JP2018052533A - Packaging material for hydrous content and manufacturing method of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a packaging material which has high slipping performance and residual prevention performance with respect to hydrous content.SOLUTION: A packaging material of this invention is a packaging material for hydrous content and it includes a base material and a heat-sealable resin film. The heat-sealable resin film contains equal to or greater than 0.1 mass% and equal to or less than 3 mass% of a hydrophilic surfactant. The heat-sealable resin is located on an inner surface of the packaging material, and the hydrophilic surfactant bleeds out to the inner surface side of the packaging material of the heat-sealable resin film.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a packaging material and a manufacturing method thereof. More specifically, the present invention relates to a packaging material capable of exhibiting high sliding performance and remaining prevention performance with respect to the water-containing contents, and a method for producing the same.

  In many product fields such as food, beverages, pharmaceuticals, and chemicals, packaging materials corresponding to their contents have been developed. In particular, as a packaging material for contents having viscous bodies such as liquids, semi-solids, and gel substances, plastic materials having excellent water resistance, oil resistance, gas barrier properties, light weight, flexibility, and design properties are used. It functions to protect the contents required for materials.

  One of the functions of the packaging material is to suppress the adhesion of the contents to the inner surface of the packaging material, that is, to have high sliding performance and residual prevention performance that can be quickly discharged without remaining inside the packaging material. ing. The contents that cannot be used up and remain in the package are discarded together with the package, but disposal of the contents is regarded as a problem from the environmental viewpoint. Such a problem becomes particularly problematic when the contents filled in the packaging material are water-containing contents.

For example, in Patent Document 1 (Japanese Patent Laid-Open No. 2005-306415), in order to prevent moisture content such as toothpaste from remaining in the packaging material, it is characterized by the type of resin used for the packaging material and its shape. A packaging material has been proposed.
However, since the releasability of the contents with respect to the package greatly affects the resin properties of the innermost layer in contact with the contents, a sufficient residual prevention effect can be obtained only by changing the shape as in the packaging material proposed in Patent Document 1. Hard to get.

In Patent Document 2 (Japanese Patent Application Laid-Open No. 2012-158373), a release agent having a low HLB and a small amount of hydroxyl groups is kneaded in the film in order to improve the ability to remove shortening and other viscous food packages. A packaging material characterized by the use of such sealant is proposed.
However, in the sealant in which a low HLB release agent is kneaded as in the packaging material proposed in Patent Document 2, when the contents are water-containing contents, the friction between the package and the sealant is increased, and the slip characteristics are reduced. However, there is concern about an increase in the remaining amount of contents.

JP 2005-306415 A JP 2012-158373 A

  This invention is made | formed in view of the said problem, The objective is to provide the packaging material which has the high sliding-off performance and the residual prevention performance with respect to the moisture content.

The packaging material according to the present invention is a packaging material for water-containing contents,
A substrate;
A heat-sealable resin film,
The heat-sealable resin film comprises 0.1% by mass or more and 3% by mass or less of a hydrophilic surfactant,
The heat-sealable resin film is located on the inner surface of the packaging material, and the hydrophilic surfactant bleeds out to the inner surface side of the packaging material of the heat-sealable resin film.

  In the above aspect, the layer comprising the hydrophilic surfactant comprises a surfactant that is solid at 0 to 85 ° C. and a surfactant that is liquid at 40 ° C. or lower as the hydrophilic surfactant.

  In the said aspect, it is preferable that a hydrophilic surfactant is a nonionic surfactant.

  It is preferable that the contact angle of water with respect to the heat-sealable resin film surface is 85 ° or less.

The method for producing the packaging material according to the present invention comprises:
Preparing a substrate;
Preparing a heat-sealable resin film;
Laminating the base material and the heat-sealable resin film to obtain a laminate,
A step of heat-sealing the laminate,
It is characterized by comprising.

  According to the packaging material of the present invention, it exhibits high sliding performance and residual prevention performance with respect to the water-containing contents, and the contents can be quickly discharged from the packaging material, and the contents remain inside the packaging material. Can be prevented.

It is the schematic cross section which showed one Embodiment of the laminated body used for manufacture of the packaging material of this invention.

<Packaging materials for water content>
The packaging material for water-containing contents according to the present invention (hereinafter sometimes simply referred to as “packaging material”) includes a base material and a heat-sealable resin film (hereinafter sometimes simply referred to as “resin film”). The resin film is produced so as to be positioned on the inner surface (content side) of the packaging material.
This packaging material can be used for packaging bags (for example, pillow bags, standing pouches, 4-way pouches), lid materials, packaging containers, and the like.

