JP7088360B2 - Packaging material and recycled base material manufacturing method - Google Patents

Description

The present invention relates to a packaging material containing a recyclable base material and a method for producing a recycled base material.

In recent years, packages made from plastic films, plastic bottles and other plastic products have been disposed of and dumped as garbage in the ocean, which has become an environmental pollution problem. These plastic products are decomposed in seawater into submicron-sized fragments (microplastics) that float in seawater. If the plastic is ingested by marine organisms such as fish, it will be concentrated in the organism and there is a concern that it will affect the health of seabirds and humans who ingest the marine organism as food. Various efforts have begun to reduce microplastics to remedy these problems.

Examples of the plastic products include food packaging packages using a plastic base material. In the package, various plastic base materials such as polyester (PET) base material, nylon (NY) base material, polypropylene (PP) base material and the like are used as the film base material. These plastic base materials are coated with a printing layer using gravure ink, flexographic ink, or other printing ink, and further bonded to a heat-melted resin base material (also referred to as a sealant base material) via an adhesive or the like to form a laminated body. Later, the laminate is cut and heat-sealed to form a package.

As an attempt to reduce the amount of microplastics, in the above package, (1) the plastic base material is replaced with paper, and (2) the plastic base material is limited to the use of only the same type to simplify recycling (referred to as monomaterialization). , (3) Remove impurities and recycle plastic.

Although the above (1) is promising in terms of safety and recyclability, there are many aspects inferior in performance to conventional plastic substrates such as gas barrier property, water vapor barrier property, and water resistance.
As for (2) above, a technique for covering the weak points of polyolefin with a functional coating agent such as a barrier coating agent is being developed, but in terms of performance as compared with conventional plastic substrates such as retort suitability and light shielding property. Due to its inferiority, replacement with polyolefin is not easy. Further, inks, functional coating agents, adhesives and the like between polyolefin substrates also have a problem of becoming impurities in recycling polyolefins.

As the above (3), an attempt has been made to remove the printed layer on the outer surface of the package, which becomes an impurity in the recycling process, with a basic aqueous solution.
For example, Cited Document 1 discloses a technique in which an undercoat layer made of an acrylic resin or a styrene maleic acid resin is provided on a plastic base material, and the printed layer arranged on the undercoat layer is removed with a basic aqueous solution. .. Further, Patent Document 2 discloses a technique of printing an ink using a polyurethane resin having an acidic group or an acrylic resin as a binder resin and removing the printing layer with a basic aqueous solution.
However, these are techniques that only remove the front printing ink on the outside of the package, and have not yet removed the ink layer in the laminated laminate and peeled off the base materials from each other.

In addition to removing the front printing ink layer for plastic recycling, the technology for removing the ink layer in the laminated laminate is an important technology that can be industrially used for environmental protection in promoting plastic recycling. However, the technology that can achieve both of these has not yet been reported.

Japanese Unexamined Patent Publication No. 2001-131484 Japanese Unexamined Patent Publication No. 11-209677

Therefore, the subject of the present invention is that it is excellent in the adhesiveness of the base material required as a packaging material, and it is possible to remove not only the printing layer on the outer side of the package but also the printing layer on the inner side of the package. It is an object of the present invention to provide a packaging material suitable for plastic recycling and a method for producing a recycled base material, which have excellent material releasability.

[1] The present invention includes a first base material, a first desorption layer for desorbing the first base material and recycling the first base material, and a second base material. , A packaging material comprising a second desorbing layer for desorbing the second substrate and recycling the second substrate.
The first desorbed layer is formed from the first desorbed layer forming composition (A).
The second desorbed layer is formed from the second desorbed layer forming composition (B).
The first desorbed layer forming composition (A) contains at least one inorganic substance selected from the group consisting of aluminum, aluminum oxide and silica, and the inorganic substance is the first desorbed layer forming composition. (A) 10% by weight or more of the total amount,
The second desorbing layer forming composition (B) is an adhesive composition containing a polyol component and a polyisocyanate component, and the polyisocyanate component is derived from an aliphatic polyisocyanate and an aromatic aliphatic polyisocyanate. It contains at least one polyisocyanate component selected from the above group, and the acid value of the reaction product of the polyol component and the polyisocyanate component is 5 mgKOH / g or more.
The present invention relates to a packaging material, wherein the polyol component contains at least two of the following three polyester polyol components.
First polyol component: Polyester polyol having an acid value of 10.0 mgKOH / g or more Second polyol component: Polyester polyol having an acid value of less than 10.0 mgKOH / g and a number average molecular weight of less than 3,000 Third polyol component: Acid Polyester polyol with a value of less than 10.0 mgKOH / g and a number average molecular weight of 5,000 or more

[2] Further, in the present invention, the packaging material according to [1], wherein the polyol component contains a polyester polyol component, and the content of the following first polyol component is 50% by mass or more with respect to the total amount of the polyester polyol component. Regarding.
First polyol component: Polyester polyol having an acid value of 10.0 mgKOH / g or more

[3] The present invention also relates to the packaging material according to [1] or [2], wherein the polyol component contains at least the following three polyester polyol components.
First polyol component: Polyester polyol having an acid value of 10.0 mgKOH / g or more Second polyol component: Polyester polyol having an acid value of less than 10.0 mgKOH / g and a number average molecular weight of less than 3,000 Third polyol component: Acid Polyester polyol with a value of less than 10.0 mgKOH / g and a number average molecular weight of 5,000 or more

[4] Further, in the present invention, the second desorbed layer forming composition (B) uses the oxygen acid of phosphorus or a derivative thereof as a reference based on the solid content of the second desorbed layer forming composition (B). , 0.01 to 5% by mass, according to any one of [1] to [3].

[5] The packaging material according to any one of [1] to [4], wherein the second desorbed layer forming composition (B) contains fine particles having an average particle size of 1 to 10 μm. Regarding.

[6] Further, according to [5], the present invention has a fine particle content of 0.1 to 10% by mass based on the solid content of the second desorbed layer forming composition (B). Regarding packaging materials.

[7] Further, the present invention is a method for producing a recycled base material, which comprises a step of immersing the packaging material according to any one of [1] to [6] in a basic aqueous solution, wherein the basic aqueous solution is basic. The present invention relates to a method for producing a recycled base material, wherein the compound is contained in an amount of 0.5 to 10% by mass based on the total amount of the basic aqueous solution, and the water temperature of the basic aqueous solution at the time of immersion is 30 to 120 ° C.

INDUSTRIAL APPLICABILITY According to the present invention, the adhesiveness of the base material required as a packaging material is excellent, and not only the printing layer on the outer side of the package but also the printing layer on the inner side can be removed, and the two types of base materials constituting the packaging material can be removed. It is possible to provide a packaging material having excellent properties and suitable for plastic recycling and a method for producing a recycled base material.

The embodiments of the present invention will be described in detail below, but the embodiments or requirements described below are examples of the embodiments of the present invention, and the present invention includes these contents as long as the gist thereof is not exceeded. Not limited.

The packaging material of the present invention comprises at least a first base material, a first desorption layer for desorbing the first base material and recycling the first base material, and a second base material. It is characterized by comprising a material and a second desorbing layer (hereinafter, also referred to as an adhesive layer) for desorbing the second base material and recycling the second base material.
In the present invention, "desorption" means that the first base material and the second base material are desorbed from the packaging material by neutralizing or dissolving the desorbed layer with a basic aqueous solution and peeling it off. , (1) When the desorbed layer dissolves and the base material desorbs, and (2) When the desorbed layer does not dissolve but peels off due to neutralization, swelling, etc. and the base material desorbs. Including the form of.
In this case, the desorption behavior of the first desorption layer and the desorption behavior of the second desorption layer may be different. That is, for example, the time until the first base material is peeled off and the time until the second base material is peeled off may be the same or different.
In the packaging material of the present invention, there may be a layer on the outside of the first base material (opposite to the first desorption layer) as long as the recycling of the base material is not hindered. There may be a layer on the outside of the substrate (opposite to the second desorbed layer).
Further, the first desorbed layer and the second desorbed layer may have the same composition. Further, the first desorbed layer and the second desorbed layer may be integrated.
Further, there may be a layer between the first desorbed layer and the second desorbed layer. In this case, if both base materials are peeled off, the first desorbed layer and the second desorbed layer may be integrated via the layer after the peeling.
Further, there may be a third base material to be recycled on the outside of the base material 1 or the base material 2, or between the base material 1 and the base material 2.
Details of the specific layer structure of the packaging material of the present invention will be described later.

In the packaging material, both base materials can be separated and both base materials can be separated and recovered by dissolving and peeling both desorbed layers with a basic aqueous solution or the like. Therefore, the packaging material of the present invention corresponds to the packaging material used for separating and recovering both base materials.
The present invention will be described in detail below, but these are examples of embodiments of the present invention, and the present invention is not limited to these contents as long as the gist thereof is not exceeded.

<First base material>
The first base material is a recyclable base material, and examples thereof include a plastic base material on a film or in the form of a sheet generally used for a packaging material, and a laminated body in which these are laminated may be used.
Examples of the plastic base material include a film made of a thermoplastic resin or a thermosetting resin, and a film made of a thermoplastic resin is preferable. Examples of the thermoplastic resin include polyolefin resins, polyester resins, polyamide resins, polystyrene resins, vinyl chloride resins, vinyl acetate resins, ABS resins, acrylic resins, acetal resins, polycarbonate resins, and fibrous plastics.

