JP2017095649A - Non-adsorbent adhesive coating agent, non-adsorbent laminate using the same, and packaging bag using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a non-adsorbent adhesive coating agent for a packaging bag using a laminate containing a plastic film as a base material which has non-adsorptivity to aroma and an active ingredient of a content without impairing heat sealability; a non-adsorbent laminate using the same; and a packaging bag using the same.SOLUTION: There are provided a non-adsorbent adhesive coating agent which is an adhesive coating agent containing at least a main agent, a curing agent, a dispersion agent and resin particles, where the resin particles are formed of polyacrylonitrile resin particles, an average particle size of the polyacrylonitrile resin particles is 0.05 μm or more, a ratio of the polyacrylonitrile resin particles to the total mass of the main agent, the curing agent, the dispersion medium and the resin particles is 0.01 mass% or more and 50 mass% or less; a non-adsorbent laminate using the same; and a packaging bag using the same.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a non-adsorptive adhesive coating agent, a non-adsorptive laminate using the same, and a packaging bag using the same. In particular, a non-adsorptive adhesive coating agent that can be used for an adhesive layer, a non-adsorptive laminate using the non-adsorptive adhesive coating agent, and a non-adsorptive laminate that can be used for an adhesive layer of a packaging bag that can be heat-sealed with a sealant layer The present invention relates to a packaging bag using an adsorbent laminate.

  In recent years, as a kind of packaging bags, those composed of single-piece or laminated bodies based on plastic films have become widespread, and various forms have been used for a wide range of applications and are indispensable for modern life It has become a thing.

  For example, it is also used as a liquid bag and widely used in the food field such as retort food as well as beverages. In the fields of pharmaceuticals, cosmetics, daily necessities, and toiletries, various products are packed in the shelves of supermarkets, drug stores, and convenience stores. In addition to liquid containers, various applications have been developed.

  The advantages of such packaging bags are that they are cheaper than containers such as cans and bottles, can be handled with fine material design depending on the required quality, or are lightweight and saved before filling the contents and in distribution and storage. It is mentioned that it is a space.

  In addition, high-definition printing on the layer visible from the surface can improve the image of the product and display necessary information about the contents. Bar code printing is used for product distribution and marketing. It is also a source of information.

  Such packaging bags are cheaper than purchasing new bottles and storage containers each time, and can be said to be environmentally friendly from the viewpoint of reducing waste. Sometimes used as a container for refill contents after the bottle is empty.

  In many cases, a packaging bag composed of a single body or a laminate made of a plastic film as a base material is provided with a sealant layer on the innermost layer side, and the sealant layers are opposed to each other and heat-sealed to form a packaging bag. The way to do is taken.

  However, phenomena such as the scent of contents and adsorption of active ingredients to the sealant layer may occur, and this is a problem particularly when used for applications such as pharmaceuticals, foods, cosmetics, and toiletries.

  On the other hand, the patent document discloses a device for a heat-sealable coating agent containing non-adsorptive particles, but it is difficult to achieve compatibility with the heat-sealability. I couldn't.

JP 2012-184357 A

  The present invention has been made in view of such a situation, and in a packaging bag using a laminate having a plastic film as a base material, it has a fragrance of contents and a non-adsorptive of active ingredients without impairing heat sealability. It is an object of the present invention to provide a non-adsorptive adhesive coating agent for a packaging bag, a non-adsorptive laminate using the same, and a packaging bag using the same.

  As a means for solving the above problems, the invention according to claim 1 is an adhesive coating agent including at least a main agent, a curing agent, a dispersion medium, and resin particles, and the resin particles are made of polyacrylonitrile resin particles. The average particle diameter of the polyacrylonitrile resin particles is 0.05 μm or more, and the ratio of the polyacrylonitrile resin particles to the total mass of the main agent, the curing agent, the dispersion medium, and the resin particles is 0.01% by mass or more, 50 It is a non-adsorptive adhesive coating agent characterized by having a mass% or less.

  The invention according to claim 2 is the non-adsorptive adhesive coating agent according to claim 1, wherein the main agent is a polyester polyol, and the curing agent is a polyisocyanate curing agent. .

  The invention according to claim 3 is a laminate composed of at least a sealant layer, an adhesive layer, and a base material layer in this order from the surface, and the other side through the sealant layer on the surface side where the sealant layer is exposed. The adhesive layer provided in contact with one surface is obtained by curing the non-adsorptive adhesive coating agent according to claim 1 or 2, wherein the proportion of polyacrylonitrile resin particles in the adhesive layer is 0.00. It is a non-adsorbent laminated body characterized by being 3 mass% or more and 60 mass% or less.

