JP2015208866A - Laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate that is free from the concern about residual solvent and the problem of decrease in laminate strength due to time degradation, and achieves strong adhesion between layers.SOLUTION: As an adhesion layer of a laminate, used is a resin composition layer comprising a ternary copolymer comprising alkene-(meta) acrylic acid ester-unsaturated carboxylic acid (unsaturated dicarboxylic acid).

Description

The present invention relates to a new laminate, and more particularly to a laminate having excellent adhesive strength between laminates and applicable to foods, pharmaceuticals, cosmetics, toiletries-related containers and packaging.
The present invention also relates to a laminate that maintains high adhesion even after processes such as bag making, molding, filling, and sterilization.

A polyester film, for example, a biaxially stretched polyester film, is excellent in transparency, toughness, oxygen barrier property, and the like, and thus is used as a base material for packaging materials such as various foods and industrial materials. And in this polyester-type film, the resin film used as a reinforcement layer is laminated | stacked, or the heat-sealable resin layer is laminated | stacked, and it is used in the wide field | area.
As a method for laminating such a laminated film, a dry laminating method using an adhesive, an extrusion laminating method using an adhesive resin, a wet laminating method and the like are known. Among these, the dry laminating method and the extrusion laminating method are widely used, and the extrusion laminating method that is most advantageous in terms of production cost and efficiency is particularly preferably used.

In general, a two-component curable urethane adhesive or the like is used for the dry laminating method (Patent Document 1).
The invention described in Patent Document 1 can obtain a strong adhesive strength to the laminate base material, and as a food packaging material, it is possible to prevent appearance deterioration due to unintentional bending during stacking after retort. In addition, even when foods with high acidity or oily foods are filled as content, the adhesive can maintain strong adhesive strength over a long period of time without causing a decrease in adhesive strength over time or pinholes. An invention intended to provide a composition, comprising 10 to 90% by weight of a polyester polyurethane polyol and 10 to 90% by weight of a polyester resin containing a carboxyl group at the molecular end, orthophosphoric acid or its ester compound and organic isocyanate It is an invention relating to an adhesive composition containing a compound or the like.

Moreover, in the general extrusion laminating method, the laminated body is obtained by apply | coating an anchor coating agent and extruding resin (patent document 2, 3).
However, the conventional lamination with dry laminate coating is concerned with residual solvent due to the use of a diluting solvent for the adhesive, and because it is a two-component reactive adhesive, it degrades with time and decomposes, resulting in a decrease in laminate strength. There is a problem. Further, lamination by extrusion lamination via an anchor coat agent has a problem of residual solvent due to a diluting solvent, and there are limitations on selection of a substrate to be laminated and its film thickness.
That is, the working environment is deteriorated due to scattering during extrusion lamination of diluted organic solvents such as ethyl acetate and toluene used for the anchor coating agent, the manufacturing cost is increased by using a relatively expensive anchor coating agent, and the final product ( There are problems such as odor generation due to residual organic solvent in the packaging material.

Japanese Patent Laid-Open No. 5-51574 Patent No. 5247199 Japanese Patent Laid-Open No. 7-90093

The present invention solves the above problems, there is no concern about residual solvent, there is no problem that the laminate strength decreases due to deterioration over time, and no anchor coating agent is required for lamination, so that the residual solvent due to the diluting solvent Another object of the present invention is to provide a new laminate having a strong adhesive force without any limitation on the selection of the substrate to be laminated and the film thickness.
That is, the present invention relates to providing a low-elution packaging material by not using an organic solvent, and also relates to a laminate having excellent laminate strength even when the amount of unsaturated carboxylic acid is small. In addition, in the production of a laminate, the invention is characterized by the use of extrusion lamination.

  As a result of research, the present inventor has developed an adhesive resin composition layer containing a terpolymer comprising an alkene- (meth) acrylate ester-unsaturated carboxylic acid (unsaturated dicarboxylic acid) as an adhesive layer of the laminate. It has been found that the above-mentioned purpose can be achieved by using it. (Hereinafter, the adhesive layer of the present invention may be referred to as a “ternary copolymer adhesive resin layer”.)

The present invention is characterized by the following points.
1. A laminate obtained by laminating at least a base film and a polyamide resin film through an adhesive resin composition layer containing an alkene- (meth) acrylic acid ester-unsaturated carboxylic acid terpolymer. .
2. The amount of unsaturated carboxylic acid component in the adhesive resin composition layer is 0.05% by mass to less than 1.0% by mass, and the amount of (meth) acrylic acid ester component is 5% by mass to 40% by mass. The laminated body as described in.
3. The peel strength when peeled between the base film and the polyamide-based resin film is 3 N / 15 mm width or more, and is 3 N / 15 mm width or more even after boiling and retorting (80 to 135 ° C.). 3. The laminate according to 1 or 2 above.
4). 4. The laminate according to any one of the above 1 to 3, wherein the base film is a polyester resin film, a polyamide resin film, or a polyolefin resin film.
5. The laminated body in any one of said 1-3 whose said base film is a polyethylene terephthalate film.

6). The laminated body in any one of said 1-5 which provides a vapor deposition film on the said polyamide-type resin film.
7). 7. The laminate according to 6 above, wherein a gas barrier coating film is provided on the vapor deposition film.
8). The gas barrier coating film has the general formula R ¹ _n M (OR ² ) _m (wherein M represents a metal atom, R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, and n is 0 or more) Wherein m is an integer of 1 or more, and n + m represents the valence of M), and a composition comprising at least one alkoxide, polyvinyl alcohol, and / or ethylene / vinyl alcohol The laminate according to 7 above, which is a hydrolyzate of alkoxide obtained by polycondensation by a sol-gel method or a hydrolyzed condensate of alkoxide.
9. 9. The method for producing a laminate according to any one of 1 to 8 above, wherein an adhesive layer made of an alkene- (meth) acrylic acid ester-unsaturated carboxylic acid terpolymer extruded onto a base film is used. The manufacturing method which bonded the polyamide-type resin film through.
10. A packaging laminate using the laminate according to any one of 1 to 8 above, wherein the laminate is heat-sealed on a surface made of a polyamide-based resin film, on a vapor deposition film, or on a gas barrier coating film Packaging material provided with a conductive resin layer.

11. 11. The packaging laminate as described in 10 above, wherein the heat-sealable resin layer is a polyolefin resin.
12 A packaging bag using the packaging laminate according to 10 or 11 above, wherein the heat-sealable resin layer side of one packaging laminate and the heat-sealable resin layer side of the other packaging laminate are A packaging bag that is overlapped so as to face each other and its end is heat-sealed.
13. 9. An adhesive comprising an adhesive resin composition comprising an alkene- (meth) acrylic acid ester-unsaturated carboxylic acid terpolymer used for adhesion between layers of the laminate according to any one of 1 to 8 above.
14 The amount of unsaturated carboxylic acid component in the adhesive resin composition is 0.05% by mass to less than 1.0% by mass, and the amount of (meth) acrylic acid ester component is 5% by mass to 40% by mass. The adhesive described in 1.

  The laminate of the present invention comprises an adhesive resin composition comprising, as an adhesive layer thereof, a terpolymer comprising an alkene- (meth) acrylic acid ester-unsaturated carboxylic acid (unsaturated dicarboxylic acid) as defined in the present invention. By using a layer, there is no concern about residual solvent and there is no problem that the laminate strength decreases due to deterioration over time. A laminate having no limitation can be obtained.

That is, the present invention provides an adhesive resin composition comprising an alkene-acrylic ester-unsaturated carboxylic acid terpolymer in an adhesive layer between a base resin film such as a polyester resin film and a polyamide resin film. By using it, it is possible to produce a packaging material having excellent strength that cannot be exhibited by conventional adhesive resins, and the present invention has excellent flexibility and bag making, molding, filling, The invention relates to a laminate that maintains high adhesion even after a sterilization treatment or the like.
In addition, it has excellent strength even in the boil / retort treatment, and has an advantage that it can be used as a boil / retort treatment packaging material.