More specifically, polyolefin resin films such as polyethylene (PE), biaxially stretched polypropylene (OPP); polyester resin films such as polyethylene terephthalate, polyethylene naphthalate (PEN), polylactic acid (PLA); Polyethylene resin film such as nylon 6, poly-p-xylylene adipamide (MXD6 nylon); polycarbonate resin film; polyacrylic nitrile resin film; polyimide resin film; these multilayers (eg, nylon 6 / MXD6 / Nylon 6, nylon 6 / polyethylene-vinyl alcohol copolymer / nylon 6), a mixture; and the like are used. Among them, those having mechanical strength and dimensional stability are preferable.
The thickness of the plastic film is preferably 5 μm or more and 200 μm or less, more preferably 10 μm or more and 100 μm or less, and further preferably 10 μm or more and 50 μm or less.
The first base material may be a plastic base material having an organic layer such as polyvinyl alcohol.

When the first base material is a laminated body, it is preferable that the base materials are laminated via an adhesive layer. The method for forming the adhesive layer is not limited, and the adhesive layer can be formed by a known method using a known adhesive.
The first substrate may contain additives such as an antistatic agent and an ultraviolet inhibitor, if necessary, and the surface of the substrate may be corona-treated or low-temperature plasma-treated.

From the viewpoint of reuse as a recycled base material, the first base material preferably contains a polyolefin resin film such as polyethylene and biaxially stretched polypropylene.

<First desorbing layer for desorbing the first substrate, first desorbing layer forming composition (A)>
The first desorbed layer in the present invention is formed from the first desorbed layer forming composition (A), is arranged in contact with the first base material, and is dissolved / peeled using a basic aqueous solution. It is a layer for desorbing the first base material.
The first desorbed layer forming composition (A) contains at least one inorganic substance selected from the group consisting of aluminum, aluminum oxide and silica, and the inorganic substance is the first desorbed layer forming composition (1). A) It is 10% by weight or more of the total amount.
As a form containing the inorganic substance, the first desorption layer is a layer having a vapor deposition layer of at least one inorganic substance selected from the group consisting of aluminum, aluminum oxide and silica, or aluminum, aluminum oxide and silica. It is preferable that the layer contains at least one inorganic substance and a binder resin selected from the group consisting of.

(Evaporation layer made of at least one inorganic substance selected from the group consisting of aluminum, aluminum oxide and silica)
The first desorption layer is preferably a thin-film deposition layer. The vapor-filmed layer is composed of at least one inorganic substance selected from the group consisting of aluminum, aluminum oxide and silica, and can be formed by a conventionally known method, and the composition and forming method thereof are not particularly limited. The thin-film deposition layer is preferably composed of a non-crystalline (amorphous) layer. Further, from the viewpoint of visible light transmission, aluminum oxide and / or silica is preferable. Aluminum is preferable in order to form a form that exhibits light-shielding properties. However, the presence of elements or compounds other than aluminum, aluminum oxide and silica is not excluded during vapor deposition.
The first desorption layer may have two or more thin-film deposition layers. When two or more thin-film deposition layers are provided, they may have the same composition or different compositions. When the packaging material has a thin-film deposition layer, it also functions as an oxygen and / or water vapor barrier layer before desorption using a basic aqueous solution.

The vapor-filmed layer made of aluminum oxide and silica is preferably in the form of containing Al2O3 and SiO2, respectively. For example, when aluminum oxide is expressed in the form of AlOn, silica is expressed in SiOn, etc., the value of n is in the range of 0.5 to 1.5 for aluminum oxide and in the range of 1 to 2 for silica. Often, it does not exclude the forms of aluminum oxide and silica other than Al2O3 and SiO2. On the other hand, the thin-film deposition layer formed of aluminum is preferably a thin-film deposition film formed substantially only of aluminum from the viewpoint of light-shielding property.

The thickness of the vapor-film vapor film used in the present invention may be usually in the range of 1 to 400 nm, preferably in the range of 5 to 300 nm, and more preferably in the range of 10 to 200 nm.

When the vapor-filmed layer is aluminum, the thickness is preferably 5 to 300 nm, more preferably 10 to 100 nm, and even more preferably 10 to 60 nm. When the vapor-filmed layer is aluminum oxide and / or silica, the thickness is preferably 5 to 300 nm, more preferably 10 to 100 nm, and even more preferably 10 to 60 nm.
The thickness of the thin-film deposition film can be measured by a fundamental parameter method using, for example, a fluorescent X-ray analyzer (model name: EA6000VX or EA8000) manufactured by Hitachi High-Tech Science.

(Formation of thin-film deposition layer)
Examples of the method for forming the vapor deposition layer include a physical vapor deposition method (PVD method) such as a vacuum vapor deposition method, a sputtering method, and an ion plating method; a plasma chemical vapor deposition method and a thermochemical vapor deposition method. A method and a chemical vapor deposition method such as a photochemical vapor deposition method (Chemical Vapor Deposition method, CVD method); are preferable methods.
Commercially available products of the plastic base material having the vapor-deposited layer include, for example, "GL FILM" (manufactured by Toppan Printing Co., Ltd.) in which a vapor-filmed layer such as alumina is laminated on the first base material, and IB-FILM (manufactured by Toppan Printing Co., Ltd.). (Manufactured by Dai Nippon Printing Co., Ltd.).

The vapor-filmed layer may further have an easy-adhesive layer. The easy-adhesive layer is preferably, for example, an easy-adhesive layer made of a resin selected from a polyurethane resin layer, an acrylic resin layer, a polyester resin and polyvinyl alcohol, and is an easy-adhesive layer made of the water-based resin. Is more preferable. The easy-adhesive layer can be formed by printing or other known methods.

(A layer containing at least one inorganic substance and a binder resin selected from the group consisting of aluminum, aluminum oxide and silica)
It is also preferable that the first desorption layer is a layer containing at least one inorganic substance selected from the group consisting of aluminum, aluminum oxide and silica and a binder resin. The thickness of such a layer is preferably 1 to 10 μm, and preferably 1 to 6 μm.
The mass ratio of the binder resin to the inorganic substance (binder resin / inorganic substance) is preferably 90/10 to 20/80.

Among the inorganic substances, aluminum oxide (Al2O3) is preferably contained, and α particle crystals and / or γ particle crystals are preferable. The average particle size of aluminum oxide is preferably 0.1 to 4 μm. The average particle size means a value with a cumulative frequency of 50% (D50) measured by dynamic light scattering.
The amount of aluminum contained in the layer containing the inorganic substance and the binder resin is preferably 80% by mass or more of the entire layer. Further, the amount of aluminum oxide contained in the layer is preferably 10% by mass or more of the entire layer. Further, the silica contained in the layer is preferably 10% by mass or more of the entire layer.
The packaging material of the present invention does not exclude that the printing layer described later contains aluminum, aluminum oxide and silica, but the amount of aluminum, aluminum oxide and silica contained in the printing layer is higher than that of the first desorption layer. Few.

(Binder resin)
The inorganic substance and the binder resin are preferably resins of the same type as in the case of the easy-adhesion layer, and may be an aqueous resin or a resin soluble in an organic solvent. For example, a resin selected from a polyurethane resin layer, an acrylic resin layer, a polyester resin, and polyvinyl alcohol is preferable. These may be used in combination of a plurality of types.

The first desorption layer containing the inorganic substance and the binder resin is gravure using the first desorption layer forming composition (A) composed of the inorganic substance, the binder resin and the organic solvent on the first base material. It can be formed by a printing method, a flexographic printing method or other printing method, or a known coating method.

The composition preferably contains an inorganic substance and a binder resin in a total mass of 5 to 60% by mass. It is still more preferable to contain it in an amount of 8 to 50% by mass.
Examples of the organic solvent include isopropyl alcohol (IPA), ethanol, normal propanol and other alcohol-based organic solvents, ethyl acetate, normal propyl acetate and other ester-based organic solvents, methyl ethyl ketone, methyl isobutyl ketone and other ketone-based organic solvents, and toluene. , Xylene and other aromatic organic solvents are preferable. It is preferable to use it as a mixed solvent of two or more kinds.

(Manufacturing of a composition composed of an inorganic substance, a binder resin and an organic solvent)
The composition consisting of an inorganic substance, a binder resin and an organic solvent is prepared by dissolving and / or dispersing at least one inorganic substance selected from the group consisting of aluminum, aluminum oxide and silica, and a binder resin in an organic solvent solution. Can be manufactured.
For example, such a composition is produced by dispersing it in aluminum oxide particles and a polyurethane resin organic solvent, and blending the polyurethane resin, if necessary, an organic solvent, other resins, additives, etc. with the inorganic substance dispersion. be able to. The viscosity of the composition should be adjusted by appropriately adjusting the size of the crushed media of the disperser, the filling rate of the crushed media, the dispersion treatment time, the discharge rate of the metal particle dispersion, the viscosity of the pigment dispersion, and the like. Can be done. As the disperser, commonly used, for example, a roller mill, a ball mill, a pebble mill, an attritor, and a sand mill can be used. It is preferably manufactured using a sand mill or other bead mill.

(Additive)
The composition composed of an inorganic substance, a binder resin and an organic solvent can appropriately contain conventionally known additives, for example, pigment derivatives, dispersants, wetting agents, adhesive aids, leveling agents, defoaming agents, etc. Antistatic agents, viscosity modifiers, metal chelate, trapping agents, antiblocking agents, wax components can be used.

<Print layer>
The printed layer in the present invention is a layer provided in contact with the first desorbed layer on the side opposite to the first base material of the first desorbed layer, and is used for decoration, imparting aesthetics, contents, and the like. A layer that forms an arbitrary print pattern for the purpose of expiration date, display of a manufacturer or a seller, and the like, and includes a solid print layer. The printing layer can be provided, for example, between the first desorption layer and the adhesive layer, and may be provided on the entire surface or a part of the first desorption layer.
The printing layer can be formed by using a conventionally known pigment or dye, and may be formed by using a printing ink containing the pigment or dye, and the forming method thereof is not particularly limited. The print layer may be formed of a single layer or a plurality of layers. Further, the printed layer may include an anchor coat (AC) layer, or may have both a layer containing a pigment or a dye and a layer not containing a pigment or a dye.
The thickness of the printed layer is preferably 0.1 μm or more and 100 μm or less, more preferably 0.1 μm or more and 10 μm or less, and further preferably 1 μm or more and 5 μm or less.

