JPS60190352A - Gas barrier property laminated film - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention]

The present invention relates to a gas-barrier laminated film with a quick printing finish, and its history is detailed. This invention relates to a gas-barrier laminated film with an excellent printing finish, in which the PVDC-coated surface of a heat-sealable film coated with a PVDC-based resin is laminated via a contact layer. , X'9. packaging for the purpose of preventing deterioration such as dehumidification, rancidity (?1 former 111 minute oxidation), discoloration, rotting, etc.
Packaging techniques such as heat sterilization packaging and aseptic packaging are used, and films that block gases such as oxygen and carbon dioxide gas and water vapor are used as packaging materials for these packaging techniques. As such a gas barrier film, P V 1) C
type films, polyvinyl alcohol resin films, saponified ethylene vinyl acetate copolymer films, polyamide films, acrylonitrile resin films, etc., but these films alone have a #14 mechanical strength and heat sealability. . Because it has insufficient moisture resistance, water resistance, and heat resistance, it is usually used by laminating it with other plastic films. Among these, a thermoplastic film coated with PVDC is widely used as a gas barrier film, and a heat-sealable film is laminated thereto to further impart heat-affecting properties. however. Packaging is not just for the purpose of preserving the packaged items such as food and protecting them from moxibustion.1In addition to the part names and product descriptions of the packaged items, the packaging also includes photographs on the PVDC coated surface for eye-catching purposes. In many cases, decorative printing such as printing is applied. In such cases, the requirements for printing quality are very strict, and there are 9 different hues of printing. In addition to stains, packaging material processors also give considerable feedback regarding printing defects such as pinhole-like ink omissions and swimming, but printing on a surface coated with PVT')C? When applied, pinhole-like ink dropouts may occur, which is currently causing problems in the printing process 1'. The inventor of the present invention has improved this drawback of printability. As a result of extensive research, we have created a packaging film that has both gas leakage and heat-sealing properties.The base film is printed in advance, and the printed surface is laminated with a gas-source-blocking heat-sealable film. By. The present invention was achieved by discovering that it is possible to obtain a laminated packaging film with a good printing finish, b,,'x body blocking properties, and heat sealing properties. That is, the present invention provides printing on a base film and applying a P V DC agent to the printed surface of the base film and a heat-sealable film having a softening temperature lower than that of the base film, if necessary, via an anchor coat layer. The laminated packaging film of the present invention is characterized by laminating the coated surface after coating and drying.1 The laminated packaging film of the present invention has a good printing finish, and has good sealing properties, gas barrier properties, and heat sealability. It is a highly durable packaging film. The base film used in the present invention is a transparent film such as cellophane. Biaxially oriented polypropylene film, biaxially oriented polyethylene terephthalate film, 21llll+ffi stretched 6-
Examples include, but are not limited to, general-purpose plastic films such as nylon films and biaxially oriented polyvinyl alcohol films, and laminated films that combine these with other resin layers. A film having a softening temperature higher than the softening temperature of the heat-sealable film, preferably 15"C or more higher than that of the heat-sealable film is suitable. A film having a softening temperature lower than that of the heat-sealable film may be susceptible to deformation, shrinkage, etc. when heat-sealing is performed. Not only will the appearance deteriorate, but depending on one condition, problems such as the heat-sealed part breaking may occur.In other words, the surface of the base film to be printed is usually corona treated in advance, and if necessary, anchored. After the coating layer is provided, printing is performed using methods such as gravure printing and flexographic printing using inks suitable for the substrate to be used.1 The printing inks used include water-soluble, ice-dispersed, and solvent-based inks. solvent-based inks are preferred for 417F. Vehicles of 1 ctf-t in solvent-based in' HD are nitrocellulose binder type, polyamide binder type. Chlorinated rubber binder type, chlorinated polypropylene binder type I, polyester. Binder type, ethylene vinyl acetate binder type.There are vinyl chloride-vinyl acetate binder type, polyurethane binder type, and mixed types of these.
