Packaging container

Abstract

To provide a highly versatile packaging container that can achieve both reduction in resin amount and ease of recyclability.SOLUTION: A packaging container comprises a film laminated with an easily peelable adhesive that contains a polyester polyol and a polyisocyanate and has a solid content acid value of 5 mg KOH / g or more.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a packaging container.

Background Art

[0002] As a type of packaging container, a refill pouch has a smaller amount of resin per unit volume compared to a main body bottle container, and can reduce the environmental load. However, in order to ensure the quality of the packaging container, a laminated film in which films of materials having different characteristics are laminated via an adhesive is used for the pouch, so recycling is not easy.

[0003] Patent Document 1 discloses an adhesive that enables peeling of a laminated film to make it a single material.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] As the use of the above adhesive, it was limited only to food applications and did not require high load resistance or resistance to the contents.

[0006] The present invention has been made in consideration of the above points, and an object thereof is to provide a packaging container that can achieve both reduction of the resin amount and easy recyclability and has high versatility.

Means for Solving the Problems

[0007] The present invention has the following aspects. [1] A packaging container having a film laminated using an easily peelable adhesive containing polyester polyol and polyisocyanate and having a solid acid value of the adhesive of 5 mgKOH / g or more. [2] The packaging container according to [1] above, wherein the polyisocyanate contains at least one polyisocyanate component selected from the group consisting of an aliphatic polyisocyanate component and an araliphatic polyisocyanate component. [3] The packaging container according to [1] or [2] above, wherein the solid content acid value of the polyester polyol is 5 to 100 mgKOH / g. [4] The packaging container according to any one of [1] to [3] above, wherein the easily peelable adhesive further contains a compound having an acidic group. [5] The packaging container according to any one of [1] to [4] above, having a container body having the film and a spout protruding from the container body. [6] The packaging container according to any one of [1] to [5] above, having a container body having the film and containing the content, wherein the content contains a liquid composition selected from kitchen detergents, laundry detergents, fabric softeners, bleaches, and cosmetics. [Effect of the Invention]

[0008] In the present invention, it is possible to achieve both a reduction in the resin amount and easy recyclability, and a highly versatile packaging container can be provided. [Brief Description of the Drawings]

[0009]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

[0010] Hereinafter, embodiments of the packaging container of the present invention will be described with reference to FIGS. 1 to 5. Note that the following embodiments show one aspect of the present invention, do not limit this invention, and can be arbitrarily changed within the scope of the technical idea of the present invention. Also, in the following drawings, in order to make each configuration easy to understand, the actual structure, the scale, the number, etc. in each structure are made different.

[0011] [First Embodiment] FIG. 1 is a front view showing a first embodiment of the packaging container 1. The packaging container 1 of the first embodiment is a pouch 1A.

[0012] As shown in FIG. 1, the pouch 1A includes a container body 10 and a pouring portion 14. The container body 10 includes a storage chamber 12 for storing the contents.

[0013] The contents include a liquid composition selected from kitchen detergents, laundry detergents, fabric softeners, bleaches, and cosmetics. Examples of the liquid composition stored in the storage chamber 12 include a liquid detergent composition, a liquid fabric softener composition, a liquid bleach composition, a liquid toothpaste composition, a mouthwash composition, a liquid disinfectant composition, and a liquid seasoning. Examples of the liquid detergent composition include a liquid laundry detergent composition, a liquid bathroom detergent composition, a liquid toilet detergent composition, and a liquid dishwashing detergent composition. Among these, a liquid detergent composition, a liquid fabric softener composition, a liquid toothpaste composition, and a mouthwash composition, and a liquid bathroom detergent composition are preferable.

[0014] The container body 10 is substantially rectangular, and the corner portion on the side where the pouring portion 14 is provided at the upper part thereof is narrowed in the width direction (the left - right direction in FIG. 1), and the width of the upper part of the container body 10 is narrower than the width of the bottom part. And the pouring portion 14 is formed to protrude obliquely upward from the side end of the narrow - width portion at the upper part of the container body 10.

[0015] The pouring part 14 protrudes from the container body 10. At the tip of the pouring part 14, a half-cut line 16 is formed in a direction intersecting the outflow direction of the content for the purpose of improving the unsealing property and regulating the unsealing direction. By cutting off the tip of the pouring part 14 along the half-cut line (inclined easy-opening line) 16 to open it, an opening can be formed at the tip of the pouring part 14.

[0016] Examples of the half-cut line 16 include those formed by a method of partially removing the surface of a flexible film by laser light irradiation. An example of the laser is a CO2 laser. The half-cut line 16 may be one or a plurality. Further, it is preferable that notches are formed at the ends of the half-cut line 16 at the start positions of unsealing. Examples of the shape of the notches include a semi-circular shape, an I-shaped shape, a V-shaped shape, etc.

[0017] The container body 10 and the pouring part 14 are integrally formed by laminating at least two laminates 30 and sealing their peripheries. Specifically, the front-side flexible film 31 and the back-side flexible film 32 that constitute the side wall of the container body 10 and the pouring part 14, and one bottom-surface flexible film 33 that constitutes the bottom wall of the container body 10 are overlapped, and their peripheries are heat-sealed inseparably to be integrally formed.

[0018] Heat-bonding parts 7 and 8 are formed on both sides in the width direction of the front-side flexible film 31 and the back-side flexible film 32. A heat-bonding part 13 is formed on the bottom side of the front-side flexible film 31 and the back-side flexible film 32. The upper ends of the front-side flexible film 31 and the back-side flexible film 32 are open for filling the content, and after the content is filled inside, they are heat-sealed in the same way as the other parts.