Examples of the printing ink for forming the printing layer include printing inks containing a medium such as a pigment, a binder resin, a solvent, or water. The binder resin for the printing ink preferably has a composition that suppresses the dissolution or fine dispersion of the printing layer in the basic aqueous solution in order to facilitate the removal of the printing layer. Examples of the binder resin include fiber materials such as nitrocellulose and cellulose acetate propionate, chlorinated polypropylene, vinyl chloride-vinyl acetate copolymer, polyester, acrylic, polyurethane and acrylic urethane, and polyamide. , Polybutyral type, cyclized rubber type, chloride rubber type, or a binder in which they are appropriately used can be used.

[Pigment]
The packaging material containing the printing layer used in the present invention is obtained by immersing a 2 cm × 2 cm cut piece in 50 ml of a 2 mass% sodium hydroxide aqueous solution at 70 ° C. for 2 hours in the visible light region of the aqueous solution (400 to 400 to”. The transmittance at the maximum absorption wavelength of 760 nm) is preferably 75% or more. A major factor in lowering the transmittance is that the ink pigment contained in the print layer elutes into the sodium hydroxide aqueous solution.
Recycled base materials for packaging materials are generally colored and are often used for applications where coloring is not a problem. However, if uncolored recycled base materials are obtained, the range of applications will be expanded. It is expected. It is meaningful to satisfy the regulation of the transmittance, which is an index of whether or not the recycled base material is colored.
In order for the pigment to satisfy the regulation of the transmittance, it is necessary that the pigment has alkali resistance. The alkali resistance of pigments can be roughly estimated from the pigment skeleton and structure. It can be said that those derived from dyes that dissolve in an alkaline aqueous solution and those that decompose in an alkaline aqueous solution do not have alkali resistance.
Further, even if the pigment itself has alkali resistance, the auxiliary component contained in the pigment may lower the transmittance, which is also not preferable in the application in which coloring is a problem.
For example, examples of the alkali-resistant pigment include inorganic pigments, P.I. B. 15, P.I. Y. 83 and the like can be mentioned.

The method of applying the printing ink is not particularly limited, and the printing ink can be applied by a method such as a gravure coating method, a flexographic coating method, a roll coating method, a bar coating method, a die coating method, a curtain coating method, a spin coating method, and an inkjet method. .. The printed layer can be formed by leaving it as it is or, if necessary, by blowing air, heating, drying under reduced pressure, irradiating with ultraviolet rays, or the like.

<Second base material>
The packaging material of the present invention has a form in which the second base material is located on the uppermost side of the packaging material when the first base material is on the lower side, but if necessary, further of the second base material. A protective layer or the like may be provided on the upper side.
The second base material may be, for example, the base material mentioned in the above-mentioned first base material or the sealant base material, and may be a laminated body in which these are laminated. The second base material is preferably a sealant base material and contains polyolefin. The second base material may have a vapor-deposited film such as silica or alumina.
Examples of the sealant base material include low-density polyethylene (LDPE), polyethylene such as linear low-density polyethylene (LLDPE) and high-density polyethylene (HDPE), acid-modified polyethylene, unstretched polypropylene (CPP), and acid-modified polypropylene. Examples thereof include polyethylene copolymer, polyethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid ester copolymer, polyethylene- (meth) acrylic acid copolymer, and ionomer.
From the viewpoint of recyclability, the second base material is preferably polyolefin such as low-density polyethylene, linear low-density polyethylene, high-density polyethylene, acid-modified polyethylene, unstretched polypropylene, acid-modified polypropylene, and copolymerized polypropylene.
From the viewpoint of retort resistance, polypropylene is preferable, and from the viewpoint of heat sealability, unstretched polypropylene is preferable.

The thickness of the second base material is not particularly limited, and is preferably 10 μm or more and 150 μm or less, and more preferably 20 μm or more and 70 μm or less in consideration of processability to the packaging container, heat sealability, and the like. By providing the second base material with irregularities having a height difference of about several μm, slipperiness and tearability of the packaging material can be imparted.
The method of laminating the second base material is not particularly limited, and for example, the printed surface of the laminated film having the first base material, the first desorption layer and the printing layer, and the second base material are laminated. Examples thereof include a method of bonding with an adhesive; a method of melting a resin constituting a second base material, extruding it onto a printing layer, and cooling and solidifying it.

The following is an example of the configuration of the packaging material of the present invention, but the present invention is not limited thereto. As described above, the first base material and the second base material may be a laminated body in which a plurality of base materials are laminated.
-First base material / first desorption layer / adhesive layer / second base material-first base material (laminated body) / first desorption layer / printing layer / adhesive layer / second Base material / first base material / first desorption layer / printing layer / adhesive layer / second base material / first base material / first desorption layer / printing layer / adhesive layer / Second base material (laminated body)

<Second Desorption Layer Forming Composition (B) (hereinafter, also referred to as Adhesive Composition)>
The second desorbed layer in the present invention is formed from the second desorbed layer forming composition (B), is arranged in contact with the second base material, and is dissolved / peeled using a basic aqueous solution. It is a layer for desorbing the second base material.
The second desorption layer forming composition (B) is composed of a two-component curable adhesive composition containing a polyol component and a polyisocyanate component, and the polyol component and the polyisocyanate component are urethane-bonded. Is formed and cured, and then becomes a reactant. The second desorption layer is also referred to as an adhesive layer.

[Polyol component]
The polyol component includes a polyester polyol component. The polyester polyol component can be selected from conventionally known polyol components, but contains at least two of the following three polyester polyol components.
First polyol component: Polyester polyol having an acid value of 10.0 mgKOH / g or more Second polyol component: Polyester polyol having an acid value of less than 10.0 mgKOH / g and a number average molecular weight of less than 3,000 Third polyol component: Acid A polyester polyol having a value of less than 10.0 mgKOH / g and a number average molecular weight of 5,000 or more.

(Polyester polyol)
The polyol component preferably contains a polyester polyol because the desorption property is improved when it has an ester bond having a high affinity with a basic aqueous solution.
Polyester polyols include, but are not limited to, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, phthalic anhydride, adipic acid, azelaic acid, sebacic acid, succinic acid, glutaric acid, tetrahydrophthalic anhydride, and the like. Dibasic acids such as phthalic anhydride, maleic anhydride, and itaconic anhydride, dialkyl esters thereof, or mixtures thereof (hereinafter, also referred to as carboxy group components),
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'-dimethylolheptan, 1,9-nonanediol, polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol , Polyether polyols, polycarbonate polyols, polyolefin polyols, acrylic polyols, polyurethane polyols and other diols or mixtures thereof (hereinafter, also referred to as hydroxyl group components).
Examples thereof include polyester polyols obtained by reacting with the above; or polyester polyols obtained by ring-opening polymerization of lactones such as polycaprolactone, polyvalerolactone, and poly (β-methyl-γ-valerolactone).
Two or more kinds of the above-mentioned carboxy group component and hydroxyl group component may be used in combination.

The polyester polyol preferably has a urethane bond, and may be, for example, a polyester polyurethane polyol further reacted with diisocyanate. Further, the polyester polyol and the polyester polyurethane polyol may be further reacted with an acid anhydride.
Examples of the diisocyanate include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, hexamethylene diisocyanate, and hydrogenated diphenylmethane diisocyanate. Will be.
Examples of the acid anhydride include pyromellitic anhydride, melitric anhydride, trimellitic anhydride, and trimellitic acid ester anhydride. Examples of the trimellitic acid ester anhydride include ethylene glycol bisamhydrotrimellitic acid and propylene glycol bisamhydrotrimellitic acid.

Above all, the polyester polyol preferably contains an acid anhydride modified product of the polyester polyurethane polyol. When the polyester polyol has a urethane bond, it can exhibit excellent heat resistance and adhesiveness. When the polyester polyol is an acid anhydride modified product, the acid value can be finely controlled, and a polyester polyol in a suitable acid value range as described later can be easily obtained, which is preferable.

The polyol component in the present invention preferably contains a polyester polyol having an acid value of 10.0 mgKOH / g or more (also referred to as a first polyol component), and the first polyol component is 50% by mass based on the total amount of the polyester polyol component. The above is preferable.
In this case, the first polyol component is further added to the polyester polyol (also referred to as the second polyol component) having an acid value of less than 10.0 mgKOH / g and a number average molecular weight of less than 3,000, and / or an acid value of 10.0 mgKOH. It is preferable to use a polyester polyol (also referred to as a third polyol component) having a number average molecular weight of 5,000 or more and less than / g.

The adhesive composition, which is the second desorbed layer forming composition (B), preferably has an acid value. When the adhesive composition has an acid value, the neutralizing action with the basic compound facilitates peeling of the second base material in the basic aqueous solution. Therefore, the polyol component preferably has an acid value, and the acid value of the polyol component is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more.

When the polyol component contains a plurality of polyols, the acid value of the polyol component can be obtained from the acid value of each polyol and its mass ratio.

The polyol component preferably contains a polyol having a number average molecular weight of 5,000 to 15,000, and further preferably contains a polyester polyol having a number average molecular weight of less than 3,000 in order to improve substrate adhesion.

