Laminate

Abstract

To provide a fragrance-retaining coating composition and a laminate that can provide excellent fragrance-retaining properties and water vapor barrier properties regardless of the type of fragrance. A laminate having a substrate layer, a layer made of an aroma-retaining coating composition, an adhesive layer, and a sealant layer, The layer made of the aroma-retaining coating composition is a layer made of an aroma-retaining coating composition containing a hydroxyl group-containing polyester resin having a glass transition temperature in the range of 30 to 120°C and / or an acrylic resin having a glass transition temperature of 20°C or higher and a hydroxyl value of 40 mgKOH / g or higher, a curing agent, and a solvent, The substrate layer and / or the sealant layer are a laminate having a vapor deposition layer.

Description

[Technical Field]

[0001] The present invention relates to a laminate used for packaging beverages, foods, detergents, cosmetics, etc. containing aroma components, such as alcoholic beverages, flavored beverages, coffee powder, fragrance powder, fabric softener, liquid detergent, shampoo, conditioner, perfume, etc. [Background technology]

[0002] Films with high aroma retention properties (such as films laminated with polyvinyl alcohol resin or ethylene-vinyl alcohol copolymer resin, which have high barrier properties) have been used to package beverages containing aroma components, such as alcoholic beverages, flavored beverages, coffee powder, fragrance powder, fabric softener, liquid detergent, shampoo, conditioner, and perfume, as well as foods, detergents, and cosmetics, in order to prevent the aroma from escaping from the container. Furthermore, packaging materials having gas barrier properties are known that are made by providing a metal layer or a metal oxide layer on a resin film.

[0003] The tendency of films to prevent the penetration of fragrance components and retain them may seem to be related to the tendency of gas barrier properties, but in reality these tendencies do not necessarily coincide, and it is known that even packaging materials with gas barrier properties can have insufficient aroma retention. Furthermore, if an item containing a large amount of fragrance components is stored in a container with insufficient aroma retention, the fragrance components will escape from the container over time, even if the container is stored airtight. As a result, when fragrance components escape from products displayed in a store, because there are so many products on display, even if a small amount of fragrance components permeates out of one product, the total amount that permeates is large, and as a result, the entire sales floor is filled with the fragrance. Furthermore, it is known that the deterioration rate of packaged contents can be slowed by suppressing moisture absorption and desorption, and therefore, by improving the water vapor barrier properties of packaging materials, deterioration of the quality of the contents can be suppressed.

[0004] For this reason, in recent years, there has been a demand for the development of films that have better aroma retention properties and excellent water vapor barrier properties, regardless of the type of fragrance.

[0005] Patent Documents 1 and 2 describe laminates having a cured coating film containing polyester polyol, which has low oxygen permeability but whose permeability to aroma components is unknown. Patent Document 3 describes a laminate for liquid packaging that has low oxygen permeability and excellent aroma retention properties due to the combination of a specific heat seal layer, a coating layer, and an adhesive layer. However, it was unclear whether the laminates described in Patent Documents 1 to 3 fully satisfy both aroma retention and water vapor barrier properties. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Patent No. 7207617 [Patent Document 2] Patent No. 7529179 [Patent Document 3] International Publication No. 2024 / 135510 Summary of the Invention [Problem to be solved by the invention]

[0007] The present invention has been made in view of the above-mentioned circumstances, and an object of the present invention is to provide an aroma-retaining coating composition and a laminate that can provide excellent aroma retention regardless of the type of fragrance and that also have excellent water vapor barrier properties. [Means for solving the problem]

[0008] As a result of extensive research into solving the above problems, the present inventors have found that the above problems can be solved by the laminate described below, and have thus completed the present invention. That is, the present invention is as follows. 1. A laminate having a substrate layer, a layer made of an aroma-retaining coating composition, an adhesive layer, and a sealant layer, wherein the layer made of the aroma-retaining coating composition is a layer made of an aroma-retaining coating composition containing a hydroxyl-containing polyester resin having a glass transition temperature in the range of 30 to 120°C and / or an acrylic resin having a glass transition temperature of 20°C or higher and a hydroxyl value of 40 mgKOH / g or higher, a curing agent, and a solvent, and the substrate layer and / or sealant layer are laminates having a vapor-deposited layer. 2. The laminate according to 1, wherein the solid content ratio of the acrylic resin to the polyester resin is acrylic resin / polyester resin=90 / 10 to 10 / 90. 3. The laminate according to 1 or 2, wherein the curing agent is a polyisocyanate curing agent. 4. The laminate according to 3, wherein the polyisocyanate curing agent is a tri- or higher functional isocyanate curing agent. 5. The coating amount of the layer made of the aroma-retaining coating composition after drying is 0.15 to 1.5 g / m 2 5. The laminate according to any one of 1 to 4, wherein the above ranges. [Effects of the Invention]

[0009] According to the present invention, a laminate having excellent aroma retention properties and excellent water vapor barrier properties can be obtained regardless of the type of fragrance. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present invention provides a laminate having a substrate layer, a layer made of an aroma-retaining coating composition, an adhesive layer, and a sealant layer. The layer made of the aroma-retaining coating composition is a layer made of an aroma-retaining coating composition containing a hydroxyl-containing polyester resin having a glass transition temperature in the range of 30 to 120°C and / or an acrylic resin having a glass transition temperature of 20°C or higher and a hydroxyl value of 40 mgKOH / g or higher, a curing agent, and a solvent, and the substrate layer and / or sealant layer are based on a laminate having a vapor-deposited layer.

[0011] The present invention will be described below. As mentioned above, the aroma retention property in the present invention does not necessarily coincide with so-called gas barrier property. Aroma retention property is the property of preventing aroma components from leaking outside the container without allowing them to permeate, while gas barrier property is usually the property of preventing carbon dioxide, oxygen, and sometimes water vapor from entering from outside the container and volatilizing out of the container. Since aroma retention property and gas barrier property prevent different gas components from permeating, a layer that has gas barrier property cannot simply be said to have aroma retention property.

[0012] (Laminate) The laminate of the present invention can be used in applications that require excellent aroma retention and water vapor barrier properties. Such applications include sealed containers, at least a portion of which is formed from the laminate of the present invention, which can be sealed after contents are placed inside. The contents can be placed inside the laminate of the present invention alone, or the laminate containing the contents can be further packaged with a known packaging material. The contents contain sufficient aroma components, and can be in either solid or liquid form. The laminate of the present invention has a layer formed by laminating, in order, a substrate layer, either a layer made of an aroma-retaining coating composition or an adhesive layer, the other layer made of an aroma-retaining coating composition or an adhesive layer, and a sealant layer, and the substrate layer and / or sealant layer are based on a laminate having a vapor-deposited layer. When the laminate of the present invention has a printed layer, the printed layer can be provided between the outermost layer or any other layer. Preferably, the laminate of the present invention has (1) a substrate layer, a layer made of an aroma-retaining coating composition, and optionally a printed layer, an adhesive layer, and a sealant layer, or (2) a substrate layer, and optionally a printed layer, an adhesive layer, a layer made of an aroma-retaining coating composition, and a sealant layer, and the substrate layer and / or sealant layer are based on a laminate having a vapor-deposited layer.