FIG. 1 is a schematic cross-sectional view showing an example of the layer structure of the laminate of the present invention. FIG. 2 is a schematic cross-sectional view showing another example of the layer configuration of the laminate of the present invention.

The laminated body of this invention is demonstrated in detail, referring drawings.
1 and 2 are schematic cross-sectional views showing an example of the layer configuration of the laminate of the present invention.
As shown in FIG. 1, the laminate of the present invention comprises an adhesive resin containing a base film 1 and a polyamide resin film 3 containing an alkene- (meth) acrylate-carboxylic acid terpolymer. A structure formed by laminating through the composition layer 2 is a basic structure.
As another embodiment of the laminate of the present invention, as shown in FIG. 2, an inorganic oxide vapor deposition film 4 is provided on the surface made of the polyamide-based resin film 3, and in some cases, the inorganic oxide vapor deposition film is further provided. The structure in which the gas barrier coating film 5 is provided on the base 4 is the basic structure.

  Next, materials constituting the laminate of the present invention, manufacturing methods thereof, and the like will be described. The resin names used in the present invention are those commonly used in the industry.

A. Base film The base film constituting the laminate of the present invention is excellent in chemical or physical strength, withstands conditions for forming a vapor-deposited inorganic oxide film, etc., and characteristics of the vapor-deposited inorganic oxide film, etc. A film or sheet that can be held satisfactorily without damaging the film is used.
Specifically, as such a film or sheet, polyolefin resin such as paper, cellophane, polyethylene resin or polypropylene resin, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene , Oriented polypropylene, K-coated oriented polypropylene, cyclic polyolefin resin, K-coated oriented nylon, polyvinyl alcohol, polyacrylonitrile, ethylene-vinyl acetate copolymer resin, ionomer resin, ethylene- (meth) acrylic acid copolymer resin, ethylene -(Meth) ethyl acrylate copolymer resin, ethylene-propylene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, methylpentene resin, polybutene resin, acid modification Reolefin resins, various polyamide resins such as nylon, polystyrene resins, low crystalline saturated polyesters or amorphous polyester resins such as polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyvinyl chloride, poly Vinylidene chloride, polyvinylidene fluoride, ethylene tetrafluoroethylene resin, polyethylene tetrafluoroethylene resin, polycarbonate resin, polyurethane resin, acetal resin, cellulose resin, and the like can be used.

In the present invention, among the above resins, it is preferable to use a film or sheet of a polyester resin, a polyolefin resin, or a polyamide resin, and it is particularly preferable to use stretched polyethylene terephthalate.
The polyester resin film or sheet such as stretched polyethylene terephthalate can also be used as a polyester resin film in other layers in the present invention.
The resin film or sheet may be formed by using the film forming method such as extrusion method, cast molding method, T-die method, cutting method, inflation method, etc. It is produced by a method of forming a multilayer co-extrusion film using the above-described various resins, a method of using two or more kinds of resins, mixing them before forming a film, and forming a film.
Furthermore, if necessary, it can be used as various resin films or sheets stretched uniaxially or biaxially using a tenter method or a tubular method.

In the present invention, the thickness of the base film is preferably from 0.1 to 300 μm, more preferably from 1 to 100 μm, from the viewpoints of moldability and transparency. The base material is preferably subjected to a treatment for improving wettability, such as corona, ozone, or flame treatment, on the adhesive layer side.
In addition, when using one or more of the above-described various resins and forming the film, for example, film processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, Various plastic compounding agents and additives can be added for the purpose of improving and modifying mold release properties, flame retardancy, antifungal properties, electrical properties, strength, etc. From a very small amount to several tens of percent, it can be arbitrarily added depending on the purpose.
In the above, as a general additive, for example, a lubricant, a crosslinking agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a filler, a reinforcing agent, an antistatic agent, a pigment, and the like can be used. In this case, a modifying resin or the like can also be used.

B. Ternary Copolymer Adhesive Resin Layer The ternary copolymer adhesive resin layer of the present invention is composed of an adhesive between a base film and a polyamide resin film, a polyamide resin film or a deposited film, a gas barrier coating film, and a heat seal. It can be used for adhesion to a layer.
The adhesive resin used in the ternary copolymer adhesive resin layer of the present invention is preferably a resin containing an alkene- (meth) acrylic acid ester-unsaturated carboxylic acid terpolymer resin.
Alkenes include ethylene, propylene, butene, and isobutene, with ethylene being preferred.

Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and isobutyl (meth) acrylate, and methyl acrylate. , Ethyl acrylate, butyl acrylate, and isobutyl acrylate are preferable, and methyl acrylate is more preferable.

Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, ethacrylic acid, fumaric acid, maleic acid, monomethyl maleate, and maleic anhydride. In the adhesive layer of the present invention, alkene, (meth) acrylic acid ester, and unsaturated carboxylic acid are randomly copolymerized by the autoclave method.
In particular, an ethylene-acrylic acid ester-maleic anhydride terpolymer resin is preferable. The compounding ratio of these components is preferably 5 to 40% by mass of the (meth) acrylic acid ester-derived component (residue), more preferably 10%, based on the total mass of the ternary copolymer adhesive resin. -30 mass%.
Further, the unsaturated carboxylic acid-derived component (residue) is contained in an amount of 0.05 to 3.0% by mass, more preferably less than 0.05 to 1.0% by mass, and the rest are all alkene-derived components. (Residue).

  When the unsaturated carboxylic acid component amount of the adhesive resin used in the terpolymer adhesive resin layer of the present invention is more than the above range, the acid content of the laminated laminate is increased, so that the hygroscopicity is increased, There is a possibility of foaming during extrusion. Moreover, since there is also elution from the ternary copolymer adhesive resin layer, there is concern about hygiene, which is not preferable.

On the other hand, when the amount of the unsaturated carboxylic acid component is too small, chemical interaction with the base film or the polyamide resin film is difficult to occur.
When the content of the (meth) acrylic acid ester-derived component is more than the above range, the resin itself is liable to be liquefied and handling becomes worse, which is not preferable. In addition, when the content of the (meth) acrylic acid ester-derived component is less than the above range, adhesion due to the reaction of the acrylate is difficult to occur, and thus the adhesive strength is lowered with respect to a substrate such as polypropylene or polyester resin. It is not preferable.

The MFR of the terpolymer adhesive resin of the present invention is preferably 3 to 100 g / 10 min at 190 ° C., more preferably 5 to 20 g / 10 min.
If the MFR is above the above range, the resin becomes liquid and there is a problem that it is difficult to laminate easily. Moreover, when it is below the range, there arises a problem that the adhesive resin cannot be easily extruded.

Moreover, it is preferable that the thickness of a ternary copolymer adhesive resin layer is 0.1-200 micrometers, More preferably, it is 1-100 micrometers.
When the film thickness is not more than the above range, it is difficult to extrude easily and the adhesive strength is not exhibited. When the film thickness exceeds the range, problems such as adhesive strength are solved, but the packaging material cost increases due to excessive use of the resin.

  As an adhesion mechanism of the terpolymer adhesive resin layer of the present invention, a mechanism for bonding with the flexibility of the adhesive resin, a mechanism for bonding by compatibilization with the resin, the surface of the counterpart substrate and the unsaturated carboxylic acid There are a mechanism for bonding by chemical interaction, a mechanism for bonding by chemical interaction of unsaturated carboxylic acid and acrylate to the surface of the counterpart substrate, and a mechanism for bonding by radical generation by extrusion at high temperature.