The packaging material by this invention can be obtained by heat-sealing the laminated body mentioned later. More specifically, the laminate is folded or the two laminates are overlapped so that the heat seal layers of the laminate are opposed to each other, and the peripheral end portions thereof are heat sealed (side seal type, two-side seal type, three-sided It can be manufactured by a seal type, a four-sided seal type, an envelope-attached seal type, a palm-attached seal type (pillow seal type), a pleated seal type, a flat bottom seal type, a square bottom seal type, a gusset type).
In one embodiment, the laminate can be folded in two so that the resin films face each other, and the two vertical sides and one horizontal side can be heat sealed to produce a cylindrical packaging material.
Moreover, in one embodiment, two laminated bodies are overlapped so that the heat-sealable resin films face each other, and two vertical sides and one horizontal side are heat-sealed to produce a cylindrical packaging material. it can.
Examples of the heat sealing method include known methods such as bar sealing, rotary roll sealing, belt sealing, impulse sealing, high frequency sealing, and ultrasonic sealing.

<Laminate>
The laminated body 100 used for manufacture of the packaging material of this invention is equipped with the base material 101 and the heat-sealable resin film 102 in the outermost surface, as shown in FIG.
In addition, the laminate may include layers such as a gas barrier layer, a thermoplastic resin layer (not shown), and an adhesive layer (not shown) between the base material 101 and the resin film 102.
Moreover, you may equip the surface on the opposite side to the side which provided the heat-sealable resin film 102 of the base material 101 with the printing layer.

  Lamination of the base material and the resin film can be performed by a known method such as dry lamination, non-solvent lamination, sand lamination, etc. via an adhesive.

  When laminating by dry lamination, the adhesive for dry laminating is dispersed or dissolved in a solvent, applied onto a substrate, dried, and overlaid with a resin film, and then aged at 30 to 120 ° C. for several hours to several days. Thereby, a base material and a resin film can be laminated | stacked.

  When laminating by non-solvent lamination, the adhesive is applied directly to the substrate and dried without dispersing or dissolving the non-solvent laminating adhesive in a solvent, and after the resin film is stacked, 30 to 120 ° C. By storing for several hours to several days, the substrate and the resin film can be laminated.

Examples of the adhesive that can be used for laminating the substrate and the resin film include a thermosetting type, an ultraviolet curable type, and an electron beam curable type. For example, polyvinyl acetate adhesives such as polyvinyl acetate and vinyl acetate-ethylene copolymers, polyacrylic acid adhesives made of copolymers of polyacrylic acid and polystyrene, polyester, polyvinyl acetate, and cyanoacrylate Adhesives, ethylene copolymer adhesives consisting of copolymers of ethylene and monomers such as vinyl acetate, ethyl acrylate, acrylic acid, methacrylic acid, cellulose adhesives, polyurethane adhesives, polyester adhesives, Polyamide adhesive, polyimide adhesive, polyolefin adhesive, amino resin adhesive made of urea resin or melamine resin, phenol resin adhesive, epoxy adhesive, reactive (meth) acrylic adhesive, Elastomer made of chloroprene rubber, nitrile rubber, styrene-butadiene rubber, etc. System adhesive, a silicone adhesive, an alkali metal silicate, inorganic adhesive or the like made of a low-melting glass.
In addition, the adhesive may be in any form such as aqueous type, solution type, emulsion type, dispersion type, and the property may be any form such as film / sheet shape, powder shape, solid shape, Further, the bonding mechanism may be any form such as a chemical reaction type, a solvent volatilization type, a heat melting type, and a hot pressure type.

  When the lamination is performed by the sand lamination, the thermoplastic resin heated and melted is extruded onto the base material, and the resin film can be laminated on the base material through this.

In addition to the above-described embodiment, the base material and the resin film can be laminated using an anchor coating agent.
Examples of such anchor coating agents include organic titanium-based, isocyanate-based, polyethyleneimine-based, acid-modified polyethylene-based, and polybutadiene-based anchor coating agents.

The adhesive can be applied by a known method such as roll coating, gravure roll coating, kiss coating, and the coating amount is not particularly limited, but is 0.1 g / m ² from the viewpoint of adhesiveness. It is preferable that it is 10 g / m ² or less.
In addition to the lamination of the base material and the resin film, the above-described adhesive can be used for the lamination of the base material and other layers such as a gas barrier layer.