[0019] The bottom-surface flexible film 33 is folded in half, and the folded part 33a is arranged to face the inside of the pouch 1A. In this way, the pouch 1A is a self-standing standing pouch because the bottom-surface flexible film 33 is pushed and spread downward by the weight of the content.

[0020] As an example, the front-side flexible film 31 and the back-side flexible film 32 may be a multilayer laminate film having at least an outer layer and an inner layer.

[0021] The film F is not particularly limited, and known films can be used. Specifically, for example, a multilayer laminate film composed of an outer layer made of biaxially stretched polyester film, biaxially stretched polyamide film, or stretched nylon (hereinafter abbreviated as ONY), and an inner layer made of a heat-sealable resin such as low-density polyethylene, high-density polyethylene, linear low-density polyethylene (hereinafter abbreviated as LLDPE), polypropylene, or metallocene polyethylene is used. Further, if necessary, a film obtained by vapor-depositing an ethylene-vinyl alcohol copolymer, an aluminum foil, an inorganic substance such as silicon oxide (for example, aluminum vapor-deposited polyethylene terephthalate: hereinafter abbreviated as aluminum vapor-deposited PET), or the like, or a gas barrier film laminated with such a film is also used. For these, environmental materials obtained by recovering and processing the peeled film, or polyethylene recycled by other mechanical recycling or chemical recycling may be used.

[0022] The flexible film in the body portion of the container body is preferably composed of 2 to 4 layers containing polyethylene. When the flexible film has 2 layers, the peeling time can be shortened. By making the flexible film 3 to 4 layers, the standing property and storage stability can be improved. If the flexible film exceeds 4 layers, the cost will increase, which is not preferable. By making the flexible film 2 to 4 layers, cost reduction can be contributed. By making the flexible film 4 layers, the effect of suppressing bending can be enhanced.

[0023] As an example of the layer structure of the 2-layer laminate film, stretched nylon (ONY) / linear low-density polyethylene (LLDPE) is exemplified.

[0024] As the layer structure of the three-layer laminate film, ONY / vapor-deposited aluminum PET / LLDPE, PET / ONY / LLDPE, ONY / aluminum / LLDPE, PET / PET / LLDPE, and PET / vapor-deposited aluminum PET / LLDPE are preferred, and ONY / vapor-deposited aluminum PET / LLDPE, PET / ONY / LLDPE, and ONY / PET / LLDPE are more preferred. As the layer structure of the four-layer laminate film, PET / vapor-deposited aluminum PET / ONY / LLDPE, PET / aluminum / ONY / LLDPE, PET / PET / ONY / LLDPE, ONY / vapor-deposited aluminum PET / ONY / LLDPE, ONY / aluminum / ONY / LLDPE, ONY / PET / ONY / LLDPE, ONY / vapor-deposited aluminum PET / PET / LLDPE, ONY / aluminum / PET / LLDPE, and ONY / PET / PET / LLDPE are preferred, and PET / vapor-deposited aluminum PET / ONY / LLDPE, PET / aluminum / ONY / LLDPE, PET / PET / ONY / LLDPE, ONY / vapor-deposited aluminum PET / ONY / LLDPE, ONY / aluminum / ONY / LLDPE, and ONY / PET / ONY / LLDPE are more preferred.

[0025] Note that the layer structure is described in order from the outer layer. That is, in the case of "ONY / vapor-deposited aluminum PET / LLDPE", the outer layer is ONY, the inner layer is LLDPE, and the intermediate layer between the outer layer and the inner layer is vapor-deposited aluminum PET.

[0026] The thickness of each layer of the multilayer laminate film is determined in consideration of the internal volume of the container body 10, the composition of the liquid composition to be contained, and the like. It is preferable that the thickness of the outer layer is 10 to 30 μm, the thickness of the intermediate layer is 10 to 30 μm, and the thickness of the inner layer is 80 to 200 μm. The total thickness of the multilayer laminate film (overall thickness) is preferably 140 to 240 μm, and more preferably 160 to 240 μm.

[0027] The above laminate 30 is formed by laminating an adhesive layer made of a laminate adhesive having releasability from a multilayer laminate film between at least two films F. Hereinafter, the laminate may be referred to as a composite film. In the laminate 30 of the present embodiment, the adhesive exhibits excellent releasability with an alkaline aqueous solution, and the adhesive layer can be detached from the film F. The alkaline aqueous solution is not particularly limited, but is preferably an aqueous solution containing at least one selected from the group consisting of sodium hydroxide and potassium hydroxide. For example, an aqueous solution having a temperature of 25 to 120°C and a concentration of 0.5 to 20% by mass is used. The alkaline aqueous solution may contain components such as a surfactant, an antifoaming agent, and a compatibilizing agent from the viewpoints of improving separation recoverability and compatibility when used as a recycled material. In addition, the laminate 30 of the present embodiment can be suitably used for pouches for refilling detergents, chemicals, etc., and can also be used for food packaging pouches because it also has retort suitability.

[0028] The laminate adhesive having releasability from the composite film contains a polyester polyol and a polyisocyanate, and the solid content acid value of the adhesive is 5 mgKOH / g or more. Since the adhesive is a combination of a polyester polyol and a polyisocyanate and has a specific solid content acid value, it has the effect of achieving both excellent resistance to contents and alkali releasability. Hereinafter, the adhesive will be described in detail.