It is appropriately selected from these depending on the base material used. The printed surface obtained in this way is similar to the conventional PV
Unlike the finish of the printed surface printed on the PVI) 0 side of the DC coated film. There is no ink leakage or swimming, resulting in a beautiful finish. 2. Heat-sealable films used in the present invention include, for example, unstretched films made of polypropylene resins or polyethylene resins, etc.; Examples include, but are not limited to, films that have substantial heat-sealing properties, but a film that has a softening temperature lower than that of the front F base film, preferably 15°C or more lower, is selected. If necessary, surface treatment such as corona treatment may be applied to the surface to which PVDC is applied. The above polypropylene resin is a polypropylene homopolymer, 50% or more of propylene and ethylene,
Phthene, 4-methyl-1-pentene 1-hexene, ■-
1 selected from the group consisting of α-olefins such as octene
Blends of these homopolymers or copolymers with other polymers in a range in which the propylene component is 50% or more are referred to as resins 1 to 1. Further, the above polyethylene resin is a polyethylene homopolymer, 50% ethylene J'J,j nidopropylene. -Selected from the group consisting of α-olefins such as ■-butene, 4-methyl-1-pentene, ]-hexene, ■-octene, vinyl acetate, acrylic acid, acrylic ester, methacrylic acid, and methacrylic ester] Co-Mr combination consisting of glaze or two or more types. It refers to a resin obtained by blending these homopolymers or copolymers with other polymers in such a range that the ethylene component is 5() or more. Next, in the present invention, the sealing film and P
The anchor coat layer coating agent provided between the VDC coating layers includes, for example, vinyl-based, acrylic-based, ethylene-vinyl acetate-based, rubber-based, polyethyleneimine-based, polybutadiene-based, polyester-based, polyether-based, polyurethane-based, Examples include aqueous dispersions or organic solvent solutions of enclosing agents such as epoxy and polyvinylidene chloride, and the solid content is 0.03 to IO, more preferably 0.1 to 0.
5 caps are applied. Next, examples of PVT)C used in the present invention include vinyl chloride 11-dene monomer and vinyl chloride. An aqueous dispersion or an inorganic or organic solvent solution of a resin copolymerized with one or more selected from the group consisting of acrylonitrile, vinyl acetate, styrene, acrylic acid, acrylic ester, methacrylic acid, and methacrylic ester. However, it is not limited to these as long as it has gas barrier properties. Also, to improve the processing properties of the PVDC coating layer. 4 depending on need! I1. A mechanical anti-blocking agent, wax, antistatic agent, etc. may be mixed (~ may also be used.) The method for applying PVDC on the sealant film or the anchor coat layer of the sealant film is to apply a solid content of 1 to 20 cm using a conventional method. All you need to do is apply and dry. If necessary, after application, aging may be performed at a temperature of 1 to 81°C at 80 to 50 °C to improve gas barrier properties, water vapor barrier properties, solvent resistance, slip properties, etc. 9) In addition, a method of laminating the printed surface of the printed base film and the coated surface of the heat-sealable film coated with P V DC.

[7] Ordinary lamination methods such as dry lamination, non-solvent lamination, polyethylene extrusion lamination, etc. are applied. The contact materials used for the above dry lamination include vinyl, acrylic, ethylene/vinyl acetate, polyethyleneimine, polybutadiene, vinylidene chloride, rubber, polyester, polyether, polyurethane, and epoxy. , a shielding agent such as incyanate thread is used. In addition, any adhesive used in the above-mentioned solvent lamination may be used as long as it has fluidity when heated and solidifies or hardens after cooling, but polyurethane adhesives are especially suitable for ships. preferable. In addition, in polyethylene extrusion lamination, the adhesive described above for dry lamination can be used as an anchor coating agent applied to the inner adhesive surface of the printed base material and PVDC (heat-sealable (lO)) film. The laminated film obtained as described above has an excellent finish with no printing ink color loss, and can be used as a useful packaging material with gas barrier properties and heat sealability. The present invention will be specifically explained below with reference to Examples.Methods for measuring each physical property in Examples, Actual Examples, and Comparative Examples are as follows: T1
According to the method. Oxygen permeation! f: ASTM D184:20'C, 0%
R,H moisture permeability: JIS Z 02 (1840℃, 90
%R,H printing sufficiency: In five-color gravure printing including photographic printing, ink transferability and ink swimming state in highlight areas and halftone areas were visually judged. Example 1 Polypropylene with a softening temperature of 155°C (Noblen FS
-2011. Biaxially oriented polypropylene (hereinafter referred to as OPP) with a thickness of 20μ was obtained by extruding a polypropylene (manufactured by Sumitomo Chemical Co., Ltd.) through a T-die and sequentially biaxially stretching it (11).