[0013] (base material layer) The substrate layer used in the laminate of the present invention may be any known one, as long as it can be used as a packaging material for foods, daily necessities, etc. containing aroma components, by providing a layer made of an aroma-retaining coating composition, and then providing a sealant layer via an adhesive layer or the like on a printed layer, if necessary, and then serving as the outermost layer of the laminate in the packaged state. The substrate layer can be selected from uniaxially oriented resin films, biaxially oriented resin films, and non-oriented resin films, paper, and woven or nonwoven fabrics capable of forming a printing layer, made of polyolefins such as polyethylene, polypropylene, and ethylene-propylene copolymers, polyesters such as polyethylene terephthalate, polyamides such as nylon and aramid, and the like. Among these, uniaxially oriented resin films and biaxially oriented resin films are preferred. The substrate layer may be a single layer or a multi-layer. When the substrate layer is a multi-layer, a plurality of the above-mentioned films may be laminated by any method, such as a method using an adhesive. Furthermore, the surface of the substrate layer on which the layer of the aroma-retaining coating composition is to be formed may be subjected to a corona discharge treatment or primer treatment in advance to improve adhesion to the layer of the aroma-retaining coating composition, but this treatment is not necessary. In terms of water vapor barrier properties, the substrate layer preferably has a vapor-deposited layer of an inorganic oxide such as silica or alumina or a metal, although when the sealant layer has a vapor-deposited layer, the substrate layer may or may not have a vapor-deposited layer. Specific examples of such a substrate layer include the following four types. VM-OPP (aluminum-deposited biaxially oriented polypropylene film (ML OP 102, thickness 25 μm, Mitsui Chemicals Tocello Co., Ltd.)) OPP (biaxially oriented polypropylene film (P2161, thickness 25 μm, Toyobo Co., Ltd.)) MDOPE (uniaxially oriented polyethylene film (PE3K-H, thickness 25 μm, Futamura Chemical Co., Ltd.)) NY (Nylon film (ONY-15, thickness 12 μm, Unitika))

[0014] (Layer consisting of aroma-retaining coating composition) The layer made of the aroma-retaining coating composition is a layer made of an aroma-retaining coating composition containing a hydroxyl-containing polyester resin having a glass transition temperature in the range of 30 to 120°C and / or an acrylic resin having a glass transition temperature of 20°C or higher and a hydroxyl value of 40 mgKOH / g or higher, a curing agent, and a solvent. The layer made of this aroma-retaining coating composition is a layer formed by applying, under normal conditions, an aroma-retaining coating composition containing an unsaturated polyester resin with a glass transition temperature of 30°C or higher and / or an acrylic resin with a glass transition temperature of 20°C or higher and a hydroxyl value of 40 mgKOH / g or higher, a curing agent, and a solvent, followed by drying and / or curing.

[0015] Here, the hydroxyl value in the present invention is defined as follows. (Hydroxyl value of polyester resin) The hydroxyl value of a polyester resin can be determined by applying the method specified in JIS K1557-1:2007. Specifically, the hydroxyl groups are acetylated by dissolving the polyester resin sample in a pyridine solution containing an acetylating reagent (e.g., acetic anhydride). The excess acetylating reagent is then hydrolyzed with water, and the amount of acetic acid produced is determined by titrating with potassium hydroxide. Since the carboxyl groups contained in the polyester resin are also titrated with potassium hydroxide, the hydroxyl value (mgKOH / g) is calculated by subtracting the acid value of the polyester resin from the titration result. (hydroxyl value of acrylic resin) The hydroxyl value of the acrylic resin is determined based on the molecular weight of a monomer having a hydroxyl group among the monomers constituting the acrylic resin and the content ratio of that monomer to the total amount of the monomer.

[0016] The glass transition temperature in the present invention is defined as follows: (glass transition temperature of polyester resin) The glass transition temperature of the polyester resin is determined by thermal analysis. The thermal analysis method conforms to JIS K7121 (Method for measuring transition temperature of plastics), and for example, the glass transition temperature can be measured using a PerkinElmer Pyris1 DZC under conditions of a temperature rise rate of 20°C / min and a nitrogen gas flow rate of 20 ml / min. (glass transition temperature of acrylic resin) The glass transition temperature of the acrylic resin in the present invention is a theoretical glass transition temperature calculated by the following Wood's formula. Wood's formula: 1 / Tg = W1 / Tg1 + W2 / Tg2 + W3 / Tg3 + + Wx / Tgx [In the formula, Tg1 to Tgx represent the glass transition temperatures of the respective homopolymers of monomers 1, 2, 3, x constituting the acrylic resin, W1 to Wx represent the polymerization fractions of the respective monomers 1, 2, 3, x, and Tg represents the theoretical glass transition temperature. However, the glass transition temperature in Wood's formula is expressed in absolute temperature.]