  The invention according to claim 4 is the non-adsorbent laminate according to claim 3, wherein the base material layer is made of a plastic film.

  The invention according to claim 5 is the non-adsorbent laminate according to claim 3 or 4, wherein the plastic film of the base material layer is provided with a gas barrier layer.

  The invention according to claim 6 is characterized in that the dry thickness of the adhesive layer is 0.005 μm or more and 10 μm or less, and the non-adsorbing layer area according to any one of claims 3 to 5. Is the body.

  The invention described in claim 7 is a packaging bag using the non-adsorbent laminate according to any one of claims 3 to 6.

  According to the present invention, in a packaging bag using a laminate based on a plastic film, the non-adsorption for a packaging bag having a non-adsorptive property of the scent of the contents and the active ingredient without impairing the heat sealability It is possible to provide an adhesive bonding coating agent, a non-adsorbing laminate using the non-adsorbing adhesive coating agent, and a non-adsorbing packaging bag using the non-adsorbing laminate.

  In particular, according to the invention described in claim 4, in a packaging bag using a laminate having a plastic film as a base material, the packaging bag has a non-adsorptive property of the components of the contents without impairing the heat sealability. It is possible to provide a non-adsorbable laminate.

In particular, according to the invention described in claim 5, in a packaging bag using a laminate having a plastic film as a base material, the gas bag has a barrier property and the scent of the contents and the active ingredient without impairing the heat sealability. It is possible to provide a non-adsorbing laminate for a non-adsorbing packaging bag.

  In particular, according to the invention described in claim 6, in a packaging bag using a laminate having a plastic film as a base material, the packaging bag has a non-adsorbing property of the components of the contents without impairing the heat sealability. Thus, it is possible to provide a non-adsorbing laminate having stronger adhesion and non-adsorbing properties.

  In particular, according to the invention described in claim 7, it is possible to provide a packaging bag having a non-adsorptive property to the scent of the contents and the active ingredient by a laminate having a non-adsorptive property without impairing the heat sealability. Is possible.

FIG. 1 is a partial cross-sectional schematic view for explaining one embodiment of a non-adsorbent laminate according to the present invention.

  DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Modes for carrying out the present invention will be described in detail below with reference to the drawings. However, the present invention is not limited to the examples shown here, but only by the claims.

  FIG. 1 is a partial cross-sectional schematic view for explaining one embodiment of a non-adsorbent laminate according to the present invention. The laminate (10) has a plastic film as a base material (4), and a gas barrier layer (3) is provided on one surface thereof. A sealant layer (1) is provided on the content side of the laminate (10), that is, on the side that becomes the innermost layer when the packaging bag is formed using the laminate, and the innermost layer of the sealant layer (1). A non-adsorptive adhesive layer (2) according to the present invention is provided on the surface opposite to the side to be.

  The non-adsorptive function is to prevent, for example, fragrances and active ingredients of the contents stored inside the packaging bag from being transferred to the laminated body constituting the packaging bag or being adsorbed.

  Moreover, a printing layer (6) can be provided as needed. The print layer (6) can be provided in a layer visible from the outside of the packaging bag. For example, after the print layer (6) is provided on the film layer (5), it is laminated to form a part of the laminate (10). be able to.

  Hereinafter, each element constituting the present invention will be described in more detail.

(Sealant layer)
The sealant layer is a thermoplastic resin layer, and is disposed in the innermost layer on the content side when the laminate is made into a bag. Two laminates can be stacked by facing the sealant layers and welded together by heating and pressurization to produce a bag.

  As a material for the sealant layer, a polyolefin resin is generally used among thermoplastic resins. Specifically, a low density polyethylene resin (LDPE), a medium density polyethylene resin (MDPE), and a linear low density polyethylene resin. (LLDPE), ethylene-vinyl acetate copolymer (EVA), ethylene-α olefin copolymer, ethylene-methacrylic acid resin copolymer and other ethylene resins, polyethylene and polybutene blend resins, and homopolypropylene resins Polypropylene resins such as (PP), propylene-ethylene random copolymer, propylene-ethylene block copolymer, and propylene-α olefin copolymer can be used.