(Acrylic polyol)
Acrylic having a hydroxy group, which is obtained by monopolymerizing a (meth) acrylic monomer having a hydroxy group such as 2-hydroxyethyl (meth) acrylate as a polyol component, or copolymerizing with another (meth) acrylic monomer or a vinyl monomer. Acrylics can also be suitably used.

(Other polyols)
The adhesive composition which is the second desorption layer forming composition (B) may contain other polyols other than the polyester polyol. The polyols that may be contained in addition to the polyester polyols are not particularly limited, and examples thereof include polycarbonate polyols, polycaprolactone polyols, polyether polyols, polyolefin polyols, silicone polyols, castor oil-based polyols, and fluorine-based polyols. These may be used alone or in combination of two or more.

[Polyisocyanate component]
The polyisocyanate component is not particularly limited as long as it contains at least one polyisocyanate component selected from the group consisting of aliphatic polyisocyanates and aromatic aliphatic polyisocyanates. These may be used alone or in combination of two or more.

(Aliphatic polyisocyanate)
The aliphatic polyisocyanate is not limited to the following, and a well-known aliphatic diisocyanate or a compound derived from an alicyclic diisocyanate can be used.
Examples of the aliphatic polyisocyanate that can be used in the present invention include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylenediocyanate, 2,3-butylenediocyanate, and 1 , 3-Butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate, aliphatic diisocyanates such as methylcaproate; 1,4-cyclohexanediisocyanate, 1,3- Cyclohexanediisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate, 4,4'-methylenebis (cyclohexylisocyanate), methyl2,4-cyclohexanediisocyanate, methyl2,6-cyclohexanediisocyanate, 1,4- Alicyclic diisocyanates such as bis (isocyanatemethyl) cyclohexane and 1,3-bis (isocyanatemethyl) cyclohexane; allophanate type, nurate type, biuret type, adduct type derived from the above aliphatic diisocyanate or alicyclic diisocyanate. Polyisocyanates such as derivatives or complexes thereof; may be mentioned.
The derivative is preferably a nurate type or adduct type derivative, and particularly preferably an adduct type.
The aliphatic polyisocyanate is preferably a polyisocyanate derived from hexamethylene diisocyanate (hereinafter referred to as HDI), which makes it easy to secure a balance between desorption and laminate physical characteristics.

(Aromatic aliphatic polyisocyanate)
The aromatic aliphatic polyisocyanate may be any aliphatic polyisocyanate having an aromatic ring, and a compound derived from a well-known aromatic aliphatic diisocyanate can be used.
Examples of the aromatic aliphatic polyisocyanate that can be used in the present invention include 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, ω, ω'-diisocyanate-1,4-diethylbenzene, 1,3-. Alternatively, aromatic aliphatic diisocyanates such as 1,4-bis (1-isocyanate-1-methylethyl) benzene or a mixture thereof; polyisocyanates such as derivatives of the above aromatic aliphatic diisocyanates or composites thereof; may be mentioned.

<Manufacturing of adhesive composition>
The adhesive composition, which is the second desorbed layer forming composition (B), may further contain other components. Other components may be added to either the polyol component or the polyisocyanate component, or may be added when the polyol component and the polyisocyanate component are mixed.

[Other ingredients]
(Silane coupling agent)
The adhesive composition may further contain a silane coupling agent in order to increase heat resistance and water resistance. Examples of the silane coupling agent include trialkoxysilanes having a vinyl group such as vinyltrimethoxysilane and vinyltriethoxysilane; 3-aminopropyltriethoxysilane and N- (2-aminoethyl) 3-aminopropyltrimethoxy. Trialkoxysilane having an amino group such as silane; glycidyl group such as 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane Trialkoxysilanes with; The amount of the silane coupling agent added is preferably 0.1 to 5% by mass, more preferably 0.5 to 3% by mass, based on the solid content of the adhesive composition.

(Oxygen acid of phosphorus or its derivative)
The adhesive composition may further contain an oxygen acid of phosphorus or a derivative thereof in order to enhance acid resistance. Among the oxygen acids of phosphorus or derivatives thereof, the oxygen acid of phosphorus may be any one having at least one free oxygen acid, for example, hypophobic acid, phobic acid, orthoric acid, the following. Examples thereof include phosphoric acids such as phosphoric acid, and condensed phosphoric acids such as metaphosphate, pyrophosphate, tripolyphosphate, polyphosphate, and ultraphosphate. Examples of the derivative of the oxygen acid of phosphorus include those obtained by partially esterifying the oxygen acid of phosphorus with alcohols while leaving at least one free oxygen acid. Examples of these alcohols include fatty alcohols such as methanol, ethanol, ethylene glycol and glycerin; aromatic alcohols such as phenol, xylenol, hydroquinone, catechol and fluoroglycinol. Oxygen acid of phosphorus or a derivative thereof may be used in combination of two or more. The amount of phosphorus oxygen acid or its derivative added is 0, based on the solid content of the adhesive composition.
It is preferably 01 to 10% by mass, more preferably 0.05 to 5% by mass, and particularly preferably 0.1 to 1% by mass.

In addition, the adhesive composition may contain the above-mentioned oxygen acid of phosphorus or a derivative thereof in order to improve the desorption property of the second desorbing layer and enhance the recyclability. From the viewpoint of the strength and detachability of the packaging material, the content of oxygen acid or a derivative thereof of phosphorus is preferably 0.01 to 5% by mass based on the solid content of the adhesive composition. That is, the second desorbed layer contains an oxygen acid of phosphorus or a derivative thereof, preferably in the range of 0.01 to 5% by mass based on the mass of the second desorbed layer.
More specifically, the amount of oxygen acid in phosphorus is more preferably 0.01 to 1% by mass, still more preferably 0.01 to 0.5% by mass, based on the solid content of the adhesive composition. be. When the blending amount is 0.01% by mass or more, the detachability is further improved while maintaining the strength of the packaging material. When it is within 1% by mass, it is more excellent in strength as a packaging material.

The blending amount of the phosphoric acid derivative is preferably 0.01 to 5% by mass, more preferably 0.1 to 3% by mass, based on the solid content of the adhesive composition. When the blending amount is 0.01% by mass or more, the detachability is further improved while maintaining the strength of the packaging material. When it is within 5% by mass, it is more excellent in strength as a packaging material.

(Leveling agent or antifoaming agent)
The adhesive composition may further contain a leveling agent or an antifoaming agent in order to improve the appearance of the laminate. 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, and acrylic copolymer. , Methacrylate-based copolymers, polyether-modified polymethylalkylsiloxanes, acrylic acid alkyl ester copolymers, methacrylic acid alkyl ester copolymers, and lecithin.
Examples of the defoaming agent include known ones such as a silicone resin, a silicone solution, and a copolymer of an alkyl vinyl ether, an acrylic acid alkyl ester, and a methacrylic acid alkyl ester.

(Reaction accelerator)
Since the adhesive composition promotes the urethanization reaction, a reaction accelerator can be further contained. Examples of the reaction accelerator include metal-based catalysts such as dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, and dibutyltin dimarate; 1,8-diazabicyclo (5,4,0) undecene-7,1, Tertiary amines such as 5-diazabicyclo (4,3,0) nonen-5,6-dibutylamino-1,8-diazabicyclo (5,4,0) undecene-7; reactive tertiary amines such as triethanolamine ; Can be used, and one or more selected from these groups can be used.

The adhesive composition may contain various additives as long as the effects of the present invention are not impaired. Examples of the additive include inorganic fillers such as silica, alumina, mica, talc, aluminum flakes, and glass flakes, layered inorganic compounds, stabilizers (antioxidants, heat stabilizers, ultraviolet absorbers, hydrolysis inhibitors, etc.). ), Anti-rust agent, thickener, plasticizer, antistatic agent, lubricant, anti-blocking agent, colorant, filler, crystal nucleating agent, catalyst for adjusting the curing reaction and the like can be exemplified.

(Particles with an average particle size of 1 to 10 μm)
In addition, the adhesive composition can contain fine particles having an average particle size of 1 to 10 μm as the above-mentioned additive in order to improve the desorption property of the second desorbing layer and enhance the recyclability.
It is presumed that the inclusion of such fine particles improves the detachability because the contact area between the adhesive composition and the base material is reduced while the strength of the packaging material is maintained due to the anchoring effect on the base material.
When the average particle size is 1 μm or more, the detachability is further improved while maintaining the strength of the packaging material. When the average particle size is within 10 μm, the strength as a packaging material can be maintained. The average particle diameter in the present specification means the median diameter as measured by a particle diameter distribution measuring device using a laser diffraction / scattering method.
The fine particles having an average particle diameter of 1 to 10 μm are not particularly limited, and are, for example, inorganic fillers such as silica, alumina, mica, talc, aluminum flakes, and glass flakes, as well as aluminum hydroxide and precipitated barium sulfate. , Magnesium carbonate, calcium carbonate, zeolite, and resin beads such as acrylic beads and urethane beads.

From the viewpoint of the strength and detachability of the packaging material, the blending amount of the fine particles is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% based on the solid content of the adhesive composition. It is 0.0% by mass. That is, the second desorbed layer in the present invention contains fine particles having an average particle diameter of 1 to 10 μm, preferably in the range of 0.1 to 10% by mass based on the mass of the second desorbed layer. It is more preferably contained in the range of 0.5 to 5.0% by mass. When the blending amount is 0.5% by mass or more, the strength of the packaging material is maintained and the detachability is further improved. When it is within 5.0% by mass, it is more excellent in strength as a packaging material.

The second desorbed layer preferably contains both the oxygen acid of phosphorus or a derivative thereof and the fine particles having an average particle size of 1 to 10 μm. By including both, the desorption property and the removal rate are further improved.