[0017] (Hydroxyl group-containing polyester resin with glass transition temperature ranging from 30 to 120°C) In the present invention, one or more hydroxyl group-containing polyester resins having a glass transition temperature in the range of 30 to 120°C can be used. The hydroxyl group-containing polyester resin of the present invention is preferably a hydroxyl group-containing polyester resin which is a condensation product of a low molecular weight diol and a dibasic acid. The low molecular weight diol is preferably at least one of an aliphatic diol, an alicyclic diol, and an aromatic diol. For example, one or more selected from low molecular weight diols having or not having a branched structure, such as ethylene glycol, diethylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,2-propanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 1,4-pentanediol, 3-methyl-1,5-pentanediol, 2,5-hexanediol, 2-methyl-1,4-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-methyl-1,8-octanediol, 2,2,4-trimethyl-1,3-pentanediol, 2,2,4-trimethyl-1,6-hexanediol, cyclohexanedimethanol, and tricyclodecanedimethanol, are preferred. However, the low molecular weight diol may consist of only ethylene glycol, or may be used in combination with other low molecular weight diols. Examples of aromatic diols include hydroquinone, resorcinol, catechol, naphthalenediol, biphenol, bisphenol A, bisphenol F, tetramethylbiphenol, ethylene oxide-extended products thereof, and hydrogenated alicyclic diols. Furthermore, if necessary, the low-molecular-weight diol may be blended with a trihydric or higher polyhydric alcohol such as glycerin, trimethylolpropane, trimethylolethane, tris(2-hydroxyethyl)isocyanurate, 1,2,4-butanetriol, pentaerythritol, or dipentaerythritol, but this does not necessarily have to be blended. The dibasic acid is preferably a polycarboxylic acid such as an aliphatic dibasic acid or an aromatic dibasic acid, such as adipic acid, phthalic acid, isophthalic acid, terephthalic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, maleic acid, fumaric acid, succinic acid, sebacic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, suberic acid, or azelaic acid, or an anhydride thereof. If necessary, the dibasic acid may be blended with a trifunctional or higher polybasic acid such as trimellitic acid or pyromellitic acid, but this is not necessary. The hydroxyl group-containing polyester resin having a glass transition temperature in the range of 30 to 120° C. does not have to be a polyester polyol having an isocyanuric ring. In the present invention, the diol compound and dibasic acid are reacted in the presence of a catalyst to obtain a polyester polyol. As such a catalyst, any of the general catalysts used in the reaction of a diol compound with a dibasic acid can be used. The glass transition temperature of the hydroxyl group-containing polyester resin is in the range of 30 to 120°C. Among these, the glass transition temperature is preferably 40° C. or higher, 45° C. or higher, or 50° C. or higher, more preferably 55° C. or higher, even more preferably 58° C. or higher, and most preferably 62° C. or higher. The glass transition temperature is also preferably 110° C. or lower, more preferably 100° C. or lower, even more preferably 95° C. or lower, and most preferably 90° C. or lower. If the glass transition temperature of the polyester resin is lower than 30° C., the aroma retention tends to decrease, and if it is higher than 120° C., the resulting coating film will harden, tending to decrease adhesion and aroma retention. The hydroxyl-containing polyester resin having a glass transition temperature in the range of 30 to 120° C. preferably has a hydroxyl value in the range of 1 to 200 mgKOH / g, more preferably in the range of 1 to 100 mgKOH / g. Examples of such polyesters include Elitel UE-9800 (Unitika Ltd.) (a copolymer polyester containing ethylene glycol and propylene glycol as diol copolymerization components and terephthalic acid as a dicarboxylic acid copolymerization component), Elitel UE-9200 (Unitika Ltd.), DYNAPOL L 912 (EVONIK Co., Ltd.), and Pluscoat RZ-105 (Goo Chemical Co., Ltd.).

[0018] (An acrylic resin with a glass transition temperature of 20°C or higher and a hydroxyl value of 40 mgKOH / g or higher) The acrylic resin of the present invention having a glass transition temperature of 20°C or higher and a hydroxyl value of 40 mgKOH / g or higher is obtained by polymerizing the following monomer having an unsaturated double bond in a solvent using a polymerization initiator: By using such an acrylic resin in the present invention, the aroma retention can be improved. Examples of the monomer having an unsaturated double bond include alkyl ester compounds of (meth)acrylic acid such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, decyl (meth)acrylate, and lauryl (meth)acrylate; (meth)acrylic acid amide derivatives containing at least one N-substituted methylol group such as N-methylol (meth)acrylamide; dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dipropylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylaminopropyl (meth)acrylate, and dipropylaminopropyl (meth)acrylate; Examples of suitable hydroxyl groups include aminoalkyl esters of (meth)acrylic acid such as methacrylate, mono- or diesters of (meth)acrylic acid of glycols such as diethylene glycol and dipropylene glycol, styrene derivatives such as styrene and α-methylstyrene, hydroxyalkyl ester compounds of (meth)acrylic acid such as hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate, and vinyl compounds having an acid group such as vinyl alcohol, allyl alcohol, acrylic acid, methacrylic acid, maleic acid, and itaconic acid. In order to exhibit the aroma-retaining properties of the present invention, and further in terms of adhesion of the aroma-retaining layer to the substrate, it is necessary to polymerize the hydroxyalkyl ester compounds of (meth)acrylic acid or vinyl alcohol so as to achieve the above-mentioned hydroxyl value. The glass transition temperature of the acrylic resin in the present invention is 20° C. or higher, preferably 30° C. or higher, and more preferably 40° C. or higher. It is also preferably 100° C. or lower, and more preferably 80° C. or lower. If the glass transition temperature of the acrylic resin is lower than 20° C., the aroma retention tends to decrease. The hydroxyl value of the acrylic resin having a glass transition temperature of 20°C or higher and a hydroxyl value of 40 mgKOH / g or higher is preferably in the range of 40 to 250 mgKOH / g, more preferably 60 mgKOH / g or higher, and even more preferably 75 mgKOH / g or higher, and more preferably 200 mgKOH / g or lower. If it is less than 40 mgKOH / g, the amount of residual solvent in the formed layer will be large. The weight average molecular weight of the acrylic resin having a glass transition temperature of 20° C. or higher and a hydroxyl value of 40 mgKOH / g or higher is preferably in the range of 5,000 to 100,000.

[0019] From the viewpoint of aroma retention, when a printed layer (described later) is present, it is preferable to use the above acrylic resin and the above polyester resin in combination to improve aroma retention. When the acrylic resin and the polyester resin are used in combination, the content ratio in terms of solid content of the acrylic resin and the polyester resin can be any ratio within a range that does not impair the effects of the present invention, but from the viewpoint of aroma retention, the content ratio in terms of solid content of the acrylic resin and the polyester resin (solid content ratio) is preferably acrylic resin / polyester resin = 90 / 10 to 10 / 90, 80 / 20 to 20 / 80, 70 / 30 to 30 / 70, 60 / 40 to 40 / 60, or 50 / 50. Furthermore, when an acrylic resin and a polyester resin are used in combination, the aroma retention is improved, so the glass transition temperature of the polyester resin is preferably 40°C or higher, 45°C or higher, or 50°C or higher, more preferably 55°C or higher, even more preferably 58°C or higher, and most preferably 62°C or higher.