  For the formation of the sealant layer, materials previously formed on the film can be laminated and laminated, or the melted resin can be laminated to form a sealant layer using an extruder.

(Non-adsorptive adhesive layer)
The non-adsorptive adhesive layer is formed by applying, drying and curing the non-adsorptive adhesive coating agent of the present invention. It arrange | positions in contact with the surface on the opposite side to the surface which contacts the contents of a sealant layer.

The non-adsorptive adhesive coating agent contains at least a main agent, a curing agent, a dispersion medium, and resin particles. As will be described below, it is preferable to use polyacrylonitrile resin particles as the resin particles.
The proportion of the polyacrylonitrile resin particles in the adhesive layer is preferably 0.3% by mass or more and 60% by mass or less, and more preferably 1.5% by mass or more and 40% by mass or less. If the concentration of the polyacrylonitrile resin particles is equal to or higher than the lower limit value, the polyacrylonitrile resin particles have a sufficient non-adsorption property. If the concentration is lower than the upper limit value, stable coating with a machine is possible and the cost is low.

  The adhesive layer itself contains polyacrylonitrile resin particles (sp value 15.4) which are easy to take in the active ingredients of the contents inside the packaging bag (polyurethane sp value 10.0) but hardly adsorb the active ingredients etc. The ratio of the portion that is difficult to adsorb in the adhesive layer increases, and the amount of adsorption of, for example, l-menthol (sp value 9.2), dl-camphor (sp value 9.4), such as aroma and active ingredient, should be reduced. Can do.

  Examples of active ingredients that require suppression of adsorption include limonene contained in orange juice and the like as volatile ingredients, methyl salicylate, l-menthol, and dl-camphor contained in pharmaceuticals. As active ingredients that require suppression of adsorption, non-volatile ingredients include various drugs used as anti-inflammatory analgesics, such as ketoprofen, flurbiprofen, and loxoprofen sodium hydrate.

  The main component of the non-adsorptive adhesive coating agent is preferably made of polyester polyol. As the polyester polyol, for example, a polyester polyol obtained by reacting at least one polybasic acid with at least one diol can be used. Examples of polybasic acids include aliphatic dibasic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, spellic acid, azelaic acid, sebacic acid, and brassic acid, and aromatics such as isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid. And dibasic acids such as group dibasic acids.

  Diols include ethylene glycol, propylene glycol, butanediol, neopentyl glycol, methylpentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, dodecanediol and other aliphatic diols, cyclohexanediol, hydrogenated xylylene Examples thereof include alicyclic diols such as lenglycol and aromatic diols such as xylylene glycol.

The curing agent is preferably a polyisocyanate curing agent. Examples of the polyisocyanate curing agent include 2,4- or 2,6-tolylene diisocyanate, xylylene diisocyanate, 4,4′-diphenylmethane diisocyanate, methylene diisocyanate, isopropylene diisocyanate, lysine diisocyanate, 2,2,4. -Or selected from 2,4,4-trimethylhexamethylene diisocyanate, 1,6-hexamethylene diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, isopropylidene dicyclohexyl-4,4'-diisocyanate, etc. Isocyanate compound alone or at least one isocyanate compound selected from the above isocyanate compounds. Adducts, biuret body, isocyanurate and the like.

  The ratio between the main agent and the curing agent is a molar ratio of the functional group (A) in the main agent to the reactive functional group (B) in the curing agent, and (B) / (A) is 0.5 or more and 5.0 or less. It is preferably 0.8 or more and 3.5 or less. If (B) / (A) is not less than the lower limit, the main agent can be sufficiently cured, and if it is not more than the upper limit, the film can be prevented from becoming too hard and the adhesive layer from becoming brittle.

  The dispersion medium is a liquid that dissolves or disperses the main agent and the curing agent, and is not particularly limited as long as it can be dissolved and diluted. As the dispersion medium, an alcohol solvent, a ketone solvent, an ester solvent, a glycol solvent, or a hydrocarbon solvent can be used.

  Examples of alcohol solvents include methanol, ethanol, isopropanol, n-propanol, 1-butanol, and 2-butanol.

  Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and isophorone.

  Examples of the ester solvent include methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, isobutyl acetate, and propylene glycol monomethyl ether acetate.

  Examples of glycol solvents include butyl cellosolve and propylene glycol monomethyl ether.

  Examples of the hydrocarbon solvent include toluene, xylene, n-hexane, and methylcyclohexane.

