JP4871232B2 - Method for producing barrier laminated film - Google Patents

Description

  The present invention relates to a method for producing a barrier laminate film having a metal or metal compound vapor-deposited layer. More specifically, the present invention relates to a method for producing a barrier laminate film that is less likely to cause cracks in a deposited layer due to bending.

  Conventionally, a polyester film is used as a base material layer, an alkoxide coating layer is formed on the base material layer, a vapor deposition layer of a metal or a metal compound is formed on the alkoxide coating layer, and polypropylene is further formed on the vapor deposition layer via an adhesive layer. When a barrier laminate film in which a heat-adhesive resin layer is laminated, the adhesion between the base material layer and the vapor deposition layer is improved, and the alkoxide coating layer is flexible and heat resistant. It is known that the deterioration of the barrier property due to the occurrence of cracks can be prevented (for example, see Patent Document 1).

JP-A-7-207431

  However, the conventional barrier laminate film has a problem that a vapor deposition layer is likely to crack when it is repeatedly bent.

  An object of this invention is to enable it to suppress generation | occurrence | production of the crack to the vapor deposition layer by bending about the barriering laminated film which has a vapor deposition layer of a metal or a metal compound.

  By the way, in the conventional barrier laminate film, the heat-adhesive resin layer laminated on the vapor deposition layer via the adhesive layer is for enabling the barrier laminate film to be heat-sealed. It is not intended to protect the layer. Further, Patent Document 1 only discloses that a heat-adhesive resin layer is provided by a dry laminating method, but does not disclose a specific dry laminating procedure.

  The present invention is intended to prevent the occurrence of cracks in the vapor deposition layer by providing a coating agent layer as a protective layer on the vapor deposition layer via the adhesive layer. It was made by discovering that a protective effect of a large vapor deposition layer can be obtained by applying the coating agent repeatedly while uncured.

  That is, the present invention relates to a method for producing a barrier laminate film in which an adhesive layer and a coating agent layer are sequentially laminated on a vapor deposition layer formed on the surface of a base material layer. Solvent-based reaction curable adhesive, solvent-based reaction curable coating agent based on polyester, polyurethane or mixed resin of polyester and polyurethane as coating agent, and the adhesive applied on the deposited film is cured It is a manufacturing method of the barriering laminated film characterized by applying a coating agent in layers before carrying out.

  Moreover, this invention includes apply | coating a coating agent immediately after drying of an adhesive agent (after volatilization of a solvent) as the preferable aspect.

  Although it is not clear why the coating layer is applied before the adhesive is cured, the high protective effect of the deposited layer can be obtained, but the adhesive and coating agent are mixed and mixed at the interface, It is speculated that the improvement of the integrity of the two leads to a high protective effect of the deposited layer due to the partial reaction between the agent and the coating agent. As a result of protecting the vapor deposition layer, it is possible to suppress a decrease in barrier properties due to bending.

  FIG. 1 is a cross-sectional view showing an example of a barrier laminate film produced by the production method of the present invention, in which 1 is a base material layer, 2 is a vapor deposition layer, 3 is an adhesive layer, and 4 is a coating agent layer. . A vapor deposition layer 2 is formed on the base material layer 1, and an adhesive layer 3 and a coating agent layer 4 are sequentially laminated on the vapor deposition layer.

  As the base material layer 1, for example, a film of polyester, polyamide, polypropylene, or the like can be used. Although it may be a stretched film or an unstretched film, a stretched film excellent in strength is preferable, and a stretched polyester film excellent in strength, heat resistance and transparency is most preferable.

  The vapor deposition layer 2 is comprised with the thin film of the metal or the metal compound. This thin film can be formed by, for example, vacuum deposition, ion plating, sputtering, or the like. As the constituent material of the thin film, metals such as aluminum, silicon, titanium, zinc, zirconium, magnesium, tin, copper, and iron, and metal compounds such as oxides, nitrides, sulfides, and fluorides of these metals are used. be able to. As the metal compound, aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, magnesium oxide, tin oxide, zinc oxide, magnesium fluoride, or the like can be used.

  Prior to the formation of the vapor deposition layer 2, an anchor coat layer for improving the adhesion between the base material layer 1 and the vapor deposition layer 2 can be provided on the surface on which the vapor deposition layer 2 is formed.

  The adhesive layer 3 is formed by applying and curing an adhesive. As the adhesive constituting the adhesive layer 3, a solvent-based reaction curable adhesive mainly composed of a polyester resin is used. It is done. As the curing agent, an isocyanate curing agent can be used. The adhesive can be selected from those commercially available for dry lamination. Specific examples include a combination of a main agent “TM265” manufactured by Toyo Morton and a polyisocyanate curing agent “CAT-RT-37” And a combination of a main agent “Takelac A-525” and a polyisocyanate curing agent “Takenate A-52” manufactured by Mitsui Chemicals Polyurethanes.

  The coating agent layer 4 is formed by applying and curing a coating agent. The coating agent constituting the coating layer 4 is a solvent mainly composed of polyester, polyurethane, or a mixed resin of polyester and polyurethane. A system reaction curable coating agent is used. As the curing agent, an isocyanate curing agent can be used. Specific examples of the main component of the polyester resin include “P-11” manufactured by Unitika. Specific examples of the main component of the polyurethane resin include “Byron UR1700” manufactured by Toyobo Co., Ltd. and “PU-305” manufactured by Arakawa Chemical Co., Ltd. Specific examples of the main component of the mixed resin of polyester and polyurethane include “KY-3” manufactured by The Inktec Co., Ltd. and “Byron UR8200” manufactured by Toyobo Co., Ltd. Specific examples of the curing agent combined with the above main agent include “Coronate L” manufactured by Nippon Polyurethane Co., Ltd. and “XEL” manufactured by The Inktech Co., Ltd.