[0029] <Polyester polyol> The polyester polyol can be selected from conventionally known polyester polyols, and may be used alone or in combination of two or more. The polyester polyol component (A) is not limited to the following, but for example, polycarboxylic acids such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, phthalic anhydride, adipic acid, azelaic acid, sebacic acid, succinic acid, glutaric acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, itaconic anhydride, etc., or their dialkyl esters or their mixtures (hereinafter also referred to as carboxy group components), and for example, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, butylene glycol, neopentyl glycol, dineopentyl glycol, trimethylolpropane, glycerin, 1,6 - hexanediol, 1,4 - butanediol, 1,4 - cyclohexanedimethanol, 3 - methyl - 1,5 - pentanediol, 3,3′ - dimethylolheptane, 1,9 - nonanediol, polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol, polyether polyol, polycarbonate polyol, polyolefin polyol, acrylic polyol, polyurethane polyol, etc., or their mixtures (hereinafter also referred to as hydroxyl group components), are reacted to obtain a polyester polyol; or polyester polyols obtained by ring - opening polymerization of lactones such as polycaprolactone, polyvalerolactone, poly(β - methyl - γ - valerolactone), etc. can be mentioned. Two or more kinds of the above - mentioned carboxy group components and hydroxyl group components may be used in combination.

[0030] The above - mentioned polyester polyol may be a polyester polyurethane polyol obtained by reacting with diisocyanate, or may be further reacted with an acid anhydride. Examples of the diisocyanate include 2,4 - tolylene diisocyanate, 2,6 - tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, 1,5 - naphthalene diisocyanate, hexamethylene diisocyanate, hydrogenated diphenylmethane diisocyanate, etc. Examples of the acid anhydride include trimellitic anhydride and trimellitate ester anhydride. Examples of the trimellitate ester anhydride include ethylene glycol anhydrotellurate.

[0031] The polyester polyol preferably has an acid value. The solid content acid value of the polyester polyol is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more. Also, the solid content acid value of the polyester polyol is preferably 100 mgKOH / g or less, more preferably 70 mgKOH / g or less. By having the above acid value, in a laminate in which an adhesive layer made of a laminate adhesive is laminated between two films F, when contacted with an alkaline aqueous solution, the alkaline aqueous solution penetrates and decomposes, exhibiting excellent composite film peelability. When the adhesive contains a plurality of polyester polyols, the solid content acid value of the polyester polyol can be determined from the solid content acid value and mass ratio of each polyester polyol.

[0032] The above polyester polyol can contain a polyester polyol having a number average molecular weight (Mn) of 3,000 or more and 25,000 or less. When the number average molecular weight is 3,000 or more, the coatability and content resistance are improved. When it is 25,000 or less, the coatability and releasability are improved. The number average molecular weight of the polyester polyol is preferably 5,000 or more, more preferably 7,000 or more. Also, it is preferably 20,000 or less, more preferably 15,000 or less.

[0033] From the viewpoints of substrate adhesion and coatability, the polyester polyol may contain a polyester polyol having a number average molecular weight of less than 3,000. From the viewpoint of resistance to contents properties, the content of the polyester polyol having a number average molecular weight of less than 3,000 is preferably 0 to 40% by mass, more preferably 0 to 30% by mass, based on the total mass of the polyester polyol. That is, the content of the polyester polyol having a number average molecular weight of less than 3,000 may be preferably 40% by mass or less, more preferably 30% by mass or less, based on the total mass of the polyester polyol. In one embodiment, the blending amount may be 0% by mass.

[0034] [Other polyols] The adhesive of the present embodiment may contain a polyol other than the polyester polyol (hereinafter referred to as other polyol) as long as the effects of the present invention are not impaired. Examples of such other polyols include polycarbonate polyol, polycaprolactone polyol, polyether polyol, polyolefin polyol, acrylic polyol, silicone polyol, castor oil-based polyol, and fluorine-based polyol.

[0035] [Polyisocyanate] Polyisocyanate is a compound having two or more isocyanate groups in one molecule. Examples of polyisocyanate include aromatic polyisocyanate, aliphatic polyisocyanate, and araliphatic polyisocyanate. The above polyisocyanate may be used alone or in combination of two or more.

[0036] Examples of the aromatic polyisocyanate include aromatic diisocyanates such as diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, phenylene diisocyanate, toluene diisocyanate, naphthalene diisocyanate; polyisocyanates such as allophanate type, nurate type, biuret type, adduct type derivatives derived from the above diisocyanates, or their composites (for example, polymethylene polyphenyl polyisocyanate).

[0037] Examples of the aliphatic polyisocyanate include acyclic aliphatic diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate; alicyclic diisocyanates such as 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate; polyisocyanates such as allophanate type, nurate type, biuret type, adduct type derivatives derived from the above diisocyanates, or their composites. Preferably, the derivatives are of nurate type and adduct type. As the aliphatic polyisocyanate, polyisocyanates derived from hexamethylene diisocyanate, which can easily ensure the balance between desorbability and laminate physical properties, are preferred.

[0038] Examples of the araliphatic polyisocyanate include araliphatic diisocyanates such as 1,3- or 1,4-xylylene diisocyanate or its mixture, ω,ω'-diisocyanate-1,4-diethylbenzene, 1,3- or 1,4-bis(1-isocyanate-1-methylethyl)benzene or its mixture; polyisocyanates such as allophanate type, nurate type, biuret type, adduct type derivatives derived from the above diisocyanates, or their composites.

[0039] The polyisocyanate preferably contains at least one selected from the group consisting of aliphatic polyisocyanates and araliphatic polyisocyanates from the viewpoint of releasability.

[0040] The blending amount of the polyisocyanate may be adjusted so that the ratio (NCO / OH) of the total number of isocyanate groups in the polyisocyanate to the total number of hydroxyl groups in the polyester polyol is 0.3 to 10.0. The above ratio (NCO / OH) is preferably 0.3 to 7.0, more preferably 0.5 to 5.0.

[0041] <Compound having an acidic group> From the viewpoint of improving releasability, the adhesive may contain a compound having an acidic group (excluding polyester polyol). As the compound having an acidic group, for example, a resin having an acidic group or a low molecular weight compound having an acidic group can be used. The addition amount is preferably 1% by mass to 70% by mass, more preferably 2% by mass to 60% by mass, based on the solid content of the adhesive.

