JP2016028856A - Laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate having high interlayer bonding strength, and excellent resistance to contents comprising alcohols such as ethanol, and an alcohol-resistant self-standing bag comprising the same.SOLUTION: A laminate has at least a substrate layer, a barrier layer, an adhesion layer and a sealant layer. The adhesion layer between the barrier layer and the sealant layer comprises an adhesive resin composition that has alcohol resistance and comprises at least one of a ternary copolymer of alkene-(meth) acrylic acid ester-unsaturated carboxylic acid and a binary copolymer of alkene-unsaturated carboxylic acid. There is also provided an alcohol-resistant self-standing bag comprising the same.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a new laminate and an alcohol-resistant self-supporting bag comprising the same, and more specifically, has a high interlayer adhesive strength and has excellent resistance to contents containing alcohol such as ethanol. The present invention relates to a laminate and an alcohol-resistant self-supporting bag comprising the laminate.

  As a packaging bag for sealing and packaging a substance containing alcohol, a packaging bag made of a laminate in which a base material layer, a barrier layer, and a sealant layer are laminated via an adhesive layer is used. However, there is a problem that the alcohol component in the contents penetrates into the sealant layer, in particular, erodes the adhesive layer between the barrier layer and the sealant layer and causes delamination.

The occurrence of delamination is a particularly serious problem in a self-supporting bag such as a stand pouch, the strength that can withstand the weight of the contents is lost, the self-supporting shape cannot be maintained, and bag breakage occurs.
As a method of laminating the sealant layer on the barrier layer, a method of laminating by a dry laminating method using a dry laminating adhesive such as a two-component curable urethane adhesive is known (patent) Reference 1).

  However, the laminate obtained by this method has insufficient alcohol resistance, and by long-term storage, the alcohol component in the contents penetrates through the sealant layer to the adhesive layer, and the bond of the adhesive is decomposed. There was a problem that the interlayer adhesive strength was lowered. In addition, there is a problem that low molecular weight substances such as unreacted monomers and decomposition products in the adhesive elute into the contents.

Japanese Patent Laid-Open No. 5-51574

  The present invention has been made to solve such a problem, and has a high interlayer adhesion strength and an alcohol-resistant laminate having excellent resistance to contents containing alcohol such as fermented ethanol and the like. An object of the present invention is to provide an alcohol-resistant self-supporting bag.

  As a result of various studies, the present inventors have at least a laminate having a base material layer, a barrier layer, an adhesive layer and a sealant layer, and the adhesive layer located between the barrier layer and the sealant layer is: Adhesive resin having alcohol resistance and containing at least one of alkene- (meth) acrylic acid ester-unsaturated carboxylic acid terpolymer and alkene-unsaturated carboxylic acid binary copolymer It has been found that the above laminate and a self-supporting bag made of the composition achieve the above object.

The present invention is characterized by the following points.
(1) A laminate having at least a base material layer, a barrier layer, an adhesive layer, and a sealant layer, wherein the adhesive layer located between the barrier layer and the sealant layer has alcohol resistance, and And an adhesive resin composition containing at least one of an alkene- (meth) acrylic acid ester-unsaturated carboxylic acid terpolymer and an alkene-unsaturated carboxylic acid binary copolymer. The laminate described above.
(2) The laminate according to (1) above, further comprising an intermediate layer between the base material layer and the barrier layer.
(3) A reinforcing layer is further provided at any position between the barrier layer and the sealant layer, and all adhesive layers positioned between the barrier layer and the sealant layer have alcohol resistance. And an adhesive resin composition containing at least one of an alkene- (meth) acrylic acid ester-unsaturated carboxylic acid terpolymer and an alkene-unsaturated carboxylic acid binary copolymer. The laminate according to (1) or (2) above, wherein
(4) The amount of the unsaturated carboxylic acid component in the adhesive resin composition is 0.05% by mass or more and less than 1.0% by mass, in any one of the above (1) to (3) The laminated body of description. (5) Alcohol-resistant self-supporting bag which consists of a laminated body in any one of said (1)-(4).
(6) The method for producing a laminate according to any one of (1) to (4) above, wherein the barrier layer and the sealant layer, or the barrier layer and the reinforcing layer, and the reinforcing layer and the sealant layer, Sandwich lamination via an adhesive resin composition comprising at least one of an alkene- (meth) acrylic acid ester-unsaturated carboxylic acid terpolymer and an alkene-unsaturated carboxylic acid binary copolymer The manufacturing method as described above.

  The laminate of the present invention can achieve extremely high interlayer adhesion strength between the barrier layer and the sealant layer without using a dry laminate adhesive. Therefore, there is no concern about the elution of residual solvent and low molecular weight substances, and there is no problem of a decrease in laminate strength due to deterioration of the adhesive layer over time, and it can be applied to a wide variety of uses.

