JPH08252890A - Manufacture of gas barrier laminated film - Google Patents

Abstract

PURPOSE: To provide a gas barrier laminated film in which anchor coating agent is not used by press-bonding the corona treated surface of a gas barrier plastic base material obtained by a corona discharging step and coated with vinylidene chloride resin to the ozone treated surface of the film obtained by an ozone treating step. CONSTITUTION: The K-coated surface of a gas barrier plastic base material which is coated (K coat) with vinylidene chloride resin is corona discharged to generate a functional group effective to be adhered to the treated surface, thereby performing rigid adhering. The corona discharging density is 10W.min/ m<2> or more. Extrusion laminated resin is melt extruded in a film state at 180 to 340 deg.C, and ozone-treated at least on one surface of the film. The treated surface of the K-coated plastic base material obtained in the corona discharging step is brought into contact with the ozone treated surface of the film obtained by the ozone treating step, and the film is press-bonded to the base material.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a gas barrier laminated film. For more details,
The present invention relates to a gas barrier plastic substrate coated with a vinylidene chloride resin (hereinafter referred to as K coat), a polyethylene resin, a polypropylene resin, an ethylene-vinyl ester copolymer resin and an ethylene- (meth) acrylic. A method for producing a gas barrier laminate film comprising a resin for extrusion laminating, which is one kind selected from the group consisting of acid ester-based copolymer resins, which comprises extruding a K-coated plastic base material without using an anchor coating agent. The present invention relates to a method for producing a gas barrier laminated film in which a laminating resin is firmly adhered.

[0002]

2. Description of the Related Art Film-like moldings of different materials such as plastics, papers and metal foils are adhered to each other to supplement properties which cannot be obtained by themselves, such as strength, gas barrier property, moisture proof property, heat seal property and appearance. It is common practice to manufacture laminated films, and the products thus obtained are widely used mainly for packaging materials and the like. As a method for producing such a laminated film, there are a dry lamination method, a wet lamination method, a hot lamination method, an extrusion lamination method, a coextrusion lamination method and the like, and these are applied according to their characteristics. As a method for forming a heat-sealing layer on a base material in packaging materials and the like, an extrusion lamination method, which is advantageous in terms of cost, is widely used. As the heat seal layer, a polyolefin resin such as polyethylene, polypropylene, an ethylene copolymer, or an ionomer resin is generally used, but a polyolefin resin is used in a much larger amount from the viewpoint of cost. ing.

In order to promote the adhesiveness with the base material, these resins are generally melt-extruded on the adhesive surface with the base material after applying an anchor coating agent on the base material in advance. is there. As the anchor coating agent, an organic titanate-based adhesive, an organic isocyanate-based adhesive, a polyethyleneimine-based adhesive, or the like is used. These adhesives are usually diluted with an organic solvent such as toluene, ethyl acetate, methanol or hexane before use. However, these methods using the anchor coating agent, the problem of increasing the manufacturing cost due to the use of expensive anchor coating agent, the problem of requiring a complicated step of coating and drying the anchor coating agent, the anchor coating agent The organic solvent harmful to the human body is scattered during the evaporation and drying process of the organic solvent contained in
Due to hygiene problems in the work environment and its surroundings, fire problems caused by the use of flammable organic solvents, and anchor coating agent components such as organic solvents remaining in the final product film or sheet. Due to the odor, there is a problem that the application of the product to food packaging and the like is restricted.

Further, in the method using the anchor coating agent, the processing speed is limited in order to coat the K-coated plastic substrate uniformly. For example, when coating is performed at a speed higher than the mechanical design, In some cases, unevenness may occur or the organic solvent may be insufficiently dried, resulting in impaired adhesiveness. Also,
In order to solve these problems, the equipment for the coating process and the drying process becomes very large, and there is a problem that productivity is poor.