<Base material>
The base material constituting the laminate is prepared using various materials depending on the type of contents to be packaged and the mechanical strength, chemical resistance, solvent resistance, manufacturability, etc. required in logistics. can do.
For example, polyethylene resin, polypropylene resin, cyclic polyolefin resin, fluorine resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyvinyl chloride Resins, fluorine resins, poly (meth) acrylic resins, polycarbonate resins, polyethylene terephthalate (PET), polyester resins such as polyethylene naphthalate, polyamide resins such as various nylons, polyimide resins, polyamideimide resins Various resins such as resins, polyaryl phthalate resins, silicone resins, polysulfone resins, polyphenylene sulfide resins, polyether sulfone resins, polyurethane resins, acetal resins, cellulose resins, etc. It can be made using.
In particular, in the present invention, from the viewpoint of stability to radiation and the like, a film made using a polypropylene resin, a polyester resin, or a polyamide resin is preferable.
In the present invention, the base material may be a single layer or a multilayer film formed using a film forming method such as an extrusion method, a cast molding method, a T-die method, a cutting method, or an inflation method.

  In order to improve the adhesion with a resin film or the like, it is preferable that the surface of the base material is subjected to a surface activation treatment such as a corona treatment, a flame treatment, a plasma treatment, or a flame treatment.

  The film thickness of the substrate can be appropriately determined by those skilled in the art depending on the packaging application, but is preferably 6 μm or more and 100 μm or less, more preferably 9 μm or more and 50 μm or less.

<Heat sealable resin film>
The heat-sealable resin film contains a hydrophilic surfactant in an amount of 0.1% by mass to 3% by mass. In the heat-sealable resin film, the hydrophilic surfactant bleeds out on the heat-sealable resin film. When a packaging material is prepared using such a resin film, moisture contained in the contents is attracted to the bleed-out hydrophilic surfactant, and a water film is formed between the contents and the resin film. . When the contents are discharged from the packaging material, the contents move in the packaging material so as to slide on the water film, so that the contents are quickly discharged without remaining in the packaging material.
Further, by making the content of the hydrophilic surfactant in the heat-sealable resin film within the above numerical range, the resin film has a high content with respect to the water content while maintaining the heat-sealability and productivity of the resin film. Sliding performance and remaining prevention performance can be imparted.
The heat-sealable resin film may be a single layer or a multilayer composed of a layer containing a hydrophilic surfactant.

  More preferably, the content of the surfactant in the heat-sealable resin film is 0.2% by mass or more and 2.7% by mass or less, and more preferably 0.3% by mass or more and 2.5% by mass. It is below mass%.

The hydrophilic surfactant contained in the resin film is not particularly limited as long as it can bleed out from the surface of the resin film and impart hydrophilicity to the resin film, but food, cosmetics, pharmaceuticals, etc. From the viewpoint of safety, a nonionic surfactant is preferable.
For example, sorbitan surfactants such as sorbitan monostearate, sorbitan distearate, sorbitan monopalmitate, sorbitan dipalmitate, sorbitan monobehenate, sorbitan dibehenate, sorbitan monolaurate, sorbitan dilaurate, glycerin monolaurate Rate, glycerol dilaurate, diglycerol monopalmitate, diglycerol dipalmitate, glycerol monostearate, glycerol distearate, diglycerol monostearate, diglycerol distearate, diglycerol monolaurate, diglycerol dilaurate, etc. Glycerin surfactants, polyethylene glycol surfactants such as polyethylene glycol monostearate and polyethylene glycol monopalinate, Trimethylolpropane surfactants such as rollpropane monostearate, diethanolalkylamine and diethanolalkylamide surfactants such as lauryl diethanolamine, oleyl diethanolamine, stearyl diethanolamine, lauryl diethanolamide, oleyl diethanolamide, stearyl diethanolamide, Examples include pentaerythritol surfactants such as pentaerythritol monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan distearate, mono and distearate of sorbitan-diglycerin condensate, and the like.
The resin film may contain two or more hydrophilic surfactants as described above.

  The resin film preferably contains a surfactant that is solid at 0 ° C. to 85 ° C. and a surfactant that is liquid at 40 ° C. or less as a hydrophilic surfactant. Thereby, the productivity of the resin film can be improved, and the sliding performance and the remaining prevention performance of the resin film can be maintained for a long time.

The HLB of the hydrophilic surfactant is preferably 3.5 or more and 20 or less, and preferably 4 or more and 19 or less. By setting the HLB of the hydrophilic surfactant within the above numerical range, the sliding performance of the resin film with respect to the water content can be further improved.
The HLB of the hydrophilic surfactant can be calculated by the Griffin method (that is, HLB = 20 × sum of the formula weight of the hydrophilic part / molecular weight).

