JP6175768B2 - Composite unstretched film for laminating - Google Patents

Description

  The present invention particularly relates to a composite unstretched film for laminating that can be suitably used as a cover material to be heat-sealed with a molded container of APET (amorphous polyethylene terephthalate) or PS (polystyrene).

  Conventionally, various hot-melt films and polyester films have been used for the sealing layer for APET and PS molded containers containing mekabu, mozuku, salty salt, etc. A film obtained by dry laminating a stretched film such as a stretched polyethylene terephthalate film (hereinafter sometimes abbreviated as PET film) or a stretched polypropylene film (hereinafter sometimes abbreviated as OPP) has been used.

  However, such a hot-melt film or polyester film does not have antifogging properties and has a problem that the contents are difficult to see due to condensation due to moisture in the contents. Also, when an anti-fogging agent such as a surfactant is kneaded into a hot melt film or polyester film, the anti-fogging agent bleeds on the seal surface, impairing heat sealability, or the surface opposite to the seal surface There is also a problem that the presence of wrinkles on the laminated surface is obstructing the lamination.

JP 2002-275362 A

  This invention is made | formed in view of the said situation, and the solution subject is to provide the composite unstretched film for lamination which does not inhibit the lamination, without the heat seal intensity | strength with APET and PS sheet | seat falling.

  As a result of intensive investigations in view of the above-described solution, the present inventor has found that the above problem can be easily solved by a film having a specific configuration, and has completed the present invention.

That is, the gist of the present invention is that an outer layer containing a polyamide layer or a saponified ethylene vinyl acetate copolymer layer, an innermost layer made of a hot melt resin, a polyolefin resin, and an antifogging agent of 0.3 to 2.0% containing a composite non-stretched film having an intermediate layer, and innermost layer of thickness 5 ～20Myuemu a thickness of the intermediate layer is 10 to 70 [mu] m, the hot melt resin, 5 to the base polymer of the polyethylene-based resin % To 60% of a tackifier and a wax component.

  According to the composite unstretched film for laminating of the present invention, it is possible to provide a laminating film that does not deteriorate the heat seal strength with an APET or PS sheet and does not inhibit the laminating, and the industrial value of the present invention is high.

  The hot melt resin constituting the film of the present invention may be heat-sealable with APET or PS. As the composition of the hot-melt resin, a polyethylene resin base polymer containing a tackifier and a wax component can be suitably used.

  Examples of polyethylene resins include low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ethylene-vinyl acetate copolymer (EVA), ethylene-methyl methacrylate copolymer (EMMA), and ethylene-acrylic acid. Methyl copolymer (EMA) ethylene-acrylic acid copolymer (EAA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methacrylic acid copolymer (EMAA), ethylene-acrylic acid copolymer (EAA) ) Ionomer, ethylene-methacrylic acid copolymer (EMAA) ionomer, and a resin composed of at least one selected from the group consisting of these ionomers.

  The tackifier is not particularly limited as long as it can improve the hot tackiness and wettability of the base polymer, but rosin, modified rosin or ester compounds thereof, terpene resin, aliphatic petroleum resin, alicyclic group A petroleum petroleum resin, an aromatic petroleum resin, a styrene resin having the highest molecular weight, an isoprene resin, an alkylphenol resin and the like can be suitably used, and two or more kinds may be blended alone.

  As a content of the tackifier in the hot melt resin, the lower limit is usually 5%, preferably 10%. The upper limit is usually 60%, preferably 50%. By setting the content to 5% or more, good heat sealability can be obtained, and by setting the content to 60% or less, the cohesive strength of the hot melt resin itself can be maintained, and as a result, good heat sealing is achieved. Strength can be obtained.

  As a wax component, it is not necessary to add it, but by adding it, film blocking can be prevented, and petroleum wax such as paraffin and microcrystalline wax, and synthetic wax such as low molecular weight polyethylene wax can be suitably used. However, you may mix | blend 2 or more types.