The terpolymer adhesive resin layer of the present invention is not necessarily bonded by one bonding mechanism, but is bonded by utilizing at least two or more of the above reactions.
As a representative example, the paper is bonded mainly by the flexibility of the ternary copolymer adhesive resin layer. For resins such as polyethylene and ethylene copolymers, adhesion is mainly due to the compatibility of the alkene portion. The aluminum foil, the metal vapor deposition film, and the primer are bonded to each other by a reaction between the unsaturated carboxylic acid and the polar group of the counterpart substrate. The stretched polypropylene, stretched polyethylene terephthalate, unstretched polypropylene, and unstretched polyethylene terephthalate are bonded to each other by chemical interaction of acrylate and unsaturated carboxylic acid. The vapor deposition film is bonded using the radical generation of the resin and the chemical interaction of the acrylate and unsaturated carboxylic acid with the substrate surface.

The adhesive resin composition containing the ternary copolymer used in the present invention may be composed of only an alkene- (meth) acrylic acid ester-unsaturated carboxylic acid terpolymer.
In another embodiment, the adhesive resin composition containing the ternary copolymer may be used in a range where the ratio of the unsaturated carboxylic acid-derived component is a specified concentration in addition to the ternary copolymer. The alkene- (meth) acrylic acid ester or the alkene-unsaturated carboxylic acid binary copolymer may be contained in the range of 0 to 90% by mass, preferably up to 60% by mass. By adding a binary copolymer, a relatively expensive terpolymer resin can be reduced, and by adding a comonomer, processability can be improved.
In yet another embodiment, the adhesive resin composition containing the terpolymer is further added to the terpolymer or the mixture of the terpolymer and the binary copolymer. Modification resin such as polyolefin resin, polyamide resin, polyester resin, ethylene-vinyl alcohol copolymer, polyvinyl chloride, polyvinylidene chloride, etc., within the range where the ratio of saturated carboxylic acid-derived components is within the specified concentration Can be included.

  In addition, the adhesive resin composition containing the terpolymer includes, for example, processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slip properties, mold release properties, flame retardancy, Various plastic compounding agents and additives can be added for the purpose of improving and modifying antifungal properties, electrical characteristics, strength, etc. Depending on the purpose, it can be added arbitrarily. As a general additive, for example, a lubricant, a crosslinking agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a filler, a reinforcing agent, an antistatic agent, a pigment and the like can be used.

C. Laminate Adhesive Layer A laminate adhesive layer that is used for bonding a portion other than the ternary copolymer adhesive resin layer that constitutes the laminate will be described.
Examples of the adhesive constituting the adhesive layer for laminating include, for example, polyvinyl acetate adhesive, homopolymers such as ethyl acrylate, butyl acrylate, and 2-ethylhexyl ester, and these and methyl methacrylate, acrylonitrile, and styrene. Polyacrylic acid ester adhesives, cyanoacrylate adhesives, and copolymers of ethylene and monomers such as vinyl acetate, ethyl acrylate, acrylic acid, and methacrylic acid. Polymer-based adhesives, cellulose-based adhesives, polyester-based adhesives, polyamide-based adhesives, polyimide-based adhesives, amino resin-based adhesives such as urea resins or melamine resins, phenolic resin-based adhesives, epoxy-based adhesives, Polyurethane adhesives, reactive (meth) acrylic adhesives, Ropurengomu, nitrile rubber, styrene - rubber adhesive consisting of such butadiene rubber, silicone adhesive, an alkali metal silicate, may be used adhesives inorganic adhesive or the like made of a low-melting-point glass or the like.

The above-mentioned adhesive may be in any form of composition such as aqueous type, solution type, emulsion type, and dispersion type, and the property may be any form such as film / sheet, powder or solid. Further, the adhesion mechanism may be any form such as a chemical reaction type, a solvent volatilization type, a heat melting type, and a hot pressure type.
In the present invention, the above-mentioned adhesive is applied to the entire surface including the printing layer by, for example, a coating method such as a roll coating method, a gravure roll coating method, a kiss coating method, or a printing method, and then the solvent is dried. Thus, an adhesive layer for laminating can be formed, and the coating or coating amount is preferably 0.1 to 10 g / m ² (dry state).

D. Polyamide-based resin film The polyamide-based film of the present invention imparts functions such as flex resistance and impact resistance to the laminate of the present invention. In particular, the provision of bending resistance can suppress a decrease in gas barrier properties after bending. The polyamide-based resin film contains an aliphatic polyamide and / or an aromatic polyamide.

  Examples of the aliphatic polyamide include aliphatic nylon and copolymers thereof. Specifically, polycapramide (nylon-6), poly-ω-aminoheptanoic acid (nylon-7), poly-ω-aminononanoic acid (nylon-9), polyundecanamide (nylon-11), polylauryllactam ( Nylon-12), polyethylenediamine adipamide (nylon-2,6), polytetramethylene adipamide (nylon-4,6), polyhexamethylene adipamide (nylon-6,6), polyhexamethylene Bacamide (nylon-6,10), polyhexamethylene dodecamide (nylon-6,12), polyoctamethylene adipamide (nylon-8,6), polydecamethylene adipamide (nylon-10,8) , Caprolactam / lauryl lactam copolymer (nylon-6 / 12), caprolactam / ω-aminononanoic acid copolymer Body (nylon-6 / 9), caprolactam / hexamethylenediammonium adipate copolymer (nylon-6 / 6,6), lauryllactam / hexamethylenediammonium adipate copolymer (nylon-12 / 6,6), Ethylenediamine adipamide / hexamethylene diammonium adipate copolymer (nylon-2,6 / 6,6), caprolactam / hexamethylene diammonium adipate / hexamethylene diammonium sebacate copolymer (nylon-6 / 6,6) / 6,10), ethyleneammonium adipate / hexamethylenediammonium adipate / hexamethylenediammonium sebacate copolymer (nylon-6 / 6,6 / 6,10), etc. Even if you mix the aliphatic polyamide There.

  Preferred aliphatic polyamides include nylon-6, nylon-6,6, nylon-6 / 6,6 (copolymer of nylon 6 and nylon 6,6), more preferably nylon-6, nylon. -6/6, 6 and more preferably nylon-6. As the two or more kinds of aliphatic polyamides, a combination of nylon-6 and nylon-6 / 6,6 (mass ratio of about 50:50 to 95: 5) is preferable.

As the aromatic polyamide, for example, an aromatic diamine such as meta-xylene diamine and para-xylene diamine and a dicarboxylic acid such as adipic acid, suberic acid, sebacic acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid or a derivative thereof can be used. Examples thereof include crystalline aromatic polyamides obtained by a condensation reaction. A crystalline aromatic polyamide such as polymetaxylene adipamide (MXD-nylon) is preferable. Specific examples include S-6007 and S-6011 (both manufactured by Mitsubishi Gas Chemical Co., Inc.).
Alternatively, an amorphous aromatic polyamide (amorphous nylon) obtained by a polycondensation reaction between an aliphatic diamine such as hexamethylenediamine and a dicarboxylic acid such as terephthalic acid or isophthalic acid or a derivative thereof can be used. Preferred is a copolymer of hexamethylenediamine-terephthalic acid-hexamethylenediamine-isophthalic acid. Specific examples include sealer PA (manufactured by Mitsui DuPont Polychemical Co., Ltd.) and the like.

As the polyamide-based resin film of the present invention, preferable combinations of aliphatic polyamide and aromatic polyamide include a combination of nylon-6 and MXD-nylon, and a combination of nylon-6 and amorphous aromatic polyamide (amorphous nylon). .
Particularly preferable polyamide-based resins include metaxylenediadipamide (MXD-6) -based nylon, 6-nylon, and 6,6 nylon. Further, the barrier layer may be an intermediate layer.