The resin film can comprise a thermoplastic resin.
Examples of the thermoplastic resin include polyolefin resins such as polyethylene and polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene / vinyl alcohol copolymer, polyacrylonitrile, polyamide, acrylate ester, and methacrylate ester. Acrylic resin having a main component, polyethylene terephthalate, polybutylene terephthalate, polyester such as polyethylene naphthalate, polyacetal and the like.
The resin film may contain two or more of the above thermoplastic resins.

  The content of the thermoplastic resin in the resin film is preferably 90% by mass or more and 99.9% by mass or less, and more preferably 91% by mass or more and 99.5% by mass or less. By making content of the thermoplastic resin in a resin film into the said numerical range, the heat seal property of a resin film can be improved.

  Various additives other than the thermoplastic resin as the main component may be added to the resin film as long as the characteristics are not impaired. Examples of additives include plasticizers, UV stabilizers, anti-coloring agents, matting agents, deodorants, flame retardants, weathering agents, antistatic agents, yarn friction reducing agents, slip agents, mold release agents, An oxidizing agent, an ion exchange agent, a coloring pigment, and the like may be included.

Moreover, the contact angle of water with respect to the resin film surface is preferably 85 ° or less, and more preferably 80 ° or less.
In addition, the contact angle of water with respect to the resin film surface can be measured using a contact angle measuring device (Kyowa Interface Science Co., Ltd., trade name: Drop Mater 700).

  The film thickness of the resin film is preferably 5 μm or more, more preferably 10 μm or more and 200 μm or less from the viewpoint of film forming properties and heat sealability.

  The resin film is obtained by kneading the above-described hydrophilic surfactant, resin material, additive, and the like by a known method to obtain a mixture, heat-melting the mixture, and then extruding it by a T-die method or an inflation method. be able to.

  In one embodiment, the mixture is a so-called MB-type blending method in which a hydrophilic surfactant is dispersed in a resin material to produce a pellet-like masterbatch (MB), which is dispersed again in the resin material. Can be obtained. According to this method, the hydrophilic surfactant can be efficiently dispersed in the resin film.

When a resin film is produced by an inflation method, the melt flow rate (MFR) of the mixture is preferably 0.2 g / 10 min or more and 5 g / 10 min or less, and is 0.2 g / 10 min or more and 4 g / 10 min or less. It is more preferable. By making MFR of a mixture into the said numerical range, while being able to reduce the extrusion load at the time of extrusion molding, the mechanical strength of a resin film can be raised.
The MFR is a value measured by the method A under the conditions of a temperature of 190 ° C. and a load of 2.16 kg in the method defined in JIS K7210-1995.

  In one embodiment, the resin film can be produced by a T-die method. In this case, the resin film and the laminate can be produced in the same manner by extruding the resin film onto the substrate via an adhesive.

<Other layers>
In one embodiment, the laminate may include a gas barrier layer between the base material and the resin film.
As the gas barrier layer, a gas barrier film made of a resin such as PET, polybutylene terephthalate, polyethylene naphthalate, polyamide, polyimide, polyvinyl alcohol, ethylene / vinyl alcohol copolymer, or at least one of these gas barrier films is used. A metal foil such as a vapor deposition film or an aluminum foil provided with a vapor deposition film formed using an inorganic substance or inorganic oxide such as a silica vapor deposition film or an alumina vapor deposition film on the surface can be used.
By providing the laminate with a gas barrier layer, gas barrier properties that prevent permeation of oxygen gas, water vapor, and the like can be imparted or improved. The laminate may include two or more gas barrier layers. When two or more gas barrier layers are provided, they may have the same composition or different compositions.
Among these, a silica vapor deposition film, an alumina vapor deposition film, and an aluminum foil are preferable because of their particularly high gas barrier properties.
Moreover, by using an aluminum foil, light-shielding properties can be imparted to or improved on the laminate, whereby the contents filled in the packaging material produced using this laminate can be irradiated with light. Even if it is a medicine etc. which are easy to deteriorate by this, it can be used conveniently.
The film thickness of the gas barrier layer is preferably 5 μm or more and 30 μm or less.

In one embodiment, the laminate may include a printing layer on the surface opposite to the surface on which the resin film of the substrate is provided.
The printing layer can be formed by a printing method such as an ink jet method, a gravure printing method, an offset method, or a flexographic printing method using an ink composition containing a conventionally known dye or pigment.