  In particular, the laminate of the present invention is excellent in alcohol resistance, and even if the alcohol component in the contents penetrates into the sealant layer, the adhesive layer is not eroded and high laminate strength can be maintained over a long period of time.

  Therefore, the alcohol-resistant laminate of the present invention can be applied to a self-supporting bag that requires extremely high laminate strength, such as a stand pouch, and can be suitably used as an alcohol-resistant self-supporting bag. .

It is the schematic cross section which showed an example of the layer structure of the laminated body of this invention. It is the schematic cross section which showed the other example of the layer structure of the laminated body of this invention. It is the schematic cross section which showed the other example of the layer structure of the laminated body of this invention.

The laminated body of this invention is demonstrated in detail, referring drawings.
1 to 3 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 has a basic structure in which a base material layer 1, a barrier layer 3, and a sealant layer 5 are laminated via adhesive layers 2 and 4. It is. Here, the adhesive layer 2 is formed by using an arbitrary adhesive such as a dry laminate adhesive or an adhesive resin, and the base layer 1 and the barrier layer 3 by an arbitrary method such as a dry laminate method or a sandwich laminate method. May be adhered. Alternatively, when the barrier layer 3 is a deposited film, the barrier layer 3 may be provided directly on the base material layer 1 without providing the adhesive layer 2. On the other hand, the adhesive layer 4 has alcohol resistance and is at least one of an alkene- (meth) acrylic acid ester-unsaturated carboxylic acid terpolymer and an alkene-unsaturated carboxylic acid binary copolymer. An adhesive resin composition containing one kind (hereinafter also referred to as “adhesive resin composition of the present invention”) is melt-extruded, and the barrier layer and the sealant layer are bonded together by sandwich lamination.

  As another aspect of the laminate of the present invention, as shown in FIG. 2, the intermediate layer 6 is interposed between the base material layer 1 and the barrier layer 3 through adhesive layers 2a and 2b made of an arbitrary adhesive. The structure which laminated | stacked these may be sufficient.

  As another aspect of the laminate of the present invention, as shown in FIG. 3, the adhesive layers 4a and 4b made of the adhesive resin composition of the present invention are interposed between the barrier layer 3 and the sealant layer 5. Alternatively, the reinforcing layer 7 may be laminated.

  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 material layer In the laminate of the present invention, as the base material layer, a single layer film or a multilayer laminate film is used, but is not particularly limited, and any film used for various packaging bags can be used. Among these, a suitable one is freely selected and used according to the use conditions such as the type of contents to be packaged and the presence or absence of heat treatment after filling. Specific examples of the film preferably used as the base material layer include paper, cellophane, polyamide resin film, polyester resin film, olefin resin film, acid-modified polyolefin resin film, polystyrene resin film, uniaxial or Biaxially stretched film, K coat film, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, polybutene, polyvinyl alcohol, ethylene-vinyl acetate copolymer, ionomer, ethylene- ( (Meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, ethylene-propylene copolymer, methylpentene, polyacrylonitrile, polycarbonate, polyvinyl chloride (PVC), polyvinyl chloride Resin film made of dendri (PVDC), polyvinylidene fluoride (PVDF), ethylene-tetrafluoroethylene copolymer (ETFE), polytetrafluoroethylene (PTFE), polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate, etc. , A K-coated stretched polypropylene film, a K-coated stretched nylon film, a composite film in which two or more of these films are laminated, and the like. When applied as a self-supporting bag, a polyester resin film such as a PET film, a biaxially stretched nylon film, or the like can be suitably used.

  The thickness of the base material layer is preferably 5 to 300 μm, more preferably 10 to 100 μm. The base material layer may be subjected to surface treatment for improving wettability such as corona treatment, ozone treatment, flame treatment, etc. on the sealant layer side.

B. Barrier layer In the laminate of the present invention, as the barrier layer, any barrier film or barrier film that has gas barrier properties that prevent permeation of oxygen gas, water vapor, and the like and that prevents permeation of alcohol components in the contents is used. can do.

  Examples of such a barrier film or barrier film include a vapor-deposited film made of an inorganic substance or an inorganic oxide, a metal foil, a barrier resin film, and a vapor-deposited film provided with the vapor-deposited film on a resin film.

Specifically, aluminum vapor deposition film, alumina vapor deposition film, silica vapor deposition film, aluminum foil, aluminum vapor deposition polyester resin film, aluminum vapor deposition polypropylene film, silica vapor deposition polyester resin film, silica vapor deposition polyamide resin film, alumina vapor deposition polyester system Examples of the barrier film or barrier film include a resin film, an ethylene-vinyl alcohol copolymer film, a polyvinylidene chloride film, a polyvinyl alcohol film, and an MXD6 film.
When providing a vapor deposition film as a barrier layer, it can provide directly on a base material layer, without passing through adhesive layers, such as an adhesive agent.