It is abbreviated as ) is treated with corona discharge on one side, and ink for polypropylene (Lamicd G, Dainichiseika Kogyo ■) is applied to this treated side.
Five-color printing '5c, which imitates a photographic plate, is applied using a polyurethane absorbent (Takerac A-810/
Takenate A-3゜manufactured by Takeda Pharmaceutical Co., Ltd.) ethyl acetate/
A toluene-50150 solvent solution was applied and dried so that the solid content was 0.2 cm. Also, high-pressure polyethylene (F' (122, Ube Industries 14' JJ) with a softening temperature of 96'C and a density of #122 was used. )'
f: One side of a 50 μm thick polyethylene film formed by the inflation method was subjected to corona discharge treatment. An aqueous dispersion containing mainly acrylic ester (
Movinyl981. manufactured by Hoechst Synthesis@) with a solid content of 0.
Apply and dry to make 8 sheets. Furthermore, on this coated surface, a P V DC aqueous dispersion (Saran Latex L-511.
Polyethyleneimine (EL-402° (12) manufactured by Toyo Morton ■) was applied to the PVDC coated surface to give a solid content of 0.053' and dried. The coated side of this polyethyleneimine coated polyethylene film and the adhesive coated side of the polypropylene film coated on the adhesive side were extruded and laminated with polyethylene 20μ by a conventional method, and then aged at 40°C for one day, and the performance of the laminated film was measured. . Show the results on the table. Example 2 6-nylon (Tsubamitsu 102) with a softening temperature of 205°C
0, Mitsubishi Kosei Korai@M) was formed into a film by the tubular method, and then simultaneously biaxially stretched, and one side of the obtained 15μ biaxially stretched film (hereinafter abbreviated as 0-NY) was subjected to corona discharge. Example 1 is applied to this treated surface.
Print in the same manner as above, and then apply polyurethane adhesive 1 (Polybond N5-80/CA-30, manufactured by Sanyo Kasei Pottery).
An ethyl acetate solution of 100% was applied so that the solid content was 8 μ% and dried. Also, it consists of ethylene and 1-butene. (Temperature: 15℃, Density: 1i0.985 glue)
Corona discharge treatment was applied to one side of a polyethylene film with a thickness of 4゜0μ formed by a die-casting method, and a polyester adhesive (Vylon 8 (10, manufactured by Toyobo ■/Coronate 1 Japan) was applied to this treated side. polyurethane adsorbent)
The solid content of the solution is 0, 259 in? Apply it so that
Dry and further. Water-dispersed PVDC (Tarehalon Latex D) is applied on this surface.
O-870, Kureha Jigaku (manufactured by Kiki) was coated and dried to a solid content of 5 sheets. This PVDC coated surface and the 0-N Y adhesive coated surface are dry laminated by a conventional method, and 4. (2 at 1℃
After aging for one day, the performance of the obtained laminated film was measured and the results are shown in Table 1. Example 8 Polyethylene terephthalate (E
Corona is applied to one side of a 12 μm polyethylene terephthalate film (5J, PI (abbreviated as T film)) obtained by forming a film using the T-die method and then simultaneously biaxially stretching FG-6 (manufactured by Kanebo Gosen ■). Lightning treatment was applied to L7. This treated surface was printed using the same ink as in Example/, and a polyurethane non-solvent type adhesive (L7) was applied on the printed surface.
F" 188-D. Inu Nippon Ink Kogyo ■ flI! 10 times. Separately, a softening temperature [18
5”C propylene random polymer (Noblen F
One side of a 1g x 80μ polypropylene film (hereinafter abbreviated as CPP film) produced by the T die casting method using L 6411 (manufactured by Sumitomo Chemical Co., Ltd.) was subjected to a silicon treatment, and polyurethane water was dispersed on this treated surface. Liquid (Seiryoku Bond w-s6-1/C-87, manufactured by Dainichiseika Kogyo ■)″f
t Apply so that the solid content is 0.4%. After drying, apply solution type PVDC (Saran Resin F') to this coated surface.