When the viscosity of the adhesive composition is room temperature to 150 ° C., preferably 100 to 10,000 mPa · s, preferably 100 to 5,000 mPa · s at room temperature to 100 ° C., the adhesive composition can be used in a solvent-free form. .. If the viscosity of the adhesive composition is higher than the above range, it may be diluted with an organic solvent. As the organic solvent, for example, an ester-based solvent such as ethyl acetate, a ketone-based solvent such as methyl ethyl ketone, and an aromatic hydrocarbon-based solvent such as toluene and xylene, which are inert to polyisocyanate components, are preferably used. It can be selected and used as appropriate.

The acid value of the reaction product of the polyol component and the polyisocyanate component in the second desorbed layer forming composition (B) is preferably 5 mgKOH / g or more, more preferably 7 mgKOH / g or more, still more preferably 10 mgKOH. / G or more, particularly preferably 20 mgKOH / g or more. When the acid value is 5 mgKOH / g or more, the peeling of the second base material with a basic aqueous solution becomes easy.

When blending the polyol component and the polyisocyanate component, it is preferable to blend them so that the equivalent ratio (NCO / OH) of the isocyanate group of the polyisocyanate to the hydroxyl group in the polyol is 0.3 to 5.0. It is more preferably 0.3 to 2.0, and particularly preferably 0.5 to 1.5.

As a method for forming the second desorption layer, generally, when there is a print layer, a print layer is formed on the first base material via an inorganic layer, and the adhesive composition is formed on the print layer. After applying the substance and volatilizing the organic solvent through a drying step if necessary, it is bonded to the second base material using a laminator and cured at room temperature or under heating to form the second desorbed layer. The method of forming is mentioned.
The amount of the adhesive composition applied after drying is not limited and is usually in the range of 0.001 to 6 g / m2, preferably 1 to 2.5 g / m2 for the solvent-free type and 1 to 6 g / m2 for the solvent type. Is the range of.
The thickness of the adhesive layer is not limited and is usually in the range of 0.001 to 5 μm, preferably 1 to 2 μm in the solvent-free type and 1 to 5 μm in the solvent type.

<Packaging container>
The packaging material of the present invention can be used alone by being processed into a bag shape, a tubular shape, or the like, but can be used as a packaging container in combination with other packaging materials. Since at least a part of the packaging container is made of the packaging material, a packaging container in which the first substrate mainly used as a printing substrate can be recycled can be obtained from the packaging material portion. Be done.
The type and use of the packaging material and the packaging container of the present invention are not particularly limited, but can be suitably used for, for example, food containers, detergent containers, cosmetic containers, and pharmaceutical containers. The shape of the packaging container is not limited, and it can be molded into a shape according to the contents, and is preferably used for a pouch or the like.

<Manufacturing method of recycled base material>
In the method for producing a recycled base material of the present invention, at least the first base material, the first desorbing layer for desorbing the first base material, the second base material, and the second base material are desorbed. By the step of immersing the packaging material provided with the second desorbing layer for the purpose of immersing in a basic aqueous solution, the first base material and the second base material are desorbed from the packaging material, and the first base material and the first base material are desorbed. The base material of 2 can be recycled.

Since the present invention aims to obtain each of the desorbed base materials as a recycled base material and a recycled base material, it is preferable to remove as much of each desorbed layer as possible from each base material. Is. Specifically, it is preferable that at least 50% by mass or more of each desorbed layer is desorbed in the area and film thickness direction. It is more preferable that 60% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass or more are desorbed.

The basic compound used in the basic aqueous solution is not particularly limited, and is, for example, sodium hydroxide (NaOH), potassium hydroxide (KOH), calcium hydroxide (Ca (OH) 2), ammonia, barium hydroxide (Ba (Ba). OH) 2) and sodium carbonate (Na2CO3) are preferably used, but are not limited thereto. More preferably, it is at least one selected from the group consisting of sodium hydroxide and potassium hydroxide.
The basic aqueous solution preferably contains the basic compound in an amount of 0.5 to 20% by mass, more preferably 1 to 15% by mass, and particularly preferably 3 to 10% by mass, based on the total amount of the basic aqueous solution. When the concentration is within the above range, the basic aqueous solution can be stripped by dissolving or swelling each desorbed layer and retain sufficient basicity to desorb each base material.

The basic aqueous solution permeates from the end portion of the packaging material or the packaging container, contacts each desorbed layer, dissolves or swells, and desorbs each base material and each desorbed layer. Therefore, in order to efficiently proceed with the desorption step, the packaging material or the packaging container must be in a state where each desorption layer is exposed on the cross section when the packaging material or the packaging container is cut or crushed and immersed in a basic aqueous solution. preferable. In such a case, each base material layer can be desorbed in a shorter time.

The temperature of the basic aqueous solution when the packaging material is immersed is preferably 25 to 120 ° C, more preferably 30 to 120 ° C, and particularly preferably 30 to 80 ° C. The immersion time in the basic aqueous solution is preferably 1 minute to 24 hours, more preferably 1 minute to 12 hours, and preferably 1 minute to 6 hours. The amount of the basic aqueous solution used is preferably 1 to 1,000,000 times the mass of the packaging material, and it is preferable to stir or circulate the basic aqueous solution in order to improve the desorption efficiency. The rotation speed is preferably 80 to 250 rpm, more preferably 80 to 200 rpm.

After removing and recovering each base material from the packaging material, each base material can be obtained by washing and drying each base material with water. The removal rate of the printed layer on the surface of each substrate is preferably 70% or more, more preferably 80% or more, and particularly preferably 90% or more with respect to the area of the packaging material before desorption.

Therefore, according to the present invention, preferably, the step of immersing the packaging material or the packaging container in the basic aqueous solution, the respective desorption layers are dissolved or peeled from the packaging material or the packaging container, and the respective base materials are desorbed. A recycled base material of each base material can be obtained by going through a step, a step of recovering each base material, and a step of washing and drying each base material with water. Further, the obtained recycled base material can be processed into pellets by an extruder or the like and reused as a recycled resin.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. The "parts" and "%" in the present invention mean "parts by mass" and "% by mass" unless otherwise specified.

<Number average molecular weight (Mn), weight average molecular weight (Mw)>
The number average molecular weight and the weight average molecular weight were measured using GPC (gel permeation chromatography) "Shodex GPC System-21" manufactured by Showa Denko KK. In the measurement, tetrohydrofuran was used as a solvent, and the value converted to standard polystyrene was obtained.

<Measurement of acid value>
The method for measuring the acid value is as follows. First, about 1 g of a sample is precisely weighed in an Erlenmeyer flask with a stopper, and 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol = 2/1) mixed solution is added to dissolve the sample, and a phenolphthalein test solution is added as an indicator. It was held for 30 seconds. Then, the solution was titrated with a 0.1N alcoholic potassium hydroxide solution until the solution turned pink, and the acid value was determined by the following formula.
Acid value (mgKOH / g) = (5.611 × a × F) / S
S: Sample collection amount (g)
a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml)
F: Factor of 0.1N alcoholic potassium hydroxide solution

<Manufacturing of printing ink>
[Manufacturing Example A] (Printing Ink R1)
PU (KL-593 manufactured by Arakawa Chemical Co., Ltd .: polyurethane resin combined with polyester polyether, solid content concentration 30%, mixed solution of ethyl acetate and isopropanol) 30 parts, PVC (solvine TAO manufactured by Nisshin Chemical Co., Ltd .: solid content concentration 30%) , 10 parts of ethyl acetate solution), 10 parts of indigo pigment (Rionol Blue FG7330 manufactured by Toyo Color Co., Ltd.), and 20 parts of a mixed solvent of NPAC and IPA were stirred and mixed, and dispersion treatment was performed for 20 minutes using a sand mill. .. Then, 30 parts of the mixed solvent of NPAC and IPA was stirred and mixed to obtain printing ink R1.

[Manufacturing Examples B to E] (Printing Inks R2 to R5)
Printing inks R2 to R5 were obtained by the same method as in Production Example A except that the raw materials and compounding ratios shown in Table 1 were used.

The abbreviations in Table 1 are shown below.
-PU: Polyurethane resin solution (KL-593 manufactured by Arakawa Chemical Co., Ltd .: Polyester polyether combined polyurethane resin, solid content concentration 30%, mixed solution of ethyl acetate and isopropanol)
-PVC: Vinyl chloride-vinyl acetate copolymer resin solution (Solvine TAO manufactured by Nissin Chemical Co., Ltd .: solid content concentration 30%, ethyl acetate solution)
NC: Nitrocellulose resin solution (nitrocellulose content 11.5%, nitrocellulose Mw 50,000, solid content concentration 30% solution)
-PAM: Polyamide resin solution (polyamide resin having a dimer acid-derived structure, solid content concentration 30% solution)
AC: Acrylic resin solution (Mw40,000, acid value 60 mgKOH / g styrene-acrylic copolymer resin solid content concentration 30% solution)
-Indigo pigment: Lionol Blue FG7330 manufactured by Toyo Color Co., Ltd.
-NPAC: Normalpropyl acetate-IPA: Isopropyl alcohol-Curing agent B: HDI-based polyisocyanate (Duranate P301-75E manufactured by Asahi Kasei Corporation: Solution diluted with ethyl acetate to a solid content concentration of 50%)

<Manufacturing of anchor coat layer composition>
[Production Example F] (Anchor Coat Layer Composition S1)
In a reactor equipped with a reflux cooling tube, a dropping funnel, a gas introduction tube, a stirrer, and a thermometer, while introducing nitrogen gas, PPA (polycondensate of propylene glycol and adipic acid, number average molecular weight 2) 147.9 parts of 000 polyester polyol, 14.8 parts of PPG (polyether polyol consisting of polypropylene glycol having a number average molecular weight of 2,000), 2,2-dimethylolpropanoic acid (hereinafter, DMPA) 25.2 96.8 parts of isophorone diisocyanate (hereinafter, IPDI) and 200 parts of normal propyl acetate (hereinafter, NPAC) were charged and reacted at 90 ° C. for 5 hours to obtain a urethane prepolymer solution having an isocyanate group at the terminal.
Then, a mixture of 15.4 parts of 2- (2-aminoethylamino) ethanol (hereinafter, AEA) and 350 parts of isopropyl alcohol (hereinafter, IPA) was added dropwise at room temperature over 60 minutes, and then at 70 ° C. The reaction was carried out for 3 hours to obtain an oil-based polyurethane resin solution.
NPAC is added to the obtained polyurethane resin solution to adjust the solid content, and the oil-based polyurethane resin has a solid content concentration of 30%, a mass average molecular weight of 29,000, Mw / Mn = 3.2, and an acid value of 35.1 mgKOH / g. A solution of P1 was obtained.
Further, 87 parts of a solution of polyurethane resin P1, 5 parts of ethyl acetate (hereinafter referred to as EA), 5 parts of IPA, and 3 parts of silica particles (P-73 manufactured by Mizusawa Chemical Co., Ltd .: hydrophilic silica particles having an average particle diameter of 3.8 μm) were added. The mixture was stirred and mixed using a disper to obtain an anchor coat layer composition S1.