As a method without using these anchor coating agents, (a) ethylene, (b) unsaturated polybasic acid, (c) acrylic acid lower alkyl ester, methacrylic acid lower alkyl ester, vinyl ester are selected. The ethylene-based copolymer obtained by copolymerizing the obtained unsaturated monomer is melt-kneaded and extruded into a film at a temperature of 150 ° C to 330 ° C, and then the film is ozone-treated, and then this ozone-treated A method for producing a laminate by pressure-bonding and laminating on a substrate with the surface as an adhesive surface has been reported (Japanese Patent Laid-Open No. Hei 4-
368845). However, in the method of using an ethylene-based copolymer that has an adhesive function using these unsaturated polybasic acids as comonomer components, roll release during extrusion lamination processing is accompanied by an increase in the manufacturing cost and low melting point components. Inferior in properties, not only restricted by processing temperature and the like, but also complicated such as resin change in the extruder, which is not preferable.

Further, the ethylene-α-olefin copolymer is subjected to ozone treatment of the adhesive surface to the base material using a known ozone treatment device, and pressure-bonded and laminated on the base material without applying an anchor coating agent to the laminate. The method of manufacturing the body, or using an adhesive resin that is graft-modified with a polyolefin resin such as unsaturated carboxylic acid, combined with a co-extrusion laminating machine, pressure-bonded to the base material with no anchor to produce a laminated body. A method of doing so has been reported (Convertec (8), p. 36, 1991). However, the adhesive strength between the laminate resin and the base material of the laminate obtained by these methods is not sufficient, and its application range is restricted. Furthermore, in the method of using an adhesive resin obtained by graft-modifying an unsaturated carboxylic acid or the like on a polyolefin-based resin, not only the coextrusion apparatus is required and the manufacturing cost is increased, but also
It is not preferable due to the complexity of changing the resin in the extruder.

[0007]

In view of the present situation, the problem to be solved by the present invention is to provide a K-coated plastic substrate having excellent gas barrier properties, polyethylene resin, polypropylene resin, and ethylene-vinyl ester copolymer copolymer. A method for producing a gas barrier laminate film comprising a resin for extrusion lamination, which is one kind selected from the group consisting of a united resin and an ethylene- (meth) acrylic acid ester-based copolymer resin, and using an anchor coating agent The present invention is to provide a method for producing a gas barrier laminate film that does not.

[0008]

That is, the present invention provides a salt
Gas barrier property plus coated with vinylidene chloride resin
Tick substrate, polyethylene resin, polypropylene
Resin, ethylene-vinyl ester copolymer resin and
Ethylene- (meth) acrylic acid ester-based copolymer resin
A tree for extrusion lamination, which is a kind selected from the group consisting of
A method for producing a gas barrier laminate film comprising fat.
The following (x) corona discharge treatment step, (y) ozone treatment
Manufactured by the heat treatment process and the (z) pressure bonding process, and
-For gas barrier laminated films that do not use coating agents
A manufacturing method is provided. (X) Corona discharge treatment step A vinylidene chloride resin as a plastic base material was coated.
10 (w · min / m) ²) Corona discharge at the above treatment density
Process of applying treatment. (Y) Ozone treatment step Extruded laminated resin at a temperature of 180 to 340 ° C
Melt extruded into a film, at least one side of the film
Step of applying ozone treatment to. (Z) Pressure bonding step Vinylidene chloride resin obtained in the corona discharge treatment step
Corona of gas barrier plastic base material coated with
Ozone of the treated surface and the film obtained in the ozone treatment process
The process of crimping the treated surface.

The present invention will be described in detail below. Examples of the plastic substrate that is the base of the K-coated plastic substrate used in the present invention include nylon resins, polyester resins, ethylene-vinyl alcohol copolymers, polyvinyl alcohol, polypropylene resins, cellophane, polystyrene, polyvinyl chloride. , Polycarbonate, polymethylmethacrylate, polyurethane, fluororesin, polyacrylonitrile, polybutene resin, polyimide resin, polyarylate resin, simple substances of resins such as acetylcellulose, and laminated films thereof, and further stretched products, unstretched products, and the like. . Among them, the plastic base material is a biaxially oriented polypropylene resin (hereinafter referred to as OPP
Unstretched polypropylene resin (hereinafter referred to as CPP)
Biaxially stretched nylon resin (hereinafter referred to as ONy),
Unstretched nylon resin (hereinafter referred to as CNy), biaxially stretched polyester resin (hereinafter referred to as PET), cellophane (hereinafter referred to as PT), biaxially stretched polyvinyl alcohol resin (hereinafter referred to as PVA) , Biaxially stretched ethylene-vinyl alcohol copolymer resin (hereinafter referred to as EVOH), unstretched ethylene-vinyl alcohol copolymer resin (hereinafter referred to as CEVOH) or unstretched polyvinyl chloride resin (hereinafter, (Referred to as PVC)) is preferred.