  The thickness of the hot melt resin layer is 3 μm or more, preferably 5 μm or more, 20 μm or less, and preferably 15 μm or less. By setting the lower limit value to 3 μm, good heat sealability can be maintained, and by setting the upper limit value to 20 μm, the antifogging agent from the intermediate layer can be moderately bleed.

  Although it does not specifically limit as polyolefin resin of an intermediate | middle layer, Low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE), polypropylene (PP), ethylene-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer (EAA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methacrylic acid copolymer (EMAA), ethylene-methyl methacrylate copolymer (EMMA), Consists of at least one selected from the group consisting of ethylene-methyl acrylate copolymer (EMA), ethylene-acrylic acid copolymer (EAA) ionomer, and ethylene-methacrylic acid copolymer (EMAA) ionomer. It is preferable that

  The thickness of the intermediate layer containing the polyolefin resin is 10 to 70 μm or more, preferably 15 μm or more, more preferably 20 μm or more, and by making the thickness 10 μm or more, the film can have appropriate flexibility, and the upper limit is 70 μm. By doing, it can prevent that a transparency deterioration and the total thickness of a film become thick.

  The antifogging agent added to the intermediate layer is not particularly limited as long as antifogging property is satisfied, but glycerin fatty acid ester, polyglycerin fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid ester, etc. Is preferred. The addition amount is 0.3 to 2.0%, preferably 0.4% or more, and more preferably 0.5% or more. The upper limit is preferably 1.7%, and more preferably 1.5%. By setting the lower limit to 0.3%, good antifogging properties can be obtained, and by setting the upper limit to 2.0%, appearance defects due to bleeding can be prevented.

  The outer layer of the present invention includes at least one layer of polyamide resin (PA) or ethylene-vinyl acetate copolymer saponified resin for imparting formability in order to prevent bleeding of the antifogging agent on the laminate surface. It is necessary to provide a layer made of (EVOH). These resins may be mixed to form an outer layer.

  The polyamide resin is not particularly limited, but specific examples include, for example, 4 nylon, 6 nylon, 7 nylon, 11 nylon, 12 nylon, 46 nylon, 66 nylon, 69 nylon, 610 nylon, 611 nylon, 6T nylon, 6I nylon, MXD6 nylon, 6-66 nylon, 6-610 nylon, 6-611 nylon, 6-12 nylon, 6-612 nylon, 6-6T nylon, 6-6I nylon, 6-66-610 nylon, 6- 66-12 nylon, 6-66-612 nylon, 66-6T nylon, 66-6I nylon, 6T-6I nylon, 66-6T-6I nylon and the like.

  Among these, as the polyamide, it is preferable to use 6 nylon or 6-66 nylon from the viewpoint of pinhole resistance. Moreover, the layer which consists of PA can also provide two or more layers, In that case, each layer may be formed with the polyamide of a different kind.

  The thickness of the layer made of PA is not particularly limited, but is preferably 3 μm or more, more preferably 5 μm or more, and further preferably 7 μm or more. Moreover, 20 micrometers or less are preferable, 17 micrometers or less are more preferable, and 15 micrometers or less are further more preferable. By setting the lower limit of the thickness of the layer made of PA to 3 μm or more, the film-forming property of the film is stabilized, and by setting it to 20 μm or less, it is possible to prevent the film from becoming excessively thick.

  The ethylene content of the ethylene-vinyl acetate copolymer saponified resin (EVOH) in the EVOH layer is not particularly limited, but is preferably 32 mol% or more from the viewpoint of film formation stability, and 38 mol. % Or more is more preferable, 47 mol% or less is preferable and 44 mol% or less is more preferable.

  The saponification degree of EVOH is preferably 90 mol% or more, more preferably 95 mol% or more. By maintaining the ethylene content and the saponification degree of EVOH within the above ranges, the coextrudability of the composite film of the present invention and the strength of the composite film can be improved.