-216゜Made by Asahi Kasei Kogyo ■) 100 parts has a melting point of 68℃
A solution (disintegrated tetrahydrofuran/toluene-50150) to which 0.5 part of paraffin wax has been added has a solid content of 8
The coating was applied so as to cover the surface of the film, dried, and further aged at 40 (15)° C. for 2 days. After heating and laminating the PVDC-coated surface of the PVDC-coated surface and the adhesive-coated surface of the printed P. The results are shown in Table 1. Comparative Example 1 A polyisocyanate adhesive (Titabond 1) was applied to the treated surface of the corona discharge treated CPP film obtained in Example 1.
04. ．． Propylene dichloride/toluene-F+ from Bhonsoda ■)! 1/50 solvent solution with solid content of 0.
l 5 f/lr? Apply the same P V DC as in Example 1 to this coated surface so that the solid content is 8.
It was applied and dried so that it became seedy. This PVDC coating layer was printed with the same pattern using the same ink as in Example 1, and the same polyurethane adhesive as in Example 1 was added to the solid content at 1 to 11.2 f/rr? Coated. In addition, in Example 8, the same poly(16
) Ethyleneimine was applied as a solid content (1, (15&-). This coated surface and the adhesive coated surface of the printed O P I film were extrusion laminated with 20 μm of high-pressure polyethylene using a conventional method. ``L4 ging was performed for 1 day at -c.The performance of the obtained laminated film was measured,
The results are shown in Table 1. Comparative Example 2 On the corona discharge treated surface of the biaxially stretched nylon film obtained in Example 2, 05 parts of paraffin wax (PVI)C (Saran Resin '-21,6 from NA Chemical Industry) 100 sheets 61 was added with tetrahydrofuran. 50 parts toluene 50
This PVDC-coated biaxially oriented 6 nylon film was coated and dried in a solvent consisting of 100% of solids, and dried at 40"C for 2 days.
The same ink as in Example 2 was applied to the printed surface of the VDC-coated biaxially stretched 6 nylon film (the same pattern was printed using Lamic Fψ. The acetic acid treatment (17) of Polybond N5-80/CA-80 from Sanyo Chemical Industries (1) shown in Example 2 shows the surface of the cold cloth where a chill solution was applied to a solid content of 8 seams, dried and allowed to wander. Density 0.98 obtained with
5. The corona-treated surface of a polyethylene film made of 1-butene and ethylene having a softening temperature of 115°C was laminated and aged at 40°C for 2 days. The performance of the processed laminated film was measured. The results are shown in Table 1. Although gas barrier properties and water vapor barrier properties were excellent, ink swimming was observed on the printed surface, and the printing finish was unsatisfactory. As can be seen from the results in Table 1 above, the conventional method, namely PVD.
C: After printing on the coated surface, the laminated film that is laminated with the sealant film has pinhole-like ink leakage and ink swimming on the printed surface. Although the finish was unsatisfactory for beautiful printing, the laminated film of the present invention has gas barrier properties. Both water vapor barrier properties and printing finish were good. [Left below] /IQN Table (■))

Claims (1)

[Claims] 1. A printed surface of a base film printed on one side. A gas-permeable laminated film with an excellent printing finish, which is made by laminating the polyvinylidene chloride #-1 resin coated side of a heat-sealable film with a polyvinylidene chloride resin coating layer on one side via a contact layer. 2. The gas-permeable laminated film according to claim 1, wherein the heat-sealable film coated with polyvinylidene chloride resin is an unstretched polypropylene thread film or an unstretched polyethylene film. 8. The printed base film is a biaxially oriented polyamide film. 4. The gas barrier laminate film according to claim 2, wherein the printed base film is a biaxially oriented polyglopyrene film. 5. The gas barrier i1'# layer film according to claim 2, wherein the printed base film is a 2411 stretched polyester film. 6. The gas-barrier laminate film according to claim 2, wherein the printed base film is a 7-layer film.