Further, a laminate of these K-coated plastic substrates and aluminum, iron, paper, etc., in which a K-coated surface of these K-coated plastic substrates is provided on the joint surface, or the like is used. . If necessary, the K-coated plastic substrate may have a surface previously subjected to surface treatment such as corona discharge treatment, plasma treatment, flame treatment, or may be pre-printed. K
The thickness of the coated plastic substrate is not particularly limited as long as extrusion laminating can be performed, but the range is preferably 1 to 1000 μ, and more preferably 5 to 50 μ.

The K-coated plastic base material used in the present invention may be a base plastic base material coated on at least one side thereof with a coating agent containing a vinylidene chloride resin as a main component and having a gas barrier property. Good.
Further, it may be a base material coated on both sides.

The method for producing the K-coated plastic substrate used in the present invention is not particularly limited, and as the method for applying the K-coating agent to the base plastic substrate, for example, the emulsion method and the solvent method are known. Has been.

The K-coating agent used for the K-coated plastic substrate may be one having a vinylidene chloride resin as a main component, and may be, for example, a single composition of the resin. Further, the K coating agent may be a copolymer or mixture with two or more other resin components. Examples of copolymers with other resins include copolymers of vinylidene chloride and acrylic compounds and copolymers of vinylidene chloride and vinyl chloride. In addition, the K coating agent component may include a component that promotes adhesion to the base plastic substrate, a coating aid component, a component that improves printability, and the like.

Further, the coating thickness of the K coating agent coated on the plastic substrate is not particularly limited and is properly used depending on its function, but generally 1 to 8
Those around μ are commercially available. Note that these K-coated plastic base materials have oxygen gas barrier properties, moisture proof properties, etc., and are useful for long-term storage of foods, pharmaceuticals, life-related products, industrial products, etc., and are often used as packaging materials. .

Further, the K-coated surface of the K-coated plastic substrate used in the present invention may be printed.

The resin for extrusion lamination used in the present invention includes polyethylene resins, polypropylene resins, ethylene-vinyl ester copolymer resins and ethylene-based resins.
It is one kind selected from the group consisting of (meth) acrylic acid ester-based copolymer resins, and these can be used alone or as a mixture of two or more kinds. If necessary,
Other resins may be mixed in the range of less than 50%.

The production method of the polyethylene resin is not limited, and it can be produced by, for example, a radical polymerization method or an ionic polymerization method. Examples of the polyethylene-based resin include low-density polyethylene produced by radical polymerization, high-density polyethylene produced by ionic polymerization, and ethylene-α-olefin obtained by copolymerizing ethylene and α-olefin. Examples thereof include copolymers. As the α-olefin, for example, propylene, butene-1, 4-methylpentene-1, hexene-1, octene-1, decene-1, octadecene-1 or the like having 3 to 18 carbon atoms is used. These α-olefins may be used alone or in combination of two or more. The content of the α-olefin contained in the ethylene-α-olefin copolymer is preferably 1 to 30% by weight, more preferably 5 to 20% by weight.

The method for producing the polypropylene resin is not limited, and it can be produced by, for example, an ionic polymerization method. Examples of the polypropylene resin include a homopolymer of propylene, a copolymer of propylene and ethylene, a copolymer of propylene and butene-1, a copolymer of propylene and α-olefin, and the like. The α-olefin copolymerized with propylene may be used alone or in combination of two or more. The content of the α-olefin contained in the propylene-α-olefin copolymer is preferably 0.1 to 40% by weight, more preferably 1 to 30% by weight.

The ethylene-vinyl ester copolymer resin and the ethylene- (meth) acrylic acid ester copolymer resin can be produced by a radical polymerization method, and are obtained by copolymerizing ethylene and a radically polymerizable monomer. To be

Examples of the vinyl ester of the ethylene-vinyl ester copolymer include vinyl acetate, vinyl propionate and vinyl neoate.