These solvents can be used alone or in a mixture containing two or more thereof. Methyl ethyl ketone and ethyl acetate are preferable from the viewpoint of stability during dissolution and drying after coating.
Polyacrylonitrile resin particles are used as the resin particles. The polyacrylonitrile resin particles are a homopolymer of acrylonitrile or a copolymer thereof, containing 50% by mass or more of acrylonitrile monomer, and preferably 75% by mass. Examples of the copolymer component include acrylic esters such as methyl acrylate, ethyl acrylate, and propyl acrylate, methacrylic esters such as methyl methacrylate and ethyl methacrylate, vinyl esters such as vinyl acetate, and the like. These may be contained alone or in combination of two or more.

The lower limit of the average particle size of the polyacrylonitrile resin particles is preferably 0.05 μm or more, and more preferably 1.0 μm or more. When the average particle size of the polyacrylonitrile resin particles is equal to or greater than the lower limit, stable quality polyacrylonitrile resin particles are prepared. Here, the average particle size referred to in the present invention refers to a particle size of 50% cumulative from the small diameter side in the particle size measured by the microtrack type particle size distribution measuring method.
The lower limit of the ratio of the polyacrylonitrile resin particles to the total mass of the main agent, the curing agent, the dispersion medium, and the resin particles is preferably 0.01% by mass or more, and more preferably 0.05% by mass or more. Moreover, 50 mass% or less is preferable and, as for the upper limit of the ratio of polyacrylonitrile resin particle | grains, 30 mass% or less is more preferable. If the concentration of the polyacrylonitrile resin particles is equal to or higher than the lower limit value, the polyacrylonitrile resin particles have a sufficient non-adsorption property. If the concentration is lower than the upper limit value, stable coating with a machine is possible and the cost is low.

  If necessary, other particles than the polyacrylonitrile resin particles may be added. For example, inorganic particles such as silica, calcium carbonate, barium sulfate, and alumina, organic particles, oils, waxes, and the like can be used.

Moreover, it is preferable that the solid content concentration of this coating agent is 3-80 mass%, and it is more preferable that it is 4-45 mass%. If the solid content concentration of the coating agent is equal to or higher than the lower limit value, a non-adsorbing adhesive layer having a sufficient thickness can be easily formed by one coating, and if it is equal to or lower than the upper limit value, the viscosity is appropriately low. Thus, the coatability is improved. The solid content concentration is a total mass ratio of the polymer (net amount) constituting the main agent in 100% by mass of the non-adsorbing adhesive coating agent, the curing agent (net amount), and the polyacrylonitrile resin particles (net amount). .
The coating thickness of the coating agent is preferably 0.005 to 10 μm, more preferably 0.01 to 5 μm, based on the thickness of the non-adsorbing layer after drying. If the coating thickness is equal to or greater than the lower limit value, it can be easily applied by a general-purpose coating apparatus. If the coating thickness is equal to or less than the upper limit value, the amount of coating is reduced, so that cost reduction can be realized. is there.

  Further, according to the present invention, the polyacrylonitrile resin particles exhibiting a non-adsorbing function are in contact with the content side with the sealant layer interposed therebetween. As to which layer the component is adsorbed, it is clear that it is adsorbed by the sealant layer and the adhesive layer that bonds the sealant layer and the base material layer. It was found that a non-adsorbing effect was obtained.

  According to the non-adsorptive adhesive coating agent of the present invention, it is not necessary to provide a new non-adsorptive layer or a new sealant layer for heat sealing, and the conventional adhesive layer is changed to an adhesive layer by a non-adsorptive adhesive coating agent. It is only necessary to replace it, and it is possible to achieve both non-adsorbability and heat sealability.

  Since the polyacrylonitrile resin particles exhibiting a non-adsorbing function can be obtained not only in the adhesive layer but also in a non-adsorbing effect, it is not necessary to blend in the sealant layer. That is, since the sealant layer for heat seal can be used as it is, the heat seal property and heat seal strength of the sealant itself can be exhibited without being affected by the heat seal property by the resin particles.

(Base material layer)
A plastic film can be used for the base material layer. The plastic film is a film made of a polymer resin composition. For example, polyolefin (polyethylene, polypropylene, etc.), polyester (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.), polyamide (nylon-6, nylon-66, etc.), polyimide Etc. can be used, and is appropriately selected according to the product and contents.