[0020] (hardening agent) As the curing agent in the present invention, a curing agent containing a polyisocyanate compound (polyisocyanate curing agent) can be used. Examples of the polyisocyanate compound include aromatic aliphatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates. Among these, trifunctional or higher isocyanate curing agents are preferred. Specific examples of aromatic aliphatic diisocyanates include 1,3- and / or 1,4-phenylene diisocyanate, 4,4-diisocyanatobiphenyl, 3,3-dimethyl-4,4-diisocyanatobiphenyl, 1,3- or 1,4-xylylene diisocyanate, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene or a mixture thereof, ω,ω'-diisocyanato-1,4-diethylbenzene, and α,α,α',α'-tetramethylxylylene diisocyanate. Specific examples of aliphatic diisocyanates include 1,6-hexamethylene diisocyanate, tetramethylene diisocyanate, 2-methyl-pentane-1,5-diisocyanate, 3-methyl-pentane-1,5-diisocyanate, lysine diisocyanate, and trioxyethylene diisocyanate. Specific examples of alicyclic diisocyanates include isophorone diisocyanate, cyclohexane diisocyanate, hydrogenated diphenylmethane diisocyanate, norbornane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, and hydrogenated tetramethylxylene diisocyanate. Two or more of these polyisocyanate compounds may be mixed and used. It is also preferable to use components such as adducts obtained by reacting the above polyisocyanate compounds with low-molecular-weight active hydrogen compounds such as ethylene glycol, propylene glycol, meta-xylylene alcohol, 1,3-bishydroxyethylbenzene, 1,4-bishydroxyethylbenzene, trimethylolpropane, glycerol, pentaerythritol, erythritol, sorbitol, ethylenediamine, monoethanolamine, diethanolamine, triethanolamine, and meta-xylylenediamine, and alkylene oxide adducts thereof, various polyester resins, polyether polyols, and high-molecular-weight active hydrogen compounds such as polyamides; biuret compounds obtained by trimerizing the above diisocyanate compounds; and isocyanurate compounds obtained by isocyanating the above diisocyanate compounds. From an environmental perspective, the curing agent is preferably a biomass curing agent containing a biomass polyol compound and a biomass polyisocyanate compound, but a non-biomass curing agent may also be used. The biomass curing agent may be a trifunctional isocyanate compound having an isocyanurate ring obtained by nurating biomass diisocyanate. Biomass isocyanates can also be obtained by using plant-derived amino acids as raw materials and converting their amino groups to isocyanate groups, resulting in plant-derived isocyanate compounds. For example, lysine diisocyanate (LDI) can be obtained by methyl esterifying the carboxyl groups of lysine and then converting the amino groups to isocyanate groups. 1,5-pentamethylene diisocyanate can also be obtained by decarboxylating the carboxyl groups of lysine and then converting the amino groups to isocyanate groups. Polymers or oligomers obtained by polymerizing the above-mentioned isocyanate compounds with diol compounds so that the terminals are isocyanate groups can also be used. As the trifunctional isocyanate compound having an isocyanurate ring, a trifunctional isocyanate compound having an isocyanurate ring obtained by nurating an isocyanate having two isocyanate groups in the molecule can be used. The chemical equivalent ratio of the hydroxyl group of the polyol compound to the isocyanate group of the polyisocyanate compound in the curing agent is preferably 1:1 to 1:5.

[0021] (solvent) As the solvent in the present invention, an organic solvent and / or water can be used. Examples of organic solvents include toluene, ketone-based organic solvents (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), ester-based solvents (e.g., methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, isobutyl acetate, etc.), alcohol-based solvents (e.g., methanol, ethanol, n-propanol, isopropanol, butanol, etc.), and hydrocarbon-based solvents (toluene, methylcyclohexane, etc.).

[0022] (Other ingredients) The aroma-retaining coating composition may contain any known components within the scope of the present invention, provided that the effects of the present invention are not impaired. Such components include hydroxyl-containing polyester resins other than those having a glass transition temperature in the range of 30 to 120°C, other polyol compounds, etc. Furthermore, known pigments such as extender pigments and coloring pigments, pigment dispersants, dyes, etc. may also be contained. A catalyst can be used during the reaction between the polyester polyol and the isocyanate curing agent. Among them, it is preferable to use an organometallic compound, and examples of such organometallic compounds include titanium compounds such as dibutyltitanium dichloride, tetrabutyltitanate, and butoxytitanium trichloride, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate, dibutyltin diacetate, dioctyltin dilaurate, and tributyltin. Examples of suitable tin compounds include tin acetate, tributyltin chloride, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin trichloroacetate, and tin 2-ethylhexanoate; lead compounds include lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate; and iron 2-ethylhexanoate, iron acetylacetonate, cobalt benzoate, cobalt 2-ethylhexanoate, zinc naphthenate, zinc 2-ethylhexanoate, and zirconium naphthenate. Among these, titanium compounds such as tetrabutyl titanate are preferred. Tertiary amine compounds can also be used, such as triethylamine, triethylenediamine, 1,4-diazabicyclo(2,2,2)octane, and 1,8-diazabicyclo(5,4,0)-undecene-7 (DBU).

[0023] A coating layer can be formed using the aroma-retaining coating composition of the present invention by known means, such as roll coating using a gravure cylinder or the like, doctor knife coating, air knife / nozzle coating, bar coating, spray coating, dip coating, and a combination of these methods. If necessary, a urethane-based, acrylic-based anchor coating agent (AC agent) may be applied in advance to the surface of the base layer by a known method. In the case of packaging containers obtained by printing ink using a reverse printing method, it is preferable to coat the surface that will become the inside when the container is processed, as with printing ink, from the viewpoint of protecting the aroma-retaining coating composition layer. The amount of coating of the layer of the aroma-retaining coating composition in the laminate of the present invention after drying varies depending on the base layer and the desired level of aroma retention, but is generally in the range of 0.08 to 5.0 g / m 2 It is preferable that: In addition, in order to reduce the residual solvent in the layer made of the aroma-retaining coating composition and to obtain aroma-retaining properties, when the polyester resin and the acrylic resin are used in combination, the amount of the resin is set to 1.5 g / m 2 The coating amount is preferably 0.08 g / m or less. 2 If it is less than 5.0 g / m, the desired aroma retention may not be achieved. 2 Even if the temperature exceeds this range, it is difficult to further improve the aroma retention, and moreover, a large amount of residual solvent may remain in the aroma-retaining coating composition layer. More preferably 0.15 g / m 2 More preferably, it is 0.2 g / m or more. 2 That's all. In the laminate of the present invention, the coating amount of the solid content of the layer made of the aroma-retaining coating composition is 0.08 to 1.5 g / m 2 Even a very thin layer has sufficient aroma retention.

[0024] (adhesive layer) The adhesive layer in the present invention functions to bond the substrate layer and the sealant layer to each other. When the substrate layer or the sealant layer has a layer or a printed layer made of an aroma-retaining coating composition, the adhesive layer is formed on the layer or printed layer made of the aroma-retaining coating composition, and the substrate layer and the sealant layer are bonded to each other via these layers. In other words, the adhesive layer can be formed between any layers. The adhesive that forms such an adhesive layer is not particularly limited as long as it exhibits the above-mentioned functions.