Examples of the (meth) acrylic acid ester of the ethylene- (meth) acrylic acid ester type copolymer include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n acrylate.
-Acrylic acid esters such as butyl, t-butyl acrylate, isobutyl acrylate, and the like, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, methacrylic acid. Examples of the methacrylic acid ester such as isobutyl include unsaturated carboxylic acid esters having 4 to 8 carbon atoms. These comonomers may be used alone or in combination of two or more.

The content of the comonomer component contained in the ethylene-vinyl ester copolymer and the ethylene- (meth) acrylic acid ester copolymer is preferably 30% by weight or less, more preferably 20% by weight or less. .

From the viewpoint of processing suitability, the polyethylene resin, the ethylene-vinyl ester copolymer resin and the ethylene- (meth) acrylic acid ester copolymer resin have a melt flow rate (M
FR) is preferably in the range of 1 to 100 g / 10 min, and for polypropylene resins, it is 23
The MFR at 0 ° C. is preferably in the range of 1 to 100 g / 10 min.

In the corona discharge treatment step of the present invention, the K coat is used.
Corona discharge treatment is applied to the K-coated surface of the plastic substrate
By doing so, a functional group effective for adhesion is generated on the treated surface.
This is a process that enables strong adhesion. The roller of the present invention
The discharge treatment density is 10 (W ・ min / m²) Or more is preferable,
More preferably 20 (W · min / m²) That is all. Moreover
And preferably 30 (W · min / m ²) That is all. corona
The upper limit of the discharge treatment density is not particularly limited, but it is economical.
From the viewpoint, usually 200 (W ・ min / m²) The following is preferable.

The ozone treatment step of the present invention is a step in which the resin for extrusion lamination is melt extruded into a film at a temperature of 180 to 340 ° C., and at least one surface of the film is subjected to ozone treatment. The ozone treatment is performed, for example, by blowing a gas containing ozone (air or the like) onto the molten film from a nozzle provided in an air gap under the T-die or a slit-shaped outlet. If the ozone nozzle cannot be installed under the T-die, it may be sprayed onto the K-coated plastic substrate immediately before pressure-bonding and laminating. The amount of ozone blown is to the passage unit area of melt film is preferably 1 to 30 mg / m ^2, more preferably from 2~12mg / m ^2. The temperature at which the resin for extrusion lamination is melt extruded into a film is 180
˜340 ° C., preferably 210˜330 ° C. If the temperature is less than 180 ° C., not only the spreadability of the resin becomes poor, it is difficult to obtain a molten film having a uniform thickness, but also the adhesive strength with the K-coated plastic substrate becomes insufficient. On the other hand, when the temperature exceeds 340 ° C., the surface oxidation of the molten resin due to the heat is increased, the odor is deteriorated, and the low odor is deteriorated.

In the pressure-bonding step of the present invention, the treated surface of the K-coated plastic substrate obtained in the corona discharge treatment step is brought into contact with the ozone-treated surface of the film obtained in the ozone treatment step, and the film and the K-coat are coated. This is a step of pressure-bonding a plastic substrate.

Further, the K-coated plastic substrate to be subjected to the pressure bonding step of the present invention does not need to be coated with an AC agent,
The apparatus for applying the AC agent and the drying process of the organic solvent used when applying the AC agent are not required at all.

Therefore, for example, in the case of performing high-speed processing of 150 (m / min) or more, the AC using the conventional AC agent is used.
Although the process of applying the agent was rate-determining, the present invention has no such problem.

Further, the laminated film and the product obtained by the present invention do not have a concern that the AC agent and the organic solvent are caught in the product.

The method for producing the gas barrier laminate film of the present invention may be restricted by the mechanical strength inherent to the resin such as the type and thickness of the K-coated plastic substrate, but basically the processing speed is not restricted. In addition, high-speed processing is possible and productivity is improved.

Incidentally, some commercially available K-coated plastic substrates have been subjected to surface oxidation treatment such as corona discharge treatment in order to improve the printability on the surface. When it is used without carrying out the corona discharge treatment, the sufficiently strong adhesive force aimed at by the present invention cannot be obtained.

A known extrusion laminator can be used in the pressure bonding step of the present invention.