The polyamide-based resin film of the present invention may be composed of the above-mentioned polyamide-based resin, but may be a known flex resistance improver, inorganic or organic additive as long as the effects of the present invention are not impaired. Etc. can be blended. Examples of the bending resistance improver include polyolefins, polyester elastomers, polyamide elastomers, and the like, and they can be appropriately blended in the range of about 0.5 to 10% by mass. Examples of inorganic or organic additives include antiblocking agents, nucleating agents, water repellents, antioxidants, thermal stabilizers, lubricants, antistatic agents, and the like. For example, if it is an antiblocking agent, a silica, a talc, a kaolin etc. can be mix | blended suitably in the range of about 100-5000 ppm. Note that it is possible to provide not only one polyamide-based resin layer but also two or more layers.
For example, the polyamide-based resin film is longitudinally stretched 2 to 4 times by a roll stretching machine at 50 to 100 ° C., and further stretched 3 to 5 times by a tenter stretching machine in an atmosphere at 90 to 150 ° C. It can be obtained by heat treatment in an atmosphere of 100 to 240 ° C. with the same tenter. The stretched film of the present invention may be subjected to simultaneous biaxial stretching and sequential biaxial stretching, and the obtained multilayer stretched film may be provided with any surface treatment layer on both surfaces or one surface if necessary. .

In the present invention, the above-described resin film or sheet is used. For example, the above-described laminating adhesive or the like is used for dry lamination or the like, and the laminating adhesive layer and the heat-sealable resin are used. Can be sandwiched between layers.
As the resin film or sheet, any of an unstretched film or a stretched film stretched in a uniaxial direction or a biaxial direction can be used. In the present invention, the thickness of the resin film or sheet may be a thickness that can be kept to the minimum necessary for strength, puncture resistance, and the like, and if it is too thick, the cost increases. On the other hand, if it is too thin, the strength, puncture resistance and the like are reduced, which is not preferable.
In the present invention, from the above reasons, 1 to 100 μm, preferably 5 to 50 μm is preferable.

Further, when the laminate of the present invention is used as a packaging bag, it is subjected to severe physical and chemical conditions, and therefore, the laminate material constituting the packaging bag is required to have severe packaging suitability. Various conditions such as deformation prevention strength, drop impact strength, pinhole resistance, heat resistance, sealing performance, quality maintenance, workability, and hygiene are required.
For this reason, in the present invention, in addition to the above materials, other materials that satisfy the above-described conditions can be arbitrarily used.

Specifically, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer Copolymer, ethylene-acrylic acid or methacrylic acid copolymer, methylpentene polymer, polybutene resin, polyvinyl chloride resin, polyvinyl acetate resin, polyvinylidene chloride resin, vinyl chloride-vinylidene chloride copolymer, poly ( (Meth) acrylic resin, polyacrylonitrile resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyester resin, polyamide resin, Polycarbonate Any known resin film or sheet such as resin, polyvinyl alcohol resin, saponified ethylene-vinyl acetate copolymer, fluorine resin, gen resin, polyacetal resin, polyurethane resin, nitrocellulose, etc. Can be used. In addition, for example, synthetic paper or the like can also be used. Furthermore, in the present invention, the film or sheet may be any form of film such as extrusion film formation, inflation film formation, and coating film.

E. Barrier layer (deposition layer)
In the present invention, a barrier layer can be appropriately provided.
When the barrier layer is provided, it may be provided mainly on the inner surface side from the base material layer, or when the intermediate layer is provided, it may be provided on the inner surface side from the intermediate layer.
The barrier layer is made of a barrier resin, an inorganic substance, or an inorganic oxide, and includes a vapor deposited film of an inorganic substance or an inorganic oxide, or a metal foil.

Specifically, the following deposited films, aluminum foil, aluminum deposited polyester film, aluminum deposited polypropylene film, silica deposited polyester film, silica deposited polyamide film, alumina deposited polyester film, ethylene-vinyl alcohol copolymer film, polychlorinated Vinylidene, polyvinyl alcohol, MXD6, etc. are mentioned. Except for the aluminum foil and the ethylene-vinyl alcohol copolymer film, it can be used as a barrier layer / base material layer.
By having a barrier layer, the gas barrier property which prevents permeation | transmission of oxygen gas, water vapor | steam, etc. can be improved. In addition, if necessary, light shielding properties that prevent transmission of visible light, ultraviolet light, and the like can be imparted. Note that two or more barrier layers may be provided. When two or more barrier layers are provided, each may have the same composition or a different composition.

Usually, the thickness of the barrier layer is preferably 0.01 to 500 μm, more preferably 1 to 300 μm from the viewpoint of gas barrier properties and transparency.
The barrier layer may be subjected to a treatment for increasing wettability, such as corona treatment, ozone treatment, or frame treatment, on both the base material layer side and the heat seal layer side.
A conventionally known metal foil can be used as the inorganic or inorganic metal foil. Aluminum foil or the like is preferable from the viewpoint of gas barrier properties that prevent the transmission of oxygen gas, water vapor, and the like, and light shielding properties that prevent the transmission of visible light, ultraviolet light, and the like.
A vapor deposition film can be formed by a conventionally well-known method using an inorganic substance or an inorganic oxide, The composition and formation method are not specifically limited. As a method for forming a vapor deposition film, for example, a physical vapor deposition method (Physical Vapor Deposition method, PVD method) such as a vacuum vapor deposition method, a sputtering method, and an ion plating method, or a plasma chemical vapor deposition method, a thermochemical method, or the like. Examples thereof include a chemical vapor deposition method (chemical vapor deposition method, CVD method) such as a vapor phase growth method and a photochemical vapor deposition method.

  Examples of the deposited film include silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), and titanium (Ti). ), Lead (Pb), zirconium (Zr), yttrium (Y) and other inorganic or inorganic oxide vapor deposition films can be used. In particular, an aluminum metal vapor-deposited film or a silicon oxide or aluminum oxide vapor-deposited film is preferably used as a packaging material.

Representation of the inorganic oxide, for example, SiO _X, as such AlO _X MO _X (In the formula, M represents an inorganic element, the value of X, varies each of an inorganic element range.) In expressed. As a range of the value of X, silicon (Si) is 0 to 2, aluminum (Al) is 0 to 1.5, magnesium (Mg) is 0 to 1, calcium (Ca) is 0 to 1, potassium(
K) is 0 to 0.5, tin (Sn) is 0 to 2, sodium (Na) is 0 to 0.5, boron (B) is 0 to 1.5, titanium (Ti) is 0-2, lead (Pb) can take values in the range of 0-1, zirconium (Zr) in the range of 0-2, and yttrium (Y) in the range of 0-1.5. In the above, when X = 0, it is a complete inorganic simple substance (pure substance) and is not transparent, and the upper limit of the range of X is a completely oxidized value. Silicon (Si) and aluminum (Al) are preferably used for the packaging material, silicon (Si) is in the range of 1.0 to 2.0, and aluminum (Al) is in the range of 0.5 to 1.5. Values can be used.

  In the present invention, the film thickness of the inorganic material or inorganic oxide vapor-deposited film as described above varies depending on the kind of inorganic material or inorganic oxide used, but is, for example, about 10 to 2000 mm, preferably about 10 to 1000 mm. It is desirable to select and form arbitrarily within the range. Specifically, in the case of an aluminum deposited film, the film thickness is preferably about 10 to 600 mm, more preferably about 10 to 400 mm. In the case of a silicon oxide or aluminum oxide deposited film, the film thickness is preferably about 10 to 500 mm, more preferably 10 to 300 mm.