  In the present invention, the coating agent layer 4 is formed by applying an adhesive on the vapor deposition layer 2, applying the coating agent before the adhesive is cured, and then reacting and curing the adhesive and the coating agent simultaneously. Is called. The phrase “before the adhesive is cured” means before the curing reaction of the adhesive is completed. The coating agent is preferably applied after drying the applied adhesive so as not to cause unevenness in the application state of the adhesive and the coating agent. Moreover, since it is preferable to apply the coating agent before the curing reaction of the adhesive proceeds, it is preferable to perform the coating immediately after the adhesive is dried. More specifically, it is preferable to apply the coating agent as early as possible in a state where the solvent of the adhesive is evaporated and the fluidity of the adhesive is lost. By applying the coating agent in such a state, the integrity between the adhesive layer 3 and the coating agent layer 4 is increased, and the occurrence of cracks in the vapor deposition layer 2 due to bending can be suppressed.

It is preferable to form the coating layer 4 after applying an adhesive on the vapor deposition layer 2 and within a curing reaction rate of the adhesive within 25%. This curing reaction rate can be measured from the change state (decrease rate) of the absorption amount by measuring the infrared absorption spectrum peculiar to the curing agent over time. For example, when isocyanate is used as a curing agent, there is absorption specific to 2275 to 2250 cm ⁻¹ , and it can be measured from the magnitude of this absorption amount.

Application of the adhesive and the coating agent can be performed by, for example, a bar coater. Applying charges of the adhesive 0.1 to 2.0 g / cm ² in terms of solid content, applied fees of the coating agent is preferably 0.5 to 3.0 g / cm ² in terms of solid content.

  For example, a heat seal layer can be laminated on the surface of the base material layer 1 opposite to the vapor deposition layer 2 or the surface of the coating material 4. A preferred surface on which the heat seal layer is laminated is the surface of the coating material 4.

Example 1
On the surface of the vapor-deposited layer of a polyester film (thickness 12 μm) on which a thin film of SiO ₂ was formed as the vapor-deposited layer, 17 parts by weight of the main agent (“TM-265” manufactured by Toyo Morton Co., Ltd.) and a solvent (ethyl acetate) 54.4 1. A polyester-based reaction curable adhesive prepared by mixing 1 part by weight with 1.2 parts by weight of a polyisocyanate-based curing agent (“CAT-RT-37” manufactured by Toyo Morton Co., Ltd.) is 1. 5 g / m ^{2 was} applied.

Immediately after drying for 1 minute at 60 ° C. after application of the adhesive, a coating agent was applied to the adhesive application surface. As the coating agent, 100 parts by weight of the main agent (“KY-3” manufactured by The Inktec Co., Ltd.), 33 parts by weight of a solvent (mixed solution of methyl ethyl ketone and toluene mixed at a weight ratio of 1: 1), and isocyanate curing A reaction curable coating agent of a mixed system of polyester and polyurethane in which 7 parts by weight of an agent (“XEL” manufactured by The Inktec Co., Ltd.) was mixed was used. The coating material was 2.0 g / m ^{2 in} terms of solid content.

  After the coating agent was applied, the barrier laminate film obtained by aging at 40 ° C. for 24 hours was subjected to gelbo flex treatment 6 times, and the oxygen permeability was measured at 25 ° C. and 0% RH. The oxygen permeability was measured based on the JIS / K / 7126B method.

  The results are shown in Table 1.

Example 2
The adhesive consists of 9 parts by weight of the main agent (“Takelac A-525” manufactured by Mitsui Chemicals Polyurethanes), 10 parts by weight of the solvent (ethyl acetate), and a polyisocyanate curing agent (“Takenate A-52 manufactured by Mitsui Polychemical Co., Ltd.). ") 1 and the weight portion and the mixture was polyester reactive curable adhesive, and two kinds of 0.5 g / m ² and 1.5 g / m ² in terms of solid content of the coating charge. The coating agent coating was 1.6 g / m ^{2 in} terms of solid content. Except for these, oxygen permeability was measured in the same manner as in Example 1.

  The results are shown in Table 1.

Comparative Example 1
After application of the adhesive, oxygen permeability was measured in the same manner as in Example 1 except that the coating agent was applied after aging at 40 ° C. for 24 hours and sufficiently curing.

  The results are shown in Table 1.

Comparative Example 2
After application of the adhesive, oxygen permeability was measured in the same manner as in Example 2 except that the coating agent was applied after aging at 40 ° C. for 24 hours and sufficiently curing.

  The results are shown in Table 1.

Reference example 1
The oxygen permeability was measured in the same manner as in Example 1 alone without applying an adhesive and a coating agent to the polyester film (thickness 12 μm) on which the SiO ₂ thin film was used. It was.

  The results are shown in Table 1.

It is sectional drawing which shows an example of the barriering laminated film manufactured by the manufacturing method of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Base material layer 2 Evaporation layer 3 Adhesive layer 4 Coating agent layer

Claims (2)

  In a method for producing a barrier laminate film in which an adhesive layer and a coating agent layer are sequentially laminated on a vapor deposition layer formed on the surface of a base material layer, a solvent-based reaction curable type mainly comprising a polyester-based resin as an adhesive. A solvent-based reaction-curing coating agent based on polyester, polyurethane, or a mixture of polyester and polyurethane is used as the adhesive and coating agent, and the coating agent is applied before the adhesive applied on the deposited film is cured. The manufacturing method of the barriering laminated | multilayer film characterized by apply | coating repeatedly.   2. The method for producing a barrier laminate film according to claim 1, wherein the coating agent is applied immediately after the adhesive is dried.

Images