<Manufacturing of polyol>
(Synthesis Example 1) Polyester polyol (A-1)
830 parts of diethylene glycol and 870 parts of adipic acid are charged in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping tank and a nitrogen gas introduction pipe, and the temperature is raised to 240 ° C. while stirring under a nitrogen stream to esterify. An esterification reaction was carried out. A predetermined amount of water was distilled off, and the reaction was continued until the acid value became 5 mgKOH / g or less, then the pressure was gradually reduced, and the deglycolation reaction was carried out at 1 mmHg or less for 5 hours to obtain a polyester polyol. Then, by diluting with ethyl acetate until the non-volatile content became 50%, a solution of a polyester polyol (A-1) having a number average molecular weight of 2,300 and an acid value of 0.7 mgKOH / g was obtained.

(Synthesis Example 2) Polyester polyol (A-2)
279 parts of ethylene glycol, 242 parts of neopentyl glycol, 189 parts of 1,6-hexanediol, 81 parts of terephthalic acid, isophthalic acid in a reaction vessel equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping tank and a nitrogen gas introduction tube. 710 parts of acid and 218 parts of adipic acid 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 became 5 mgKOH / g or less, then the pressure was gradually reduced, and the deglycolation reaction was carried out at 1 mmHg or less for 5 hours to obtain a polyester polyol. Then, 2 parts of isophorone diisocyanate was gradually added, and the reaction was carried out at 150 ° C. for about 2 hours to obtain a polyester polyurethane polyol. 2.5 parts of trimellitic acid anhydride was added to 100 parts of this polyester polyurethane polyol, reacted at 180 ° C. for about 2 hours, and then diluted with ethyl acetate until the non-volatile content became 50%, so that the number average molecular weight was 6,000. , A solution of a partially acid-modified polyester polyol (A-2) having an acid value of 14.6 mgKOH / g was obtained.

(Synthesis Example 3) Polyester Polyol (A-3)
142 parts of ethylene glycol, 156 parts of diethylene glycol, 148 parts of neopentyl glycol, 350 parts of 1,6-hexanediol, terephthalic acid in a reaction vessel equipped with a stirrer, thermometer, reflux cooling tube, dropping tank and nitrogen gas introduction tube. 437 parts, 437 parts of isophthalic acid, and 192 parts of adipic acid 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 became 5 mgKOH / g or less, then the pressure was gradually reduced, and the deglycolation reaction was carried out at 1 mmHg or less for 5 hours to obtain a polyester polyol. 0.5 part of trimellitic acid anhydride was added to 100 parts of this polyester polyol, reacted at 180 ° C. for about 2 hours, and then diluted with ethyl acetate until the non-volatile content became 50%. A solution of a partially acid-modified polyester polyol (A-3) having an acid value of 3.1 mgKOH / g was obtained.

(Synthesis Example 4) Polyester polyol (A-4)
95 parts of ethylene glycol, 632 parts of neopentyl glycol, 498 parts of isophthalic acid, and 474 parts of adipic acid are charged in a reaction vessel equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping tank and a nitrogen gas introduction tube, and under a nitrogen stream. The temperature was raised to 250 ° C. with stirring in 1 and the esterification reaction was carried out. A predetermined amount of water was distilled off, and the reaction was continued until the acid value became 5 mgKOH / g or less, then the pressure was gradually reduced, and the deglycolation reaction was carried out at 1 mmHg or less for 5 hours to obtain a polyester polyol. Then, 4.0 parts of isophorone diisocyanate was gradually added, and the reaction was carried out at 150 ° C. for about 2 hours to obtain a polyester polyurethane polyol. Then, the mixture was diluted with ethyl acetate until the non-volatile content became 50% to obtain a solution of a polyester polyol (A-4) having a number average molecular weight of 12,000 and an acid value of 0.5 mgKOH / g.

<Adjustment of polyisocyanate>
(Preparation Example 1) Polyisocyanate (C-1)
Coronate 2785 (biuret-type polyisocyanate derived from hexamethylene diisocyanate, manufactured by Tosoh Corporation) is diluted with ethyl acetate to adjust the non-volatile content to 50% and the NCO content to 9.6% to obtain polyisocyanate (C-1). Solution was obtained.

(Preparation Example 2) Polyisocyanate (C-2)
Bestanato T1890 / 100 (nurate-type polyisocyanate derived from isophorone diisocyanate, manufactured by Evonik Corporation) is diluted with ethyl acetate to adjust the non-volatile content to 50% and the NCO content to 8.7%, and the polyisocyanate (C-2). ) Was obtained.

(Preparation Example 3) Polyisocyanate (C-3)
Takenate D-110NB (trimethylolpropane adduct-type polyisocyanate derived from xylylene diisocyanate (XDI), manufactured by Mitsui Chemicals, Inc.) is diluted with ethyl acetate to have a non-volatile content of 50% and an NCO content of 7.9%. To obtain a solution of polyisocyanate (C-3).

(Preparation Example 4) Polyisocyanate (C-4)
Coronate L (trimethylolpropane adduct-type polyisocyanate derived from toluene diisocyanate (TDI), manufactured by Tosoh Corporation) is diluted with ethyl acetate to adjust the non-volatile content to 50% and the NCO content to 8.8%. A solution of polyisocyanate (C-4) was obtained.

<Manufacturing of adhesive composition>
(Adhesives T1 to T5 and TT1 to TT3)
The polyol solution obtained in Synthesis Examples 1 to 4 and the polyisocyanate solution obtained in Preparation Examples 1 to 4 were blended at the ratios (mass ratios) shown in Table 3, and ethyl acetate was added to add a non-volatile content of 30. % The adhesive solution was adjusted.

(Adhesives T6 to T17)
Table 5 shows the polyol solution obtained in Synthesis Examples 1 and 2, the polyisocyanate solution obtained in Preparation Example 1, oxygen acid of phosphorus or a derivative thereof, and fine particles having an average particle size of 1 to 10 μm. The mixture was mixed in a ratio (mass ratio), and ethyl acetate was added to prepare an adhesive solution having a non-volatile content of 30%.

The abbreviations in Table 5 are shown below.
Phosphoric acid: 85% phosphoric acid aqueous solution Phosphoric acid derivative: Phosphanol RL-310, Aluminum hydroxide 1: BF013 manufactured by Toho Kagaku Kogyo Co., Ltd., Japan Light Metal Co., Ltd., average particle size 1 μm
Aluminum hydroxide 2: BX103, manufactured by Nippon Light Metal Co., Ltd., average particle size 5 μm
Aluminum hydroxide 3: BF083, manufactured by Nippon Light Metal Co., Ltd., average particle size 10 μm
Acrylic resin beads: Art Pearl J-7P, manufactured by Negami Kogyo Co., Ltd., average particle size 6 μm

<Manufacturing of packaging materials>
In the production of the following packaging materials, the following gravure plates were used for printing the anchor coat layer composition and the printing ink. The printing speed was 70 m / min.
Anchor coat layer composition S1: Laser 175 lines / inch, 25 μm solid gravure plate Printing ink R1 to R5: Laser 175 lines / inch, 25 μm solid gravure plate The thickness of the anchor coat layer and the print layer is 0. It was set to 0.8 μm. A 120-line / inch, 60 μm gravure plate was used for coating the adhesive layer, which is the second desorption layer. The laminating speed was 200 m / min. The thickness of the adhesive layer was 3 μm in each case.

(About the thin-film deposition base material used)
Substrate a: Polyethylene terephthalate (PET) substrate having a vapor-deposited layer (30 nm) in which aluminum oxide is deposited in an amorphous form, with a thickness of 12 μm.
Substrate b: PET substrate having a vapor-deposited layer (30 nm) in which silica is deposited in an amorphous form, thickness 12 μm.
Base material c: Biaxially stretched polypropylene base material (OPP) base material having a vapor-deposited layer (30 nm) in which aluminum oxide is deposited in an amorphous form, thickness 20 μm.
Substrate d: OPP substrate having a vapor-deposited layer (50 nm) in which aluminum is deposited in an amorphous form, thickness 20 μm.
Substrate e: Non-stretched polypropylene substrate (CPP) substrate having a vapor-deposited layer (50 nm) in which aluminum is deposited in an amorphous form, thickness 25 μm.
(The above base materials a to e correspond to the first base material / the first desorbed layer, and the first desorbed layer corresponds to the thin-film deposition layer.)