Hereinafter, the deposited film of silicon oxide will be described. The vapor-deposited film (thin film) of silicon oxide is represented by the general formula: SiO _x (wherein x represents a number from 0 to 2), and the value of x is preferably 1.3 to 1.9. The silicon oxide thin film may be mainly composed of silicon oxide, and may further contain at least one kind of compound composed of one kind of carbon, hydrogen, silicon or oxygen, or two or more kinds of elements by chemical bonding or the like. For example, when a compound having a C—H bond, a compound having a Si—H bond, or a carbon unit is in the form of graphite, diamond, fullerene, or the like, the raw material organosilicon compound or a derivative thereof is further added. It may be contained by a chemical bond or the like. Examples thereof include hydrocarbons having a CH ₃ site, hydrosilica such as SiH ₃ silyl and SiH ₂ silylene, and hydroxyl derivatives such as SiH ₂ OH silanol. As content which said compound contains in the vapor deposition film | membrane of a silicon oxide, it is 0.1-50 mass%, Preferably it is 5-20 mass%. Moreover, when a silicon oxide thin film contains the said compound, it is preferable that content of a compound is reducing toward the depth direction from the surface of the vapor deposition film | membrane of a silicon oxide. As a result, the impact resistance and the like are enhanced by the above compound on the surface of the silicon oxide vapor deposition film, and on the other hand, the vapor deposition of the base material layer and the silicon oxide at the interface with the base material layer due to the low content of the above compound. The tight adhesion with the film becomes strong.

Formation of vapor-deposited film by chemical vapor deposition As chemical vapor deposition , specifically, for example, chemical vapor deposition such as plasma chemical vapor deposition, thermal chemical vapor deposition, and photochemical vapor deposition A vapor deposition film of an inorganic oxide can be formed by using (Chemical Vapor Deposition method, CVD method).
More specifically, on one surface of the resin film or sheet, an evaporation monomer gas such as an organosilicon compound is used as a raw material, an inert gas such as argon gas or helium gas is used as a carrier gas, and oxygen Can be used as a supply gas, and a vapor deposition film of an inorganic oxide such as silicon oxide can be formed by a low temperature plasma chemical vapor deposition method using a low temperature plasma generator or the like.
In the above, as the low-temperature plasma generator, for example, generators such as high-frequency plasma, pulse wave plasma, microwave plasma can be used, but in the present invention, in order to obtain a highly active stable plasma, It is desirable to use a high frequency plasma generator.

Formation of Vapor Deposition Film by Physical Vapor Deposition Method In the present invention, the inorganic oxide vapor deposition film may be, for example, a physical vapor deposition method (Physical Vapor) such as a vacuum vapor deposition method, a sputtering method, an ion plating method, or an ion cluster beam method. (Deposition method, PVD method).
Specifically, a metal oxide is used as a raw material, and this is heated to deposit on a resin film or sheet, or a metal or metal oxide is used as a raw material and oxygen is introduced. An amorphous thin film of inorganic oxide is formed using an oxidation reaction deposition method that oxidizes and deposits on a resin film or sheet, and a plasma-assisted oxidation reaction deposition method that assists the oxidation reaction with plasma. can do.
In the above, the heating method of the vapor deposition material can be performed by, for example, a resistance heating method, a high frequency induction heating method, an electron beam heating method (EB), or the like.

Examples of the deposited film of the inorganic oxide include a deposited film of a metal oxide. Specifically, silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K ), Tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y), etc. it can. Preferable examples include metals such as silicon (Si) and aluminum (Al).
After forming a vapor-deposited film of an inorganic oxide on a substrate by chemical vapor deposition or physical vapor deposition as described above, the vapor-deposited film may be further subjected to glow discharge treatment, plasma treatment, or microwave treatment. Good. This further improves the adhesion between the deposited film and the following gas barrier coating film.

F. Gas barrier coating film In the present invention, it is preferable to further provide a barrier coating film on the above-described vapor deposition film in order to improve the gas barrier property.
In the present invention, various gas barrier coatings can be used as the gas barrier protective layer without limitation, but a coating coated with a solution containing a water-soluble polymer and an alkoxide, a hydrolyzate thereof, or tin chloride is preferable.
The gas barrier coating film can be formed by coating with a solution containing at least a water-soluble polymer having a hydroxyl group and an alkoxide. Examples of the water-soluble polymer having at least a hydroxyl group include polyvinyl alcohol, polyvinyl pyrrolidone, starch, methyl cellulose, carboxymethyl cellulose, sodium alginate, an ethylene-vinyl alcohol copolymer, and the like. Polyvinyl alcohol is preferred.

  These resins may be commercially available. For example, as an ethylene / vinyl alcohol copolymer, Kuraray Co., Ltd., Eval EP-F101 (ethylene content: 32 mol%), Nippon Synthetic Chemical Industry Co., Ltd., Soarnol D2908 (ethylene content; 29 mol%) and the like can be used. Moreover, as polyvinyl alcohol, RS-110 (degree of saponification = 99%, degree of polymerization = 1,000) manufactured by Kuraray Co., Ltd., Kuraray Poval LM-20SO (degree of saponification = 40%) manufactured by Kuraray Co., Ltd. Polymerization degree = 2,000), Gohsenol NM-14 manufactured by Nippon Synthetic Chemical Industry Co., Ltd. (degree of saponification = 99%, degree of polymerization = 1,400) and the like can be used.

As the alkoxide, a general formula:
R _1n M (OR ₂ ) _m
(In the formula, M represents silicon, zirconium, titanium, aluminum or other metal atoms, R ₁ and R ₂ each independently represents an organic group having 1 to 8 carbon atoms, and n represents an integer of 0 or more. , M represents an integer of 1 or more, and n + m represents the valence of M. In the above formula, specific examples of the organic group represented by R ₁ include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group. , T-butyl group, n-hexyl group, n-octyl group, and other alkyl groups. Specific examples of the alkoxide include, for example, tetramethoxysilane: Si (OCH ₃ ) ₄ , tetraethoxysilane: Si (OC ₂ H ₅ ) ₄ , tetrapropoxysilane: Si (OC ₃ H ₇ ) ₄ , tetrabutoxysilane: Si (OC ₄ H ₉ ) ₄ or the like can be used.

The above-mentioned water-soluble polymer and alkoxide are mixed, and if desired, a solution to which a sol-gel catalyst, water, and an organic solvent are added is applied to the surface of a thin film made of aluminum oxide or silicon oxide, and polycondensation is performed. By doing so, a gas barrier coating film can be formed. In the present invention, a composite polymer layer in which two or more of the above-described coating films are stacked may be formed on a thin film made of aluminum oxide or silicon oxide.
Moreover, in this invention, a silane coupling agent can be added to said coating liquid for gas barrier coating-film formation, The gas barrier coating film obtained by this is especially preferable.
As the above-mentioned silane coupling agent, known organic reactive group-containing organoalkoxides can be used. Particularly, organoalkoxides having an epoxy group are suitable, for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, or the like can be used. The above silane coupling agents may be used alone or in combination of two or more. In this invention, the usage-amount of the above silane coupling agents can be used within the range of about 1-20 mass parts with respect to 100 mass parts of said alkoxides.

As a coating method of the coating liquid for forming a gas barrier coating film, conventionally known means such as roll coating such as a gravure roll coater, spray coating, spin coating, dipping, brush, bar code, applicator and the like are used. .
Although the thickness of a coating film changes with kinds of coating liquid, the thickness after drying becomes like this. Preferably it is the range of 0.01-100 micrometers, More preferably, it is 0.01-50 micrometers. If the thickness after drying is 100 μm or less, the occurrence of cracks can be suppressed.

  As a sol-gel method catalyst for polycondensation with a coating solution, a tertiary amine that is substantially insoluble in water and soluble in an organic solvent is used. Specifically, for example, N, N-dimethylbenzylamine, tripropylamine, tributylamine, tripentylamine and the like can be used. In particular, N, N-dimethylbenzylamine is suitable, and for example, about 0.01 to 1.0 parts by mass, especially about 0.03 parts by mass is used per 100 parts by mass of the total amount of alkoxide and silane coupling agent. It is preferable to do.