In one embodiment, the laminate may include a thermoplastic resin layer between the base material and the resin film.
Examples of the resin that forms the thermoplastic resin layer include polyvinyl acetate resins such as polyvinyl acetate and vinyl acetate-ethylene copolymers, and polymers made of copolymers of polyacrylic acid and polystyrene, polyester, polyvinyl acetate, and the like. Acrylic acid resin, cyanoacrylate resin, ethylene copolymer resin consisting of copolymer of ethylene and monomers such as vinyl acetate, ethyl acrylate, acrylic acid, methacrylic acid, cellulose resin, polyurethane resin, polyester Resins, polyamide resins, polyimide resins, polyolefin resins, urea resins or melamine resins, amino resins, phenol resins, epoxy resins, reactive (meth) acrylic resins, chloroprene rubber, nitrile rubber, styrene-butadiene Elastomeric resin made of rubber, etc. Recone resins.

  In one embodiment, the laminate may include an adhesive layer between arbitrary layers. An adhesive layer is a layer formed in order to laminate any two layers by lamination. The type and amount of the adhesive constituting the adhesive layer are as described above.

<Contents>
The content filled in the packaging material of the present invention is a water-containing content.
The moisture contained in the contents is attracted to the hydrophilic surfactant contained in the resin film located on the inner surface of the packaging material, thereby forming a water film between the contents and the resin film. When the contents are discharged from the packaging material, the contents move within the packaging material so as to slide on the water film, so that the contents are quickly discharged without remaining in the packaging material.

The moisture content of the contents is preferably 10% by mass or more and 70% by mass or less, and more preferably 15% by mass or more and 65% by mass or less.
The moisture content of the contents can be measured by using an infrared moisture meter (trade name: AD-4715, manufactured by Atex Co., Ltd.).
When the moisture content of the contents is within the above numerical range, the packaging material according to the present invention can exhibit particularly good sliding performance and remaining prevention performance.

  The water-containing content that can be filled in the packaging material of the present invention is not limited to this, but for example, paste-like contents such as ointments, dentifrices, and eggplants, pickles, such as cut Takana And granular contents such as cut pepper and potato salad.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

(Example 1-1)
<Preparation of heat-sealable resin film>
LLDPE (manufactured by Prime Polymer Co., Ltd., trade name: UZ-2021) 96% by mass and a resin composition containing 10% by mass of synthetic zeolite in a polyethylene resin (manufactured by Sumitomo Chemical Co., Ltd., trade name: EMB- 21) Mixture A consisting of 4% by mass, and nonionic surfactant-containing MB (manufactured by Riken Vitamin Co., Ltd., trade name: Riquemaster EAM-760, surfactant content 4.8%) 34.75% % And LLDPE (manufactured by Prime Polymer Co., Ltd., trade name: UZ-2021) 65.25% by mass obtained by kneading the mixture B containing 1.67% by mass of the surfactant by the inflation method Co-extrusion film formation (extrusion temperature: 180 ° C.), multilayer resin film comprising a layer consisting of mixture A (10 μm) / a layer consisting of mixture B (30 μm) / a layer consisting of mixture A (10 μm) Obtained free.
When the contact angle of water with respect to the resin film surface was measured using a contact angle measuring device (Kyowa Interface Science Co., Ltd., trade name: Drop Mater 700), it was 50 °, and the nonionic surfactant bleeded out. It was confirmed that

<Production of laminate>
As a substrate, on a PET film (film thickness 12 μm, manufactured by Toyobo Co., Ltd., trade name: Espet T4102), an anchor coating agent (manufactured by Toyo Morton Co., Ltd., trade name: EL510 / CAT-RT80, dilution solvent: (Ethyl acetate) was applied so that the coating amount after drying was about 0.3 g / m ² to form an adhesive layer, and on this, an ethylene acrylic acid copolymer (Mitsui / Dupont Polychemical Co., Ltd.) , Trade name: Nucrel N-11081C) is extruded to form a thermoplastic resin layer so that the film thickness is 25 μm, and the thermoplastic resin layer and the resin film produced as described above are further laminated. Got the body.

(Example 1-2)
A laminate was obtained in the same manner as in Example 1-1 except that the resin film was produced as follows.
LLDPE (manufactured by Prime Polymer Co., Ltd., trade name: UZ-2021) 96% by mass and a resin composition containing 10% by mass of synthetic zeolite in a polyethylene resin (manufactured by Sumitomo Chemical Co., Ltd., trade name: EMB- 21) Mixture A consisting of 4% by mass, and nonionic surfactant-containing MB (manufactured by Riken Vitamin Co., Ltd., trade name: Riquemaster LAM-360, surfactant content 15%) 11.25% by mass , LLDPE (manufactured by Prime Polymer Co., Ltd., trade name: UZ-2021) 88.75% by mass, kneaded with a mixture C containing 1.67% by mass of a surfactant by coextrusion film formation ( Extrusion temperature: 180 ° C.) to obtain a multilayer resin film consisting of a layer consisting of mixture A (10 μm) / a layer consisting of mixture C (30 μm) / a layer consisting of mixture A (10 μm)
Similarly to Example 1-1, when the contact angle of water with respect to the resin film surface was measured, it was 46 °, and it was confirmed that the nonionic surfactant was bleeding out.