(Film thickness of thin-film deposition layer)
In the following examples, the thicknesses of aluminum, aluminum oxide and silica were measured by the fundamental parameter method using a fluorescent X-ray analyzer (model name: EA6000VX) manufactured by Hitachi High-Tech Science.

[Example 1] (Packaging material L1-1)
The printing ink R1 was diluted with a mixed solvent of EA / IPA (mass ratio 70/30) at Zahn Cup # 3, 25 ° C. for 15 seconds.
The diluted printing ink R1 is printed on the vapor-deposited surface of the base material a using a gravure two-color printing machine equipped with a gravure plate, dried at 50 ° C., and the first base material (PET) / first. A laminate having the structure of the desorption layer (alumina vapor deposition) / printing layer was obtained.
Next, the adhesive T1 was applied onto the printed layer of the obtained laminate using a dry laminating machine so that the coating amount was 3 g / m ² , and then bonded to a CPP film having a thickness of 25 μm. rice field. The obtained laminate was kept warm at 40 ° C. for 4 days, and the first base material (PET) / first desorption layer (alumina vapor deposition) / printing layer / second desorption layer / second base material ( A packaging material L1-1 having a composition of CPP) was obtained.

[Examples 2 to 5, Comparative Examples 1 to 3] (Packaging materials L1-2 to L1-5, LL1 to 3)
Packaging materials L1-2 to L1-5 and LL1 to 3 were obtained by the same method as the packaging material L1-1 except that the adhesives shown in Table 4 were used.

[Examples 6 to 9] (Packaging materials L1-6 to L1-9)
Packaging materials L1-6 to L1-9 were obtained by the same method as the packaging material L1-1 except that the printing layer shown in Table 4 was used.

[Example 10] (Packaging material L2)
The packaging material L2 was obtained by the same method as the packaging material L1-1 except that the base material b was used.

[Example 11] (Packaging material L3)
The packaging material L3 was obtained by the same method as the packaging material L1-1 except that the base material c was used.

[Example 12] (Packaging material L4)
The adhesive T1 was applied to the vapor-filmed surface of the base material d using a dry laminating machine so that the coating amount was 3 g / m2, and then bonded to the vapor-deposited surface of a CPP film having a thickness of 25 μm. The obtained laminate was kept warm at 40 ° C. for 4 days to form a first substrate (OPP) / first desorbed layer (aluminum vapor deposition) / second desorbed layer / second substrate (CPP). The packaging material L4 having the composition was obtained.

[Example 13] (Packaging material L5)
The anchor coat layer composition S1 was diluted with a mixed solvent of EA / IPA (mass ratio 70/30) at Zahn Cup # 3, 25 ° C. for 15 seconds.
The diluted anchor coat layer composition S1 was printed on the vapor-deposited surface of the base material d using a gravure two-color printing machine equipped with a gravure plate, dried at 50 ° C., and subjected to the first base material (OPP). / A laminated body having a structure of a first desorption layer (aluminum vapor deposition) / an anchor coat layer was obtained. Next, the adhesive T1 was applied onto the anchor coat layer of the obtained laminate using a dry laminating machine so that the coating amount was 3 g / m ² , and then attached to a CPP film having a thickness of 25 μm. I matched it. The obtained laminate was kept warm at 40 ° C. for 4 days, and the first base material (OPP) / first desorption layer (aluminum vapor deposition) / anchor coat layer / second desorption layer / second base material A packaging material L5 having a composition of (CPP) was obtained.

[Example 14] (Packaging material L6)
The adhesive T1 is applied to the OPP base material (second base material) using a dry laminating machine so that the coating amount is 3 g / m ² , and then attached to the vapor-deposited surface of the base material e. Matched. The obtained laminate was kept warm at 40 ° C. for 4 days to form a first substrate (CPP) / first desorbed layer (aluminum vapor deposition) / second desorbed layer / second substrate (OPP). The packaging material L6 having the composition was obtained.

[Example 15] (Packaging material L7)
The printing ink R1 was diluted with a mixed solvent of EA / IPA (mass ratio 70/30) at Zahn Cup # 3, 25 ° C. for 15 seconds.
The diluted printing ink R1 is printed on the vapor-deposited surface of the base material d using a gravure two-color printing machine equipped with a gravure plate, dried at 50 ° C., and the first base material (OPP) / first. A laminate having the structure of the desorption layer (aluminum vapor deposition) / printing layer was obtained. Next, the adhesive T1 was applied to the OPP substrate surface of the obtained laminate using a dry laminating machine so that the coating amount was 3 g / m ² , and then a CPP film having a thickness of 25 μm was applied. I pasted it together. The obtained laminate was kept warm at 40 ° C. for 4 days, and the printed layer / first desorbed layer (aluminum vapor deposition) / first substrate (OPP) / second desorbed layer / second substrate ( A packaging material L7 having a composition of CPP) was obtained.

[Example 16] (Packaging material L8)
The printing ink R1 was diluted with a mixed solvent of EA / IPA (mass ratio 70/30) at Zahn Cup # 3, 25 ° C. for 15 seconds.
The diluted printing ink R1 is printed on the vapor-deposited surface of the base material a using a gravure two-color printing machine equipped with a gravure plate, dried at 50 ° C., and the first base material (PET) / first. A laminate having the structure of the desorption layer (alumina vapor deposition) / printing layer was obtained. Next, the adhesive T1 was dried on the printed layer of the obtained laminate using a dry laminating machine so that the coating amount was 3 g / m2, and then dried, and then one side of both treated NY films having a thickness of 15 μm. A laminated body having a composition of a first base material (PET) / a first desorption layer (alumina vapor deposition) / a printing layer / an adhesive layer / a third base material (NY) was obtained.
Further, the adhesive T1 is applied to the NY surface of the obtained laminate using a dry laminating machine so that the coating amount is 3 g / m2, and then bonded to a CPP film having a thickness of 25 μm. rice field. The obtained laminate was kept warm at 40 ° C. for 4 days, and the first base material (PET) / first desorption layer (alumina vapor deposition) / printing layer / adhesive layer / third base material (NY) / A packaging material L8 having a composition of a second desorption layer / a second base material (CPP) was obtained.

[Example 17] (Packaging material L9)
The packaging material L9 was obtained by the same method as the packaging material L8 except that TT2 was used as the adhesive between the printing layer and the third substrate.

[Example 18] (Packaging material L10)
The adhesive T1 is applied to the vapor-filmed surface of the base material a using a dry laminating machine so that the coating amount is 3 g / m ² , and then bonded to one side of both treated NY films having a thickness of 15 μm. A laminated body having a composition of a first base material (PET) / a first desorption layer (alumina vapor deposition) / an adhesive / a third base material (NY) was obtained.
Further, the adhesive T1 is applied to the NY surface of the obtained laminate using a dry laminating machine so that the coating amount is 3 g / m ² , and then attached to a CPP film having a thickness of 25 μm. I matched it. The obtained laminate was kept warm at 40 ° C. for 4 days, and the first base material (PET) / first desorption layer (alumina vapor deposition) / adhesive layer / third base material (NY) / second base material (NY) / second. A packaging material L10 having a desorbed layer / second substrate (CPP) composition was obtained.

[Example 19] (Packaging material L11)
The packaging material L11 was obtained by the same method as the packaging material L10 except that TT2 was used as the adhesive between the first desorption layer and the third substrate.

[Examples 20 to 31] (Packaging materials L1-10 to L1-21)
Packaging materials L1-10 to L1-21 were obtained by the same method as the packaging material L1-1 except that the adhesives shown in Table 6 were used.

<Evaluation of packaging material 1>
The following evaluations were performed on the obtained packaging materials L1-1 to L1-9, L2 to L11, and LL1 to 3. The results are shown in Table 4.

(Yield of transparent substrate 1)
100 samples of the obtained packaging material cut into a size of 1 cm × 1 cm and 800 g of a 2% aqueous solution having a solid content of sodium hydroxide were placed in a 1 L flask and stirred at 70 ° C. and a rotation speed of 200 rpm for 4 hours. After washing and drying the sample with water, a transparent film from which the print layer was visually removed by 80% or more was collected and the number of sheets was counted. The yield of the transparent substrate was calculated by the following formula.
For packaging materials (L10, 11) that are difficult to visually determine desorption because there is no printing layer or no aluminum vapor deposition, and between the second base material and the third base material having a three-layer structure, FT- on both sides of the film. Desorption was determined by the difference in absorption peaks of the film using IR.
Yield = number of recovered transparent films / number of plastic base materials constituting the original packaging material The yield was evaluated according to the following criteria. ○ and △ are ranges where there is no practical problem.
◯: Yield of transparent substrate is 80% or more (good)
Δ: Yield of transparent substrate is 60% or more and less than 80% (usable)
X: Yield of transparent substrate is less than 60% (cannot be used)

(Removal rate of the printed layer / adhesive layer of the base material after desorption 1)
100 samples of the obtained packaging material cut into a size of 1 cm × 1 cm and 800 g of a 2% aqueous solution having a solid content of sodium hydroxide were placed in a 1 L flask and stirred at 70 ° C. and a rotation speed of 200 rpm for 4 hours. After washing and drying the sample with water, the removal rate of the print layer was visually confirmed. A transparent film was collected from the obtained sample, and the presence or absence of an absorption peak of the adhesive composition was confirmed at five locations on the front and back of the film using FT-IR, and the removal rate of the adhesive composition was confirmed. The removal rate of the printed layer and the adhesive layer was evaluated according to the following criteria. ○ and △ are ranges where there is no practical problem.
◯: The removal rate of the print layer and the adhesive layer is 80% or more (good).
Δ: The removal rate of the print layer and the adhesive layer is 60% or more and less than 80% (usable).
X: The removal rate of the print layer and the adhesive layer is less than 60% (cannot be used).

