JP2016068396A - Method for producing laminated body, and laminated body and medical packaging container composed of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a laminated body which has high interlayer adhesive strength and keeps it even after heat sterilization treatment, and has low elution and excellent hygienic properties; a laminated body; and a medical packaging container.SOLUTION: A method for producing a laminated body includes: a step of laminating a melted adhesive resin composition, which contains at least one kind of a ternary copolymer of alkene-(meth)acrylic acid ester-unsaturated carboxylic acid and a binary copolymer of alkene-unsaturated carboxylic acid as an adhesive layer 2, on a transparent gas barrier film as a substrate layer 1 through an extrusion coating method, and producing an adhesive resin film 3; a step of producing a heat sealable tube 4 having heat sealability therein through an inflation method; a step of crushing the heat sealable tube 4 in a planar shape; and a step of bonding the adhesive resin film 3 on both of outer surfaces of the crushed heat sealable tube 4 through an adhesive layer 3 at such a temperature that the inner surface of the heat sealable tube 4 is not heat-fused to form a laminated body.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for producing a laminate, and a laminate and a medical packaging container produced thereby. More specifically, a method for producing a laminate having a high interlayer adhesion strength and maintaining it after heat sterilization, and having excellent low elution properties and hygiene, and a laminate produced thereby and medical use It relates to packaging containers.

  2. Description of the Related Art Conventionally, packaging containers made of a laminate composed mainly of a resin film, particularly packaging containers for medical use and food use, are required to have high hygiene in addition to excellent heat sealability and appearance. However, in the manufacturing process of the packaging container, foreign matter such as dust and insects, contamination by bacteria, etc. occur. In order to prevent these, various measures such as dust removal in the manufacturing environment and manufacturing and processing in a clean room are used. It was necessary to deal with this, and it took a lot of work and cost.

  In addition, in the laminate forming the packaging container, there are various low molecular weight components caused by the adhesive for dry lamination, etc., and these are transferred to the contents in the packaging container during the storage period. It has been known. However, in packaging containers for medical use and food use, such elution should be strictly suppressed, that is, excellent low elution is required.

In order to solve this problem, as a laminate that forms a packaging container, for example, a low-elution laminate such as a non-solvent adhesive has been proposed (Patent Document 1).
Or the laminated body etc. which use the cyclic polyolefin which shows low elution as a sealant layer are proposed (for example, patent document 2).

  However, these laminates are expensive in terms of material, and it is desired to use a cheaper material as a general medical or food packaging material. Further, sufficient interlayer adhesion strength as a packaging material cannot be obtained, and particularly when subjected to heat sterilization treatment such as boil treatment or retort treatment, there is a problem that interlayer adhesion strength is lowered and delamination is likely to occur.

  In addition, a laminate in which a barrier resin and a sealing resin are integrally formed by coextrusion without using an adhesive is proposed as a laminate that forms a packaging container. However, in this laminate, usable resin is limited, and a film having high gas barrier properties such as a vapor deposition film and a metal foil cannot be used.

Japanese Patent No. 4733420 Japanese Patent No. 4144320

  The present invention has been made to solve such a problem, and has a high interlayer adhesive strength, maintains this even after heat sterilization treatment, and further provides a method for producing a laminate excellent in low elution and hygiene And a laminate and a medical packaging container manufactured thereby.

As a result of various studies, the inventor has found that at least an alkene- (meth) acrylic ester-unsaturated carboxylic acid terpolymer and alkene-as an adhesive layer on a transparent gas barrier film as a base material layer. A process of producing an adhesive resin film by laminating a molten adhesive resin composition containing at least one binary copolymer of unsaturated carboxylic acids by an extrusion coating method, and heat sealing with an inner surface having heat sealability A step of producing a heat-resistant tube by an inflation method, a step of crushing the heat-sealable tube into a flat shape, and the adhesive resin film on both outer surfaces of the crushed heat-sealable tube. Forming a laminate by bonding through the adhesive layer at a temperature at which the inner surface of the substrate is not thermally fused. A method for manufacturing a laminate, and thereby laminate and medical packaging containers are produced were found to achieve the above object.

The present invention is characterized by the following points.
(1) On the transparent gas barrier film as a base material layer, as an adhesive layer, at least a ternary copolymer of alkene- (meth) acrylic acid ester-unsaturated carboxylic acid and binary of alkene-unsaturated carboxylic acid A process for producing an adhesive resin film by laminating a melted adhesive resin composition containing at least one copolymer by an extrusion coating method, and a heat-sealable tube having a heat-sealable inner surface by an inflation method. The step of crushing the heat-sealable tube into a flat shape, and the adhesive resin film on both outer surfaces of the crushed heat-sealable tube, and the inner surface of the heat-sealable tube is not heat-sealed And a step of forming a laminate by bonding through the adhesive layer at a temperature.
(2) At least one of alkene- (meth) acrylic acid ester-unsaturated carboxylic acid terpolymer and alkene-unsaturated carboxylic acid binary copolymer as an adhesive layer on the transparent gas barrier film. The molten adhesive resin composition containing seeds and the molten polyolefin resin are laminated in this order by a coextrusion coating method to produce an adhesive resin film, as described in (1) above Production method.
(3) The method according to (1) or (2), wherein the transparent gas barrier film is a vapor deposition film in which a silicon oxide vapor deposition film or an aluminum oxide vapor deposition film is provided on a plastic film. .
(4) The vapor deposition film further comprises a gas barrier coating film on the silicon oxide vapor deposition film or the aluminum oxide vapor deposition film, and the gas barrier coating film has the general formula R ¹ _n M (OR ² ) _m. (In the formula, M represents a metal atom, R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, n is an integer of 0 or more, m is an integer of 1 or more, and n + m is M's. And a hydrolyzate or alkoxide of an alkoxide obtained by polycondensation of a composition comprising polyvinyl alcohol and / or ethylene / vinyl alcohol by a sol-gel method. The production method according to (3) above, which is a hydrolysis-condensation product of
(5) Any of (1) to (4) above, wherein the amount of unsaturated carboxylic acid component in the adhesive resin composition is 0.05% by mass or more and less than 1.0% by mass. The manufacturing method as described in.
(6) The production method according to any one of (1) to (5) above, wherein the amount of the (meth) acrylic acid ester component in the adhesive resin composition is 5 to 40% by mass.
(7) The method according to any one of (1) to (6) above, wherein in the step of producing the heat-sealable tube by an inflation method, the inflation method is a water-cooled inflation method. .
(8) A laminate produced by the production method according to any one of (1) to (7) above.
(9) A medical packaging container obtained by heat-sealing both sides of a heat-sealable tube in the flow direction and further heat-sealing in the width direction.
(10) The interlayer adhesion strength after heat sterilization treatment at 105 ° C. for 30 minutes is maintained at 60% or more, more preferably 70% or more, with respect to the interlayer adhesion strength before the heat sterilization treatment. The medical packaging container according to (9) above.
(11) The interlayer adhesive strength after the heat sterilization treatment at 121 ° C. for 25 minutes is maintained at 60% or more, more preferably 70% or more, with respect to the interlayer adhesion strength before the heat sterilization treatment. The medical packaging container according to the above (9) or (10).