(Example 1-3)
A laminate was obtained in the same manner as in Example 1-1 except that the resin film was produced as follows.
LLDPE (manufactured by Prime Polymer Co., Ltd., trade name: UZ-2021) 96% by mass and a resin composition containing 10% by mass of synthetic zeolite in a polyethylene resin (manufactured by Sumitomo Chemical Co., Ltd., trade name: EMB- 21) Mixture A composed of 4% by mass, and nonionic surfactant-containing MB (manufactured by Riken Vitamin Co., Ltd., trade name: Riquemaster MOE-39, surfactant content 6%) 27.5% by mass , LLDPE (manufactured by Prime Polymer Co., Ltd., trade name: UZ-2021) 72.5% by mass, kneaded with a mixture D containing 1.67% by mass of a surfactant by coextrusion film formation ( Extrusion temperature: 180 ° C. to obtain a multilayer resin film consisting of a layer consisting of mixture A (10 μm) / a layer consisting of mixture D (30 μm) / a layer consisting of mixture A (10 μm).
Similarly to Example 1-1, when the contact angle of water with respect to the resin film surface was measured, it was 52 °, and it was confirmed that the nonionic surfactant was bleeding out.

(Example 1-4)
Adhesion between the substrate and the resin film is performed via an adhesive for dry lamination (manufactured by Rock Paint Co., Ltd., trade name: RU004 / H-1, coating amount: 2.5 g / m ² , drying temperature 70 ° C.). A laminate was obtained in the same manner as in Example 1 except that the thermoplastic resin layer was not provided.
As in Example 1-1, when the contact angle of water with the resin film surface was measured, it was 65 °, and it was confirmed that the nonionic surfactant was bleeding out.

(Example 1-5)
A laminate was obtained in the same manner as in Example 1-1 except that the resin film was produced as follows.
LLDPE (manufactured by Prime Polymer Co., Ltd., trade name: SP-2020) 96% by mass and a resin composition containing 10% by mass of synthetic zeolite in a polyethylene resin (manufactured by Sumitomo Chemical Co., Ltd., trade name: EMB- 21) Mixture A composed of 4% by mass, and 37% by mass of nonionic surfactant-containing MB (manufactured by Riken Vitamin Co., Ltd., trade name: Riquemaster EAM-760, surfactant content 4.8%) , LLDPE (manufactured by Prime Polymer Co., Ltd., trade name: SP-2020) obtained by kneading 63% by mass, a mixture E containing 1.78% by mass of a surfactant and LLDPE (Prime Polymer Co., Ltd.) Product name: SP-2020) 100% by mass of resin composition F is co-extruded (extrusion temperature: 180 ° C.) by the inflation method, and layer (25 μm) / layer E composed of mixture E (45 μm) / multilayer resin film composed of layer A composed of mixture A (10 μm) was obtained.
Similarly to Example 1-1, when the contact angle of water with respect to the resin film surface was measured, it was 45 °, and it was confirmed that the nonionic surfactant was bleeding out.

(Comparative Example 1-1)
LLDPE (manufactured by Prime Polymer Co., Ltd., trade name: UZ-2021) was extrusion-formed by an inflation method (extrusion temperature 180 ° C.) to obtain a film having a thickness of 50 μm.
As a substrate, on a PET film (film thickness 12 μm, manufactured by Toyobo Co., Ltd., trade name: Espet T4102), an anchor coating agent (manufactured by Toyo Morton Co., Ltd., trade name: EL510 / CAT-RT80, dilution solvent: Ethyl acetate) was applied so that the coating amount after drying was about 0.3 g / m ^2, and further, an ethylene acrylic acid copolymer (manufactured by Mitsui-Dupont Polychemical Co., Ltd., trade name: Nucrel) N-11081C) was extruded to a film thickness of 25 μm, and this was laminated with the film produced as described above to obtain a laminate.