  If necessary, light blocking properties that prevent transmission of visible light, ultraviolet light, and the like can be imparted. Moreover, you may have two or more barrier layers. When it has two or more barrier layers, each may have the same composition or a different composition. Usually, the thickness of a barrier film becomes like this. Preferably it is 0.01-500 micrometers, More preferably, it is the range of 1-300 micrometers. Further, the thickness of the deposited film is, for example, about 10 to 2000 mm, preferably selected and formed within a range of 10 to 1000 mm. 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.

Moreover, you may perform the process which improves wettability, such as a corona process, an ozone process, and a flame | frame process, on the one or both surfaces of a barrier layer.
A conventionally known metal foil can be used as the metal foil made of an inorganic substance or an inorganic oxide. 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 known method using a conventionally known inorganic substance or inorganic oxide, and its composition and formation method are not particularly 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, a plasma chemical vapor deposition method, a thermochemistry, 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.

The case where a silicon oxide vapor deposition film is provided as the vapor deposition film will be described in more detail. 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.

A gas barrier coating film may be further provided on the deposited film in order to improve the gas barrier property.
In the present invention, the gas barrier coating film is an alkoxide hydrolyzate obtained by polycondensation of an alkoxide and a water-soluble polymer by the sol-gel method in the presence of a sol-gel method catalyst, acid, water and an organic solvent. It is a film | membrane which consists of a hydrolysis condensate of an alkoxide. In some cases, the gas barrier composition may further contain a silane coupling agent.

Examples of the alkoxide that can be used in the gas barrier composition include a general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M Represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents an atomic valence of M), and preferably at least one alkoxide represented by Can be used. Here, as the metal atom M, silicon, zirconium, titanium, aluminum or the like can be used. Specific examples of the organic group represented by R ¹ and R ² include alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and an i-butyl group. Can be mentioned. In the same molecule, these alkyl groups may be the same or different. Examples of such alkoxides include 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 and the} like.

  As the water-soluble polymer that can be used in the gas barrier composition, either a polyvinyl alcohol-based resin or an ethylene / vinyl alcohol copolymer or both can be preferably used. These resins may be commercially available, for example, as an ethylene / vinyl alcohol copolymer, manufactured by Kuraray Co., Ltd., Eval EP-F101 (ethylene content; 32 mol%), manufactured by 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 sol-gel catalyst, a tertiary amine that is substantially unnecessary 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 preferable, and for example, about 0.01 to 1.0 part by weight, particularly about 0.03 part by weight per 100 parts by weight of the total amount of alkoxysilane and silane coupling agent. It is preferable to use it.

Examples of the acid used in the gas barrier composition include mineral acids such as sulfuric acid, hydrochloric acid and nitric acid, organic acids such as acetic acid and tartaric acid, and others. The amount of the acid used is preferably 0.001 to 0.05 moles, more preferably 0.01 to 0.05 moles, based on the total mole amount of the alkoxide and the alkoxysilane component (for example, silicate moiety) of the silane coupling agent. 0.03 mole.
As the organic solvent, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butanol and the like can be used.

As the silane coupling agent, a known organic reactive group-containing organoalkoxysilane can be used, and in particular, an organoalkoxysilane having an epoxy group is 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.

  The content of the water-soluble polymer in the gas barrier composition is preferably in the range of 5 to 500 parts by weight with respect to 100 parts by weight of the total amount of the alkoxide. In the above, if it exceeds 500 parts by weight, the formed gas barrier coating film becomes more brittle and its weather resistance and the like are also unfavorable.

Specific examples of the method for forming the 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 catalyst, water, an organic solvent, and, if necessary, a silane coupling agent. To do. In the gas barrier coating liquid, the polycondensation reaction gradually proceeds.

  Next, the gas barrier coating solution is applied onto the deposited film by a conventional method and dried. By drying, the polycondensation of the alkoxide and vinyl alcohol polymer (and silane coupling agent) further proceeds to form a composite polymer layer. Preferably, a plurality of composite polymer layers can be laminated by repeating the above operation.

  Finally, the laminate 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. Thereby, a gas barrier coating film can be formed on the vapor deposition film.

  The gas barrier coating film may be a composite polymer layer in which one layer or two or more layers are laminated. Further, the dry film thickness may be 0.01-100 μm, preferably 0.01-50 μm. If the thickness after drying is 100 μm or less, the occurrence of cracks can be suppressed.