  The laminate manufactured in a tube shape by the manufacturing method of the present invention is excellent in hygiene because the inner surface of the tube is free from contamination by microorganisms and the like, and foreign matter adherence / mixture.

  In addition, since the production method of the present invention does not use an adhesive for dry lamination, the laminate produced by the production method of the present invention exhibits excellent low elution, and has a transparent gas barrier film and heat sealability. Extremely high interlayer adhesion strength between the tubes can be achieved. Furthermore, the laminated body of the present invention can maintain high interlayer adhesion strength even after being subjected to heat sterilization treatment such as boil treatment or retort treatment.

  Therefore, the laminate of the present invention can be suitably used as a medical packaging container or the like that requires high hygiene and low elution.

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. It is explanatory drawing which shows an example of the manufacturing process of the laminated body of this invention. It is the figure which showed an example of the laminated body of the winding state of this invention. It is the figure which showed the other example of the laminated body of the winding state of this invention. It is a schematic diagram which shows arrangement | positioning at the time of bag-making the laminated body of this invention. It is a schematic diagram which shows an example of the packaging container of this invention.

  The present invention will be described in more detail below. Hereinafter, the resin names used in the present invention are those commonly used in the industry.

<1> Layer structure of the laminate of the present invention The laminate of the present invention will be described in detail with reference to the 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 is obtained by laminating an adhesive resin film 3 composed of a transparent gas barrier film 1 and an adhesive layer 2 as a base material layer on both outer surfaces of a heat sealable tube 4. This is the basic structure. Here, the adhesive layer 2 includes at least one of an alkene- (meth) acrylic acid ester-unsaturated carboxylic acid terpolymer and an alkene-unsaturated carboxylic acid binary copolymer. It is a layer formed by extrusion coating the resin composition on the base material layer 1.

  As shown in FIG. 2, the adhesive layer 2 includes at least one of an alkene- (meth) acrylic acid ester-unsaturated carboxylic acid terpolymer and an alkene-unsaturated carboxylic acid binary copolymer. The layer formed by coextrusion coating on the base material layer 1 with the layer 2a which consists of an adhesive resin composition, and the polyolefin resin layer 2b may be sufficient.

Moreover, the transparent gas barrier film 1 as a base material layer may be a vapor deposition film formed by providing a silicon oxide vapor deposition film or an aluminum oxide vapor deposition film 1b on a plastic film 1a. Alternatively, as shown in FIG. 3, a gas barrier coating film 1c may be further provided on the vapor deposition film 1b.
If necessary, further layers such as a printing layer and a reinforcing layer can be provided at any position, for example, between the base material layer 1 and the adhesive layer 2 or outside the base material layer 1.

The heat-sealable tube 4 may be a single-layer tube made of a heat-sealable resin or a co-extruded multilayer tube made of a heat-sealable resin and another thermoplastic resin. The multilayer tube may have two or more layers, but the innermost layer is a layer made of a heat-sealable resin.
Next, materials constituting the laminate of the present invention, manufacturing methods thereof, and the like will be described.

<2> Base material layer In the laminate of the present invention, a gas barrier film is used as the base material layer. In the present invention, various gas barrier films can be used depending on the application, but for use in medical packaging containers, for example, infusion packaging materials or infusion bag packaging materials, it may have visibility. A transparent gas barrier film is preferably used. Moreover, it is preferable not to contain the aluminum foil with the risk of Alzheimer's onset depending on a use.

  In the present invention, being transparent means that it is necessary to have the transparency necessary for the application, and includes colorless or colored and transparent, particularly when used as a medical packaging container. For example, the average light transmittance in the visible light region of 380 nm to 780 nm is 70% or more. In addition, the measurement of light transmittance uses the value measured in room temperature and air | atmosphere using the ultraviolet visible spectrophotometer (For example, Shimadzu Corporation UV-3100PC).

The gas barrier film used in the present invention can be appropriately selected by those skilled in the art to exhibit a necessary level of gas barrier properties depending on the application. For use as a medical packaging container, for example, the oxygen permeability is 0.5 cc / m ² / day · atm or less, more preferably 0.3 cc / m ² / day · atm or less, and the water vapor permeability is It is 0.3 g / m ² / day or less, more preferably 0.1 g / m ² / day or less. In this application, the oxygen transmission rate is a condition of a temperature of 23 ° C. and a humidity of 90% RH using an oxygen gas transmission rate measuring device (OX-TRAN 2/20 manufactured by MOCON) in accordance with the JIS K7126 isobaric method. It is a value measured by. Further, the water vapor transmission rate is measured under the conditions of a temperature of 40 ° C. and a humidity of 90% RH using a water vapor transmission rate measuring device (PERMATRAN-W 3/31 manufactured by MOCON) in accordance with JIS K7129 B method. Value.

  Examples of such a transparent gas barrier film include a vapor deposition film, an ethylene-vinyl alcohol copolymer film, a polyvinylidene chloride film, a polyvinyl alcohol film, an MXD6 film, or a multilayer film obtained by laminating two or more layers thereof. In the case of a multilayer film, each layer may have the same composition or a different composition.

  Usually, the thickness of the transparent gas barrier film forming the base material layer is preferably 0.01 to 500 μm, more preferably 1 to 300 μm from the viewpoints of gas barrier properties and transparency. And this transparent gas barrier film may perform surface treatment which improves wettability, such as a corona treatment, an ozone treatment, and a flame treatment, on at least one surface thereof.

  In the present invention, a vapor-deposited film in which an inorganic oxide vapor-deposited film is provided on a plastic film is particularly preferably used because it exhibits excellent gas barrier properties, transparency, and interlayer adhesion strength.