In the present invention, it is preferable that the corona discharge treatment step and the crimping step are provided in-line, and the plastic substrate after the corona discharge treatment step is immediately subjected to the crimping step. As a result, a higher level of adhesive strength is exhibited and undesired blocking of the base film is prevented. In addition, the above-mentioned "providing a pressure bonding step in-line and immediately subjecting the plastic substrate after the corona discharge treatment step to the pressure bonding step" means that in extrusion lamination processing,
Plastic substrate feeding process, corona discharge treatment process,
The crimping process and the product winding process use an apparatus that is sequentially installed on the same line along the flow direction of the plastic base material.
It means performing these steps promptly in a series of operations.

In the present invention, from the viewpoint of further improving the adhesive strength, it is preferable to provide an aging step, which is a step of aging the laminated film obtained in the pressure-bonding step under heat retention after the pressure-bonding step.

The aging temperature is usually 30 ° C. or higher and lower than 50 ° C., preferably 40 to 45 ° C.

The aging time is usually 1 to 120 hours, preferably 10 to 80 hours. If the aging time is too short, the improvement of the adhesive strength may be insufficient. On the other hand, if it is too long, the extrusion-laminated resin may be deteriorated, which is also disadvantageous in terms of productivity.

To carry out the aging step, an ordinary oven or a room in which the temperature can be adjusted may be used.

In the present invention, a corona discharge treatment step,
By performing all of the ozone treatment step, the pressure bonding step, and the aging step in combination, it is possible to realize stronger adhesive strength.

In the present invention, the resin extruded and laminated on the K-coated plastic substrate can be applied to the laminated film heat-sealing layer, and can also be applied to the intermediate layer of the laminated film. function,
For example, the heat-sealability and moisture-proof property are used properly. The present invention can also be applied to the sandwich extrusion lamination method.

The resin for extrusion laminating according to the present invention is a known additive such as an antioxidant, an antiblocking agent, a weathering agent, a neutralizing agent, a flame retardant, an antistatic agent, within a range that does not impair the effects of the present invention. An antifogging agent, a lubricant, a dispersant, a pigment, an organic or inorganic filler and the like may be used in combination.

The laminated film of the present invention can be used for packaging materials such as food packaging materials, pharmaceutical packaging materials and industrial article packaging materials.

[0042]

EXAMPLES The present invention will now be described with reference to examples, but the present invention is not limited to these examples.

(1) Measurement of Membrane Adhesive Strength A laminated film having a width of 15 mm was measured at 200 mm / mi using an auto strain type tensile tester manufactured by Toyo Seiki Co., Ltd.
The film adhesiveness was evaluated from the peel strength when peeled 180 degrees at a pulling speed of n.

Example 1 Linear low density polyethylene (LLDPE; Sumikasen αCS8026 MFR 10 g / 1 manufactured by Sumitomo Chemical Co., Ltd.)
0 minutes, density 0.914 g / cm ³ ), caliber 65 mmφ
Multi-slot type T
The resin temperature from the die is 305 ° C, 290 ° C, the film width is 450 mm, and the thickness of the laminated layer is 2
5 μm (50 μm in total) and extruded at a laminating speed of 220 m / min to form a molten thin film, and then from the nozzle provided at a position 30 mm below the die on the surface of the molten thin film to be adhered to the substrate.
Air containing ozone at a concentration of 0 (g / Nm ³ ) is 2 (Nm
By spraying under the condition of ³ / Hr), the adhesive surface of the molten thin film to the substrate was treated with ozone. The ozone treatment amount at this time is 10.1 (
It was mg / m ² ). Then, by a corona discharge device provided in-line with the extrusion laminator, a treatment density of 15 (W · min / min) was applied to the K-coated surface of the biaxially oriented polypropylene film base material (hereinafter referred to as KOP) coated with vinylidene chloride resin. m ² ) and corona treated. Next, the molten film obtained in the ozone treatment step was pressure-laminated on the K-coated surface of the surface-modified 20 μ KOP film. The adhesive strength between the polyethylene film and the KOP film substrate of the laminate obtained in this example was measured.
It was 0 (g / 15 mm). The results are shown in Table 1.