  Moreover, an acid can also be used as a catalyst of a sol-gel method, for example, mineral acids, such as a sulfuric acid, hydrochloric acid, nitric acid, organic acids, such as an acetic acid and tartaric acid, and others can be used. The amount of the acid used is preferably 0.001 to 0.05 mol, more preferably 0.01 to 0.00 mol, based on the total molar amount of the alkoxide and the alkoxide content (for example, silicate moiety) of the silane coupling agent. 03 moles.

  The water contained in the coating solution is preferably added in a proportion of 0.1 to 100 mol, more preferably 0.8 to 2 mol, with respect to 1 mol of the total molar amount of the solution alkoxide. Moreover, it is preferable that the polyvinyl alcohol and the ethylene-vinyl alcohol copolymer contained in the coating liquid for forming a gas barrier coating film are in a state of being dissolved in the coating liquid containing the alkoxide or the silane coupling agent. An organic solvent may be appropriately selected and added. For example, as the organic solvent, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butanol and the like can be used.

In the gas barrier laminate film of the present invention, a specific example of a method for forming a gas barrier coating film will be described below.
First, a gas barrier coating solution is prepared by mixing an alkoxide, a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, a sol-gel method catalyst, water, and an organic solvent. In the gas barrier coating liquid, the polycondensation reaction gradually proceeds.
Next, the gas barrier coating solution is applied by a conventional method on an inorganic oxide vapor-deposited film provided on one surface of the substrate, and dried. By drying, the polycondensation of the alkoxide and vinyl alcohol polymer further proceeds, and a composite polymer layer is formed. Preferably, the above operation is repeated to laminate a plurality of composite polymer layers.
Finally, the film coated with the coating solution is heated at a temperature of 20 to 250 ° C., preferably 50 to 220 ° C., for 1 second to 10 minutes, preferably 30 to 90 seconds.

In the present invention, an ethylene / vinyl alcohol copolymer or a composition using both an ethylene / vinyl alcohol copolymer and polyvinyl alcohol may be used instead of the vinyl alcohol polymer. A laminated film using both an ethylene / vinyl alcohol copolymer and polyvinyl alcohol is further improved in gas barrier properties after hot water treatment such as boil treatment and retort treatment.
As another aspect of forming the gas barrier coating film, the following laminated film is preferably formed in order to improve the gas barrier property after the hot water treatment.
That is, a composition containing polyvinyl alcohol is previously formed on at least one surface of a base film to form a first composite polymer layer, and then the ethylene / vinyl alcohol copolymer is contained on the coated surface. The object is applied to further form a second composite polymer layer. Thereby, the gas barrier property of the laminated film obtained improves.

Furthermore, in the present invention, a plurality of gas barrier coating films may be formed on the substrate film. By providing a plurality of gas barrier coating films, the gas barrier property can be further improved.
As a method for applying the gas barrier coating film forming composition, for example, a roll coating such as a gravure coater, a spray coating, a spin coating, a dipping, a brush, a barcode, an applicator or the like is applied once or a plurality of times. With this coating, it is possible to form the gas barrier coating film of the present invention having a dry-baked film thickness of 0.01 to 30 μm, preferably 0.1 to 10 μm.
If necessary, when applying the gas barrier composition of the present invention, a primer agent or the like can be applied on the inorganic oxide vapor-deposited film in advance.

Further, in the embodiment of the present invention, after providing the vapor deposition layer and the gas barrier coating film on the substrate, further providing the vapor deposition layer, and forming the gas barrier coating film on the vapor deposition layer in the same manner as described above. Good. Thus, by increasing the number of laminated layers, it is possible to realize a laminated film having further excellent gas barrier properties.
Since the gas barrier laminate film of the present invention has excellent gas barrier properties and flexibility, it is useful as a packaging material and is particularly suitably used as a food packaging film.
Furthermore, the gas barrier laminate film of the present invention is excellent in gas barrier properties after hot water treatment, particularly after high pressure hot water treatment (retort treatment).

G. Surface treatment layer In the present invention, a surface treatment layer can be formed on the intermediate layer, the base material and the like for improving the tight adhesion with the adjacent layer.
As the surface treatment layer, for example, corona discharge treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, oxidation treatment using chemicals, etc. are optionally applied. , For example, corona discharge treatment layer, ozone treatment layer, plasma treatment layer,
An oxidation treatment layer or the like can be formed and provided.
The surface pretreatment is carried out as a method for improving the close adhesion between various resin films or sheets and the inorganic oxide vapor-deposited film, but as a method for improving the close adhesion, for example, A surface treatment layer is formed by arbitrarily forming a primer coating layer, an undercoating layer, an anchor coating layer, an adhesive layer, a vapor deposition anchor coating layer or the like on the surface of various resin films or sheets in advance. It can also be.

  Examples of the pretreatment coating agent layer include polyester resins, polyamide resins, polyurethane resins, epoxy resins, phenol resins, (meth) acrylic resins, polyvinyl acetate resins, polyethylene, and polypropylene. A resin composition containing a polyolefin resin or a copolymer or modified resin thereof, a cellulose resin, or the like as a main component of the vehicle can be used. In particular, it is preferable to use a coating agent comprising polyester, acrylic, urethane resin, and isocyanate curing agent as the primer coating agent.

H. Heat Seal Layer The heat seal layer of the present invention may be any one that can be melted by heat and fused to each other, and can be changed depending on the required physical properties.
For example, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene- (meth) ethyl acrylate copolymer, ethylene -Polyolefin resins such as (meth) acrylic acid copolymer, ethylene-propylene copolymer, methylpentene polymer, polyethylene or polypropylene with unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, etc. Modified polyolefin resin, ethylene- (meth) acrylic ester-unsaturated carboxylic acid terpolymer resin, cyclic polyolefin resin, cyclic olefin copolymer, polyethylene terephthalate (PET), polyacrylonitrile (PAN), etc. It can be of use one or a film or sheet or other coated film such as a resin consisting of more resin. The base material layer side of the heat seal layer preferably has improved wettability by corona treatment, flame treatment, ozone treatment or the like.

Moreover, although the thickness of a heat seal layer is not specifically limited, Preferably it is 5-500 micrometers, More preferably, it is 10-250 micrometers.
If the thickness of the film is below the range, sufficient laminating strength cannot be obtained even by heat sealing, does not function as a packaging container, and if the film is above the above range, the cost of the film increases and the film Becomes harder and workability becomes worse.

I. Production of Laminated Film The laminated film in the present invention can be produced using an extrusion laminating machine. A basic example using a biaxially stretched polyethylene terephthalate as a base material layer and an ethylene-methyl acrylate-maleic anhydride terpolymer resin as an adhesive layer is shown below.
It can be obtained by hanging ethylene-methyl acrylate-maleic anhydride melt-extruded from a T-die onto a thin film on biaxially stretched polyethylene terephthalate and laminating it at the laminate.
The laminate surface of the biaxially stretched polyethylene terephthalate film preferably has a surface wetting tension of 45 dyn / cm or more in order to maintain a sufficient laminate strength with the adhesive resin. To achieve the above surface wetting tension, corona treatment, flame treatment, etc. can be used.

The extrusion temperature at the time of extrusion laminating is 280 to 330 ° C, more preferably 290 to 320 ° C. When the resin temperature is 280 ° C. or lower, generation of radicals is difficult to occur, and sufficient laminate strength with the substrate cannot be exhibited. Further, if the temperature is 330 ° C. or higher, the adhesive resin is thermally decomposed, so that the laminate strength is not preferable. Moreover, when laminating with a base material, it is preferable to oxidize the base-material surface by performing ozone treatment. This is because the ozone treatment increases the polar groups and increases the reactivity with the adhesive resin.
Since the film has a strong laminate strength between the base material and the adhesive layer, and the adhesive layer can also be a heat seal layer, it can be used as a packaging container in the food, pharmaceutical, cosmetic and toiletry industries.