As the plastic film for forming the vapor deposition film, a plastic film that has excellent chemical or physical strength, can withstand the conditions for forming the vapor deposition film, etc., and can be well maintained without impairing the characteristics of the vapor deposition film is used. be able to.

  As such a plastic film, for example, a polyolefin film such as polypropylene or polyethylene, a polyester film such as polyethylene terephthalate (PET) or polyethylene naphthalate, a film or sheet made of various resins such as a polyamide film or a polyimide film is used. can do.

  Plastic film is treated with corona discharge treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, chemical treatment, etc. as necessary before providing a vapor deposition film. Etc. can be arbitrarily applied. In addition, the surface pretreatment is performed as a method for improving the adhesion between the plastic film and the vapor deposition film. As a method for improving the adhesion, for example, the surface of the plastic film is preliminarily formed. In addition, a primer coating agent layer, an undercoat layer, an anchor coating agent layer, or the like can be arbitrarily formed.

  The material for forming the vapor deposition film may be an inorganic oxide having transparency and gas barrier properties such as oxygen and water vapor, such as aluminum oxide, silicon oxide, magnesium oxide, calcium oxide, zirconium oxide, Although oxides such as titanium oxide, boron oxide, hafnium oxide, and barium oxide are used, aluminum oxide and silicon oxide are particularly preferably used from the viewpoint of gas barrier properties and production efficiency.

  As a method for forming a deposited film, physical vapor deposition methods (Physical Vapor Deposition method, PVD method) such as vacuum deposition method, sputtering method and ion plating method, plasma chemical vapor deposition method, thermal chemical vapor deposition method, etc. And film forming methods such as chemical vapor deposition (chemical vapor deposition, CVD) such as photochemical vapor deposition.

  Moreover, the vapor deposition film may consist of a single layer formed by a single vapor deposition process, or may have a multilayer structure formed by repeating the vapor deposition process a plurality of times. In the case of a multilayer structure, each layer may be made of the same material or different materials, and may be formed by the same forming method or by different forming methods. Good. For example, a vapor deposition film made of silicon oxide may be formed on a plastic film by chemical vapor deposition, and then a vapor deposition film made of aluminum oxide may be formed by physical vapor deposition.

  The layer thickness of the deposited film can be appropriately set within the range of 1 to 200 nm, preferably 1 to 100 nm, more preferably 1 to 50 nm, and still more preferably 1 to 30 nm as the thickness of the entire layer. For example, if it exceeds 200 nm, the flexibility is lowered, and there is a possibility that the deposited film may be cracked by an external force such as bending or pulling after film formation, transparency may be lowered, and the stress of the material itself may be reduced. It becomes undesirably large and colored. On the other hand, when the thickness of the deposited film is less than 1 nm, the transparency is good, but it is difficult to obtain a uniform layer and it is difficult to sufficiently perform the gas barrier function.

Hereinafter, as a preferred embodiment of the present invention, a deposited film of silicon oxide 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, at the interface with the plastic film, the plastic film and the silicon oxide vapor deposition film The tight adhesion is strong.

  In the case of forming a silicon oxide vapor-deposited film containing carbon as described above, the organic silicon compound used as a raw material is 1.1.3-3 tetramethyldisiloxane, hexamethyldisiloxane (HMDSO). , Vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltri Methoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane and the like can be used.

In the present invention, by further providing a gas barrier coating film as described below on the vapor deposition film, not only a further excellent gas barrier property can be obtained, but also a close adhesion with an adhesive layer described later is enhanced. .
In the present invention, the gas barrier coating film is a film obtained by applying and drying a gas barrier composition obtained by polycondensation of an alkoxide and a water-soluble polymer by a sol-gel method.

The alkoxide used in the gas barrier composition has 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, and M is a metal An atom is represented, n represents an integer greater than or equal to 0, m represents an integer greater than or equal to 1, n + m represents the valence of M.) At least 1 type or more alkoxide represented by this can be mentioned. .

As the water-soluble polymer, either a polyvinyl alcohol resin or an ethylene / vinyl alcohol copolymer or both can be preferably used.
In the present invention, as the metal atom M, silicon, zirconium, titanium, aluminum or the like can be used as the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m . Moreover, in this invention, the alkoxide of a single or 2 or more types of different metal atoms can be mixed and used in the same solution.

In the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , specific examples of the organic group represented by R ¹ include, for example, a methyl group, an ethyl group, an n-propyl group, i Examples include -propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-hexyl group, n-octyl group and other alkyl groups.

In the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , specific examples of the organic group represented by R ² include, for example, a methyl group, an ethyl group, an n-propyl group, i -Propyl group, n-butyl group, sec-butyl group and the like.

In the present invention, these alkyl groups may be the same or different in the same molecule.
In the present invention, as the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , for example, an alkoxysilane in which M is Si can be used. As the alkoxysilane, for example, tetramethoxy Examples thereof include silane 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.

  Moreover, in this invention, it is preferable that content of a polyvinyl alcohol-type resin and / or an ethylene vinyl alcohol copolymer is the range of 5-500 weight part with respect to 100 weight part of total amounts of said 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.

  In the present invention, as the polyvinyl alcohol-based resin, generally obtained by saponifying polyvinyl acetate can be used. Specific examples of the polyvinyl alcohol resin include PVA110 (degree of saponification = 98 to 99%, degree of polymerization = 1100), PVA117 (degree of saponification = 98 to 99%, degree of polymerization = 1700), PVA124 (made by Kuraray Co., Ltd.) Degree of saponification = 98-99%, degree of polymerization = 2400), PVA135H (degree of saponification = 99.7% or more, degree of polymerization = 3500), RS-110 (degree of saponification = 99%) manufactured by the same company , Degree of polymerization = 1,000), Kuraray Poval LM-20SO (degree of saponification = 40%, degree of polymerization = 2,000) manufactured by the same company, Gohsenol NM-14 (degree of saponification = 99%, degree of polymerization = 1,400) and gohsenol NH-18 (degree of saponification = 98 to 99%, degree of polymerization = 1700) and the like can be used.