[0025] The adhesive layer is used to adhere a sealant film in the case of dry lamination, and is used to adhere a molten resin in the case of extrusion lamination. The adhesive layer is formed by a known method such as applying an adhesive composition onto a substrate layer, a layer made of an aroma-retaining coating composition, a printed layer, or a sealant layer, and then curing the adhesive composition as necessary.

[0026] As the adhesive used in the dry lamination method, a layer formed from a two-component curing polyurethane resin adhesive is preferred in order to achieve both better adhesion and aroma retention of the entire laminate. In particular, it is preferred to use an adhesive containing a polyol compound and a polyisocyanate compound, and for the adhesive layer to contain a reaction product of the polyol compound and the polyisocyanate compound, in order to further achieve this effect. As the adhesive composition, from an environmental point of view, a two-component curing biomass polyurethane resin adhesive is more preferable. (Polyol compound) The polyol compound contained in the two-component curing polyurethane resin adhesive is preferably a polyol component that is an aromatic polyol, aliphatic polyol, aliphatic polyester, or aliphatic polyester compound having at least two hydroxyl groups in the molecule. Examples of such polyol components include aromatic or aliphatic polyurethane polyols, polyester polyols, polyether polyols, and acrylic polyols. Two or more of these polyol components may be mixed together. Among these, aromatic or aliphatic polyurethane polyols, polyester polyols, and polyether polyols are preferred, as they allow for easy control of the glass transition temperature and storage modulus. From an environmental perspective, biomass polyol components are preferred as the polyol component. Biomass polyether polyols and biomass polyester polyols are particularly preferred. (Polyisocyanate compounds) Similarly, the polyisocyanate compound is preferably a polyisocyanate compound having at least two isocyanate groups in the molecule, such as an aromatic aliphatic diisocyanate, an aliphatic diisocyanate, or an alicyclic diisocyanate, and two or more of such polyisocyanate compounds may be mixed and used. Examples of the aromatic aliphatic diisocyanate include 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene or a mixture thereof, and ω,ω'-diisocyanato-1,4-diethylbenzene. Examples of the aliphatic diisocyanate include hexamethylene diisocyanate, tetramethylene diisocyanate, 2-methyl-pentane-1,5-diisocyanate, 3-methyl-pentane-1,5-diisocyanate, lysine diisocyanate, and trioxyethylene diisocyanate. Examples of alicyclic diisocyanates include isophorone diisocyanate, cyclohexyl diisocyanate, hydrogenated diphenylmethane diisocyanate, norbornane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, and hydrogenated tetramethylxylene diisocyanate. Two or more of these polyisocyanate compounds may be mixed and used. It is also preferable to use an isocyanate component having three or more functionalities. Examples of adhesive compositions used in dry lamination include DIC Dry LX-401A, 75A, 719, 703VL, 500, and 510 (DIC Graphics), Takelac / Takenate A-969 / A-5, A-909 / A-5, A-977 / A-92, A-606 / A-50, A-515 / A-50, A-626 / A-50, A-525 / A-52, and A-666 / A-65 (Mitsui Chemicals), and RU-77, 771, 3600, and 3900 (Rock Paint). From the standpoint of environmental and safety considerations, it is preferable to use a biomass polyol compound and a biomass polyisocyanate compound as the polyol compound and the polyisocyanate compound.

[0027] Suitable adhesives used in extrusion lamination include imine-based anchor coating agents, isocyanate-based anchor coating agents, etc. Specific examples of commercially available anchor coating agents include A-3210 / A-3070, A-3210 / A-3072, and A-3210 / A-3075 (all manufactured by Mitsui Chemicals, Inc.), Secadyne 2710A / Secadyne 2810C(T), Secadyne 2730A / Secadyne 2730B, and Secadyne 2710A / Secadyne 2710C (all manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.), and DicDry LX-500, DicDry LX-901, and DicDry LX-747A (all manufactured by DIC Graphics).

[0028] (sealant layer) The sealant layer is provided on the surface of the adhesive layer, the layer made of the aroma-retaining coating composition, or the printed layer, and in the case of the dry lamination method, a known sealant film can be used, and in the case of the extrusion lamination method, a resin for forming a sealant film can be used. Examples of sealant films used in dry lamination include polyolefins such as uniaxially oriented polyethylene, uniaxially oriented polypropylene, biaxially oriented polyethylene, biaxially oriented polypropylene, unoriented polyethylene, and unoriented polypropylene, ethylene-vinyl acetate copolymers, and films for dry lamination. In order to provide a water vapor barrier property, the sealant layer and / or the substrate layer has a vapor-deposited layer of an inorganic oxide such as silica or alumina or a metal. When the substrate layer has a vapor-deposited layer, the sealant layer may or may not have a vapor-deposited layer. Specific examples of films for dry lamination include the following four types: CPP (non-oriented polypropylene film (P1128, thickness 25 μm, Toyobo Co., Ltd.)) LLDPE (linear low-density polyethylene unstretched film (UNILAX LS-711C, thickness 50 μm, Idemitsu Unilux Co., Ltd.)) VM-CPP (aluminum-coated non-oriented polypropylene film (ML CP WS, thickness 25 μm, Mitsui Chemicals Tocello Co., Ltd.)) VM-LLDPE (non-stretched aluminum-coated linear low-density polyethylene film (ML TUX-F, thickness 50 μm, Mitsui Chemicals Tocello Co., Ltd.)) Examples of resins for forming sealant films used in extrusion lamination include resins for forming sealant films such as polyethylene, polypropylene, and ethylene-vinyl acetate copolymer.

[0029] (Lamination method) The laminate of the present invention can be produced by dry lamination, extrusion lamination, wet lamination, non-solvent lamination, etc., but from the viewpoint of adhesive strength, it is preferable to produce it by dry lamination or extrusion lamination. As a dry lamination method, in the case of the laminate (1) above, which is formed by laminating in order a substrate layer, a layer made of an aroma-retaining coating composition, and optionally a printed layer, an adhesive layer, and a sealant layer, a method can be used in which the above-mentioned known adhesive is applied to the surface of the layer made of an aroma-retaining coating composition provided on one side of the substrate film, and then a sealant film having the above-mentioned vapor deposition layer is laminated using a known dry laminator.In addition, in the case of the laminate (2) above, which is formed by laminating in order a substrate layer, and optionally a printed layer, an adhesive layer, a layer made of an aroma-retaining coating composition, and a sealant layer, a method can be used in which the above-mentioned known adhesive is applied to one side of the substrate film and the layer made of an aroma-retaining coating composition provided on one side of the sealant film having the above-mentioned vapor deposition layer, and then these are laminated using a known dry laminator. When the substrate layer has a vapor-deposited layer, an extrusion lamination method can also be used. The extrusion lamination method can be used by applying an adhesive (anchor coating agent) to the surface of a layer of an aroma-retaining coating composition provided on one side of a substrate film having a vapor deposition layer, and then extruding and laminating a molten resin for forming a sealant film using a known extrusion laminator.