  A layer can be further laminated on the laminated film. As a base material, it can adhere | attach with the film mentioned by the intermediate | middle layer, the barrier layer, and the heat seal layer. When laminating the base material, the adhesive resin melted on the biaxially stretched polyethylene terephthalate film is extruded as in the case of the extrusion laminate, and at the same time, the adhesive resin is sandwiched between the base materials to be laminated, It can be obtained by laminating. Furthermore, when laminating the base materials, they may be laminated in the same manner as in the above method.

J. et al. Laminate for packaging The laminate of the present invention can be used as a laminate for packaging materials by appropriately providing a gas barrier coating film layer, an intermediate layer, a printing layer, a laminate adhesive layer, a heat sealable resin layer, and the like. .
The printing layer is composed of one or more ordinary ink vehicles as the main component, and if necessary, a plasticizer, a stabilizer, an antioxidant, a light stabilizer, an ultraviolet absorber, a curing agent, and a crosslinking agent. Add one or more additives such as additives, lubricants, antistatic agents, fillers, etc., add colorants such as dyes and pigments, and knead thoroughly with solvents, diluents, etc. The ink composition is then prepared, and then the ink composition is used, for example, using a printing method such as gravure printing, offset printing, letterpress printing, screen printing, transfer printing, flexographic printing, etc. On the gas barrier coating film, a desired printed pattern composed of characters, figures, symbols, patterns, and the like can be printed to form a printed pattern layer.

  In the above, as the ink vehicle, known ones such as sesame oil, drill oil, soybean oil, hydrocarbon oil, rosin, rosin ester, rosin modified resin, Sierrac, alkyd resin, phenolic resin, maleic acid resin, Natural resins, hydrocarbon resins, polyvinyl chloride resins, polyvinyl acetate resins, polystyrene resins, polyvinyl propylar resins, acrylic or methacrylic resins, polyamide resins, polyester resins, polyurethane resins, epoxy resins, One or more of urea resin, melamine resin, aminoalkyd resin, nitrocellulose, ethylcellulose, chlorinated rubber, cyclized rubber and the like can be used.

K. Packaging Bag A packaging bag using the laminate of the present invention will be described. The packaging bag is formed by folding the laminate of the present invention into two, and the heat-sealable resin layers face each other, and the ends are heat-sealed to form a cylindrical package, and then the bottom is sealed Then, the package can be manufactured by filling the contents and further sealing the top.
As the bag making method, the laminated material as described above is folded or overlapped so that the inner layer faces each other, and the peripheral end thereof is, for example, a side seal type, a two-side seal type, a three-side seal. Various types of heat seals such as molds, four-sided seals, envelope stickers, pillow seals, pleated seals, flat bottom seals, square bottom seals, gussets, etc. A form of wearing bag can be produced. In addition, for example, a self-supporting packaging bag (standing pouch) is also possible.
In the above, as a heat sealing method, for example, a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, and an ultrasonic seal can be used.

Examples The present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.
[Example 1]
A polyester resin film having a thickness of 2 μm is used as a base material, and an ethylene-methyl acrylate-maleic anhydride terpolymer (Lotodar 4503, Arkema Co., Ltd.) having a thickness of 1 μm is used as a terpolymer adhesive resin layer. The terpolymer has a methyl acrylate component content of 19% by mass and a maleic anhydride component content of 0.3% by mass. did.

[Example 2]
A polyester resin film having a thickness of 2 μm was used as a base material, and a 1 μm-thick ethylene-methyl acrylate-maleic anhydride terpolymer (Lotodar 4503, Arkema ( Ltd.): Polyamide resin having a thickness of 11 μm whose corona treatment was applied to the outer surface via a terpolymer with a methyl acrylate component amount of 19% by mass and a maleic anhydride component amount of 0.3% by mass). The film was laminated.
Further, this was mounted on a delivery roll of a plasma chemical vapor deposition apparatus, and then a 200-nm-thick silicon oxide vapor deposition film was formed on the corona-treated surface of the polyamide resin under the following conditions.

<Vapor deposition conditions>
Deposition surface: Corona-treated surface Introduction gas: Hexamethyldisiloxane: Oxygen gas: Helium 1.0: 3.0: 3.0 (Unit: s1m)
Degree of vacuum in the vacuum chamber: 2-6 × 10 ⁻⁶ mBar
Degree of vacuum in the deposition chamber: 2-5 × 10 ^-3 mBar
Cooling and electrode drum power supply: 10kW
Line speed: 100m / min

Next, immediately after the silicon oxide vapor deposition film having a thickness of 200 mm was formed as described above, a glow discharge plasma generator was used on the silicon oxide vapor deposition film surface, and the power was 9 kw, oxygen gas: argon gas = 7.0. : Using a mixed gas of 2.5 (unit: s1 m) and performing oxygen / argon mixed gas plasma treatment at a mixed gas pressure of 6 × 10 ⁻³ Torr, the surface tension of the deposited silicon oxide film surface is 54 dyne / A plasma-treated surface improved by at least cm was formed.
After forming a desired print pattern on the vapor deposition surface of the vapor deposition film, a two-component curing type polyurethane-based laminate adhesive (RU-004 / H1, Rock Paint Co., Ltd.) is applied to the entire surface including the print pattern. The laminate adhesive layer is formed by coating to a thickness of 4.0 g / m ² (dry state) using the gravure roll coating method, and then the surface of the laminate adhesive layer is coated with a 60 μm thick non-coated layer. A stretched polypropylene film (ZK99S, Toray Film Processing Co., Ltd.) was dry laminated to produce a laminate according to the present invention.

Next, two sheets of the laminate produced as described above are prepared, the surfaces of the unstretched polypropylene film are overlapped facing each other, and then, the end portion around the outer periphery is heat-sealed to form a seal portion. In addition, a flexible packaging bag, which is a three-sided seal type packaging bag having a width of 130 mm and a height of 170 mm, having an opening on the upper side, was produced. In the three-side seal type soft packaging bag produced above, 200 g of water is filled and packaged from the opening, and then the opening is heat-sealed to form an upper seal part to produce a packaging semi-finished product. Then, the packaged semi-finished product is put into a retort kiln and subjected to a retort treatment under a retort treatment condition of 121 ° C., pressure 2.1 kgf / cm ² · G, time 30 minutes, and the retort packaged food according to the present invention is manufactured. did.

[Example 3]
The vapor barrier layer described in Example 2 was coated with a gas barrier coating film prepared by the method described below.
According to the composition shown in the table below, a composition (b) prepared in advance in an EVOH solution dissolved in a mixed solvent of ethylene-vinyl alcohol copolymer (EVOH) of composition (a), isopropyl alcohol, and ion-exchanged water. A hydrolyzed solution composed of ethyl silicate 40, isopropyl alcohol, aluminum acetylacetone, and ion-exchanged water is added and stirred, and a mixed solution composed of polyvinyl alcohol, acetic acid, isopropyl alcohol, and ion-exchanged water of composition (c) prepared in advance is added. To obtain a colorless and transparent composition for forming a gas barrier coating film.

By coating the plasma-treated surface of the vapor-deposited film with the composition for forming a gas barrier coating film prepared above by a gravure roll coating method, and passing through a drying oven at 200 ° C. at a speed of 300 m / min after coating. Then, a heat treatment was performed to form a gas barrier coating film having a thickness of 0.4 g / m ² (dry state) to produce a gas barrier laminated film according to the present invention.
The procedure was the same as Example 1 except that the gas barrier laminate film was used.

[Example 4]
In the same manner as in Example 2, the film laminated up to the vapor deposition layer was laminated with EVOH (EFCR, Kuraray Co., Ltd.) having a thickness of 15 μm as a barrier layer through an adhesive layer. The film is coated with a two-component curable polyurethane laminate adhesive (RU1-004 / H1, Rock Paint Co., Ltd.) using a gravure roll coating method to a thickness of 4.0 g / m ² (dry state) Then, an unstretched polypropylene film (ZK99S, Toray Film Processing Co., Ltd.) having a thickness of 60 μm is dry-laminated on the surface of the laminating adhesive layer. A laminate according to the invention was produced. A packaging bag was made in the same manner as in the example and retort-treated.