  In the present invention, as the ethylene-vinyl alcohol copolymer, a saponified product of a copolymer of ethylene and vinyl acetate, that is, a product obtained by saponifying an ethylene-vinyl acetate random copolymer should be used. Can do. Such saponification products include partial saponification products in which several tens mol% of acetic acid groups remain to complete saponification products in which only several mol% of acetic acid groups remain or no acetic acid groups remain. The Although not particularly limited, it is desirable to use a saponification degree of 80 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more from the viewpoint of gas barrier properties. The content of repeating units derived from ethylene in the ethylene / vinyl alcohol copolymer (hereinafter also referred to as “ethylene content”) is usually 0 to 50 mol%, preferably 20 to 45 mol%. Is preferably used.

  Specific examples of the ethylene / vinyl alcohol copolymer include Kuraray Co., Ltd., Eval EP-F101 (ethylene content: 32 mol%), Nippon Synthetic Chemical Industry Co., Ltd., Soarnol D2908 (ethylene content: 29 mol%). ) Etc. can be used.

  In the present invention, a silane coupling agent or the like can also be added to prepare a gas barrier composition for forming a gas barrier coating film according to the present invention. Suitable silane coupling agents include N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2- Amino group-containing silane coupling agents such as aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 2 -Epoxy group-containing silanes such as (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane Coupling agent, 3-mercaptopro Examples include mercapto group-containing silane coupling agents such as rumethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane, and isocyanate group-containing silane coupling agents such as 3-isocyanatopropyltriethoxysilane and 3-isocyanatopropyltrimethoxysilane. .

  The gas barrier composition used in the present invention can be prepared by hydrolyzing and polycondensing an alkoxide and a water-soluble polymer by a sol-gel method in the presence of an acid, water and an organic solvent.

  The gas barrier coating film is obtained by applying a gas barrier composition on the vapor deposition film, and having a temperature of 20 ° C. to 200 ° C., preferably 140 ° C. or more, and a temperature not higher than the melting point of the plastic film constituting the base material layer for 10 seconds to It can be formed by heat treatment for 10 minutes.

  Moreover, as an acid used in preparation of said gas-barrier composition, organic acids, such as mineral acids, such as a sulfuric acid, hydrochloric acid, nitric acid, and an acetic acid, tartaric acid, etc. can be used, for example. Furthermore, as an organic solvent, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, etc. can be used, for example.

  Further, regarding the gas barrier composition, the polyvinyl alcohol resin and / or the ethylene / vinyl alcohol copolymer is preferably in a state of being dissolved in a coating solution containing the alkoxide, the silane coupling agent, or the like. Therefore, the type of the organic solvent is appropriately selected. In the present invention, as the ethylene / vinyl alcohol copolymer solubilized in a solvent, for example, those commercially available as Soarnol (manufactured by Nippon Synthetic Chemical Co., Ltd.) can be used.

  When the gas barrier composition is applied onto the vapor deposition film and heated to remove the solvent and the alcohol produced by the polycondensation reaction, the polycondensation reaction is completed, and a transparent gas barrier coating film is formed.

  Furthermore, since the hydroxyl group generated by hydrolysis and the silanol group derived from the silane coupling agent are bonded to the hydroxyl group on the surface of the deposited film, the tight adhesion between the deposited film and the gas barrier coating film is improved. .

  By being formed as described above, the gas barrier coating film of the present invention includes a linear polymer having crystallinity and has a structure in which a large number of minute crystals are embedded in an amorphous portion. . Such a crystal structure is the same as that of a crystalline organic polymer (for example, vinylidene chloride or polyvinyl alcohol), and a polar group (OH group) is partially present in the molecule, and the cohesive energy of the molecule is high. Good gas barrier properties.

  In the present invention, the vapor deposition film and the gas barrier coating film form, for example, a chemical bond, hydrogen bond, or coordination bond by hydrolysis / co-condensation, and the adhesion between these two layers is improved, synergistically. Due to the effect, a better gas barrier property can be exhibited.

  In the present invention, the gas barrier composition may be applied by one or more times by a coating means such as a roll coat such as a gravure roll coater, a spray coat, dipping, a brush, a bar coat, or an applicator. With this coating, it is possible to form a gas barrier coating film having a dry film thickness of 0.01 to 100 μm, preferably 0.1 to 50 μm. If the dry film thickness exceeds 100 μm, cracks may occur, which is not preferable.

  In the present invention, in order to obtain a higher gas barrier property, after providing a gas barrier coating film, a vapor deposition film and a gas barrier coating film are alternately laminated in this order one or more times. Preferably, the gas barrier coating film may be formed as an outermost layer to form a transparent gas barrier film.

<3> Adhesive layer In the present invention, the adhesive layer provided on the transparent gas barrier film as the base material layer is an alkene- (meth) acrylic acid ester-unsaturated carboxylic acid terpolymer and an alkene-nonpolymer. An adhesive resin composition containing at least one binary copolymer of saturated carboxylic acids and melted at a temperature lower than the temperature at which the inner surface of the heat-sealable tube is heat-sealed, for example, 70 to 180 ° C. (hereinafter “the present invention”). The adhesive resin composition). Throughout the present specification, the melting points of the resin and the resin composition are evaluated at a temperature at which the peak of the highest intensity appears in the melting curve measured by a differential scanning calorimeter (DSC). 10 mg of press film was heat-treated at 230 ° C. for 5 minutes in a nitrogen atmosphere, cooled to 30 ° C. at a temperature drop rate of 10 ° C./min, kept at 30 ° C. for 5 minutes, and further heated from 30 ° C. to 230 ° C. at a rate of 10 ° C. It is a value obtained as a melting peak temperature when heated at a rate of 1 min.

  This adhesive resin composition of the present invention exhibits high interlayer adhesive strength with the transparent gas barrier film by laminating on the transparent gas barrier film by an extrusion coating method. Here, the transparent gas barrier film may be made of any material, for example, a vapor film or a film made of various gas barrier resins.

  In particular, by extruding the adhesive resin composition of the present invention onto the surface comprising a vapor-deposited film of inorganic oxide or the above-mentioned surface comprising a gas barrier coating film, extremely high interlayer adhesion strength is exhibited, and The high interlayer adhesion strength is maintained even after the heat sterilization treatment.

  The adhesive resin composition of the present invention has a functional group such as a carboxyl group, thereby chemically bonding to a reactive group on the surface of a transparent gas barrier film and a heat sealable tube described later, and increasing the laminate strength between layers. Can be improved.