  The thickness of the EVOH layer is preferably 3 μm or more, more preferably 5 μm or more, and further preferably 7 μm or more. Moreover, 20 micrometers or less are preferable, 17 micrometers or less are more preferable, and 15 micrometers or less are further more preferable. By setting the thickness of the EVOH layer to 3 μm or more, the film-forming property of the film is stabilized, and by setting it to 20 μm or less, it is possible to suppress an unnecessary increase in price.

  An adhesive layer can be provided as needed for the purpose of increasing the delamination strength of each layer. There may be one or more adhesive layers. Adhesive resins that can be used as the adhesive layer include polyethylene (PE) such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), and high density polyethylene (HDPE), and polypropylene (PP). Olefin resins such as ethylene-vinyl acetate copolymer (EVA), ethylene-methyl methacrylate copolymer (EMMA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methyl acrylate copolymer (EMA) , Ethylene-ethyl acrylate-maleic anhydride copolymer (E-EA-MAH), ethylene-acrylic acid copolymer (EAA), ethylene-methacrylic acid copolymer (EMMA), ethylene ionomer (ION), etc. The ethylene copolymer resin of Polyolefin resins such as ethylene-vinyl acetate copolymer or ethylene elastomer, monobasic unsaturated fatty acids such as acrylic acid or methacrylic acid, or dibasic fatty acids such as maleic acid, fumaric acid or itaconic acid The thing which chemically couple | bonded the anhydride of this can be illustrated. Among these, it is preferable to use an adhesive resin based on polyethylene.

  When the adhesive layer is provided, the thickness of the adhesive layer is preferably 3 μm or more, more preferably 5 μm or more, and even more preferably 8 μm or more from the viewpoints of workability, economy, and handleability. Moreover, although there is no restriction | limiting in particular, 30 micrometers or less are preferable, 25 micrometers or less are more preferable, and 20 micrometers or less are more preferable. When the thickness of the adhesive layer is 3 μm or more, the delamination strength can be improved. If the adhesive layer is too thick, the transparency is deteriorated and the total thickness of the film is increased, and the manufacturing cost is increased, so the upper limit is desirably 30 μm or less.

  For the purpose of giving the film of the present invention a waist, a polyethylene terephthalate glycol resin can be disposed on the outside of the outer layer resin via an adhesive resin layer. The polyethylene terephthalate glycol resin (PETG) is not particularly limited as long as it is amorphous, but PETG6763 manufactured by Eastman Chemical Co. can be suitably used. The PETG thickness is not particularly limited, but is preferably 3 μm or more, more preferably 5 μm or more, and even more preferably 8 μm or more. Moreover, although there is no restriction | limiting in particular, 30 micrometers or less are preferable, 25 micrometers or less are more preferable, and 20 micrometers or less are more preferable. By making the lower limit of the PETG thickness 3 μm or more, the film-forming property is stabilized, and by making the upper limit of the PETG thickness 30 μm or less, it is possible to suppress an unnecessarily high price.

  In order to prevent curling of the film of the present invention, a layer made of a polyolefin resin can be disposed outside the outer layer resin via an adhesive resin layer. The polyolefin resin is not particularly limited, but polyethylene (PE) such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), and high density polyethylene (HDPE), polypropylene (PP), etc. Olefin resin, ethylene-vinyl acetate copolymer (EVA), ethylene-methyl methacrylate copolymer (EMMA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methyl acrylate copolymer (EMA), Ethylene-ethyl acrylate-maleic anhydride copolymer (E-EA-MAH), ethylene-acrylic acid copolymer (EAA), ethylene-methacrylic acid copolymer (EMMA), ethylene ionomer (ION), etc. Ethylene copolymer resin can be exemplified, Among the linear low density polyethylene (LLDPE), polypropylene (PP) can be preferably used. The thickness of the polyolefin resin is not particularly limited, but is preferably 5 μm or more, more preferably 7 μm or more, and further preferably 10 μm or more. Moreover, although there is no restriction | limiting in particular, 30 micrometers or less are preferable, 25 micrometers or less are more preferable, and 20 micrometers or less are more preferable. Curling of the film can be prevented by setting the polyolefin resin thickness to 5 μm or more, and deterioration of the transparency of the film can be suppressed by setting the polyolefin resin thickness to 30 μm or less.