Example 2 The procedure of Example 1 was repeated, except that the corona discharge treatment density was 37 (W · min / m ² ). The adhesive strength between the polyethylene film of the laminate obtained in this example and the KOP film substrate was measured, but it was very strong, and the adhesive interface could not be taken out due to the substrate itself being cut or the like and peeling was impossible. Met. The results are shown in Table 1.

Example 3 A substrate having a vinylidene chloride resin coated thickness 1
The same procedure as in Example 2 was carried out except that a 5μ biaxially stretched nylon film was used. The adhesive strength between the polyethylene film and the KONy film of the laminate obtained in this example was measured, but it was very strong and the adhesive interface could not be taken out, and peeling was impossible. The results are shown in Table 1.

Example 4 The die was changed to a single-type T-bed to form a 40 μ single-layer laminate, and a biaxially stretched polyester film (12 μ) coated with a vinylidene chloride resin was used as a substrate, and an extrusion laminating resin was used. Low density polyethylene (LDPE;
Sumikasen L718-H MFR manufactured by Sumitomo Chemical Co., Ltd.
8 g / 10 min, density 0.919 g / cm ³ ), extrusion resin temperature 280 ° C., corona treatment density 103 (W · min /
m ² ), and the ozone treatment amount was 10.4 (mg / m ² ), the same procedure as in Example 1 was carried out. The adhesive strength between the polyethylene film and the KPET film of the laminate obtained in this example was measured, but it was very strong and the adhesive interface could not be taken out, and peeling was impossible. The results are shown in Table 1.
Shown in

Comparative Example 1 Example 1 except that the ozone treatment and the corona treatment were not performed.
I went the same way. The adhesive strength between the polyethylene film and the KOP film substrate of the laminate obtained in this comparative example was measured and found to be 100 (g / 15 mm). Table 2 shows the results.

Comparative Example 2 Example 2 was repeated except that no corona treatment was applied. The adhesive strength between the polyethylene film and the KOP film substrate of the laminate obtained in this comparative example was measured to be 270.
(G / 15 mm). Table 2 shows the results.

Comparative Example 3 The procedure of Example 2 was repeated except that no ozone treatment was applied. The adhesive strength between the polyethylene film and the KOP film substrate of the laminate obtained in this comparative example was measured and found to be 220
(G / 15 mm). Table 2 shows the results.

Comparative Example 4 Instead of performing ozone treatment and corona treatment, in order to promote adhesion with the base material, AC using ethyl acetate as a solvent on the base material with an AC coating device provided in-line with the laminator
Example 1 was repeated except that the agent was applied. As the AC coater of the AC agent coating device used in this comparative example, a plain roll type was used, but since the laminating speed is high,
The AC agent could not be applied uniformly on the base material, resulting in uneven coating, resulting in uneven adhesion between the polyethylene film of the obtained laminated film and the KOP film base material. Further, not only the AC agent was scattered in the AC agent coating device, but the working environment was bad. The adhesive strength between the polyethylene film and the KOP film base material of the laminate obtained in this comparative example was measured, and variations occurred depending on the measurement site, and the minimum was 160 (g / 15 mm) and the maximum was 340 (g.
/ 15 mm). Table 2 shows the results.

Comparative Example 5 Example 3 was repeated except that ozone treatment and corona treatment were not performed.
I went the same way. The adhesive strength between the polyethylene film and the KONy film substrate of the laminate obtained in this comparative example was measured and found to be 10 (g / 15 mm). The results are shown in Table 3.

Comparative Example 6 The procedure of Example 3 was repeated except that no corona treatment was applied. The adhesive strength between the polyethylene film and the KONy film substrate of the laminate obtained in this comparative example was measured.
It was 0 (g / 15 mm). Table 2 shows the results.

Comparative Example 7 The procedure of Example 3 was repeated except that no ozone treatment was applied. The adhesive strength between the polyethylene film and the KONy film substrate of the laminate obtained in this comparative example was measured, and it was 20
(G / 15 mm). The results are shown in Table 3.