  In the present invention, an anchor coating agent layer or the like previously provided on the transparent gas barrier film during normal extrusion coating is not necessarily required. Moreover, the adhesive resin composition of this invention does not contain an organic solvent. Therefore, according to this invention, the elution of the residual solvent and low molecular-weight substance originating in an anchor coating agent or an organic solvent can be prevented. 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 heat resistance and can maintain high laminate strength over a long period of time even after being subjected to heat sterilization under high temperature and pressure.

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 yet another embodiment, the adhesive resin composition of the present invention may further comprise a polyolefin resin, a polyamide resin, a polyester resin, as desired, in addition to the terpolymer and / or the 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 is, for example, workability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, and release properties within a range that does not impair the purpose of the present invention. In order to improve and improve flame retardancy, antifungal properties, electrical properties, strength, etc., various plastic compounding agents and additives can be added. Depending on the purpose, up to several tens of percent can be arbitrarily added. Common additives include, for example, lubricants, crosslinking agents,
Antioxidants, ultraviolet absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, pigments, and the like can be used.

  In the production of the terpolymer and binary copolymer, examples of the alkene 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, imides, and the like. Examples thereof include 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 charging into a kneading machine such as a Banbury mixer, a double screw mixer or the like, 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 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 increases, so that the hygroscopicity is increased, and foaming occurs during extrusion coating. 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, if the amount of the unsaturated carboxylic acid component is too small, chemical interaction with the transparent gas barrier film or the heat-sealable tube is difficult to occur, which may cause a decrease in interlayer adhesion 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 and handling becomes worse. 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 and the adhesive strength with the layer which consists of polypropylene, PET, etc. falls.

  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 25.0 mass%, more preferably 0.05 to 15 mass% of an unsaturated carboxylic acid-derived component (residue) with respect to the total mass of the adhesive resin composition. The rest are all alkene-derived components (residues), modifying resins, additives, and the like.

  When 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. For example, for polyethylene and ethylene copolymers, the compatibility mainly due to the alkene moiety contributes to bonding. In addition, the reaction between the polar groups of the unsaturated carboxylic acid and the counterpart substrate contributes to the binding to the vapor deposition film or metal of the gas barrier film. In addition, for a layer made of polypropylene or PET, chemical interaction between the acrylate and the unsaturated carboxylic acid contributes to bonding.

  In the present invention, the adhesive layer is a layer formed by coextrusion coating in this order on a transparent gas barrier film as a base material layer and a polyolefin resin layer comprising the adhesive resin composition of the present invention. There may be. By laminating the base material layer and the polyolefin-based resin layer in this order, that is, through the layer made of the adhesive resin composition of the present invention, high interlayer adhesive strength can be obtained. Examples of the polyolefin resin or resin composition suitably used here include the same resin or resin composition as the outer surface of the heat sealable tube described later. By using the same resin or resin composition as the outer surface of the heat-sealable tube, high interlayer adhesion strength can be obtained.

<4> Heat-sealable tube In the present invention, the heat-sealable tube is a polyolefin resin, for example, polyethylene, ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ethylene / acrylic acid ester copolymer, It may be a single-layer tube made of a heat-sealable resin such as ionomer or polypropylene. Alternatively, the heat-sealable resin layer may be a co-extruded multilayer tube with any resin that can be co-extruded with these layers, such as saponified ethylene / vinyl acetate copolymer, nylon, etc. May be.
Although the thickness of said heat-sealable tube is arbitrary according to a packaging use etc., about 10-600 micrometers is preferable, More preferably, it is 90-520 micrometers.

  The heat-sealable tube according to the present invention forms a polyolefin-based resin such as polyethylene by a normal inflation method (blow tube) using a circular die. More preferably, the blown gas (air) is used by filtering and removing fine particles of 0.5 μm or less with a filter.

  Or, further, by using an inert gas such as nitrogen gas or carbon dioxide gas as a gas, the generation of solids such as resin oxides in the die is suppressed, and the fine particles of smoke in the heat-sealable tube are reduced. Has the advantage.

Alternatively, a water-cooled inflation method can be suitably used for forming a heat-sealable tube. By cooling and solidifying the outer surface of the molten resin (so-called bubble) formed into a tubular shape in the inflation step by cooling water by the water-cooled inflation method, the molten resin can be quickly cooled and solidified. Thereby, even if it is a case where a film thickness is thick, the heat-sealable tube which has high transparency can be manufactured. The laminate of the present invention comprising such a heat sealable tube is particularly suitable for an infusion bag.

  The heat-sealable tube formed into a tubular shape is crushed by a stabilizer or a pinch roll and becomes flat. This flat heat-sealable tube is wound up and subjected to a subsequent lamination process with an adhesive resin film.

<5> Manufacturing Process A method for manufacturing a laminate by laminating an adhesive resin film composed of a base material layer and an adhesive layer and a heat-sealable tube will be described.
As such a method, the flat heat-sealable tube obtained above is set in the first paper feed unit 10 shown in FIG. 4, and the adhesive resin film is set in the second paper feed unit 14 respectively. Then, a heat-sealable tube and an adhesive resin film are sent out from each paper feeding unit. In some cases, the heat-sealable tube may be heated at a temperature lower than the temperature at which the inner surface is thermally fused by passing the preheating furnace or the preheating roll 11.

  The heat-sealable tube is sandwiched from above and below so as to be sandwiched by the adhesive resin film delivered from the second paper supply unit 14, and is passed between at least one pair of upper and lower heat rolls 12. The heat roll is heated to, for example, 90 to 180 ° C. at a temperature equal to or higher than the temperature at which the adhesive layer melts and lower than the temperature at which the inner surface is thermally fused by the heat reaching the inner surface of the heat sealable tube. By passing between the heat rolls 12, the adhesive resin film is bonded to the upper and lower surfaces of the heat-sealable tube crushed on a flat surface by thermal lamination via the adhesive layer.

  The laminated body obtained by passing between the hot rolls 12 is cooled by passing through the cooling furnace 13, and wound around the roll in the winding unit 15, so that the laminated body according to the present invention is manufactured. Prior to winding, a printing layer can be provided on the surface as needed.

  The laminate obtained by the above production method does not expose the heat seal surface, which is the inner surface, to the outside air from the time of forming the heat-sealable tube until the bag making is completed. Therefore, it is possible to prevent the contamination of microorganisms or the like and the adhesion of foreign substances, and it is excellent in hygiene. Further, for example, a heat-sealable tube having a thickness of several hundreds of μm generally has a large thickness deviation, and there is a variation of ± 10% with respect to the thickness. Therefore, it is difficult to laminate on such a thick tube in a uniform manner. However, according to the manufacturing method using the thermal laminate of the present invention, accuracy can be obtained even for a thick heat-sealable tube. They can be laminated well, and are excellent in appearance, barrier properties, productivity, cost performance, and the like.