  In particular, when polypropylene or polyethylene terephthalate is used as a base film, it is more preferable in terms of film strength and price. Or when using a polyamide film, there exists an effect of an improvement of mechanical strength and the tolerance with respect to the bag breakage by a stab or other external force can be provided.

(Gas barrier layer)
Moreover, for the purpose of improving the storage stability of the contents, an opaque layer that shields ultraviolet rays such as a colored film can be provided in the laminate, if necessary. Alternatively, a gas barrier layer can be provided on the plastic film of the base material layer.

  For the gas barrier layer, for example, a metal foil such as an aluminum foil, or a film obtained by metal vapor deposition on a plastic film can be used. However, when a metal foil such as an aluminum foil cannot be used, a gas barrier film in which a gas barrier layer is provided on a plastic film can be used.

  In the case of a gas barrier film, the gas barrier layer can be composed of a vapor deposition layer and a coating layer of an inorganic compound. After providing an anchor coat on the base film, the vapor deposition layer and the coating layer are sequentially provided.

  For example, urethane acrylate can be used for the anchor coat layer of the gas barrier film. For the formation of the anchor coat layer, a coating method using a printing technique such as gravure coating with a paint in which a resin is dissolved in a solvent can be used, and a coating film can be formed using a generally known coating method.

  As a method of forming a vapor deposition layer, an inorganic compound such as SiO or AlO is coated on a base film provided with an anchor coat layer using a vacuum vapor deposition method, and an inorganic compound layer is formed by a vacuum vapor deposition method. it can. The thickness of the vapor deposition layer is preferably 15 nm to 30 nm.

  As a method for forming the coating layer, an aqueous solution or water / alcohol containing at least one of a water-soluble polymer and (a) one or more alkoxides or hydrolysates thereof, or (b) tin chloride. A coating agent mainly composed of a mixed aqueous solution is applied onto a film and dried by heating to form an inorganic compound layer by a coating method to form a coating layer. At this time, the adhesion with the anchor coat layer can be improved by adding a silane monomer to the coating agent.

  An inorganic compound layer has a gas barrier property only by a coating film formed by a vacuum deposition method, but a coating layer, which is an inorganic compound layer formed by a coating method, is formed so as to overlap with a deposited layer that is an inorganic compound layer formed by a vacuum deposition method. be able to.

  By combining these two layers, a reaction layer of both layers is formed at the interface between the inorganic compound layer by the vacuum deposition method and the inorganic compound layer by the coating method, or the inorganic compound layer by the coating method becomes an inorganic compound layer by the vacuum deposition method. A dense structure is formed by filling and reinforcing defects such as pinholes, cracks, and grain boundaries, or by reinforcing them, so that high gas barrier properties, moisture resistance, and water resistance are achieved, and flexibility that can withstand deformation is achieved. Therefore, it can be suitable as a packaging bag.

  Further, when SiO is used as the barrier layer, it is transparent, so that the contents can be seen from the outside of the packaging bag. These may be properly used depending on the application and required quality. In addition, since no metal is used, it is suitable for heating with a microwave oven, and has an advantage in restoring the shape of the container when the packaging bag is pushed from the outside.

(Print layer)
If necessary, it is possible to provide a product image and necessary information about the contents on the layer visible from the outside of the packaging bag by printing. For the base film for that purpose, a plastic film made of a polymer material can be used.

The polymer film is a film made of a polymer resin composition, such as polyolefin (polyethylene, polypropylene, etc.), polyester (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.), polyamide (nylon-6, nylon-66, etc.), A polyimide etc. can be used and it selects suitably according to a use. In particular, when polypropylene or polyethylene terephthalate is used as a base film, it is more preferable in terms of film strength and price.

  Although there are no particular restrictions on the printing method and printing ink, it is appropriate as long as the printability to film, design properties such as color tone, adhesiveness, and safety as a food container are considered among known printing methods. For example, a gravure printing method, an offset printing method, a gravure offset printing method, a flexographic printing method, an ink jet printing method, or the like can be used. Of these, the gravure printing method can be preferably used in terms of productivity and high definition of the pattern.

(Laminate)
When laminating each layer constituting the laminate, each layer can be laminated via an adhesive layer. As a material for the adhesive, for example, a polyester-isocyanate resin, a urethane resin, a polyether resin, or the like can be used.

  As a lamination method, dry lamination or non-solvent lamination can be used. Alternatively, when a thermoplastic resin is used, it can be laminated as an adhesive layer using an extruder, or a single layer can be formed and laminated using an extruder.

