10 [mu] m is formed.
[0016]
The precipitation preventing layer 42 shown in FIG. 2 has an effect of preventing the antifogging agent contained in the PP layer from coming into contact with the adhesive of the dry lamination and completing the lamination without causing the curing of the adhesive to be inhibited.
It can be selected from polypropylene homopolymer, polyamide, saponified ethylene / vinyl acetate copolymer, and the like. As a result, the amount of antifogging agent used in the PP layer can be increased, the selection range of adhesives can be widened, the pot life until dry lamination of the multilayer film can be extended, and the duration of the antifogging effect Can be made longer.
[0017]
The release layer of the present invention is provided between the permeation-inhibiting layer and the PE layer to give an easy peeling effect to the heat seal part, and can be easily peeled by performing cohesive failure between the release layers.
It is preferable that both the permeation-inhibiting layer and the PE layer have adhesive strength, and the cohesive failure force is weaker than the adhesive strength. Usually blended with polyethylene, polypropylene, ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ethylene / acrylic acid ester copolymer, ionomer, ethylene / butene rubber, ethylene / propylene rubber, polystyrene, polycarbonate, etc. It can be appropriately selected from the products. And the thickness of a peeling layer is 0.5-5 micrometers in order to exhibit the function, and is formed by 2-5 micrometers in coextrusion processing.
[0018]
The PE layer of the present invention is preferably composed of a material that has a suitable adhesive strength with the release layer and can be stably heat-sealed with polyethylene to be heat-sealed.
An ethylene / α-olefin copolymer produced using a metallocene catalyst may be used alone, linear polyethylene, low density polyethylene, ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ethylene / acrylic acid copolymer, Examples include acrylic ester copolymers and ionomers.
The thickness is preferably 1.5 to 5 μm. When coextrusion with the PP layer, the permeation inhibition layer, and the PE layer is performed, the laminar flow can be made uniform, and the film forming property of the thin film can be improved.
[0019]
When the thickness of the PE layer is 1.5 μm or less, stable film formation or heat sealing cannot be performed, and when the thickness is 5 μm or more, the hot sealability is good and the heat seal strength is stable, but the breaking strength of the PE layer when opened The stringing may become large due to the strong strength.
The total thickness of the release layer and the PE layer is preferably 2.5 to 10 μm. When the total thickness is less than 2.5 μm, there is a problem that the heat seal is not stable, and when it exceeds 10 μm, stringing occurs at the peeled portion.
Moreover, it is preferable to add the minimum necessary amount of the antifogging agent to the PE layer in direct contact with the contents, and the amount is 0.03 to 0.2% by weight. When it is less than 0.03% by weight, there is no antifogging effect, and when it is more than 0.2% by weight, heat seal inhibition may occur.
[0020]
Anti-fogging agents added to the PP layer and PE layer are nonionic surfactants (for example, glycerin fatty acid ester, polyglycerin fatty acid monoester, pentaerythritol fatty acid ester, polyoxypropylene / polyoxyethylene block polymer, etc.), negative One or more ionic surfactants (for example, alkyl sulfonate <Na, K, ammonium>, alkyl benzene sulfonate, etc.) or amphoteric surfactants may be mixed and added.
[0021]
Particularly preferred antifogging agents in the present invention are polyglycerin fatty acid esters. Polyglycerin fatty acid ester is an esterification product of polyglycerin and fatty acid obtained by polymerizing glycerin, and the degree of hydrophilicity can be adjusted by changing the degree of polymerization of polyglycerin, the type of fatty acid, and the degree of esterification. .
Monoesters are preferred for the degree of esterification, but are not limited thereto. Polyglycerin fatty acid ester is diglyceryl stearate, diglycerin laurate, diglycerin oleate, tetraglyceryl stearate, tetraglycerin laurate, tetraglycerin oleate, hexaglyceryl stearate, hexaglycerin laurate, hexaglycerin oleate, decaglycerin. From oleate etc., it can use individually or in mixture of 2 or more types.
The method for including the polyglycerin fatty acid ester in the heat sealant layer is not particularly limited, and there is a known mixing / kneading or addition method. For example, with a Banbury mixer or the like, a predetermined amount of a master batch obtained by melt blending polyglycerin fatty acid ester and polyethylene and the resin of the heat sealant layer can be mixed or directly mixed with the resin of the heat sealant layer.
[0022]
The multilayer film is preferably coextruded and formed with the PP layer from the viewpoint of thinning the permeation inhibiting layer and / or the precipitation preventing layer and the PE layer. In the coextrusion film forming method, any of a T-die method using a flat die or an inflation method using a ring die can be applied.
Moreover, multilayer coextrusion coating can also be carried out with the resin structure which has the structure of said multilayer film.
[0023]
In the T-die method, either black box type co-extrusion or multi-manifold type may be used. Also in the inflation method, a known annular die can be used.
Moreover, it is preferable to perform a corona discharge treatment, an ozone treatment, or the like in order to stabilize the adhesion with a printing film or the like on the PP layer on which the permeation inhibition layer / peeling layer / PE layer of the multilayer film is not provided.
[0024]
The PE layer, which is the heat sealant layer, is made of aliphatic hydrocarbons such as liquid paraffin, synthetic paraffin and microcrystalline wax, stearic acid esters of linear alcohols, higher fatty acid amides, etc. in order to have lubricity as desired. A lubricant can be appropriately selected and added.
However, the lubricant exhibits an action of floating on the surface of the heat sealant layer with time and imparting lubricity. Therefore, since the heat sealing property, especially the hot sealing property may be hindered, great care is required for the type and amount of addition.
In addition, the PE layer can be provided with a concavo-convex pattern, or inorganic and organic fine particles can be added to reduce the contact area with other base materials to give lubricity.
[0025]
Next, the results of evaluating the adhesiveness between the base film and the multilayer film and the continuity of the antifogging effect are described for the experimental examples.
[0026]
[Experimental example]
As the laminated body 10 shown in FIG. 1 or 2, the multilayer film 7 or 71 to be laminated on the vapor deposition surface of the aluminum vapor deposition film (12 μm thickness) as the base film 1 is configured as shown in Tables 1 to 3, and glycerin. A multilayer film 7 or 71 was prepared by a T-die method with a configuration having a PP layer 3 and a PE layer 6 to which an antifogging agent composed of mono-di-stearate and stearic acid amide was added.
In addition, the material which comprises a multilayer film used the following.
・ PP layer (propylene / ethylene copolymer) 42μm
・ Penetration inhibition layer (propylene homopolymer: not including antifogging agent) 3 μm
・ Peeling layer (ethylene butene rubber) 3μm
Next, after 72 hours of film formation of the coextruded multilayer film 7 or 71, the corona discharge treated surface of the PP layer 3 or the precipitation preventing layer 42 and the base film 1 provided with the polyester isocyanate-based adhesive layer 2 are dried. The laminate 10 of the experimental example was prepared by laminating by the lamination method.
[0027]
About each sample of an experimental example, the adhesive strength of the base film 1 and a multilayer film and the change of the anti-fogging effect were evaluated.
The results are shown in Tables 1 to 3.
-Evaluation method of anti-fogging effect After lamination, the anti-fogging effect was changed over time based on the following evaluation criteria.
Put 300cc of 25 ° C water and blue glass beads in a 500cc beaker, wrap it with PE layer of the film of Example and Comparative Example, cover it, and clear the laminate after cooling for 1 hour in 3 ° C refrigerator The properties (antifogging effect, visibility of glass beads) are visually evaluated.
A: Excellent defogging effect and continuity can be confirmed.
○: Transparency is slightly lowered, but the contents can be easily confirmed.
(Triangle | delta): Although transparency falls, it can barely confirm the content.
X: It becomes completely opaque.
-Evaluation of adhesive strength The peel strength (peel strength) between the substrate film and the PP layer or the precipitation preventing layer is measured in g / 15 mm width.
A: Peel strength is 300 g / 15 mm or more.
○: Peel strength is 200 to 300 g / 15 mm.
Δ: Peel strength is 100 to 200 g / 15 mm.
X: Peel strength is 100 g / 15 mm or less.
(The following margin)
[0028]
[Table 1]