  In the laminating step by the above heat lamination, the feeding speed of each film is not particularly limited, but is, for example, a line speed of 5 to 200 m / min, and preferably 10 to 150 m / min. Moreover, when it is slower than 5 m / min, it is not preferable from the viewpoint of productivity.

  The wound laminate 20 of the present invention is a rolled laminate for producing a bag-like packaging container 50 as shown in FIG. 5, and at least both sides are continuous in the flow direction. The side seal portion 21 may be provided by heat sealing, and the cut end portion 22, that is, the winding start and winding end portions may be continuously heat sealed in the width direction.

By continuously heat-sealing both sides and the cut end of the laminate, it is cut off from the outside. It is possible to maintain a state of high cleanliness without contamination such as contamination and foreign matter.

Moreover, as shown in FIG. 6, the laminated body 20 in a wound state of the present invention is to wind up after providing three rows of heat seal portions continuously in the flow direction on both sides and the central portion. Also good.
When a bag-shaped packaging container is manufactured by bag-making the laminated body in the wound state, for example, as shown in FIG. The bottom sealing part 24 is appropriately heat-sealed at a desired interval, and at the same time, the cutting position 30 is provided at a position slightly separated (for example, 0.5 to 2 mm) from the bottom sealing part 24.

And the bag-shaped packaging container 50 which has the opening part 40 and the bottom seal part 24 can be manufactured as shown in FIG.
In addition to the side seal portion 21 and the bottom seal portion 24, heat sealing can be performed continuously in the center of the laminated body in the flow direction, and the center seal portion 23 and the like can be provided to perform multi-row processing.

The packaging container made of the laminate obtained by the method of the present invention can package the contents without mixing foreign matters such as dust from the outside. Moreover, since the base material which shows extremely high gas barrier properties like a vapor deposition film can be used, permeation | transmission of oxygen and water vapor | steam can be prevented. Moreover, it has high interlayer adhesive strength and can be maintained even after the heat sterilization treatment, and further, elution of low molecular weight substances caused by organic solvents and the like from the laminate is suppressed. Therefore, the packaging container according to the present invention can be suitably used particularly for packaging pharmaceutical products such as infusions, blood transfusions, solutions, tablets, medical products such as medical instruments, infusion bags, and prefilled syringes. Further, it can be preferably used for packaging of various other solid, liquid and viscous articles such as confectionery, seasonings, soups and fruit juices, cosmetics, toiletries and the like.
Next, the present invention will be specifically described with reference to examples.

[Example 1]
A biaxially stretched PET film with a thickness of 12 μm with corona treatment on one side is used, and this film is attached to a feed roll of a plasma chemical vapor deposition apparatus. Hexamethyldisiloxane, an organosilicon compound, is used as a raw material on the corona treatment surface. As a result, a silicon oxide vapor deposition film having a thickness of 200 nm was formed. Next, plasma treatment was performed on the surface of the deposited film.

  On the other hand, according to the composition shown in Table 1 below, the composition a. Composition prepared in advance in EVOH solution prepared by dissolving EVOH (ethylene copolymerization ratio 29%) in a mixed solvent of isopropyl alcohol and ion-exchanged water b. A hydrolyzed liquid composed of ethyl silicate 40, isopropyl alcohol, acetylacetone aluminum, and ion-exchanged water, and stirred, and further prepared in advance c. A mixture of polyvinyl alcohol, silane coupling agent (epoxysilica SH6040), acetic acid, isopropyl alcohol and ion-exchanged water was added and stirred to obtain a colorless and transparent barrier coating solution.

Next, the plasma-treated surface on the deposited film surface is coated with the gas barrier composition produced above, and heat-treated at 100 ° C. for 30 seconds to form a gas barrier having a thickness of 0.4 g / m ² (dry operation state). An adhesive coating film was formed.

Next, the transparent gas barrier film formed above is set in an extrusion laminating machine, and an adhesive resin made of an ethylene-methyl acrylate-maleic acid terpolymer is formed on the surface of the gas barrier coating film from a T die. composition (Arkema Co. Lotader ^(R) 4503, maleic acid component content: 0.3 wt%, methyl acrylate component amount: 19 mass%, melting point 80 ° C.), and was extrusion coated at 300 ° C., the thickness A 20 μm thick adhesive layer was formed to produce an adhesive resin film.

  On the other hand, a non-stretched polypropylene (CPP) tube (thickness: 200 μm, melting point: 130 ° C.) was formed by an air-cooled inflation method, and this was crushed by a stabilizer and a pinch roll to produce a flat heat-sealable tube. In the inflation process, fine particles and the like were removed from the air sent to the inside of the cylinder in order to stretch the film into a cylindrical shape.

Next, the above-described flat heat-sealable tube winding body is set in the first paper feeding section of the laminator as shown in FIG. 4, and the adhesive resin film winding body is set in the second paper feeding section. Set. The tube and the film are respectively sent out from each paper feeding unit, and the heat-sealable tube is sandwiched from above and below by an adhesive resin film and passed between a preheating roll and a heat roll heated to 160 ° C. An adhesive resin film was thermally laminated on the upper and lower surfaces through an adhesive layer. The obtained laminate was wound through a cooling furnace to produce a laminate of the present invention. The line speed was 20 m / min.

[Example 2]
A laminate of the present invention was produced in the same manner as in Example 1, except that a low density polyethylene (LDPE) tube (thickness 200 μm, melting point 110 ° C.) was used as the heat sealable tube.

[Example 3]
Implementation was carried out except that an adhesive resin composition comprising a binary copolymer obtained by graft polymerization of maleic acid to a polyolefin resin (Modick P546V manufactured by Mitsubishi Chemical Corporation, melting point 140 ° C.) was used as the adhesive resin composition. In the same manner as in Example 1, a laminate of the present invention was produced.

[Example 4]
As an adhesive layer, an adhesive resin composition composed of an ethylene-methyl acrylate-maleic terpolymer (Lotader ^(R) 4503 manufactured by Arkema Co., Ltd., maleic anhydride component amount: 0.3 mass%, methyl acrylate component amount: 19 mass%, thickness 10 μm) and LDPE (thickness 10 μm) in this order (with the LDPE layer as the surface layer) at 300 ° C. A laminate of the present invention was produced in the same manner as in Example 2 except that extrusion coating was performed.