<< Sliding performance / residual prevention performance test >>
The laminates obtained in Examples and Comparative Examples were evaluated for sliding performance and content remaining prevention performance by the following methods.
First, the laminates of Examples and Comparative Examples were cut into 5 cm × 15 cm strips, and the surface opposite to the surface of the resin film included in the laminate was attached to cardboard.
Next, 5 g of the dentifrice composition 1 (Lion Corporation, trade name: Dent Health) is placed on one end of the laminate cut into a strip shape, and the end portion is in a strip shape so as to be on the upper side. The cardboard to which the cut laminate was attached was tilted by 80 °.
The cardboard was held in an inclined state, and the sliding performance of the laminate was evaluated based on the position of the dentifrice composition 1 on the laminate after 10 minutes. The evaluation criteria were as follows.
Moreover, the residue on a laminated body was confirmed visually and the content remaining prevention performance of the laminated body was evaluated according to the following evaluation criteria.
Furthermore, dentifrice composition 1 is used as dentifrice composition 2 (Lion Corporation, trade name: Systema Medical Cool), dentifrice composition 3 (Lion Corporation, trade name: Denter), dentifrice composition 4 (Lion Co., Ltd., trade name: free & free damage aid), and the same test was conducted. These evaluation results are summarized in Table 1.
(Evaluation criteria for sliding performance)
A: Sliding down to the bottom of the laminate.
B: It slipped down to the intermediate part of the laminated body.
C: It stayed at the upper part of the laminated body and did not slide down.
(Evaluation criteria for contents remaining prevention performance)
A: Almost no residue was formed on the laminate.
B: Some residue was produced on the laminate.
C: Many residues were generated on the laminate.

(Example 2-1)
<Preparation of heat-sealable resin film>
LLDPE (manufactured by Prime Polymer Co., Ltd., trade name: UZ-2021) 96% by mass and a resin composition containing 10% by mass of synthetic zeolite in a polyethylene resin (manufactured by Sumitomo Chemical Co., Ltd., trade name: EMB- 21) Mixture A composed of 4% by mass, and nonionic surfactant-containing MB (manufactured by Riken Vitamin Co., Ltd., trade name: Riquemaster EAM-760, surfactant content 4.8%) 41.7% % And LLDPE (manufactured by Prime Polymer Co., Ltd., trade name: UZ-2021) 58.3% by mass, and a mixture B containing 2.0% by mass of a surfactant is obtained by an inflation method. Co-extrusion film formation (extrusion temperature: 180 ° C.), a multilayer resin film consisting of a layer consisting of mixture A (10 μm) / a layer consisting of mixture D (20 μm) / a layer consisting of mixture A (10 μm) It was.
When the contact angle of water with respect to the resin film surface was measured using a contact angle measuring device (trade name: Drop Mater 700, manufactured by Kyowa Interface Science Co., Ltd.), it was 55 °, and the nonionic surfactant bleeded out. It was confirmed that

<Production of laminate>
As a base material, an anchor coat agent (trade name: A3210 / A3075, manufactured by Mitsui Chemicals, Inc.) is diluted on a PET film (film thickness: 12 μm, manufactured by Dai Nippon Printing Co., Ltd., trade name: IB-PET-MUB). Solvent: ethyl acetate) was applied so that the coating amount after drying was about 0.3 g / m ² to form an adhesive layer, and further LDPE (manufactured by Nippon Polyethylene Co., Ltd., trade name: Novatec LC600A) ) Was extruded to form a thermoplastic resin layer, and the thermoplastic resin layer and the resin film prepared as described above were laminated to obtain a laminate.

(Example 2-2)
A laminate was obtained in the same manner as in Example 2-1, except that the resin film was produced as follows.
LLDPE (manufactured by Prime Polymer Co., Ltd., trade name: UZ-2021) 96% by mass and a resin composition containing 10% by mass of synthetic zeolite in a polyethylene resin (manufactured by Sumitomo Chemical Co., Ltd., trade name: EMB- 21) Mixture A composed of 4% by mass and nonionic surfactant-containing MB (manufactured by Riken Vitamin Co., Ltd., trade name: Riquemaster LAM-360, surfactant content 15.0%) 13.34 mass % And LLDPE (manufactured by Prime Polymer Co., Ltd., trade name: UZ-2021) 86.66% by mass, and a mixture C containing 2.0% by mass of a surfactant was obtained by an inflation method. Co-extrusion film formation (extrusion temperature: 180 ° C.), multilayer resin film consisting of a layer consisting of mixture A (10 μm) / a layer consisting of mixture D (20 μm) / a layer consisting of mixture A (10 μm) Obtained free.
As in Example 2-1, when the contact angle of water with respect to the resin film surface was measured, it was 37 °, and it was confirmed that the nonionic surfactant was bleeding out.