Comparative Example 8 Instead of performing ozone treatment and corona treatment, in order to promote adhesion with the substrate, AC using ethyl acetate as a solvent was applied on the substrate with an AC coating device provided in-line with the laminator.
Example 3 was repeated except that the agent was applied. As the AC coater of the AC agent coating device used in this comparative example, a plain roll type was used, but since the laminating speed is high,
The AC agent could not be applied uniformly on the base material, resulting in uneven coating, resulting in uneven adhesion between the polyethylene film of the obtained laminated film and the KONy film base material. Further, not only the AC agent was scattered in the AC agent coating device, but the working environment was bad. The adhesive strength between the polyethylene film and the KONy film base material of the laminate obtained in this comparative example was measured, but there were variations depending on the measurement site, and the minimum was 190 (g / 15 mm) and the maximum was 530 (g.
/ 15 mm). The results are shown in Table 3.

[0056]

[Table 1]

[0057]

[Table 2]

[0058]

[Table 3]

K-coated plastic substrate KOP: PVDC-coated biaxially oriented polypropylene, Senesi KOP 6000 type manufactured by Daicel Chemical Co., Ltd. 20μ KONy: PVDC-coated biaxially oriented nylon, Unitika DCR type 15μ KPET: PVDC-coated biaxially oriented polyester, Toyobo E8002 type 12μ Extrusion laminating resin LL: Sumikasen α CS8026, MFR10g / 1
0 minutes, density 0.914 g / cm ³ LD: Sumikasen L718-H, MFR 8 g / 10
Min, density 0.919 g / cm ³ Processing conditions 1) Co-extrusion: Co-extrusion lamination processing Single layer: Single-layer lamination processing 2) “−” in the table means that no treatment was performed. 3) AC agent: Nippon Soda T120 was used.

[0060]

As described in detail above, according to the present invention,
A gas barrier laminated film having excellent adhesive strength can be obtained without using an anchor coating agent. Further, the manufacturing method of the present invention enables high-speed processing.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location B32B 27/32 B32B 27/32 C 31/12 7148-4F 31/12 31/20 7148-4F 31 / 20 31/30 7148-4F 31/30 C08J 7/00 C08J 7/00 A 303 303

Claims (6)

[Claims] 1. A gas bar coated with vinylidene chloride resin.
Rear plastic base material and polyethylene resin,
Polypropylene resin, ethylene-vinyl ester resin
Polymer resin and ethylene- (meth) acrylic acid ester
Extrusion, which is a type selected from the group consisting of copolymer resins
Gas barrier laminated film made of laminating resin
And a corona discharge treatment step (x) below,
Manufactured from (y) ozone treatment process and (z) pressure bonding process
Gas barrier that does not use an anchor coating agent
For producing a flexible laminated film. (X) Corona discharge treatment step A vinylidene chloride resin as a plastic base material was coated.
10 (w · min / m) ²) Corona discharge at the above treatment density
Process of applying treatment. (Y) Ozone treatment step Extruded laminated resin at a temperature of 180 to 340 ° C
Melt extruded into a film, at least one side of the film
Step of applying ozone treatment to. (Z) Pressure bonding step Vinylidene chloride resin obtained in the corona discharge treatment step
Corona of gas barrier plastic base material coated with
Ozone of the treated surface and the film obtained in the ozone treatment process
The process of crimping the treated surface. 2. The production method according to claim 1, wherein the corona discharge density in the corona discharge treatment step is 20 (w · min / m ² ) or more. 3. A plastic substrate as a base of a gas barrier plastic substrate coated with vinylidene chloride resin is a biaxially stretched polypropylene resin, an unstretched polypropylene resin, a biaxially stretched nylon resin, or an unstretched nylon. -Based resin, biaxially-stretched polyester-based resin, cellophane, biaxially-stretched polyvinyl alcohol-based resin, biaxially-stretched ethylene-vinyl alcohol-based copolymer resin, unstretched ethylene-vinyl alcohol-based copolymer resin or unstretched polyvinyl chloride The method according to claim 1, which is a resin. 4. The corona discharge treatment step and the crimping step are provided in-line with the extrusion laminator, and the gas barrier plastic substrate coated with the vinylidene chloride resin after the corona discharge treatment step is immediately subjected to the crimping step. Production method. 5. The manufacturing method according to claim 1, further comprising the following aging treatment step after the pressure-bonding step. Aging treatment step: a step of aging the laminated film obtained in the pressure-bonding step under heat retention. 6. The method according to claim 5, wherein the aging temperature is 30 ° C. or higher and lower than 50 ° C.