[0042] In the resin having an acidic group, "resin" means a compound having a weight average molecular weight of 1,000 or more. Examples of the resin having an acidic group include cellulose-based resins, urethane resins, polyamide resins, vinyl chloride / vinyl acetate copolymers, ketone resins, polyester resins, and (meth)acrylic resins. Examples of the above acidic group include carboxy group, phosphoric acid group, sulfo group, sulfino group or their esters or salts. As the resin having an acidic group, for example, rosin-modified resins having an acid value such as maleated rosin and fumarated rosin can be used. In addition, radical copolymers such as styrene-(meth)acrylic resins, styrene-(anhydrous)maleic acid resins, terpene-(anhydrous)maleic acid resins, etc., obtained by copolymerizing polymerizable monomers having acidic groups such as polymerizable monomers having carboxy groups such as itaconic acid, maleic acid, fumaric acid, cinnamic acid; polymerizable monomers that are acid anhydrides such as itaconic anhydride, maleic anhydride; polymerizable monomers having sulfonic acid groups such as sulfonated styrene; polymerizable monomers having sulfonamide groups such as vinylbenzenesulfonamide; and acid-modified polyolefin resins can be used.

[0043] The low molecular weight compound having an acidic group refers to a compound having a molecular weight of less than 1,000. Examples of such compounds include saturated fatty acids such as lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid; unsaturated fatty acids such as oleic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid, docosahexaenoic acid, sorbic acid; hydroxy acids such as lactic acid, malic acid, citric acid; aromatic carboxylic acids such as benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, gallic acid, mellitic acid, cinnamic acid; dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, maleic acid; tricarboxylic acids such as aconitic acid; oxocarboxylic acids such as pyruvic acid, oxaloacetic acid; carboxylic acid derivatives such as amino acids, nitrocarboxylic acids; and acid anhydrides such as trimellitic anhydride, pyromellitic anhydride.

[0044] <Manufacture of Adhesive> The adhesive of this embodiment can be manufactured by arbitrarily mixing an organic solvent, other components, etc. in addition to polyester polyol and polyisocyanate.

[0045] [Organic Solvent] The adhesive may be either a solvent-based or solventless type, and may contain an organic solvent as necessary. The organic solvent can dissolve the above-mentioned polyester polyol and polyisocyanate, and those that are inert to the polyisocyanate are preferably used. Examples of such organic solvents include ester solvents such as ethyl acetate and n-butyl acetate; ketone solvents such as methyl ethyl ketone; and aromatic hydrocarbon solvents such as toluene and xylene, which can be appropriately selected and used.

[0046] [Other components] (Silane coupling agent) In order to enhance the resistance to the contents, the adhesive can further contain a silane coupling agent. Examples of the silane coupling agent include trialkoxysilanes having a vinyl group such as vinyltrimethoxysilane and vinyltriethoxysilane; trialkoxysilanes having an amino group such as 3-aminopropyltriethoxysilane and N-(2-aminoethyl)-3-aminopropyltrimethoxysilane; trialkoxysilanes having a glycidyl group such as 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 3-glycidoxypropyltriethoxysilane. The blending amount of the silane coupling agent is preferably 0.1 to 5.0% by mass, more preferably 0.5 to 3.0% by mass, based on the solid content of the adhesive.

[0047] (Phosphorus oxyacid or its derivative) In order to enhance the acid resistance, the adhesive can further contain an oxyacid of phosphorus or its derivative. The oxyacid of phosphorus may be any one having at least one free oxyacid, for example, phosphoric acids such as hypophosphorous acid, phosphorous acid, orthophosphoric acid, and metaphosphoric acid; condensed phosphoric acids such as metaphosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, polyphosphoric acid, and ultraphosphoric acid; Examples thereof include. As derivatives of the oxyacid of phosphorus, for example, those partially esterified with alcohols in a state where at least one free oxyacid of the above oxyacid of phosphorus remains are mentioned. Examples of the alcohol include aliphatic alcohols such as methanol, ethanol, ethylene glycol, and glycerin; aromatic alcohols such as phenol, xylenol, hydroquinone, catechol, and phloroglucinol; Two or more kinds of the oxyacid of phosphorus or its derivative may be used in combination. The blending amount of the oxyacid of phosphorus or its derivative is preferably 0.01 to 10.0% by mass, more preferably 0.05 to 5% by mass, and still more preferably 0.1 to 1.0% by mass based on the solid content of the adhesive.

[0048] (Leveling agent or defoaming agent) In order to improve the appearance of the laminate, the adhesive can further contain a leveling agent or a defoaming agent. Examples of the leveling agent include polyether-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane, aralkyl-modified polymethylalkylsiloxane, polyester-modified hydroxyl group-containing polydimethylsiloxane, polyether ester-modified hydroxyl group-containing polydimethylsiloxane, acrylic copolymer, methacrylic copolymer, polyether-modified polymethylalkylsiloxane, alkyl acrylate copolymer, alkyl methacrylate copolymer, and lecithin. Examples of the defoaming agent include silicone resin, silicone solution, and copolymers of alkyl vinyl ether, alkyl acrylate, and alkyl methacrylate.

[0049] The adhesive may further contain additives such as antioxidants, ultraviolet absorbers, hydrolysis inhibitors, fungicides, thickeners, plasticizers, pigments, fillers, and catalysts for adjusting the curing reaction.

[0050] <Solid content acid value of the adhesive> The adhesive is a two-component curable urethane-based laminate adhesive containing polyester polyol and polyisocyanate. The solid content acid value immediately after compounding is 5 mgKOH / g or more, more preferably 7 mgKOH / g or more, and particularly preferably 10 mgKOH / g or more. Also, the solid content acid value immediately after compounding of the adhesive of the present invention is preferably 100 mgKOH / g or less, more preferably 70 mgKOH / g or less. The solid content acid value of the adhesive can be determined from the solid content acid value of each component and its mass ratio.