  The film of the present invention is an inorganic particle such as silica, talc, kaolin, calcium carbonate, or the like for the purpose of improving and adjusting various properties such as molding processability and productivity within a range that does not significantly impair the effects of the present invention. Add additives such as pigments such as titanium and carbon black, flame retardants, weather resistance stabilizers, heat stabilizers, antistatic agents, melt viscosity improvers, crosslinking agents, lubricants, nucleating agents, plasticizers, anti-aging agents, etc. it can.

  The layer structure of the composite unstretched film for laminating according to the present invention is such that at least a polyamide layer and / or a saponified ethylene vinyl acetate copolymer layer is disposed on the outer layer, a hot melt resin is disposed on the innermost layer, and a polyolefin resin is disposed on the intermediate layer. If it is the structure which distributes, it will not specifically limit.

  For example, when expressed by EVOH layer (A), PA layer (B), adhesive resin layer (C), polyethylene resin layer (D), polypropylene layer (E), PETG layer (F), hot melt layer (G) The following layer structure can be formed. Among these, a preferable layer configuration is the following (3), (4), (5), (6), (7) or (8), and a more preferable layer configuration is (3) or (4).

(1) A / C / D / G
(2) B / C / D / G
(3) A / B / C / D / G
(4) B / A / C / D / G
(5) F / C / A / C / D / G
(6) F / C / B / C / D / G
(7) F / C / A / B / C / D / G
(8) F / C / B / A / C / D / G
(9) B / A / B / C / D / G
(10) F / C / B / A / B / C / D / G
(11) A / C / E / G
(12) B / C / E / G
(13) A / B / C / E / G
(14) B / A / C / E / G
(15) F / C / A / C / E / G
(16) F / C / B / C / E / G
(17) F / C / A / B / C / E / G
(18) F / C / B / A / C / E / G
(19) B / A / B / C / E / G
(20) F / C / B / A / B / C / E / G

  The composite unstretched film for laminating of the present invention can be produced using a known method. For example, an extrusion lamination method, a coextrusion inflation method, a coextrusion T die method, and the like can be used, and it is particularly preferable to use a coextrusion T die method.

Examples of the present invention will be described below, but the present invention is not limited thereto.
Example 1:
(Preparation of composite unstretched film for lamination)
A composite unstretched film for laminating according to the present invention having the following layer structure was prepared by co-extrusion T-die method, and was used as Example 1.
EVOH1 (10 μm) / Ny1 (10 μm) / Adhesive resin 1 (10 μm) / LLDPE1 (20 μm) / Hot melt resin 1 (10 μm)
EVOH1: Kuraray Eval 38mol type Ny1: DSM Japan Engineering Plastics Novamid 66Ny 6-66 copolymer Ny ratio 15%
Adhesive resin 1: Admer made by Mitsui Chemicals LLDPE 1: 1.0% glycerin monostearate added to Novatec LL made by Nippon Polyethylene Hot melt resin 1: Mersen M made by Tosoh

Example 2:
A composite unstretched film for laminating according to the present invention having the following layer constitution was produced by the coextrusion T-die method, and the outer layer (Ny2) was subjected to corona treatment to give Example 2.
Ny2 (20 μm) / adhesive resin 1 (10 μm) / LLDPE1 (30 μm) / hot melt resin 1 (10 μm)
Ny2: DM Japan Engineering Plastic Novamid 6Ny