  In the embodiment of the present invention, after providing a gas barrier coating film on the vapor deposition film, a vapor deposition film may be further provided, and the gas barrier coating film may be formed on the vapor deposition film in the same manner as described above. Thus, by increasing the number of stacked layers, it is possible to realize a stacked body that is further excellent in gas barrier properties.

C. Adhesive layer In the present invention, the adhesive layer located between the barrier layer and the sealant layer has alcohol resistance and is an alkene- (meth) acrylate-unsaturated carboxylic acid terpolymer and It consists of the adhesive resin composition of this invention containing at least 1 sort (s) of the binary copolymer of an alkene-unsaturated carboxylic acid.

  Moreover, when it has further layers, such as a reinforcement layer, between a barrier layer and a sealant layer, it is preferable to use the adhesive resin composition of the said invention also at the time of adhesion | attachment with this further layer. That is, it is preferable that all the adhesive layers located between the barrier layer and the sealant layer are made of the adhesive resin composition of the present invention.

Since the adhesive resin composition of the present invention has a functional group such as a carboxyl group, the surface of the barrier layer and the sealant layer and the reactive group are chemically bonded to each other, and the laminate strength between the layers can be improved. For this reason, it is not necessary to use the anchor coat agent used in normal melt extrusion, and extremely high interlayer adhesive strength can be achieved. Moreover, the adhesive resin composition of this invention does not contain an organic solvent. Therefore, this invention does not have a concern about the elution of the residual solvent and the low molecular weight substance derived from the organic solvent contained in the anchor coating agent or the resin composition. Further, there is no problem of a decrease in laminate strength due to deterioration of the adhesive layer over time, and it can be applied to a wide variety of uses. In particular, the adhesive resin composition of the present invention is excellent in alcohol resistance, and even if the alcohol component in the contents penetrates into the sealant layer, the adhesive layer is not eroded, and high laminate strength can be maintained over a long period of time. .

The adhesive resin composition of 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 of the present invention may consist only of a binary copolymer of alkene-unsaturated carboxylic acid.
In another embodiment, the adhesive resin composition of the present invention may be a blend resin having an arbitrary mixing ratio of the terpolymer and the binary copolymer.

  In still another embodiment, the adhesive resin composition of the present invention may further include a polyolefin resin, a polyamide resin, a polyester resin, as desired, in addition to the terpolymer and / or binary copolymer. Resin, modifying resin such as ethylene-vinyl alcohol copolymer, polyvinyl chloride, and polyvinylidene chloride can be included.

  In addition, the adhesive resin composition of the present invention includes, for example, processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slip properties, mold release properties, flame retardancy, antifungal properties, Various plastic compounding agents and additives can be added for the purpose of improving and modifying electrical characteristics, strength, etc., and the addition amount can be from a very small amount to several tens of percent depending on the purpose. And can be optionally added. 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 the production of the terpolymer and binary copolymer, examples of the alkene serving as a comonomer include ethylene, propylene, butene, isobutene, pentene, hexene and the like, and in particular, α-olefins such as ethylene and propylene are preferable. Used for.

  Moreover, (meth) acrylic acid ester used as a comonomer includes methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, ( Examples include tert-butyl (meth) acrylate, ethyl-2-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, and methyl acrylate, ethyl acrylate, and butyl acrylate are preferred, and methyl acrylate is more preferred. It is.

  Examples of the unsaturated carboxylic acid serving as a comonomer include acrylic acid, methacrylic acid, ethacrylic acid, fumaric acid, maleic acid, citraconic acid, itaconic acid, and derivatives thereof such as acid anhydrides, esters, amides, and imides. Etc., for example, monomethyl maleate, maleic anhydride, citraconic anhydride, itaconic anhydride and the like. In particular, unsaturated dicarboxylic acid, maleic anhydride and the like can be preferably used. These may be used alone or in a mixture of two or more.

  The ternary copolymer of the present invention is obtained by graft polymerization or ternary copolymerization of the alkene, (meth) acrylic acid ester, and unsaturated carboxylic acid. The ternary copolymer may contain a comonomer other than the above as long as the object of the present invention is not impaired. For example, an ethylene- (meth) acrylic acid ester-maleic anhydride terpolymer resin can be preferably used.

The binary copolymer of the present invention is obtained by graft polymerization of the above alkene and unsaturated carboxylic acid. A binary copolymer obtained by graft polymerization of the unsaturated carboxylic acid or a derivative thereof onto a polymer composed of the alkene, such as an ethylene / α-olefin copolymer or polypropylene, can be particularly preferably used.
In the present invention, the polymerization reaction can be produced by various conventional methods using a comonomer as a raw material.