[0051] [Viscosity of the adhesive] The viscosity of the adhesive is preferably 100 to 10,000 mPa·s at 10 to 150°C, more preferably 100 to 10,000 mPa·s at 10 to 100°C. When it is 100 to 5,000 mPa·s at 10 to 100°C, it can be used as a solvent-free type. If the viscosity of the adhesive is higher than the above range, it may be diluted with an organic solvent.

[0052] As a method for producing the above laminate 30, for example, in the case of a three-layer structure of ONY / aluminum vapor-deposited PET / LLDPE, a diluted printing ink composition is printed on the entire surface of an ONY film (thickness 15 μm) using a gravure printing machine equipped with a gravure plate with a plate depth of 30 μm, and then dried at 50°C to obtain an ONY / printed ink layer. Next, an adhesive solution is applied and dried on the printed ink layer using a dry laminator, and then laminated with aluminum vapor-deposited PET (thickness 12 μm) to obtain an intermediate laminate. Further, an adhesive solution is similarly applied to the aluminum vapor-deposited PET surface of the intermediate laminate, the solvent is diffused, and then the coated surface is laminated with an LLDPE film (150 μm) and kept warm at 40°C for 4 days to obtain a three-layer laminate 30. The coating amount after drying of the adhesive can be appropriately selected according to the application, and is usually 1 to 10 g / m2 within the range of, preferably, a solvent-free type of 1.0 to 2.5 g / m 2 and a solvent type of 1.0 to 6 g / m 2 in the range. Also, the thickness of the adhesive layer is usually in the range of 1 to 6 μm, preferably, 1.0 to 2.5 μm for the solvent-free type and 1 to 6 μm for the solvent type.

[0053] The above container body 10 is manufactured according to a conventionally known method for manufacturing a standing pouch. For example, the front-side flexible film 31 and the back-side flexible film 32 are overlapped, and the bottom surface flexible film 33 for forming the bottom is folded between the two films, and the peripheral edges of the overlapped films are sealed to form a seal portion other than the top seal portion, whereby the pouch 1A can be obtained.

[0054] In the packaging container 1 of the present embodiment, since it has the film F laminated using a peelable adhesive having a solid acid value of 5 mgKOH / g or more, when it is brought into contact with an aqueous alkaline solution, the adhesive is decomposed by the penetration of the aqueous alkaline solution. Therefore, in the packaging container 1 of the present embodiment, it is also possible to easily peel the film F even for the refill pouch 1A formed of the film F in which the laminate 30 is laminated in multiple layers. As a result, in the packaging container 1 of the present embodiment, it is possible to achieve both a reduction in the resin amount and easy recyclability, and since it is not necessary to limit the contents, the versatility can be increased.

[0055] [Second Embodiment] Next, a second embodiment of the packaging container 1 will be described with reference to FIG. 2. In this figure, the same elements as those in the first embodiment shown in FIG. 1 are denoted by the same reference numerals, and the description thereof will be omitted.

[0056] FIG. 2 is a front view showing a second embodiment of the packaging container 1. As shown in FIG. 2, the packaging container 1 of the second embodiment is a standing pouch 1B in which the spout 20 protrudes from the container body 10.

[0057] At the upper end of the container body 10, a linear corner cut 18 is formed. The spout 20 is provided at the corner cut 18. The base end of the spout 20 is located at the corner cut 18, and the tip of the spout 20 protrudes from the pouch body 10.

[0058] The spout 20 is, for example, a molded body of a polyolefin resin such as polyethylene or polypropylene. The inner diameter of the spout 20 is appropriately determined according to the physical properties (for example, viscosity) of the liquid composition to be accommodated, and is, for example, 8.5 to 21.0 mm.

[0059] In the standing pouch 1B, the laminate 30 is, as an example, a three-layer structure of an outer flexible film 31 and an inner flexible film 32 of ONY / aluminum vapor-deposited PET / LLDPE. In the standing pouch 1B, the laminate 30 is, as an example, a two-layer structure of ONY / LLDPE. The laminate 30 is laminated using the above-described easily peelable adhesive.

[0060] The above standing pouch 1B is manufactured according to a conventionally known method for manufacturing a standing pouch. For example, the outer flexible film 31 and the inner flexible film 32 are overlapped, a flexible film 33 for the bottom surface forming the bottom is folded between the two films, and the spout 20 is sandwiched between the two films at the corner cut 18, and the periphery of the overlapped films is sealed to form a seal portion other than the top seal portion, whereby the standing pouch 1B can be obtained.

[0061] In the packaging container 1 of the present embodiment, the standing pouch 1B also has the same operations and effects as those of the first embodiment.

[0062] [Third Embodiment] Next, a third embodiment of the packaging container 1 will be described with reference to FIG. 3. In this figure, the same elements as those in the second embodiment shown in FIG. 2 are denoted by the same reference numerals, and the description thereof is omitted.

[0063] FIG. 3 is a perspective view showing a third embodiment of the packaging container 1. As shown in FIG. 3, the packaging container 1 of the third embodiment is a pouch 1C with a top surface, in which the container body 10 has a top surface.

[0064] The container body 10 in the pouch 1C with a top surface has a bottom flexible film 33 and a top flexible film 34, and is in the shape of a rectangular parallelepiped extending in the vertical direction. A spout 20 protruding upward is provided on the top flexible film 34. The laminate 30 in the pouch 1C with a top surface is laminated using the above-described easily peelable adhesive.