[0030] When measuring the laminate strength evaluation when a sealant layer is provided, for example, each laminate is cut to a width of 15 mm, and the T-type peel strength (N / 15 mm) is measured as the peel strength using a peel tester (Yasuda Seiki Seisakusho).

[0031] (Printing layer can be used as needed) If necessary, a printed layer is provided on the substrate layer, the layer comprising the aroma-retaining coating composition, or the sealant layer. The printed layer is formed by printing a printing ink composition containing a pigment, a binder resin, and an organic solvent, followed by drying and / or curing under normal conditions, and is a layer containing the pigment and the binder resin. The printing ink composition is not limited as long as it can exhibit the effects of the present invention. However, it is preferable to use a printing ink composition for flexible packaging laminates, assuming that a sealant layer is also provided. In this case, when the laminate of the present invention is used to form a packaging container, the printed layer becomes a layer that can be seen through the substrate layer from the outer surface of the packaging container. The printed layer may consist of one or more layers on the entire surface or a portion of the surface. It is not necessary for the printed layer to be formed on the entire surface of the substrate layer. In this case, the adhesive layer can be seen directly from the substrate layer side. As a specific example, a printing ink composition for laminates for flexible packaging will be mainly described. (pigment) As the pigment, for example, various inorganic pigments, organic pigments or extender pigments that are generally used in printing ink compositions can be used. Examples of the inorganic pigment that can be used include colored pigments such as titanium oxide, red iron oxide, antimony red, cadmium yellow, cobalt blue, Prussian blue, ultramarine, carbon black, and graphite. Examples of the organic pigment include soluble azo pigments, insoluble azo pigments, azo lake pigments, condensed azo pigments, copper phthalocyanine pigments, and condensed polycyclic pigments. Examples of extender pigments include silica particles, calcium carbonate, kaolin, clay, barium sulfate, aluminum hydroxide, talc, etc. Among these, it is preferable to use titanium oxide as a white pigment. The content of these pigments in the printing ink composition is usually about 1 to 50% by mass. A pigment dispersant may also be used. Examples of such pigment dispersants include polyester-based pigment dispersants that can generally be used in gravure printing ink compositions containing organic solvents. Specific examples include Ajisper PB821, PB822, PB824, and PB881 (Ajinomoto Fine-Techno Co., Ltd.), Solsperse 24000 and 56000 (Lubrizol Japan Co., Ltd.), and among these, basic group-containing polyester polymer dispersants are preferred. When a pigment dispersant is added, the content is usually preferably 1 to 200 parts by mass, more preferably 1 to 60 parts by mass, relative to 100 parts by mass of all pigments. (binder resin) The binder resin used in the printing ink composition for flexible packaging laminate in the printed layer preferably contains an amino group and a hydroxyl group in order to ensure excellent adhesion to the substrate layer. The amine value is preferably 1.00 to 13.00 mgKOH / g, and the hydroxyl value is preferably 0.50 to 12.00 mgKOH / g. As such a binder resin, a hydroxyl group-containing polyurethane resin having an amino group at its terminal is preferred. From an environmental perspective, the polyurethane resin is preferably a biomass polyurethane resin. Furthermore, one type of binder resin selected from the group consisting of vinyl chloride-vinyl acetate copolymer resins having hydroxyl groups, vinyl chloride-acrylic copolymer resins having hydroxyl groups, and cellulose resins may be used in combination. The amine value refers to the amine value per 1 g of solid content, and is measured using a 0.1 N aqueous hydrochloric acid solution by potentiometric titration (for example, COMTITE (AUTO TITRATOR COM-900, BURET B-900, TITSTATION K-900), manufactured by Hiranuma Sangyo Co., Ltd.), and then converted into an equivalent amount of potassium hydroxide. It is preferable to use one or more agents selected from adhesion improvers and anti-blocking agents, preferably adhesion improvers and anti-blocking agents, in the printing ink composition for forming the printed layer of the present invention, within a range that does not impair the intended performance of the present invention. (adhesion improver) As the adhesion improver, rosin and its derivatives, chlorinated polypropylene, dammar resin, etc. can be used. (Anti-blocking agent) As the anti-blocking agent, silica particles, polyethylene wax, fatty acid amide, etc. can be used. (organic solvent) Examples of organic solvents that can be used to form the printing layer include ketone-based organic solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ester-based organic solvents such as methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, and isobutyl acetate; alcohol-based organic solvents such as methanol, ethanol, n-propanol, isopropanol, and butanol; and hydrocarbon-based solvents such as toluene and methylcyclohexane. From the viewpoint of environmental issues, it is preferable to use an ester-based organic solvent, a mixed solvent of an alcohol-based organic solvent and a ketone-based organic solvent, or a mixed solvent of an ester-based organic solvent and an alcohol-based organic solvent, which is more environmentally friendly. From the viewpoint of monosolvents, it is more preferable not to use alcohol. (water) It is preferable to contain water as a solvent in order to reduce printing defects due to static electricity, prevent plate fogging, and improve cell reproducibility. When water is contained, the content in the printing ink composition is preferably 10.0 mass% or less, and more preferably 0.1 to 5.0 mass%. The printed layer can be obtained by printing using a gravure printing method, a flexographic printing method, etc. In the reverse printing method, a printed layer of printing ink is provided on the surface that will become the inside when processed into a container. In order to obtain a uniform aroma-retaining coating composition layer and a printed layer relative to the base layer, and from the viewpoint of residual solvent, it is preferable to provide a layer of the aroma-retaining coating composition on the surface of the base layer and then provide a printed layer on the surface of the layer of the aroma-retaining coating composition.

[0032] (Other materials that may be contained in the printing layer and method for producing a printing ink composition for flexible packaging laminate) The printing ink composition for flexible packaging laminates used to form the printing layer of the present invention may further contain various additives such as antistatic agents and plasticizers. Such a printing ink composition for a flexible packaging laminate can be produced by any known method, for example, by grinding a mixture of a pigment, a binder resin, an organic solvent, and, if necessary, a pigment dispersant, etc., using a high-speed mixer, a ball mill, a sand mill, an attritor, etc., and then adding and mixing the remaining materials, such as predetermined additives.