[Example 5]
As an adhesive layer, an adhesive resin composition composed of an ethylene-methyl acrylate-maleic terpolymer (Lotader ^(R) 4503 manufactured by Arkema Co., Ltd., maleic anhydride component amount: 0.3% by mass, methyl acrylate component amount: 19% by mass, 10 μm thickness) and polypropylene (Novatech ^™ PPFL-02A, 10 μm thickness, manufactured by Nippon Polypro Co., Ltd.) in this order (the polypropylene layer is A laminate of the present invention was produced in the same manner as in Example 1 except that the surface layer was coextruded at 300 ° C.

[Example 6]
A laminate of the present invention was produced in the same manner as in Example 1 except that an unstretched polypropylene (CPP) tube was formed by a water-cooled inflation method.

[Example 7]
A laminate of the present invention was produced in the same manner as in Example 2 except that a low-density polyethylene (LDPE) tube was formed by a water-cooled inflation method.

[Example 8]
As an adhesive resin composition, ethylene-methyl acrylate-maleic acid terpolymer (Lotader ^(R) 4503 manufactured by Arkema Co., Ltd.), ethylene-methyl acrylate (Arkema Co., Ltd. LOTRYL 18MA02, methyl acrylate) (Adhesive resin composition) diluted 3.75 times with a component amount of 18% by mass to give an unsaturated carboxylic acid component amount of 0.08% by mass and an acrylate component amount of 19% by mass in the adhesive resin composition A packaging material of the present invention was obtained in the same manner as in Example 1 except that the product was used.

[Example 9]
As an adhesive resin composition, ethylene-methyl acrylate-maleic acid terpolymer (Lotader ^(R) 4210 manufactured by Arkema Co., Ltd., unsaturated carboxylic acid 3.6% by mass, acrylic ester component amount 4.5) % By mass) ethylene-methyl acrylate (Arkema Co., Ltd. LOT)
RYL 18MA02) was diluted 4.5 times, and an adhesive resin composition was used in which the amount of unsaturated carboxylic acid component in the adhesive resin composition was 0.8 mass% and the amount of acrylic acid ester component was 15 mass%. A packaging material of the present invention was obtained in the same manner as in Example 1 except that.

[Comparative Example 1]
Instead of laminating the adhesive resin film on the upper and lower surfaces of the heat-sealable tube, the laminate was prepared in the same manner as in Example 1 except that the adhesive resin film was thermally laminated on the CPP film (thickness 200 μm). Manufactured.

[Comparative Example 2]
Example 1 except that an adhesive resin film was heat laminated on a linear low density polyethylene (LLDPE) film (thickness 200 μm) instead of laminating an adhesive resin film on both upper and lower surfaces of a heat-sealable tube In the same manner, a laminate was produced.

[Comparative Example 3]
As an adhesive layer, instead of laminating the adhesive resin composition of the present invention directly by extrusion coating on the surface of the gas barrier coating film, an anchor coating agent (Mitsui Chemical Co., Ltd., A3210 / A3072) was applied, A laminate was produced in the same manner as in Example 1 except that polypropylene (Novatec ^™ PPFL-02A, manufactured by Nippon Polypro Co., Ltd., thickness: 20 μm) was laminated thereon by extrusion coating.

[Comparative Example 4]
As an adhesive layer, instead of laminating the adhesive resin composition of the present invention directly by extrusion coating on the surface of the gas barrier coating film, an anchor coating agent (Mitsui Chemical Co., Ltd., A3210 / A3072) was applied, LDPE (Novatec ^TM LD manufactured by Nippon Polyethylene Co., Ltd.)
A laminate was produced in the same manner as in Example 2 except that LC522 (thickness 20 μm) was laminated by extrusion coating.

[Evaluation test]
(Interlayer adhesion strength test)
The laminates of Examples 1 to 9 and Comparative Examples 1 to 4 were cut into strips having a width of 15 mm, and a bonded portion between the adhesive resin film and the heat-sealable tube using a Tensilon tensile tester according to JISK6854 (implemented) Examples 1-5 and Comparative Examples 3-4) or an adhesive resin film-to-heat-sealable film adhesive part (Comparative Examples 1-2) in a 90 ° direction at 25 ° C. and a tensile speed of 50 mm / min It peeled off and the interlayer adhesive strength (initial stage) was measured.

  Moreover, about Example 1, 3, 5, 6, 8, 9 and the comparative example 3 which used the CPP tube as a heat-sealable tube, and the comparative example 1 which used the CPP film as a heat-sealable film, it is 121 degreeC. After steam sterilization for 25 minutes, interlayer adhesion strength (after heat treatment) was measured again under the same conditions.

For Examples 2, 4, 7 and Comparative Example 4 using an LDPE tube as a heat-sealable tube, and Comparative Example 2 using an LLDPE film as a heat-sealable film, after steam sterilization at 105 ° C. for 30 minutes The interlayer adhesion strength (after heat treatment) was again measured under the same conditions.
The results are shown in Table 2 below.

(Insoluble particulate test)
About the laminated body of Examples 1-7 and Comparative Examples 1-4, it carried out from the clean room in the winding-up state, and was conveyed. Then, it carries in in a clean room, and about the laminated body of Examples 1-7 and Comparative Examples 3-4, both sides of a tube are heat-sealed in the flow direction, and also heat-sealed in the width direction, and the internal capacity is 500 mL. A three-sided bag was made. Moreover, about the laminated body of Comparative Examples 1-2, two laminated bodies are prepared, it superimposes so that the CPP film side may oppose, and the surroundings are heat-sealed, and the internal volume of the same shape is 500 mL A bag was created.

  About the obtained three-sided bag body, 200 ml of clean water was sealed in a pouch by a test method according to the insoluble fine particle test of Japanese Pharmacopoeia, contained in the water taken out after shaking for 10 minutes. The number of particles was counted with an in-liquid particle counter (8000A type, HIAC / Royco). For each particle size, the number is converted to a unit volume (pieces / ml), and the results are shown in Table 3 below.