  In the present invention, the laminate is a laminate composed of at least the surface from the sealant layer, the adhesive layer, and the base material layer in this order, and the other side through the sealant layer on the surface side where the sealant layer is exposed. The adhesive layer provided in contact with the surface is a laminate obtained by curing a non-adsorptive adhesive coating agent, and the base material layer is made of a plastic film.

(Packaging bag)
Using the non-adsorbable laminate according to the present invention, it is possible to make a bag to make a packaging bag. A sealant layer is disposed on the content side of the laminate, that is, the innermost layer of the packaging bag, the sealant layers are stacked so that the sealant layers face each other, and a bag is formed by heat sealing to obtain a packaging bag. According to the present invention, the laminate is non-adsorptive, and the packaged bag is non-adsorptive.

  When the packaging bag is made, for example, one side of the rectangle is an opening, and is not heat-sealed. After the contents are stored, the opening is sealed again by heat sealing. Things are sealed.

  This packaging bag is a non-adsorptive packaging bag and has a feature that it hardly adsorbs the scent of the contents and active ingredients and has non-adsorptive properties.

  Thus, according to the present invention, in a packaging bag using a laminate based on a plastic film, non-adsorption for a packaging bag having a non-adsorptive property of the components of the content without impairing heat sealability It is possible to provide an adhesive bonding coating agent, a non-adsorbing laminate using the non-adsorbing adhesive coating agent, and a non-adsorbing packaging bag using the non-adsorbing laminate.

  Hereinafter, the details of the present invention will be described more specifically based on examples. However, the present invention is not limited to the examples shown here.

<Example 1>
A non-adsorptive adhesive coating agent was prepared with the following material composition, a non-adsorptive laminate was prepared, and a packaging bag was prepared.
(Non-adsorptive adhesive coating agent)
Polyester polyol 7.3 parts by mass (“Nipporan 131” manufactured by Tosoh Corporation)
12.7 parts by mass of polyisocyanate curing agent (“Takenate 160N” manufactured by Mitsui Chemicals, Inc.)
Ethyl acetate 50.0 parts by mass Polyacrylonitrile resin particles 30.0 parts by mass
(Toughtic ASF-7, manufactured by Toyobo Co., Ltd., average particle size: 7 μm)
By the above blending, the main agent / curing agent ratio: the molar ratio of the functional group (A) in the main agent / the reactive functional group (B) in the curing agent (B) / (A) = 2.0, solid content concentration 46 8%.

(Non-adsorbent laminate)
Polyethylene terephthalate film: “E-5100” manufactured by Toyobo Co., Ltd. 12 μm thick corona-treated surface and aluminum foil: “1N30 material” manufactured by Toyo Aluminum Co., Ltd. 7 μm thick Adhesive: “Dick Dry” manufactured by DIC Corporation LX500 / KW75 ”was used for dry lamination (film thickness after drying: 3 μm).
Furthermore, as a sealant layer, a linear low density polyethylene: “TUX-HC” manufactured by Tosero Co., Ltd., a corona-treated surface having a thickness of 40 μm, is dry-laminated using the non-adsorptive adhesive coating agent ( After drying, the film thickness was 8 μm) and then cured by aging at 40 ° C. for 2 days.

(Packaging bag)
The bag was made into a pouch shape using a heat sealer. The heat sealing conditions were 180 ° C., 1 second, and 2 kgf.

<Comparative Example 1>
A non-adsorptive adhesive coating agent was prepared with the following material composition, a non-adsorptive laminate was prepared, and a packaging bag was prepared.
(Non-adsorptive adhesive coating agent)
Polyester polyol 7.3 parts by mass (“Nipporan 131” manufactured by Tosoh Corporation)
12.7 parts by mass of polyisocyanate curing agent (“Takenate 160N” manufactured by Mitsui Chemicals, Inc.)
Ethyl acetate 15.0 parts by mass Polyacrylonitrile resin particles 65.0 parts by mass
(Toughtic ASF-7, manufactured by Toyobo Co., Ltd., average particle size: 7 μm)
By the above blending, main agent / curing agent ratio: molar ratio of functional group (A) in main agent / reactive functional group (B) in curing agent (B) / (A) = 2.0, solid content concentration 81 8%.

  In Comparative Example 1, in the non-adsorbing adhesive coating agent, the non-adsorbing laminate and the packaging bag were different except that the proportion of ethyl acetate and the proportion of resin particles that were polyacrylonitrile resin particles were different from those in Example 1. The conditions are all the same.