[0033] (Uses of the laminate of the present invention) The laminate of the present invention is used in containers such as bags for airtight packaging of foods that inherently contain aroma components, such as coffee powder, coffee beans, and tea leaves, foods that have already been flavored, and solid or liquid products that contain aroma components, such as cosmetics, detergents, shampoos, conditioners, etc. For this purpose, the laminate is sealed by heating or the like between the sealant layers, etc., to hermetically seal the packaged product and prevent even the aroma components from being released outside the container. Therefore, when the laminate of the present invention is used to form a container that can be airtightly sealed, it is possible to prevent the fragrance from leaking out of the container due to the fragrance components permeating or penetrating at least the laminate of the present invention, and it is also possible to prevent the permeation of water, etc. The shape of the container using the laminate of the present invention is not particularly limited. The laminate of the present invention may be used for the entire container, or it may be used as a member such as a lid that is tightly attached to the container body having aroma retention, such as a bag, a glass container, or a resin injection-molded or extrusion-molded product. (Aroma components) The aroma components that are prevented from permeating by the layer formed from the aroma-retaining coating composition of the present invention are the aroma components contained in the above-mentioned solids and liquids packaged in a container formed using a packaging material having this layer. Such aroma components include aroma components derived from raw materials used to obtain the solid or liquid (for example, if the solid or liquid is a food, ingredients such as spices, meat, vegetables, fruits, fish, dairy products, seasonings, oils, etc.), as well as natural or synthetic aroma components added for the purpose of scenting during the production of products such as foods, fabric softeners, liquid detergents, shampoos, conditioners, antiperspirants, wet wipes, cosmetics, room or car air fresheners, scented stationery, etc. Furthermore, the aroma components are not limited to those of these products. Furthermore, preventing the permeation of aroma components does not directly intend to prevent the permeation of substances other than aroma components, such as oxygen and nitrogen. [Example]

[0034] (Polyester resin for aroma-retaining layer, acrylic resin) (polyester resin) Polyester resin 1: Unsaturated polyester resin, glass transition temperature 80°C, hydroxyl value 25 mgKOH / g, solid content 100% by mass Polyester resin 2: Unsaturated polyester resin, glass transition temperature 35°C, hydroxyl value 25 mgKOH / g, solid content 100% by mass Polyester resin 3: saturated polyester resin, glass transition temperature 50°C, hydroxyl value 35 mgKOH / g, solid content 100% by mass Polyester resin 4: saturated polyester resin, glass transition temperature 105°C, hydroxyl value 5 mgKOH / g, solid content 100% by mass (acrylic resin) Acrylic resin 1: glass transition temperature 69°C, hydroxyl value 112 mg KOH / g, solid content 47 mass% (ethyl acetate solution) Acrylic resin 2: glass transition temperature 51°C, hydroxyl value 140 mgKOH / g, solid content 56% by mass (ethyl acetate solution)

[0035] (Hardening agent for aroma-retaining layer) Takenate D-110N: XDI-TMP adduct (Mitsui Chemicals, Inc.), NCO content = 11.5% by mass, solid content = 75% by mass (ethyl acetate solution) (Solvent for forming aroma-retaining layer) MEK: Methyl ethyl ketone

[0036] (Base film) VM-OPP (aluminum-deposited biaxially oriented polypropylene film (ML OP 102, thickness 25 μm, Mitsui Chemicals Tocello Co., Ltd.)) OPP (biaxially oriented polypropylene film (P2161, thickness 25 μm, Toyobo Co., Ltd.)) MDOPE (uniaxially oriented polyethylene film (PE3K-H, thickness 25 μm, Futamura Chemical Co., Ltd.)) NY (Nylon film (ONY-15, thickness 12 μm, Unitika))

[0037] (sealant film) VM-CPP (aluminum-coated non-oriented polypropylene film (ML CP WS, thickness 25 μm, Mitsui Chemicals Tocello Co., Ltd.)) VM-LLDPE (non-stretched aluminum-coated linear low-density polyethylene film (ML TUX-F, thickness 50 μm, Mitsui Chemicals Tocello Co., Ltd.)) CPP (non-oriented polypropylene film (P1128, thickness 25 μm, Toyobo Co., Ltd.)) LLDPE (linear low-density polyethylene unstretched film (UNILAX LS-711C, thickness 50 μm, Idemitsu Unilux Co., Ltd.))

[0038] (Preparation of Aroma-Retaining Coating Composition) Aroma-retaining coating compositions 1 to 9 were obtained so as to have the compositions shown in Table 1. The acrylic resin / polyester resin in the table is the ratio of the mass of the acrylic resin to the mass of the polyester resin in the aroma-retaining coating composition.

[0039] [Table 1]

[0040] (Method 1 for preparing aroma-retaining laminate: Coating on the base layer side) Aroma-retaining coating compositions 1 to 9 were applied to the substrate film as a 10% solids solution at a coating amount of 0.5 g / m after drying. 2 The coating was carried out with a wire bar Φ0.10 mm so that the coating amount was 30% and then dried. After aging at 40°C for 3 days, an adhesive (Takelac A-969 / Takenate A-5 (Mitsui Chemicals, Inc.), solid content 30%) was applied to the coated surface with a wire bar Φ0.15 mm, a sealant film was attached, and the coating was carried out with aging at 40°C for 1 day to obtain each laminate (Examples 1 to 12, Comparative Example 7). The solid content of the aroma-retaining coating composition 1 was diluted to 6%, and after drying, the coating amount was 0.3 g / m 2 The coating was done with a wire bar Φ0.10 mm, with a solid content of 15% and a coating amount of 1.5 g / m 2 Each laminate was obtained in the same manner as above except for the portion coated with a wire bar Φ0.15 mm so as to obtain the following laminate (Examples 14 to 15).

[0041] (Method 2 for producing aroma-retaining laminate: Coating on the sealant layer side) The aroma-retaining coating composition 1 for forming the aroma-retaining layer was applied to the sealant film as a solution with a solid content of 10% in an amount of 0.5 g / m after drying. 2 The coating was carried out using a wire bar with a diameter of 0.10 mm so that the thickness of the coating was 30% and then dried. The coating was then carried out for 3 days at 40°C. An adhesive (Takelac A-969 / Takenate A-5 (Mitsui Chemicals, Inc.), solid content 30%) was applied to the substrate using a wire bar with a diameter of 0.15 mm, and a sealant film coated with the coating agent was attached to the substrate. The coating was then carried out for 1 day at 40°C to obtain each laminate (Example 13, Comparative Example 8).