  For example, a polymer consisting of an alkene is dry blended with an unsaturated carboxylic acid and, if necessary, an organic peroxide and a radical initiator at a predetermined mixing ratio using a Henschel mixer, etc., and the system is purged with nitrogen gas. It is obtained by putting into a kneading machine such as a Banbury mixer, a double screw mixer, etc., and melt-kneading at a temperature of 120 to 300 ° C. for 0.1 to 30 minutes. At the time of the grafting reaction, the reaction can be carried out efficiently by adding a conventional radical generator.

  Although it does not specifically limit as a radical generator, For example, hydroperoxides, such as diisopropyl benzene hydroperoxide and 2, 5- dimethyl- 2, 5- di (hydroperoxy) hexane; Di-t-butyl peroxide Dialkyl peroxides such as 2,5-dimethyl-2,5-di (t-butylperoxy) hexane; organic peroxides such as diacyl peroxides such as benzoyl peroxide, or azobisisobutyronitrile An azo compound such as These radical generators may be used alone or as a mixture of two or more. The addition amount of the radical generator is preferably in the range of 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of the comonomer components.

  In one embodiment of the present invention, when the adhesive resin composition of the present invention is composed of only the ternary copolymer or contains the ternary copolymer, particularly, the hygroscopic property is suppressed and good handling is obtained. Therefore, as a suitable blending ratio of each component, the (meth) acrylic acid ester-derived component (residue) is preferably 5 to 40% by mass with respect to the total mass of the adhesive resin composition, and more Preferably it is 10-30 mass%.

  Further, the unsaturated carboxylic acid-derived component (residue) is contained in an amount of 0.05 to 3.0% by mass, more preferably 0.05% by mass to less than 1.0% by mass, and the rest is derived from an alkene. It is a component (residue), a modifying resin, an additive, and the like.

When the amount of the unsaturated carboxylic acid component in the adhesive resin composition containing the terpolymer of the present invention is more than the above range, the acid content of the laminate is increased, so that the hygroscopicity is increased and foaming is performed during coextrusion. there's a possibility that. Moreover, since the residual monomer of unsaturated carboxylic acid elutes from an adhesion layer, we are anxious about hygiene.
Further, when the amount of the unsaturated carboxylic acid component is too small, chemical interaction with the resin film constituting the barrier layer or the reinforcing layer is less likely to occur, which may cause a decrease in interlayer adhesive strength.

  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, resulting in poor handling. Moreover, when content of the component derived from (meth) acrylic acid ester is less than the said range, the adhesion | attachment by reaction of an acrylate becomes difficult to generate | occur | produce.

In the embodiment relating to the case where the ternary copolymer is included, in addition to the ternary copolymer, the adhesive resin composition of the present invention has a concentration at which the ratio of the unsaturated carboxylic acid-derived component is defined above. In particular, the alkene- (meth) acrylic acid ester or the alkene-unsaturated carboxylic acid binary copolymer is used in the range of 0 to 90% by mass, preferably in the range of up to 60% by mass. Can be included. By adding a binary copolymer, a relatively expensive terpolymer resin can be reduced, and by adding a comonomer, processability can be improved.

  In another embodiment of the present invention, when the adhesive resin composition of the present invention does not contain a ternary copolymer in a significant amount and mainly consists of a binary copolymer, Contains 0.01 to 25% by mass of an unsaturated carboxylic acid-derived component (residue), more preferably 0.05 to 15% by mass, based on the total mass of the adhesive resin composition. The rest are all alkene-derived components (residues), modifying resins, additives, and the like.

  If the amount of the unsaturated carboxylic acid component in the adhesive resin composition of the present invention is less than the above range, a strong adhesive interface with the barrier layer and the sealant layer cannot be obtained, and heat resistance cannot be obtained. Moreover, when it exceeds 25.0 mass%, the bridge | crosslinking which is not desired at the time of superposition | polymerization will be formed, and a moldability will worsen.

  The MFR of the adhesive resin composition of the present invention is preferably 3 to 100 g / 10 min at 190 ° C., more preferably 5 to 20 g / 10 min. When the MFR is outside the above range, there is a problem that extrusion becomes difficult.

  Moreover, it is preferable that the thickness of the contact bonding layer which consists of adhesive resin compositions 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.

The adhesion mechanism of the adhesive layer comprising the adhesive resin composition of the present invention includes a mechanism for adhering by the flexibility of the adhesive resin composition, a mechanism for adhering by compatibilization with the resin, the surface of the counterpart substrate and the unsaturated carboxylic acid There are a mechanism for adhering by chemical interaction with the substrate, a mechanism for adhering by chemical interaction of unsaturated carboxylic acid and acrylate to the surface of the counterpart substrate, and a mechanism for adhering by radical generation by extrusion at high temperature.
The adhesive layer made of the adhesive resin composition of the present invention is not necessarily bonded by one bonding mechanism, and is bonded by utilizing at least two or more of the above reactions.