<Comparative example 2>
A non-adsorptive adhesive coating agent was prepared with the following material composition, a non-adsorptive laminate was prepared, and a packaging bag was prepared.
(Non-adsorptive adhesive coating agent)
Polyester polyol 7.3 parts by mass (“Nipporan 131” manufactured by Tosoh Corporation)
12.7 parts by mass of polyisocyanate curing agent (“Takenate 160N” manufactured by Mitsui Chemicals, Inc.)
Ethyl acetate 79.995 parts by mass Polyacrylonitrile resin particles 0.005 parts by mass (“Toughtic ASF-7” manufactured by Toyobo Co., Ltd., average particle size: 7 μm)
By the above blending, main agent / curing agent ratio: molar ratio of functional group (A) in main agent / reactive functional group (B) in curing agent (B) / (A) = 2.0, solid content concentration 16 8%.

  In Comparative Example 2, the conditions and the like of the non-adsorbent laminate and the packaging bag are all the same except that the proportion of ethyl acetate and the proportion of resin particles that are polyacrylonitrile resin particles are different from those in Example 1.

<Comparative Example 3>
A non-adsorptive adhesive coating agent was prepared with the following material composition, a non-adsorptive laminate was prepared, and a packaging bag was prepared.
(Non-adsorptive adhesive coating agent)
Polyester polyol 7.3 parts by mass (“Nipporan 131” manufactured by Tosoh Corporation)
12.7 parts by mass of polyisocyanate curing agent (“Takenate 160N” manufactured by Mitsui Chemicals, Inc.)
Ethyl acetate 50.0 parts by mass Polyurethane particles 30.0 parts by mass
("Daimic Beads UCN-8070CM Clear" manufactured by Dainichi Seika Kogyo Co., Ltd.)
(Average particle size: 7 μm)
By the above blending, the main agent / curing agent ratio: the molar ratio of the functional group (A) in the main agent / the reactive functional group (B) in the curing agent (B) / (A) = 2.0, solid content concentration 46 8%.

  In Comparative Example 3, the conditions of the non-adsorbent laminate and the packaging bag are all the same except that the type of resin particles in the non-adsorptive adhesive coating agent is different from Example 1.

<Comparative example 4>
A non-adsorptive adhesive coating agent was prepared with the following material composition, a non-adsorptive laminate was prepared, and a packaging bag was prepared.
(Non-adsorptive adhesive coating agent)
Polyester polyol 7.3 parts by mass (“Nipporan 131” manufactured by Tosoh Corporation)
12.7 parts by mass of polyisocyanate curing agent (“Takenate 160N” manufactured by Mitsui Chemicals, Inc.)
Ethyl acetate 80.0 parts by mass * Does not contain resin particles
By the above blending, main agent / curing agent ratio: molar ratio of functional group (A) in main agent / reactive functional group (B) in curing agent (B) / (A) = 2.0, solid content concentration 16 8%.

  In Comparative Example 4, the conditions of the non-adsorbing laminate and the packaging bag are all the same except that the ratio of ethyl acetate and the resin particles are not blended in the non-adsorbing adhesive coating agent from Example 1. It is.

Evaluation items, evaluation methods, and evaluation criteria are as follows.
(1, coating suitability)
The applicability of the non-adsorptive adhesive coating agent was evaluated.
The evaluation criteria are as follows.
A: Uniform coating is possible.
X: Uniform coating is not possible.

(2, non-adsorbing)
0.1 g of l-menthol was enclosed in a packaging bag, and the remaining side was sealed and sealed.
After leaving still for 7 days in an environment of 40 ° C. and 75% RH, l-menthol was removed, the packaging bag was opened and exposed to air for 5 minutes, and the condition of l-menthol after scent was subjected to sensory evaluation.
The evaluation criteria are as follows.
◯: Residual scent is hardly felt.
Δ: A little scent is felt ×: Slight scent is felt

(3, heat seal strength)
Bag making conditions: A bag was made into a pouch using a heat sealer: 180 ° C., 1 second, 2 kgf. The heat seal strength was measured when the heat-sealed portion of the test piece bag-formed under these conditions was peeled 90 ° at a peel rate of 300 mm / min using a tensile tester.
The evaluation criteria are as follows.
A: Strength of 20 N / 15 mm or more x: Strength of less than 20 N / 15 mm.