(Dissolution test)
In the same manner as the insoluble fine particle test, a three-sided bag body was produced using the laminates of Examples 1 to 7 and Comparative Examples 1 to 4. About the obtained three-way bag body, 200 ml of clean water was enclosed in a test method according to the elution test of the plastic drug container test method of the Japanese Pharmacopoeia, and this pouch was placed at 121 ° C. for 25 minutes (Example 1, 3, 5, 6 and Comparative Examples 1 and 3) or steam sterilization at 105 ° C. for 30 minutes (Examples 2, 4, 7 and Comparative Examples 2 and 4). The pouch was opened and the collected test solution was examined for foaming, pH, potassium permanganate reducing substance, ultraviolet absorption spectrum and evaporation residue as follows.

(Bubbles)
5 mL of the test solution was placed in a stoppered test tube having an inner diameter of 15 mm and a length of 200 mm, and vigorously shaken for 3 minutes, and the time until the generated foam disappeared was measured.

(PH)
1 mL of 1 g / L aqueous potassium chloride solution was added to 20 mL each of the test solution and clean water (control), and the pH was measured to determine the difference from the control.

(Potassium permanganate reducing substance)
To 20 mL of the test solution, 20 mL of 0.002 mol / L potassium permanganate solution and 1 mL of dilute sulfuric acid were added and cooled after boiling for 3 minutes. Thereafter, 0.1 g of potassium iodide was added and left for 10 minutes. After standing, it was titrated with 0.001 mol / L sodium thiosulfate solution (indicator: starch reagent). The difference in consumption of 0.002 mol / L potassium permanganate solution relative to the test solution and control (clean water) was determined.

(UV absorption spectrum)
With respect to the test solution and the control (clean water), the maximum absorbance was measured in each of the wavelength of 220 to 240 nm and the wavelength of 241 to 350 nm by the UV-visible absorbance measurement method.

(Evaporation residue)
20 mL of each test solution was evaporated to dryness on a water bath, the residue was dried at 105 ° C. for 1 hour, and its mass was measured.
The results are shown in Table 4 below.

  As shown in Table 2, the laminates of Examples 1 to 9 and Comparative Examples 1 and 2 that were heat-laminated through the adhesive layer made of the adhesive resin composition of the present invention had sufficiently high interlayer adhesion strength even after heat treatment. Was maintained. On the other hand, the laminates of Comparative Examples 3 to 4, which were applied with an anchor coating agent and laminated via an adhesive layer made of a heat-sealable resin, showed high interlayer adhesion strength before heat treatment, but greatly increased after heat treatment. However, it was easy to peel off.

  Moreover, as shown in Table 3, the pouches of Examples 1 to 7 and Comparative Examples 3 to 4 made from heat-sealable tubes were less sanitized with foreign matters such as dust and were excellent in hygiene. On the other hand, in the pouches of Comparative Examples 1 and 2 made from a heat-sealable film, many foreign matters were mixed.

  Furthermore, as shown in Table 4, the pouch made of the laminates of Examples 1 to 7 and Comparative Examples 1 and 2 that did not use an anchor coating agent showed good low elution even after heat treatment. On the other hand, the pouch which consists of a laminated body of the comparative examples 3-4 which requires an anchor coating agent was inferior to low elution.

1. Base material layer (transparent gas barrier film)
1a. Plastic film 1b. Deposition film 1c. 1. Gas barrier coating film Adhesive layer 2a. Adhesive resin composition layer 2b. 2. Polyolefin resin layer 3. Adhesive resin film Heat-sealable tube10. First paper feeding unit 11. Preheating roll 12. Hot roll 13. Cooling furnace 14. Second paper feeding unit 15. Winding unit 20. Laminated body 21. Side seal part 22. Cutting end 23. Center seal part 24. Bottom seal part 30, 31. Cutting position 40. Opening 50. Packaging container F. Flow direction

Claims (11)

On the transparent gas barrier film as the base material layer, as an adhesive layer, at least a terpolymer of alkene- (meth) acrylic acid ester-unsaturated carboxylic acid and a binary copolymer of alkene-unsaturated carboxylic acid A step of laminating a molten adhesive resin composition containing at least one of the above by an extrusion coating method to produce an adhesive resin film;
A process for producing a heat-sealable tube having an inner surface heat-sealable by an inflation method;
Crushing the heat-sealable tube into a flat shape;
The adhesive resin film is bonded to both the outer surfaces of the crushed heat-sealable tube through the adhesive layer at a temperature at which the inner surface of the heat-sealable tube is not thermally fused to form a laminate. Process,
The manufacturing method of a laminated body characterized by including.   On the transparent gas barrier film, at least one of alkene- (meth) acrylic acid ester-unsaturated carboxylic acid terpolymer and alkene-unsaturated carboxylic acid binary copolymer is included as an adhesive layer. The manufacturing method according to claim 1, wherein an adhesive resin film is produced by laminating a molten adhesive resin composition and a molten polyolefin resin in this order by a coextrusion coating method.   The manufacturing method according to claim 1, wherein the transparent gas barrier film is a vapor deposition film in which a silicon oxide vapor deposition film or an aluminum oxide vapor deposition film is provided on a plastic film. The vapor deposition film further comprises a gas barrier coating film on the silicon oxide vapor deposition film or the aluminum oxide vapor deposition film,
The gas barrier coating film has a 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) And m is an integer of 1 or more, and n + m represents the valence of M), and a composition comprising polyvinyl alcohol and / or ethylene / vinyl alcohol The method according to claim 3, wherein the product is a hydrolyzate of alkoxide obtained by polycondensation by a sol-gel method or a hydrolyzate condensate of alkoxide.   5. The production according to claim 1, wherein 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. Method.   The production method according to any one of claims 1 to 5, wherein the amount of the (meth) acrylic acid ester component in the adhesive resin composition is 5 to 40% by mass. In the step of producing the heat-sealable tube by an inflation method,
The production method according to claim 1, wherein the inflation method is a water-cooled inflation method.   The laminated body manufactured by the manufacturing method of any one of Claims 1-7.   A medical packaging container obtained by heat-sealing both sides of a heat-sealable tube in the flow direction and further heat-sealing the laminate according to claim 8 in the width direction. The medical packaging container according to claim 9, wherein the interlayer adhesion strength after heat sterilization treatment at 105 ° C for 30 minutes is maintained at 60% or more with respect to the interlayer adhesion strength before heat sterilization treatment. .   11. The medical use according to claim 9, wherein the interlayer adhesion strength after heat sterilization treatment at 121 ° C. for 25 minutes is maintained at 60% or more with respect to the interlayer adhesion strength before heat sterilization treatment. Packaging container.

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