(Adhesion to the base material: (1) In the case of PET base material / CPP base material configuration)
Packaging materials L1-1 to L1-9, L-2, LL1 to 3 to make test pieces with a size of 15 mm × 300 mm, using a tensile tester, under the conditions of temperature 20 ° C. and relative humidity 65%, T By mold peeling, the peel strength (laminate strength, N / 15 mm) between the first base material and the second base material was measured at a peeling speed of 30 cm / min. The substrate adhesion was evaluated according to the following criteria. ○ and △ are ranges where there is no practical problem.
◯: Laminate strength is 2.0 N / 15 mm or more Δ: Laminate strength is 1.0 N / 15 mm or more, less than 2.0 N / 15 mm ×: Laminate strength is less than 1.0 N / 15 mm

(Adhesion to the base material: (2) In the case of OPP base material / CPP base material configuration)
A test piece having a size of 15 mm × 300 mm was prepared from the packaging materials L3 to L7, and the peeling speed was 30 cm / min by T-type peeling under the conditions of a temperature of 20 ° C. and a relative humidity of 65% using a tensile tester. The peel strength (laminate strength, N / 15 mm) between the base material 1 and the base material 2 was measured. The substrate adhesion was evaluated according to the following criteria. ○ and △ are ranges where there is no practical problem.
◯: Laminate strength is 1.0 N / 15 mm or more Δ: Laminate strength is 0.5 N / 15 mm or more, less than 1.0 N / 15 mm ×: Laminate strength is less than 0.5 N / 15 mm

(Adhesion to base material: (3) In the case of PET base material / NY base material / CPP base material configuration)
A test piece having a size of 15 mm × 300 mm was prepared from the packaging materials L8 to L11, and the peeling speed was 30 cm / min by T-type peeling under the conditions of a temperature of 20 ° C. and a relative humidity of 65% using a tensile tester. The peel strength (laminate strength, N / 15 mm) between the base material 1 and the base material 3 and between the base material 3 and the base material 2 was measured. The substrate adhesion was evaluated according to the following criteria. ○ and △ are ranges where there is no practical problem.
<< Peeling strength between the first base material and the third base material (in Table 4, the left side of the base material adhesion) >>
◯: Laminate strength is 2.0 N / 15 mm or more Δ: Laminate strength is 1.0 N / 15 mm or more and less than 2.0 N / 15 mm ×: Laminate strength is less than 1.0 N / 15 mm << Third base material and second base Peeling strength between materials (in Table 4, right side of substrate adhesion) >>
◯: Laminate strength is 5.0 N / 15 mm or more Δ: Laminate strength is 3.0 N / 15 mm or more and less than 5.0 N / 15 mm ×: Laminate strength is less than 3.0 N / 15 mm

(Laminate appearance)
The appearance of the obtained packaging material was visually evaluated according to the following criteria.
〇: Uniform coating is possible without repellent or unevenness (good)
Δ: No repellent, but slight unevenness (usable)
×: There is repelling or unevenness (cannot be used)

The abbreviations in Table 4 are shown below.
-Abbreviation for first base material / first desorption layer PET / alumina: Alumina-deposited polyethylene terephthalate film, thickness 12 μm (base material a)
PET / silica: silica-deposited polyethylene terephthalate film, thickness 12 μm (base material b)
OPP / Alumina: Alumina-deposited biaxially stretched polypropylene film, thickness 20 μm (base material c)
OPP / Aluminum: Aluminum-deposited biaxially stretched polypropylene film, thickness 20 μm (base material d)
CPP / Aluminum: Unstretched polypropylene base material with a vapor-deposited layer of aluminum vapor-deposited in an amorphous shape, thickness 25 μm (base material e)
-Abbreviation for second base material CPP: Unstretched polypropylene film, thickness 25 μm
NY: Both treated nylon film, thickness 15 μm

<Evaluation of packaging material 2>
The following evaluations were performed on the obtained packaging materials L1-1 and L1-10 to L1-21. The results are shown in Table 6.

(Yield of transparent substrate 2)
100 samples of the obtained packaging material cut into a size of 2 cm × 2 cm and 800 g of a 2% aqueous solution having a solid content of sodium hydroxide were placed in a 1 L flask and stirred at 70 ° C. and a rotation speed of 100 rpm for 4 hours. After washing and drying the sample with water, a transparent film from which the print layer was visually removed by 80% or more was collected and the number of sheets was counted. The yield was calculated by the following formula. Yield = number of recovered transparent films / number of plastic base materials constituting the original packaging material The yield was evaluated according to the following criteria. ◎, ○, and △ are ranges where there is no practical problem.
⊚: Yield of transparent substrate is 90% or more (very good)
◯: Yield of transparent substrate is 80% or more and less than 90% (good)
Δ: Yield of transparent substrate is 60% or more and less than 80% (usable)
X: Yield of transparent substrate is less than 60% (cannot be used)

(Removal rate of the printed layer / adhesive layer of the base material after desorption 2)
100 samples of the obtained packaging material cut into a size of 2 cm × 2 cm and 800 g of a 2% aqueous solution having a solid content of sodium hydroxide were placed in a 1 L flask and stirred at 70 ° C. and a rotation speed of 100 rpm for 4 hours. After washing and drying the sample with water, the removal rate of the print layer was visually confirmed. A transparent film was collected from the obtained sample, and the presence or absence of an absorption peak of the adhesive composition was confirmed at five locations on the front and back of the film using FT-IR, and the removal rate of the adhesive composition was confirmed. The removal rate of the printed layer and the adhesive layer was evaluated according to the following criteria. ◎, ○, and △ are ranges where there is no practical problem.
⊚: The removal rate of the print layer and the adhesive layer is 90% or more (very good).
◯: The removal rate of the print layer and the adhesive layer is 80% or more and less than 90% (good).
Δ: The removal rate of the print layer and the adhesive layer is 60% or more and less than 80% (usable).
X: The removal rate of the print layer and the adhesive layer is less than 60% (cannot be used).

(Adhesion to the base material: (1) In the case of PET base material / CPP base material configuration)
Peeling strength between the first base material and the second base material in the same manner as in <Evaluation 1 of packaging material> (base material adhesion: (1) in the case of PET base material / CPP base material configuration). Was measured and evaluated.

(Laminate appearance)
Evaluation was performed in the same manner as in (Laminate appearance) of <Evaluation 1 of packaging material>.

According to the evaluation results of Tables 4 and 6, the packaging material of the present invention has a first desorbing layer and a second desorbing layer, so that the substrate adhesion and the laminated appearance are maintained. The detachability of the printing layer and the adhesive layer in the basic aqueous solution is improved, and the recyclability of the first base material and the second base material can be improved. The packaging material of the present invention and a packaging container using the packaging material are useful as a packaging material and a packaging container suitable for plastic recycling.

Claims (6)

A first substrate, a first desorbed layer for desorbing the first substrate and recycling the first substrate, and
A packaging material comprising a second substrate and a second desorbing layer for desorbing the second substrate and recycling the second substrate.
The first desorption layer is a vapor-deposited layer of at least one inorganic substance selected from the group consisting of aluminum, aluminum oxide and silica.
The second desorbed layer is formed from the second desorbed layer forming composition (B).
The second desorbed layer forming composition (B) is an adhesive composition containing a polyol component, a polyisocyanate component, and fine particles having an average particle size of 1 to 10 μm, and has an average particle size of 1 to 10 μm. The content of the fine particles of 1 to 10 μm is 0.1 to 10% by mass based on the solid content of the second desorbed layer forming composition (B), and the polyisocyanate component is an aliphatic poly. It contains at least one polyisocyanate component selected from the group consisting of isocyanate and aromatic aliphatic polyisocyanate, and the acid value of the reaction product of the polyol component and the polyisocyanate component is 5 mgKOH / g or more.
A packaging material in which the polyol component contains at least two of the following three polyester polyol components.
First polyol component: Polyester polyol having an acid value of 10.0 mgKOH / g or more Second polyol component: Polyester polyol having an acid value of less than 10.0 mgKOH / g and a number average molecular weight of less than 3,000 Third polyol component: Acid Polyester polyol with a value of less than 10.0 mgKOH / g and a number average molecular weight of 5,000 or more The packaging material according to claim 1, wherein the polyol component contains a polyester polyol component, and the content of the first polyol component below is 50% by mass or more with respect to the total amount of the polyester polyol component.
First polyol component: Polyester polyol having an acid value of 10.0 mgKOH / g or more The packaging material according to claim 1 or 2, wherein the polyol component contains at least the following three polyester polyol components.
First polyol component: Polyester polyol having an acid value of 10.0 mgKOH / g or more Second polyol component: Polyester polyol having an acid value of less than 10.0 mgKOH / g and a number average molecular weight of less than 3,000 Third polyol component: Acid Polyester polyol with a value of less than 10.0 mgKOH / g and a number average molecular weight of 5,000 or more The second desorbed layer forming composition (B) contains an oxygen acid of phosphorus or a derivative thereof by 0.01 to 5 mass based on the solid content of the second desorbed layer forming composition (B). %, The packaging material according to any one of claims 1 to 3. A packaging container in which at least a part thereof is formed of the packaging material according to any one of claims 1 to 4 . A method for producing a recycled base material, which comprises a step of immersing the packaging material according to any one of claims 1 to 4 or the packaging container according to claim 5 in a basic aqueous solution.
A method for producing a recycled base material, wherein the basic aqueous solution contains 0.5 to 10% by mass of the total basic aqueous solution, and the water temperature of the basic aqueous solution at the time of immersion is 30 to 120 ° C.