[0042] (Method for producing a laminate without a layer made of an aroma-retaining coating composition) Laminates (Comparative Examples 1 to 6) not having a layer made of the aroma-retaining coating composition were obtained in the same manner as in the manufacturing method of the aroma-retaining laminate described above, except that the aroma-retaining coating composition was not applied to the base film and the sealant film.

[0043] The aroma retention and water vapor barrier properties of each laminate were measured.

[0044] (Aroma retention test method) The laminate was cut into 7 cm squares, and one side was folded in half, with one long side and one short side heat-sealed. Each of the four resulting pouches was filled with one of the following contents: curry powder (1 g), coffee powder (1 g), fabric softener (4 g), and liquid shampoo (4 g), and the remaining side was heat-sealed to obtain sealed pouches. The resulting pouches were placed in glass bottles and sealed. After storage at 23°C for 7 days, fragrance leakage was evaluated as follows. Five testers skilled in fragrance evaluation checked the aroma inside the glass bottle and judged it according to the following criteria. The fragrance leakage evaluated by the majority of the testers is shown in Tables 2 to 4 below. Evaluation criteria ◎: No scent leakage. 〇~◎: There is a very slight fragrance leak. 〇: There is a slight fragrance leak. △: Fragrance leaks. ×: Strong fragrance leaks.

[0045] (Details of contents) Curry powder: Red can curry powder (S&B Foods) Coffee powder: Blendy Instant Coffee (Ajinomoto AGF) Liquid shampoo: Pantene Effortless Complete Night Repair Shampoo (P&G) Fabric softener: Soflan Aroma Rich Sweet Floral Aroma (LION)

[0046] (Water vapor barrier test method) Each laminate was measured for water vapor transmission rate (WVTR value) (g / m) using a water vapor transmission rate measuring device (Mocon, product name: PERMATRAN-3 / 34G) in accordance with JIS K7129B method. 2 ·day·atm) was measured. The water vapor transmission rate (WVTR value) was measured in an atmosphere of 40°C and 90% RH. The water vapor barrier property was evaluated according to the following criteria, and the results are shown in Tables 2 to 4 below. Evaluation criteria 〇:1.0g / m 2 Less than a day. ×:1.0g / m 2 ·day or more.

[0047] Table 2 shows the test results for Examples 1 to 8, Table 3 shows the test results for Examples 9 to 15, and Table 4 shows the test results for Comparative Examples 1 to 8. [Table 2]

[0048] [Table 3]

[0049] [Table 4]

[0050] The results of Examples 1 to 12 indicate that laminates with sufficient aroma retention and water vapor barrier properties could be obtained when the substrate film and / or sealant film had a vapor-deposited layer and a coating layer was formed on the substrate film using an aroma-retaining coating composition (Coating Compositions 1 to 9 listed in Table 1) containing a hydroxyl-containing polyester resin with a glass transition temperature in the range of 30 to 120°C and / or an acrylic resin with a glass transition temperature of 20°C or higher and a hydroxyl value of 40 mgKOH / g or higher, a curing agent, and a solvent. Furthermore, the results of Examples 1 to 8 indicate that when an acrylic resin and a polyester resin were used in combination, laminates with better aroma retention could be obtained when the polyester resin had a high glass transition temperature (Coating Compositions 1, 3 to 5 listed in Table 1) than when the polyester resin had a low glass transition temperature (Coating Composition 2 listed in Table 1). Furthermore, the results of Examples 6 and 11-12 show that a laminate with better aroma retention properties was obtained when the amounts of polyester resin and acrylic resin were similar (Coating Composition 3 listed in Table 1) compared to when either the polyester resin or the acrylic resin was used in greater amounts (Coating Compositions 8-9 listed in Table 1).In addition, laminates with sufficient aroma retention properties and water vapor barrier properties were obtained even when polyolefin was used as the base film (Examples 1-3, 5-12) or polyamide (Example 4), demonstrating that aroma retention properties and water vapor barrier properties do not depend on the type of resin used in the film or their combination. Furthermore, in Example 13, in which a coating layer was provided on a sealant film, similar results to those of Examples 1 to 12 were obtained, demonstrating that a laminate with sufficient aroma retention and water vapor barrier properties can be obtained regardless of whether the coating layer is applied to a base film or a sealant film. Furthermore, the aroma-retaining coating composition 1 was applied in an amount of 0.3 g / m after drying. 2 or 1.5g / m 2 From the results of Examples 14 to 15, in which coating was performed so that the amount of aroma-retaining coating composition applied was small or large, it was found that a laminate with sufficient aroma-retaining properties and water vapor barrier properties could be obtained.

[0051] In contrast, in Comparative Examples 1 to 4, in which the base film and / or sealant film had a vapor-deposited layer but no layer made of an aroma-retaining coating composition, the water vapor barrier property was good but the aroma retention was insufficient. Furthermore, in Comparative Examples 5 and 6, in which the base film and sealant film did not have a vapor-deposited layer and also did not have a layer made of an aroma-retaining coating composition, both the aroma retention and water vapor barrier property were insufficient. Furthermore, in Comparative Examples 7 and 8, in which the base film and sealant film did not have a vapor-deposited layer, the aroma retention was sufficient but the water vapor barrier property was poor. From the above, it was found that in order to obtain a laminate with sufficient aroma retention and water vapor barrier properties, it is necessary for the base film and / or sealant film to have a vapor deposition layer, and for the coating layer to be formed using an aroma-retaining coating composition containing a hydroxyl-containing polyester resin with a glass transition temperature in the range of 30 to 120°C and / or an acrylic resin with a glass transition temperature of 20°C or higher and a hydroxyl value of 40 mgKOH / g or higher, a curing agent, and a solvent.

Claims

1. A laminate having a substrate layer, a layer made of an aroma-retaining coating composition, an adhesive layer, and a sealant layer, The layer made of an aroma-retaining coating composition is a layer made of an aroma-retaining coating composition containing a hydroxyl-containing polyester resin having a glass transition temperature in the range of 30 to 120°C, an acrylic resin having a glass transition temperature of 20°C or higher and a hydroxyl value of 40 mgKOH / g or higher, a curing agent, and a solvent, the solid content ratio of the acrylic resin to the polyester resin is acrylic resin / polyester resin=90 / 10 to 10 / 90, The substrate layer and / or the sealant layer are a laminate having a vapor deposition layer.

2. The laminate according to claim 1, wherein the curing agent is a polyisocyanate curing agent.

3. 3. The laminate according to claim 2, wherein the polyisocyanate curing agent is a tri- or higher functional isocyanate curing agent.

4. The coating amount of the layer made of the aroma-retaining coating composition after drying is 0.15 to 1.5 g / m ２ The laminate according to claim 1, wherein the thickness is in the range of

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