D. Sealant Layer The sealant layer of the present invention is a layer made of a heat-sealable resin that can be melted by heat and fused to each other.
Examples of the heat-sealable resin suitably used in the present invention include, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, Polyolefin resins such as ionomer resin, ethylene- (meth) acrylic acid ethyl copolymer, ethylene- (meth) acrylic acid copolymer, ethylene-propylene copolymer, methylpentene polymer, polyethylene or polypropylene are treated with acrylic acid, methacrylic acid, Polyolefin resin modified with unsaturated carboxylic acid such as acid, maleic anhydride, fumaric acid, etc., terpolymer resin of ethylene- (meth) acrylate-unsaturated carboxylic acid, cyclic polyolefin resin, cyclic olefin copolymer , Polyethylene tele Tallates (PET), can be exemplified polyacrylonitrile (PAN) 1 kind or resin comprising more like. A film or sheet made of these resins may be used, and the surface thereof may be subjected to corona treatment, flame treatment, ozone treatment or the like as desired.

  The thickness of the heat-sealable resin layer is not particularly limited, but is preferably 5 to 500 μm, more preferably 10 to 250 μm. If the thickness is less than 5 μm, a sufficient laminate strength cannot be obtained even if heat sealing is performed, and it does not function as a packaging container. When it is thicker than 500 μm, the cost increases and the film becomes hard and workability deteriorates.

E. Intermediate layer and reinforcing layer In the laminate of the present invention, an intermediate layer can be provided between the base material layer and the barrier layer as desired.
Similarly, a reinforcing layer can be provided as desired between the barrier layer and the sealant layer.

The intermediate layer and the reinforcing layer may be any functional layer that imparts the desired physical and chemical properties. For example, in order to improve the flexibility, toughness, flexibility and puncture resistance of the laminate, a biaxially stretched nylon film or a layer made of a polyamide resin can be provided as an intermediate layer or a reinforcing layer. Examples of the polyamide resin suitably used here include metaxylidenediadipamide (MXD-6) nylon, 6-nylon, 6,6-nylon, and the like.
The intermediate layer may be a layer having a barrier property, for example, a deposited film or a metal foil, in order to further improve the barrier property.

F. Lamination The laminate of the present invention is obtained by laminating the base material layer, (intermediate layer), barrier layer, and (reinforcing layer) sealant layer.
The base layer, the intermediate layer, and the barrier layer can be laminated by any method using a conventional adhesive resin or the like. If desired, they may be laminated by sandwich lamination via the adhesive resin composition of the present invention. Moreover, you may laminate | stack a further layer on the surface on the opposite side to the barrier layer of a base material layer.

  On the other hand, the barrier layer and the sealant layer are laminated by sandwich lamination through the adhesive resin composition of the present invention. Similarly, when the reinforcing layer is provided, the barrier layer and the reinforcing layer and the reinforcing layer and the sealant layer are laminated by sandwich lamination through the adhesive resin composition of the present invention.

  The sandwich laminate via the adhesive resin composition of the present invention is such that each of the films to be laminated is fed out at a constant speed, and the heated and melted adhesive resin composition of the present invention is extruded into a thin film between the fed films. It is performed by laminating a film using a cooling roll, a pressure roll, or the like.

  Since the adhesive resin composition of the present invention exhibits a high bonding force to the laminated surface of the film, it is not necessary to apply an anchor coating agent to the laminated surface in advance. If necessary, a surface treatment such as a corona treatment may be applied to the laminated surface of the film in advance.

  The extrusion temperature of the adhesive resin composition of the present invention is in the range of 280 to 330 ° C, more preferably 290 to 320 ° C. When the resin temperature is 280 ° C. or lower, it is difficult for radicals to occur in the adhesive layer, and sufficient interlayer adhesion strength with the barrier layer, the reinforcing layer, and the sealant layer cannot be exhibited. On the other hand, if the temperature is 330 ° C. or higher, thermal decomposition of the terpolymer and binary copolymer occurs, so that sufficient interlayer adhesion strength cannot be obtained, which is not preferable.

G. Packaging bag The laminate of the present invention is folded or overlapped so that the sealant layer is the innermost layer, and its peripheral edge is, for example, a side seal type, a two-side seal type, a three-side seal type, a four-side seal type, Manufactures various types of packaging bags by heat-sealing with heat-sealing types such as envelope-sealed seal type, palm-sealed seal type (pillow seal type), pleated seal type, flat bottom seal type, square bottom seal type, gusset type, etc. can do. In particular, the laminate of the present invention has a high interlayer adhesive strength, exhibits excellent content resistance, particularly alcohol resistance, and prevents the occurrence of delamination over a long period of time. It can be suitably used as a self-supporting bag such as a heavy bag or a refill stand pouch.