(Example 2-3)
A laminate was obtained in the same manner as in Example 2-1, except that the resin film was produced as follows.
LLDPE (manufactured by Prime Polymer Co., Ltd., trade name: UZ-2021) 96% by mass and a resin composition containing 10% by mass of synthetic zeolite in a polyethylene resin (manufactured by Sumitomo Chemical Co., Ltd., trade name: EMB- 21) Mixture A composed of 4% by mass, and nonionic surfactant-containing MB (manufactured by Riken Vitamin Co., Ltd., trade name: Riquemaster MOE-39, surfactant content 6.0%) 29.64% % And LLDPE (manufactured by Prime Polymer Co., Ltd., trade name: UZ-2021) 70.36% by mass, a mixture D containing 2.0% by mass of a surfactant was obtained by an inflation method. Co-extrusion film formation (extrusion temperature: 180 ° C.), multilayer resin film comprising layer A consisting of mixture A (10 μm) / layer consisting of mixture D (20 μm) / layer consisting of mixture A (10 μm) Obtained.
As in Example 2-1, when the contact angle of water with the resin film surface was measured, it was 67 °, and it was confirmed that the nonionic surfactant was bleeding out.

(Example 2-4)
Adhesion between the substrate and the resin film is performed via an adhesive for dry lamination (manufactured by Rock Paint Co., Ltd., trade name: RU004 / H-1, coating amount: 2.5 g / m ² , drying temperature 70 ° C.). A laminate was obtained in the same manner as in Example 2-1, except that the thermoplastic resin layer was not provided.

(Comparative Example 2-1)
Adhesive for dry laminating LLDPE film 40 (trade name: LL-XTN) manufactured by Phutamura Chemical Co., Ltd. to PET film (film thickness 12 μm, manufactured by Dai Nippon Printing Co., Ltd., product name: IB-PET-MUB) (A product made by Rock Paint Co., Ltd., trade name: RU004 / H-1, coating amount: 2.5 g / m ² , drying temperature: 70 ° C.) to obtain a laminate.

<< Sliding performance test >>
The laminates obtained in the examples and comparative examples were cut into two pieces having a size of 13.5 cm × 16.0 cm, arranged so that the surfaces of the resin films face each other, and two vertical sides and one horizontal side were 10 mm wide. Was subjected to thermocompression bonding (conditions: 160 ° C., 1 kg / cm ² , 1 second) to obtain a packaging material.
The packaging material thus obtained was filled with about 80 g of evaluation contents A (trade name: Kobukyu-chan, manufactured by Tokai Pickles Co., Ltd.), and the opening side was subjected to thermocompression bonding (conditions 160 ° C., 1 kg / cm ^2). 1 second).
Next, after performing retort sterilization at 85 ° C. for 20 minutes, it was cooled with cold water and stored in a normal temperature environment (22 ° C.) for 1 week.
After storage, one side of the packaging material was cut with a cutter, the opening of the packaging material was tilted downward, and the contents were taken out by holding for 25 seconds. The ease of taking out the contents from each packaging material was evaluated by setting the following criteria. The evaluation results are shown in Table 2. Moreover, it filled with the content B for evaluation (Miyata company make, brand name: old-fashioned Takana pickles), and evaluated similarly.
<Evaluation criteria>
A: The content of 75% or more slid down.
B: The content of 40% or more slid down.
C: The content of less than 20% slipped.

100: Laminated body 101: Base material 102: Resin film 103: Gas barrier layer 104: Colored layer

Claims (5)

A substrate;
A packaging material comprising a laminate comprising a heat-sealable resin film,
The heat-sealable resin film comprises a hydrophilic surfactant in an amount of 0.1% by mass to 3% by mass,
The heat-sealable resin film is located on the inner surface of the packaging material, and the hydrophilic surfactant is bleeding out on the inner surface side of the packaging material of the heat-sealable resin film, Packaging material for water content.   The layer comprising the hydrophilic surfactant comprises, as the hydrophilic surfactant, a surfactant that is solid at 0 to 85 ° C. and a surfactant that is liquid at 40 ° C. or lower. The packaging material described.   The packaging material according to claim 1 or 2, wherein the hydrophilic surfactant is a nonionic surfactant.   The packaging material as described in any one of Claims 1-3 whose contact angle of the water with respect to the said heat-sealable resin film surface is 85 degrees or less. It is a manufacturing method of the packaging material as described in any one of Claims 1-4,
Preparing a substrate;
Preparing a heat-sealable resin film;
Laminating the base material and the heat-sealable resin film to obtain a laminate,
A step of heat-sealing the laminate,
A method comprising the steps of:

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