[0065] The pouch 1C with a top surface is formed with a side seal portion 61 by joining the opposing inner side edge portions (the side edge portions of the opposing inner resin film layers) of the front-side flexible film 31 and the back-side flexible film 32. Further, the peripheral edge portions on the inner side of the front-side flexible film 31 and the top flexible film 34 are joined, and the inner resin film layer of the laminate 30 is formed into a packaging container having a front surface, a back surface, a bottom surface, and a top surface by being made into a bag so as to surround the storage chamber 12 for storing the contents. And a skirt portion 62 is formed on the lower side of the side seal portion 61, and a bottom gusset portion is provided in which the region including the bottom flexible film 33 has a gusset structure. Further, on the top surface side of the pouch 1C with a top surface, a top gusset portion is provided in which the region including the top flexible film 34 has a gusset structure. Furthermore, a spout 20 having a plug structure capable of storing and discharging the contents and capable of being repeatedly opened and closed is provided in this top gusset portion.

[0066] In the packaging container 1 of the present embodiment, the pouch 1C with a top surface also has the same operations and effects as those of the second embodiment.

[0067] [Fourth Embodiment] Next, a fourth embodiment of the packaging container 1 will be described with reference to FIG. 4. In this figure, the same elements as those in the first embodiment shown in FIG. 1 are denoted by the same reference numerals, and the description thereof will be omitted.

[0068] Figure 4 is a perspective view showing a fourth embodiment of the packaging container 1. As shown in FIG. 4, the packaging container 1 of the fourth embodiment is a pillow-type container 1D in which the contents are packaged in a pillow shape.

[0069] The pillow-type container 1D is formed by forming a seal portion 35A in a state where one flexible film 35, which is a laminate 30, is made into a tube shape with the backs facing each other on the back side, and sealing and cutting an end portion 35B at a prescribed length. In the laminate 30 of the pillow-type container 1D, the film F is laminated using the above-described easily peelable adhesive.

[0070] In the packaging container 1 of the present embodiment, the same operations and effects as those of the first embodiment can also be obtained for the pillow-type container 1D.

[0071] [Fifth Embodiment] Next, a fifth embodiment of the packaging container 1 will be described with reference to FIG. 5. In this figure, the same elements as those in the first embodiment shown in FIG. 1 are denoted by the same reference numerals, and the description thereof is omitted.

[0072] FIG. 5 is a perspective view showing a fifth embodiment of the packaging container 1. As shown in FIG. 5, the packaging container 1 of the fifth embodiment is a tube-type container 1E formed in a tube shape.

[0073] The tube-type container 1E has a body portion 41 and a head portion 42. The head portion 42 includes a shoulder portion 43 connected to one end of the body portion 41 and a spout portion 44 connected to the shoulder portion 43. In one embodiment, the spout portion 44 includes a screw thread 45 for screwing on a cap.

[0074] In one embodiment, the head 42 is made of a resin composition containing polyethylene and polypropylene. Examples of the polyethylene include high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear low-density polyethylene, and ultra-low-density polyethylene. Among these, high-density polyethylene is preferred from the viewpoints of shape retention and moldability. As the polyethylene, biomass polyethylene, or mechanically recycled or chemically recycled polyethylene may be used. The above resin composition may contain the above additives.

[0075] The head 42 can be manufactured by a conventionally known method. For example, the head 42 can be manufactured by a compression molding method (compression molding method) or an injection molding method (injection molding method) and joined to the body 41.

[0076] When manufacturing the tubular container body 10 using the compression molding method (compression molding method), after attaching the body 41 to a male mold having a convex portion at the upper part, the male mold and the female mold are opposed to each other, and the molten resin composition is supplied into the male and female molds, compression molded to form the head 42, and the head 42 is joined to one opening of the body 41, whereby a tubular container body 10 including the head 42 and the body 41 can be manufactured. When manufacturing the tubular container body 10 using the injection molding method (injection molding method), after attaching the body 41 to a male mold having a convex portion at the upper part, the male mold and the female mold are opposed to each other, the molten resin composition is supplied from the gate, injection molded to form the head 42, and the head 42 is joined to one opening of the body 41, whereby a tubular container body 10 including the head 42 and the body 41 can be manufactured.

[0077] The body portion 41 is connected to the shoulder portion 43 of the head portion 42. The body portion 41 is formed, for example, by overlapping one end and the other end of the flexible film 36 of the laminate 30 of the present disclosure so that they contact each other, rolling them up into a cylindrical shape, and heat-sealing the overlapped portion 36A, and includes a welded portion formed thereby. The body portion 41 includes, for example, a bottom seal portion 36B formed by heat-sealing the opening of the laminate 30 rolled up into a cylindrical shape. In the laminate 30 of the tube-shaped container 1E, the film F is laminated using the above-described easily peelable adhesive. Examples of the heat-sealing method include conventionally known methods such as bar sealing, rotary roll sealing, belt sealing, impulse sealing, high-frequency sealing, ultrasonic sealing, and flame sealing.

[0078] In the packaging container 1 of the present embodiment, the same operations and effects as those of the first embodiment can also be obtained for the tube-shaped container 1E.

Examples

[0079] Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following description.

[0080] (Examples 1 to 24, Comparative Examples 1 to 2) In this example, samples of packaging containers of Examples 1 to 24 and Comparative Examples 1 to 2 were produced according to the specifications shown in [Table 1] and [Table 2] below. The samples of the packaging containers were the pouch [1] of the first embodiment without the spout described with reference to FIG. 1 and the pouch [2] (standing pouch) of the second embodiment with the spout described with reference to FIG. 2.

[0081] The pouch [1] had the following specifications. Width: 120 mm, height 230 mm, bottom fold width 35 mm. Body configuration: Two-layer configuration of ONY (thickness 15 μm) / / LLDPE (thickness 130 μm). Bottom configuration: Two-layer configuration of ONY (thickness 15 μm) / / LLDPE (thickness 130 μm). Mouth part: Without spout. Content volume: 350 mL. Side seal width: 5 mm.