(The following margin)
[0029]
[Table 2]

(The following margin)
[0030]
[Table 3]

(The following margin)
[0031]
【The invention's effect】
Since the present invention is configured as described above, it takes a number of days for the antifogging agent contained in the PP layer to pass through the penetration inhibiting layer and reach the PE layer which is the heat sealant layer. Therefore, since the action of the antifogging agent is gradually made uniform in all layers, a durable antifogging effect is achieved. Further, since the content of the antifogging agent contained in the PP layer is small, curing of the adhesive layer is not hindered during dry lamination.
[Brief description of the drawings]
FIG. 1 is a conceptual diagram showing a cross section of a laminate according to the present invention.
FIG. 2 is a conceptual diagram showing a cross section of a laminate according to another embodiment of the present invention.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 Base film 2 Adhesive layer 3 PP layer 41 Penetration inhibition layer 42 Precipitation prevention layer 5 Peeling layer 6 PE layers 7, 71 Multilayer film 10 Laminate

Claims (4)

At least a base film, a polypropylene resin layer, a resin layer that inhibits penetration of an antifogging agent , a release layer, and a polypropylene resin layer of a multilayer film formed by laminating a polyethylene resin layer in this order via a curable adhesive layer a laminate adhered Te, a laminate which comprises only antifog agent to the polypropylene resin layer and a polyethylene resin layer. A substrate film, a resin layer to prevent the deposition of anti-fogging agent, a polypropylene resin layer, a resin layer that inhibits penetration of the anti-fogging agent, antifogging multilayer film a release layer and a polyethylene resin layer are laminated in this order a laminate for bonding the resin layer for preventing the precipitation through the adhesive layer of the curable laminate which comprises only antifog agent to the polypropylene resin layer and a polyethylene resin layer. The amount of the antifogging agent contained in the polypropylene resin layer of the multilayer film is 0.01 to 0.06% by weight, and the amount of the antifogging agent contained in the polyethylene resin layer is 0.03 to 0.2. It is weight%, The laminated body of Claim 1 or 2 characterized by the above-mentioned. The resin layer for preventing the precipitation of the resin layer or anti-fogging agent that inhibits the penetration of the anti-fogging agent of the multilayer film, a polypropylene resin layer or does not contain anti-fogging agent, an ethylene-vinyl acetate copolymer saponified layer, polyamide The laminate according to any one of claims 1 to 3 , wherein the laminate is selected from layers.

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