Example 3:
A composite unstretched film for laminating of the present invention having the following layer constitution was produced by the coextrusion T-die method, and the outer layer (Ny2) was subjected to corona treatment to give Example 3.
Ny2 (5 μm) / adhesive resin 1 (5 μm) / EVOH1 (10 μm) / Ny1 (10 μm) / adhesive resin 1 (5 μm) / LLDPE2 (20 μm) / hot melt resin 1 (15 μm)
LLDPE2: 1.5% glycerin monomonopalmitate added to Nippon Polytech Novatec LL

Example 4:
A composite unstretched film for laminating according to the present invention having the following layer structure was prepared by co-extrusion T-die method, and was used as Example 4.
PETG (10 μm) / Adhesive resin 2 (5 μm) / Ny1 (5 μm) / EVOH1 (5 μm) Adhesive resin 1 (5 μm) / LLDPE2 (22 μm) / Hot melt resin 2 (8 μm)
PETG: PETG manufactured by Eastman Chemical Company
Adhesive resin 2: Modic hot-melt resin made by Mitsubishi Chemical 2: Hirodine made by Yasuhara Chemical

Example 5:
An unstretched composite unstretched film of the present invention having the following layer constitution was produced by the coextrusion T-die method, and the outer layer (LLDPE3) was subjected to corona treatment to give Example 5.
LLDPE3 (10 μm) / Adhesive resin 1 (5 μm) / EVOH1 (5 μm) Adhesive resin 1 (5 μm) / EVA1 (20 μm) / Hot melt resin 2 (10 μm)
LLDPE3: Nippon Polytech Novatec LL
EVA1: 1.0% sorbitan laurate added to Novatec EVA (Vac 8%) made by Nippon Polyethylene

Comparative Example 1:
A composite unstretched film for laminating of the present invention having the following layer constitution was produced by the coextrusion T-die method, and the outer layer (LLDPE3) was subjected to corona treatment to obtain Comparative Example 1.
LLDPE3 (20 μm) / LLDPE1 (20 μm) / Hot melt resin 1 (10 μm)

Comparative Example 2:
A composite unstretched film for laminating according to the present invention having the following layer structure was produced by coextrusion T-die method, and used as Comparative Example 2.
EVOH1 (10 μm) / Ny1 (10 μm) / Adhesive resin 1 (10 μm) / LLDPE3 (20 μm) / Hot melt resin 3 (10 μm)
Hot melt resin 3: 1.0% sorbitan laurate added to Hirosine made by Yasuhara Chemical

Comparative Example 3:
A composite unstretched film for laminating of the present invention having the following layer constitution was produced by the coextrusion T-die method, and the outer layer (Ny2) was subjected to corona treatment to obtain Comparative Example 3.
Ny2 (20 μm) / adhesive resin 1 (10 μm) / LLDPE1 (37 μm) / hot melt resin 1 (3 μm)

Comparative Example 4:
A composite unstretched film for laminating according to the present invention having the following layer constitution was produced by the coextrusion T-die method, and the outer layer (Ny2) was subjected to corona treatment to obtain Comparative Example 4.
Ny2 (5 μm) / adhesive resin 1 (5 μm) / EVOH1 (10 μm) / Ny1 (10 μm) / adhesive resin 1 (5 μm) / EVA2 (20 μm) / hot melt resin 1 (15 μm)
EVA2: 3.0% sorbitan laurate is added to Novatec EVA (Vac8%) made by Nippon Polyethylene

Comparative Example 5:
A composite unstretched film for laminating according to the present invention having the following layer structure was produced by coextrusion T-die method, and used as Comparative Example 5.
Ny2 (20 μm) / adhesive resin 1 (10 μm) / LLDPE4 (30 μm) / hot melt resin 1 (10 μm)
LLDPE4: Add 0.3% glycerin monomonopalmitate to Novatec LL made by Nippon Polyethylene

<Evaluation method>
(Suitable for lamination)
A stretched PET film (12 μm) is dry-laminated on the opposite side of the hot melt resin surface of the films of Examples 1 to 5 and Comparative Examples 1 to 5, and those having a laminate strength of 3N / 15 mm width or more are “◯”, 3N / The thing of less than 15 mm width was made into "x". A laminate adhesive was used, and aging after lamination was performed at 40 ° C. for 48 hours.