[0082] The pouch [2] (standing pouch) has the following specifications. Width: 200 mm, height 340 mm, bottom fold-in width 60 mm. Body structure: A three-layer structure of ONY (thickness 15 μm) / aluminum-deposited PET (thickness 12 μm) / / LLDPE (thickness 150 μm). Bottom structure: A two-layer structure of ONY (thickness 25 μm) / / LLDPE (thickness 150 μm). Mouth part: With a spout. Content volume: 1200 mL. Side seal width: 5 mm. The " / / " indicating the layer interface in the above layer structure is an adhesion by an easily peelable adhesive described later, and " / " indicates an adhesion by a normal adhesive (TM-265L / CAT-RT37 (manufactured by Toyo Morton)).

[0083] In the above configuration, ONY has a white ink layer (thickness 1.5 μm) on the entire surface on the content side. The white ink layer was formed by a gravure printing method using Liorealfa R681 white (manufactured by Toyo Ink Co., Ltd.). The easily peelable adhesive layer and the normal adhesive layer have a thickness of 3.5 μm and were formed by a dry lamination method.

[0084] <Production of polyol> (Polyol a) Into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen gas inlet tube, 345 parts of isophthalic acid, 248 parts of adipic acid, 152 parts of ethylene glycol, and 255 parts of neopentyl glycol were charged, and the temperature was raised to 250 °C with stirring under a nitrogen stream to carry out an esterification reaction. A predetermined amount of water was distilled off, and the reaction was continued until the acid value reached 5 or less. Then, the pressure was gradually reduced, and a deglycolization reaction was carried out at 1 mmHg or less for 5 hours to obtain a polyester polyol. 38 parts of trimellitic anhydride was added to this polyester polyol, and the mixture was reacted at 180 °C for about 2 hours. Then, it was diluted with ethyl acetate until the non-volatile content reached 50% to obtain a solution of polyol a having a number average molecular weight (Mn) of 2,600 and a solid content acid value of 21.7 mgKOH / g.

[0085] The carboxyl group component and the hydroxyl group component were charged so that the product had the composition shown in the following [Table 3], and a solution of polyols b to e was obtained in the same manner as polyol a except that the pressure and time of the esterification reaction were changed, and the non-volatile content was adjusted to 50%. Unless otherwise specified, "parts" and "%" represent "parts by mass" and "mass %" as the pure components of each component.

[0086] (Polyol f) 90 parts of P-2000 (manufactured by ADEKA, bifunctional polyoxypropylene glycol, hydroxyl value 56.3), 418 parts of P-400 (manufactured by ADEKA, bifunctional polyoxypropylene glycol, hydroxyl value 265.7), 90 parts of T-400 (manufactured by Mitsui Chemicals, trifunctional polyoxypropylene glycol, hydroxyl value 404.0), 21 parts of dimethylolpropionic acid, 145 parts of ethyl acetate, 104 parts of tolylene diisocyanate, 132 parts of 4,4-diphenylmethane diisocyanate, and 0.24 part of dibutyltin laurate were charged, the temperature was raised to 90 °C, and the reaction was carried out until the peak of the isocyanate group disappeared in the infrared absorption spectrum. Then, it was diluted with ethyl acetate until the non-volatile content reached 50% to obtain a solution of polyol f, which is a polyether polyol having a number average molecular weight (Mn) of 9,000 and a solid content acid value of 10.2 mgKOH / g.

[0087] <Molecular Weight and Molecular Weight Distribution> The number average molecular weight (Mn) was measured by GPC (gel permeation chromatography) and determined as the converted molecular weight using polystyrene as the standard substance. The measurement conditions are shown below. GPC apparatus: Shodex GPC-104 manufactured by Showa Denko KK Columns: The following columns were connected in series and used. Two Shodex LF-404 manufactured by Showa Denko KK Shodex LF-G manufactured by Showa Denko KK Detector: RI (differential refractometer) Measurement conditions: Column temperature 40 °C Eluent: Tetrahydrofuran Flow rate: 0.3 mL / min

[0088] <Acid Value> The acid value was measured according to the method described in JIS K 0070 (1992). For the acid value of polyols and compounds having acidic groups, after removing the solvent, it was measured according to JIS K 0070 (1992).

[0089] <Production of Polyisocyanate> (Aliphatic A) The biuret type polyisocyanate derived from Coronate 2785 (hexamethylene diisocyanate (hereinafter, HDI), manufactured by Tosoh Corporation) was diluted with ethyl acetate to adjust to a non-volatile content of 50% and NCO% = 9.6% to obtain an aliphatic A polyisocyanate solution. Note that NCO% is the mass% of isocyanate groups contained in the polyisocyanate compound.

[0090] (Aliphatic B) VESTANAT T1890 / 100 (nurate type polyisocyanate derived from isophorone diisocyanate (hereinafter, IPDI), manufactured by Evonik Corporation) was diluted with ethyl acetate to adjust to a non-volatile content of 50% and NCO% = 8.7% to obtain an aliphatic B polyisocyanate solution.

[0091] (Aryl Aliphatic) Takenate D-110NB (a trimethylolpropane adduct type polyisocyanate derived from xylylene diisocyanate (hereinafter referred to as XDI), manufactured by Mitsui Chemicals) was diluted with ethyl acetate to adjust to a non-volatile content of 50% and NCO% = 7.9% to obtain an aromatic aliphatic polyisocyanate solution.