As a manufacturing method of the stand pouch, the body of the bag, that is, the laminate for the body forming the side surface, and the laminate of the present invention as the laminate for the bottom material forming the bottom, the surfaces of these sealant layers are used. It is obtained by arranging them facing each other and heat-sealing them into a stand-pouch type.
Moreover, the laminated body of this invention can be used as a laminated body for trunk | drums, and another laminated body can also be used as a laminated body for bottom materials.

  As a more specific manufacturing method of the stand pouch, for example, two laminates for the body material are prepared, and the surfaces of the sealant layers are arranged to face each other. Next, a bottom material laminate having a mountain fold in the center with the sealant surface facing outward is inserted into these lower ends, and a gusset portion is provided to heat seal the peripheral portion. A self-supporting bottom can be formed by heat-sealing the gusset portion into a boat bottom seal type. Moreover, you may provide a spout part in the corner part of a pouch upper part using the bag making machine provided with the heat seal part which forms a spout part, and the punching part for notching the both sides.

In order to manufacture the package by filling the contents, after filling the contents from the filling port left without sealing, the filling port is heat-sealed by, for example, a degassing seal or the like and sealed.
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.

The laminate of the present invention has no problem that the adhesive layer is eroded by contents such as alcohol during long-term storage, resulting in delamination. Moreover, there is no problem that low molecular weight substances such as decomposition products and unreacted monomers are eluted. Therefore, the laminated body of this invention can be utilized as various packaging bags, such as a foodstuff, a pharmaceutical, cosmetics, and the toiletry industry.
Next, the present invention will be specifically described with reference to examples.

[Example 1]
A biaxially stretched PET film (T-4102 manufactured by Toyobo Co., Ltd.) having a thickness of 12 μm is used as a base material layer, and a two-component curable urethane adhesive (main agent RU-40 / curing agent H4 lock) on its corona-treated surface. A biaxially stretched nylon (ONY) film (ONBRT manufactured by Unitika Co., Ltd.) is dry-laminated through Paint Co., Ltd., and then a two-component curable urethane adhesive (main agent RU) on the surface of the ONY film. -40 / Hardening agent H4 A 7 μm thick aluminum foil (1N30, Toyo Aluminum Co., Ltd.) was dry laminated through Rock Paint Co., Ltd. to obtain a laminated film.

The laminated film obtained above and a polyethylene film (PEF) having a thickness of 100 μm (L-4102 manufactured by Toyobo Co., Ltd.) were set in an extrusion laminating machine, and from T-die, ethylene-methyl acrylate-maleic acid An adhesive resin composition composed of a ternary copolymer (Lotader ^(R) 4503 manufactured by Arkema Co., Ltd., maleic anhydride component amount: 0.3% by mass, methyl acrylate component amount: 19% by mass) at 310 ° C. The laminate was melt-extruded to a thickness of 10 μm, the aluminum foil surface of the laminated film (with ozone treatment) and PEF were sandwich-laminated, and aged at 55 ° C. for 3 days to obtain the laminate of the present invention. .
A 180 mm × 240 mm stand pouch was manufactured using the laminate of the present invention obtained above as a laminate for a trunk and a bottom.

[Example 2]
Instead of an adhesive resin composition comprising a ternary copolymer, an adhesive resin composition comprising a binary copolymer obtained by graft polymerization of maleic acid to a polyolefin resin (Admer ^(R) SF731 manufactured by Mitsui Chemicals, Inc.) The laminate and the stand pouch of the present invention were manufactured in the same manner as in Example 1 except that (1) was used.

[Example 3]
Instead of adhesive resin made of terpolymer, adhesive resin made of ethylene-methyl acrylate-maleic terpolymer (Lotader ^(R) 4503 manufactured by Arkema Co., Ltd.) and polyolefin resin Except for using an adhesive resin composition in which an adhesive resin (Admer ^(R) SF731, Mitsui Chemicals, Inc.) made of a binary copolymer grafted with an acid is blended at a mixing ratio of 1: 1, In the same manner as in Example 1, a laminate and a stand pouch of the present invention were produced.

[Comparative Example 1]
In the same manner as in Example 1, a laminate and a stand pouch were produced. However, instead of sandwich lamination using an adhesive resin made of a terpolymer, a two-component curable urethane adhesive is used, and the aluminum foil surface of the laminated film and PEF are bonded together by dry lamination. It was.

[Alcohol resistance evaluation]
(Interlayer adhesion strength test)
The laminates of Examples 1 to 3 and Comparative Example 1 were cut into strips having a width of 15 mm, and the bonded portion of the aluminum foil and PEF was pulled at 25 ° C. in a 25 ° C. atmosphere using a Tensilon tensile tester according to JIS K6854. Was peeled off at 90 ° direction at 50 mm / min, and the interlayer adhesion strength (initial) was measured.