(Heat sealability)
Deep draw packaging machine (Omori Machinery Industry Co., FV6300) under the conditions of sealing temperature 160 ° C., sealing time 2 sec, APET sheet and stretched PET implement (12 [mu] m) was dry laminated Examples 1 to 5 and Comparative Example 1 A film seal strength of 5 to 8 N / 15 mm width or more was designated as “◯”, and a film seal strength less than 8 N / 15 mm width was designated as “X”.

(Anti-fogging property)
Using a deep-drawing packaging machine (FV6300, manufactured by Omori Machine Industry Co., Ltd.), an APET sheet (400 μm) is deep-drawn into a size of 100 mm long × 100 mm wide × 20 mm deep, and 100 cc of water is added. The films of Examples 1 to 5 and Comparative Examples 1 to 5 which were dry-laminated with stretched PET (12 μm) under the condition of time 2 seconds were heat sealed and stored in a refrigerator at 5 ° C. for 24 hours. Those with no cloudiness were marked with “◯” and those with cloudiness were marked with “x”.

  From the said Table 1, in the composite unstretched film for lamination of Examples 1-5, it turned out that evaluation of a lamination appropriateness, heat-sealing property, and antifogging property is favorable. On the other hand, in Comparative Example 1, there was a defogging agent bleed on the laminate surface, and the laminate strength was weak. In Comparative Example 2, since the antifogging agent was added directly to the hot melt layer, the antifogging agent was transferred to the laminate surface, so the laminate strength was weak. In Comparative Example 3, the heat-sealability was poor because the hot melt resin was thin. In Comparative Example 4, since the amount of the antifogging agent added to the intermediate layer EVA was large, the antifogging agent bleeded into the hot melt layer and the heat sealability was inhibited. In Comparative Example 5, the antifogging property was poor because the amount of the antifogging agent added was small.

  While the present invention has been described in connection with embodiments that are presently the most practical and preferred, the present invention is not limited to the embodiments disclosed herein. However, the present invention can be appropriately changed without departing from the gist or concept of the invention that can be read from the claims and the entire specification, and a composite unstretched film for lamination accompanying such a change is also included in the technical scope of the present invention. Must be understood as being.

  The film of the present invention can be suitably used, for example, as a lid material that is heat-sealed with a molded container of APET or PS.

Claims (5)

Composite having outer layer containing polyamide layer or saponified ethylene vinyl acetate copolymer layer, innermost layer made of hot melt resin, intermediate layer containing polyolefin resin and 0.3-2.0% antifogging agent It is an unstretched film, the thickness of the innermost layer is 5 to 20 μm, the thickness of the intermediate layer is 10 to 70 μm, and the hot melt resin is a 5% to 60% tackifier to the base polymer of the polyethylene resin And a non-stretched film for laminating, characterized in that it contains a wax component.   The composite unstretched film for lamination according to claim 1, further comprising an adhesive resin layer between the outer layer and the intermediate layer.   The composite unstretched film for laminating according to claim 1 or 2, comprising polyethylene terephthalate glycol resin (PETG) on the outside of the outer layer through an adhesive resin layer.   The composite unstretched film for lamination according to claim 1 or 2, further comprising a layer containing a polyolefin resin on the outside of the outer layer via an adhesive resin layer. The composite innermost layer surface consisting of a hot melt resin of the non-stretched film, sealing temperature 160 ° C., under the conditions of a sealing time of 2 seconds, the amorphous polyethylene terephthalate sheet is sealing strength in the case of heat sealing, 8N / 15 mm width The composite unstretched film for laminate according to any one of claims 1 to 4, which has a width of 15 N / 15 mm or less.