[0092] (Aromatic) Takenate D-103H (a trimethylolpropane adduct type polyisocyanate derived from toluene diisocyanate (hereinafter referred to as TDI), manufactured by Mitsui Chemicals) was diluted with ethyl acetate to adjust to a non-volatile content of 50% and NCO% = 8.5% to obtain an aromatic polyisocyanate solution.

[0093] (Production of a compound having an acidic group) (Compound A) Pink Crystal KE-359 (rosin ester resin, solid content acid value 15.0 mg KOH / g, manufactured by Arakawa Chemical Industries) was diluted with ethyl acetate to obtain a solution of Compound A with a non-volatile content of 50%.

[0094] (Compound B) XIRAN (registered trademark) 1000 (styrene maleic anhydride copolymer resin, solid content acid value 475.0 mg KOH / g, manufactured by Polyscope) was diluted with ethyl acetate to obtain a solution of Compound B with a non-volatile content of 50%.

[0095] The polyol constituting the easily peelable adhesive was one having the properties produced in Production Examples a-f shown in [Table 3] below.

[0096] (Production method of easily peelable adhesive) The obtained polyol solution, polyisocyanate solution, and solution of the compound having an acidic group were blended at the ratios shown in Tables 1 and 2, and ethyl acetate was added to make the non-volatile content 30% by mass to obtain the adhesives used in Examples 1 to 24 and Comparative Examples 1 to 2.

[0097] [Evaluation method and evaluation criteria] For the samples of each example, "resistance to contents properties" and "peelability" were evaluated.

[0098] "Resistance to content properties" [Table 1] and [Table 2] each content liquid shown was filled into the samples of pouches [1] and [2], and after storage at 40°C for 1 month, visual inspection / 5 times of dropping the pouch from 1 m at room temperature / laminate strength measurement were carried out. No change in appearance, no liquid leakage, and a laminate strength of 3 N / 15 mm or more were regarded as "qualified", and if any one of them was not satisfied, it was regarded as "unqualified".

[0099] In addition, for the laminate strength, the prepared pouch was cut into a size of 15 mm, and using a tensile testing machine EZ-SX (manufactured by Shimadzu Corporation), under the conditions of a temperature of 20°C, a relative humidity of 65%, T-peel, and a peel rate of 30 cm / min, the measurement was carried out between ONY / / LLDPE for pouch [1] and between vapor-deposited aluminum PET / / LLDPE for pouch [2].

[0100] "Peelability" In this evaluation, LLDPE was evaluated as the object to be recovered. A two-layer film of ONY (thickness 15 μm) / LLDPE film (thickness 150 μm) and a three-layer film of ONY (thickness 15 μm) / vapor-deposited aluminum PET (thickness 12 μm) / LLDPE (thickness 150 μm) were produced. The produced film was cut into a size of 1.5 cm × 1.5 cm, and the cut test pieces were charged into a 2000 mL flask at 60 g, and further 1500 mL of a 2% aqueous sodium hydroxide solution was added, and stirred at 70°C and a rotation speed of 500 rpm for 3 hours. After the stirring was completed, 30 sheets of the film containing LLDPE were randomly sampled, and the thickness of the film layer was measured. From the thickness of the film layer, the number of laminated films in which LLDPE and ONY or vapor-deposited aluminum PET were not peeled off was measured and evaluated according to the following criteria. ◎ (Excellent): 0 to 1 sheet 〇 (Good): 2 to 3 sheets △ (Fair): 4 to 6 sheets × (Poor): 7 sheets or more 6 sheets or less was set as the practical range.

[0101]

Table 1

[0102] [Table 2]

[0103] [Table 3]

[0104] As shown in [Table 1] and [Table 2], in the samples of Examples 1-24 having a film laminated using an easily peelable adhesive containing a polyester polyol and a polyisocyanate and having a solid content acid value of the adhesive of 5 mgKOH / g or more, good evaluations were obtained in both "resistance to content physical properties" and "peelability" regardless of the presence or absence of a spout and the content liquid.

[0105] On the other hand, in the sample of Comparative Example 1 which contains a polyester polyol and a polyisocyanate but does not satisfy the condition that the solid content acid value of the adhesive is 5 mgKOH / g or more, a good evaluation was not obtained for "peelability".

[0106] Also, in the sample of Comparative Example 2 which satisfies the condition that the solid content acid value of the adhesive is 5 mgKOH / g or more but does not contain a polyester polyol and a polyisocyanate, good evaluations were not obtained in both "resistance to content physical properties" and "peelability". From these results, it was confirmed that by applying the present invention, the effects of the present invention can be exhibited.

[0107] As described above, the preferred embodiments according to the present invention have been described with reference to the accompanying drawings, but it goes without saying that the present invention is not limited to such examples. The various shapes, combinations, etc. of the constituent members shown in the above examples are merely examples, and various modifications can be made based on design requirements and the like without departing from the gist of the present invention.

Explanation of Reference Numerals

[0108] 1…Packaging container, 1A…Pouch, 10…Container body, F…Film

Claims

1. A packaging container having a film laminated using an easily peelable adhesive containing a polyester polyol and a polyisocyanate, wherein the solid content acid value of the adhesive is 5 mg KOH / g or more.

2. The polyisocyanate contains at least one polyisocyanate selected from the group consisting of an aliphatic polyisocyanate component and an aromatic aliphatic polyisocyanate component, The packaging container according to Claim 1.

3. The solid content acid value of the polyester polyol is 5 to 100 mg KOH / g, The packaging container according to Claim 1.

4. The easily peelable adhesive further contains a compound having an acidic group, The packaging container according to Claim 1.

5. A container body having the film, A spout protruding from the container body, having, The packaging container according to Claim 1.

6. It includes a container body having the film and containing the contents, The contents include a liquid composition selected from kitchen detergents, laundry detergents, fabric softeners, bleaches, and cosmetics. The packaging container according to any one of Claims 1 to 5.

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