  Further, the stand pouches of Examples 1 to 3 and Comparative Example 1 were filled with 70% ethanol, sealed, and stored at 60 ° C. for 30 days. The pouch after storage was cut into a strip having a width of 15 mm, and the interlayer adhesion strength (after 30 days of storage) at the bonded portion between the aluminum foil and PEF was measured in the same manner as described above.

  When the interlayer adhesion strength after storage for 30 days was 3N / 15 mm width or more, it was determined that the layer had practically sufficient durability and did not cause delamination, that is, was alcohol-resistant. The results are shown in Table 1. In the table, ◯ means good alcohol resistance, and x means poor alcohol resistance.

(Drop test)
The stand-up pouches of Examples 1 to 3 and Comparative Example 1 were filled with 500 ml of water, and after sealing, 30 times horizontally from the height of 120 cm (so that the trunk hits the floor), and further vertically to the floor It was dropped 30 times (so that the bottom hits the floor) and checked for the presence of broken bags.

Further, the stand pouches of Examples 1 to 3 and Comparative Example 1 were filled with 500 ml of 70% ethanol, sealed, and stored at 60 ° C. for 30 days. About the pouch after a preservation | save, the drop test was done similarly to the above and the presence or absence of the broken bag was confirmed.
The results are shown in Table 2. ○ in the table means that there is no bag breakage, and × means that there was a bag breakage.

(Pressure resistance test)
The stand pouches of Examples 1 to 3 and Comparative Example 1 were filled with 500 ml of water, and after sealing, pressure was applied for 100 kg × 1 minute to confirm the presence or absence of bag breakage.
Further, the stand pouches of Examples 1 to 3 and Comparative Example 1 were filled with 500 ml of 70% ethanol, and after sealing, pressure was applied in the same manner as above to confirm the presence or absence of bag breakage.
The results are shown in Table 2. ○ in the table means that there is no bag breakage, and × means that there was a bag breakage.

  As shown in Table 1, the laminates of Examples 1 to 3 maintained a sufficiently high interlayer adhesive strength even after being filled with ethanol and stored, and were excellent in alcohol resistance. On the other hand, in the laminate of Comparative Example 1, during storage after filling with ethanol, ethanol collected in the adhesive portion between the aluminum foil and the PEF, the adhesive deteriorated, and the interlayer adhesive strength was 30 days later. Decreased significantly.

  Moreover, as shown in Table 2, the stand-up pouches of Examples 1 to 3 were resistant to drop impact and excellent in pressure resistance even after being filled with ethanol and stored. On the other hand, the laminated body of Comparative Example 1 was broken by a drop impact and deteriorated in pressure resistance with the deterioration of the bonded portion between the aluminum foil and PEF.

1. Base material layers 2, 2a, 2b. 2. Adhesive layer made of an arbitrary adhesive Barrier layers 4, 4a, 4b. 4. Adhesive layer comprising the adhesive resin composition of the present invention Sealant layer6. Intermediate layer 7. Reinforcement layer

Claims (6)

A laminate having at least a base material layer, a barrier layer, an adhesive layer and a sealant layer,
The adhesive layer located between the barrier layer and the sealant layer has alcohol resistance and is an alkene- (meth) acrylic ester-unsaturated carboxylic acid terpolymer and alkene-unsaturated The laminate as described above, comprising an adhesive resin composition containing at least one carboxylic acid binary copolymer.   The laminate according to claim 1, further comprising an intermediate layer between the base material layer and the barrier layer. A reinforcing layer is further provided at an arbitrary position between the barrier layer and the sealant layer,
All of the adhesive layers located between the barrier layer and the sealant layer have alcohol resistance, and the alkene- (meth) acrylic acid ester-unsaturated carboxylic acid terpolymer and alkene- The laminate according to claim 1 or 2, comprising an adhesive resin composition containing at least one binary copolymer of unsaturated carboxylic acids.   The amount of unsaturated carboxylic acid components in the adhesive resin composition is 0.05% by mass or more and less than 1.0% by mass, and the laminate according to any one of claims 1 to 3. .   The alcohol-resistant self-supporting bag which consists of a laminated body of any one of Claims 1-4.   It is a manufacturing method of the laminated body of any one of Claims 1-4, Comprising: A barrier layer and a sealant layer, or a barrier layer, a reinforcement layer, a reinforcement layer, and a sealant layer are alkene- (meta ) Sandwich lamination via an adhesive resin composition comprising at least one of an acrylate ester-unsaturated carboxylic acid terpolymer and an alkene-unsaturated carboxylic acid terpolymer. The above manufacturing method.

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