  These evaluation results are shown in Table 1.

  From the results shown in Table 1, in Example 1 according to the present invention, good evaluation results were obtained in all items of coating suitability, non-adsorption property, and heat seal strength.

  This is a non-adsorptive for a packaging bag having a non-adsorptive nature of the components of the contents in a packaging bag using a laminate based on a plastic film according to the present invention without impairing the heat sealability. It is possible to provide an adhesive coating agent, a non-adsorbing laminate using the same, and a packaging bag using the same, and show that both non-adsorbing property and heat sealing property can be realized. .

  On the other hand, in Comparative Example 1, the evaluation results were poor in coating suitability and heat seal strength. The evaluation results are all x.

  This is because the ratio of the polyacrylonitrile resin particles exceeds the upper limit of 50%, which is our knowledge for the present invention, and is 65%, leading to an increase in the viscosity of the non-adsorptive adhesive coating agent. It is considered that the workability is not uniform and as a result, the heat seal strength is reduced.

  Moreover, in the comparative example 2, it is an evaluation result in which the residual scent of 1-menthol is felt a little in non-adsorptive. The evaluation result is Δ.

This is because the ratio of the polyacrylonitrile resin particles is 0.005% below the lower limit of 0.01%, which is our knowledge for the present invention. It is thought that it was not possible.

  Moreover, in the comparative example 3, it is the evaluation result in which the residual scent of l-menthol remains in non-adsorptive. The evaluation result is x.

  This is considered to be due to the fact that the polyurethane fine particles are blended in place of the polyacrylonitrile resin particles, and that the polyurethane fine particles have almost no non-adsorbing effect. Therefore, the effect of the polyacrylonitrile resin particles according to the present invention on the non-adsorption property is supported.

  Moreover, in the comparative example 4, it is the evaluation result in which the residual scent of 1-menthol remains in non-adsorptive. The evaluation result is x.

  This is probably because the non-adsorbing adhesive coating agent was not blended with polyacrylonitrile resin particles, so that the adsorption effect was not expressed. Like Comparative Example 3, the polyacrylonitrile according to the present invention was not used. The results confirm the effect of the resin particles on the non-adsorption property.

  Thus, according to the present invention, in a packaging bag using a laminate based on a plastic film, the packaging bag has a fragrance of contents and a non-adsorbability of active ingredients without impairing heat sealability. Verifying that it is possible to provide a non-adsorptive adhesive coating agent, a non-adsorptive laminate using the non-adsorptive adhesive coating agent, and a non-adsorptive packaging bag using the non-adsorptive laminate I was able to.

DESCRIPTION OF SYMBOLS 1 ... Sealant layer 2 ... Non-adsorptive adhesive layer 3 ... Gas barrier layer 4 ... Base material layer 5 ... Film layer 6 ... Print layer 10 ... Laminate

Claims (7)

An adhesive coating agent comprising at least a main agent, a curing agent, a dispersion medium, and resin particles, the resin particles comprising polyacrylonitrile resin particles;
The average particle size of the polyacrylonitrile resin particles is 0.05 μm or more,
A non-adsorptive adhesive coating agent, wherein a ratio of polyacrylonitrile resin particles to a total mass of a main agent, a curing agent, a dispersion medium, and resin particles is 0.01% by mass or more and 50% by mass or less.   The non-adsorptive adhesive coating agent according to claim 1, wherein the main agent is a polyester polyol, and the curing agent is a polyisocyanate curing agent. A laminate comprising at least a surface in the order of a sealant layer, an adhesive layer, and a base material layer, the adhesive layer provided in contact with the other surface via the sealant layer on the surface side where the sealant layer is exposed Is obtained by curing the non-adsorptive adhesive coating agent according to claim 1 or 2,
The non-adsorbent laminate, wherein the proportion of the polyacrylonitrile resin particles in the adhesive layer is 0.3% by mass or more and 60% by mass or less.   The non-adsorbent laminate according to claim 3, wherein the base material layer is made of a plastic film.   The non-adsorbent laminate according to claim 3 or 4, wherein a gas barrier layer is provided on the plastic film of the base material layer.   The dry thickness of the said contact bonding layer is 0.005 micrometer or more and 10 micrometers or less, The nonadsorbable layered product in any one of Claims 3-5 characterized by the above-mentioned.   A packaging bag using the non-adsorbent laminate according to any one of claims 3 to 6.