[Example 5]
A 1 μm thick ethylene-methyl acrylate-maleic anhydride terpolymer (Lotodar 4503) melt-extruded as a ternary copolymer adhesive resin layer using a first polyester resin film having a thickness of 2 μm as a substrate. , Arkema Co., Ltd.) and a polyamide resin film having a thickness of 11 μm is laminated, and further, a 2 μm thick second adhesive having a thickness of 2 μm is laminated via a two-component curable polyurethane laminating adhesive. After providing the polyester-based resin layer, it was deposited and laminated in the same manner as in Example 1 to make a packaging bag and retort-treated.

[Example 6]
On the vapor deposition layer of the laminated body of Example 3, after forming the gas barrier coating film similar to Example 2, it laminated | stacked similarly to Example 1-3, and made a bag and a retort process.

[Example 7]
As the terpolymer adhesive resin of Example 2, Arkema Lotader 4503 (unsaturated carboxylic acid 0.3% by mass, acrylic ester component content 19% by mass), ethylene-methyl acrylate (Arkema Co., Ltd. LOTRYL). 18 MA02) The same procedure as in Example 2 was conducted, except that an adhesive resin was used which was diluted 3-fold with an unsaturated carboxylic acid of 0.1 mass% and an acrylic ester component content of 19 mass%.

[Example 8]
The ternary copolymer adhesive resin of Example 2 was prepared by using Arkema Lotader 3430 (3.1% by weight of unsaturated carboxylic acid, acrylic acid ester component amount 15) which is an ethylene-methyl acrylate-maleic anhydride terpolymer. (Mass%) was diluted 3.4 times with ethylene-methyl acrylate (Arkema Co., Ltd. LOTRYL 18MA02) to use 0.9% by mass of unsaturated carboxylic acid and 16% by mass of acrylate component. Example 2 was the same as in Example 2.

[Comparative Example 1]
A base material using a modified polyester elastomer (Primalloy (registered trademark) AP, Mitsubishi Chemical) was produced as an adhesive layer used for the adhesive resin layer of the base material of Example 2, bag-made, and retorted.

[Comparative Example 2]
As an adhesive layer used for the adhesive resin layer of the base material of Example 2, a base material using modified polyethylene (Mitsui Chemicals Co., Ltd. Admer SF730) was prepared, bag-made, and retorted.

[Comparative Example 3]
A base material using a modified polyester elastomer (Primalloy (registered trademark) AP, Mitsubishi Chemical) was prepared as an adhesive layer to be used for the adhesive resin layer of the base material of Example 4, bag-made, and retorted.

[Comparative Example 4]
As an adhesive layer used for the adhesive resin layer of the base material of Example 4, a base material using modified polyethylene (Mitsui Chemicals Co., Ltd. Admer SF730) was prepared, bag-made, and retorted.

[Interlayer adhesion strength test]
About the laminated body of the said Examples 1-8 and Comparative Examples 1-4, the initial stage and the interlayer strength after a retort were measured with the tensilon.
About the laminated body of Examples 1-8 and Comparative Examples 1-4, it cuts out in strip shape of width 15mm, and uses a Tensilon tensile tester (Orientec Co., Ltd. RTC-1310A), a polyester-type resin layer and a polyamide-type resin. The adhesion part of the layer was peeled off, and the interlayer strength was measured.
In a 25 ° C. atmosphere, the film was peeled in the 180 ° direction at a tensile speed of 50 mm / min, and the maximum load was measured. The measurement was performed 5 times, and the results are shown in the table with the arithmetic mean as the interlayer strength.
As a result of the test, as shown in the table, by providing the terpolymer adhesive resin layer of the present invention, at the initial stage, it has an interlayer strength more than twice that of the conventional adhesive layer shown in the comparative example. Furthermore, it was confirmed that the film has excellent interlayer strength that hardly deteriorates after retorting.

The laminate of the present invention uses an adhesive resin composition layer containing a terpolymer composed of alkene- (meth) acrylic acid ester-unsaturated carboxylic acid (unsaturated dicarboxylic acid) as the adhesive layer. There is no concern about residual solvent and there is no problem that the laminate strength decreases due to deterioration over time, and lamination with an anchor coating agent can provide a laminate with a residual solvent with a diluting solvent, a base material to be laminated, and a film thickness that is not limited. it can.
That is, the present invention is capable of producing a packaging material having an excellent strength that cannot be exhibited by conventional adhesive resins, and has excellent flexibility, so that bag making, molding, filling, and sterilization are possible. It is an invention relating to a laminate that maintains high adhesion even after processes such as treatment.
In addition, it has excellent strength in the boil / retort treatment and can be used as a boil / retort packaging material.

1. 1. Base film 2. Adhesive resin composition layer containing a ternary copolymer 3. Polyamide resin film 4. Deposition film Gas barrier coating film

Claims (14)

  A laminate obtained by laminating at least a base film and a polyamide resin film through an adhesive resin composition layer containing an alkene- (meth) acrylic acid ester-unsaturated carboxylic acid terpolymer. .   The amount of unsaturated carboxylic acid component in the adhesive resin composition layer is 0.05% by mass to less than 1.0% by mass, and the amount of (meth) acrylic acid ester component is 5% by mass to 40% by mass. 1. The laminate according to 1.   The peel strength when peeled between the base film and the polyamide-based resin film is 3 N / 15 mm width or more, and is 3 N / 15 mm width or more even after boiling and retorting (80 to 135 ° C.). The laminate according to claim 1 or 2.   The laminate according to any one of claims 1 to 3, wherein the base film is a polyester resin film, a polyamide resin film, or a polyolefin resin film.   The laminate according to any one of claims 1 to 3, wherein the base film is a polyethylene terephthalate film.   The laminated body of any one of Claims 1-5 which provides a vapor deposition film on the said polyamide-type resin film.   The laminate according to claim 6, wherein a gas barrier coating film is provided on the vapor deposition film. The gas barrier coating film has the general formula R ¹ _n M (OR ² ) _m (wherein M represents a metal atom, R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, and n is 0 or more) Wherein m is an integer of 1 or more, and n + m represents the valence of M), and a composition comprising at least one alkoxide, polyvinyl alcohol, and / or ethylene / vinyl alcohol Is a hydrolyzate of alkoxide obtained by polycondensation by a sol-gel method or a hydrolyzate of alkoxide.   It is the manufacturing method of the laminated body of any one of Claims 1-8, Comprising: The polyamide-type resin film was bonded together through the contact bonding layer which consists of the said adhesive resin composition extruded on the base film. Production method.   It is the laminated material for packaging using the laminated body of any one of Claims 1-8, Comprising: On the surface which consists of a polyamide-type resin film of the said laminated body, on a vapor deposition film, or on a gas barrier coating film A laminated material for packaging in which a heat-sealable resin layer is provided.   The laminated material for packaging according to claim 10, wherein the heat-sealable resin layer is a polyolefin-based resin.   A packaging bag using the packaging laminate according to claim 10 or 11, wherein one packaging laminate has a heat-sealable resin layer side, and the other packaging laminate has a heat-sealable resin layer side. Is a packaging bag in which the ends are heat-sealed. The adhesion | attachment which consists of an adhesive resin composition containing the terpolymer of the alkene- (meth) acrylic acid ester-unsaturated carboxylic acid used for adhesion | attachment between the layers of the laminated body of any one of Claims 1-8. Agent.   The amount of unsaturated carboxylic acid component in the adhesive resin composition is 0.05% by mass to less than 1.0% by mass, and the amount of (meth) acrylic acid ester component is 5% by mass to 40% by mass. The adhesive according to 13.

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