Fragrance-retaining coating composition and laminate

Abstract

To provide a fragrance retention coating composition and a laminate that can obtain excellent fragrance retention regardless of the type of fragrance. 【Solution means】A fragrance retention coating composition containing a hydroxyl group-containing polyester resin having a glass transition temperature in the range of 40 to 120°C and a solvent.

Description

Technical Field

[0001] The present invention relates to a fragrance-retaining coating composition and a laminate used for packaging beverages, foods, detergents, cosmetics, etc. containing fragrance components such as alcoholic beverages, flavored beverages, coffee powder, spice powder, softeners, liquid detergents, shampoos, rinses, and perfumes.

Background Art

[0002] For the packaging of beverages, foods, detergents, cosmetics, etc. containing fragrance components such as alcoholic beverages, flavored beverages, coffee powder, spice powder, softeners, liquid detergents, shampoos, rinses, and perfumes, films with high fragrance-retaining properties (films laminated with highly barrier polyvinyl alcohol resins or ethylene-vinyl alcohol copolymer resins) have been used to prevent the fragrance from escaping outside the container. The property of such a film to maintain without allowing the fragrance components to permeate initially seems to be related to the tendency of gas barrier properties, but these tendencies do not necessarily actually coincide. Also, as a packaging material having fragrance-retaining properties, those obtained by providing a metal layer or a metal oxide layer on a resin film are known. However, both the metal foil layer and the metal oxide layer contained therein are not resins, and it takes time and effort to collect and recycle them. And when an article containing a large amount of fragrance components is stored in a container with insufficient fragrance-retaining properties, even if it is stored airtight, the fragrance components will come out of the container over time. As a result, when fragrance components come out from the products displayed in the store, due to the large number of displayed products, even if a small amount of fragrance components permeate outside the product from one product, the total permeation amount will be large, and as a result, the entire sales floor will be filled with fragrance.

[0003] Patent Documents 1 and 2 describe polyester polyols having a low oxygen transmission rate but an unknown permeability to fragrance components. Patent Document 3 describes a laminate for liquid packaging materials having a low oxygen transmission rate and excellent fragrance-retaining properties by combining a specific heat-sealing layer, a coating layer, and an adhesive layer.

Prior Art Documents

Patent Document

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0005] In recent years, there has been a demand for the development of films with high fragrance retention regardless of the type of fragrance. The present invention has been made in view of the above circumstances, and an object thereof is to provide a fragrance retention coating composition and a laminate that can obtain excellent fragrance retention regardless of the type of fragrance.

Means for Solving the Problems

[0006] As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by the following composition, and have completed the present invention. 1. A fragrance retention coating composition containing a hydroxyl group-containing polyester resin having a glass transition temperature in the range of 40 to 120°C and a solvent. 2. The fragrance retention coating composition according to 1, further containing a polyisocyanate curing agent as a curing agent. 3. The fragrance retention coating composition according to 2, wherein the polyisocyanate curing agent is a trifunctional or higher isocyanate curing agent. 4. A laminate having at least a base material layer, a layer made of the fragrance retention coating composition according to any one of 1 to 3, and a heat seal layer. 5. The laminate according to 4, wherein the coating amount after drying of the layer made of the fragrance retention coating composition is in the range of 0.15 to 1.0 g / m 2 of.

Effects of the Invention

[0007] Since the present invention is a fragrance-retaining coating composition containing a hydroxyl group-containing polyester resin having a glass transition temperature in the range of 40 to 120°C and a solvent, when applied to a film, it has excellent fragrance-retaining properties regardless of the type of fragrance.

Embodiments for Carrying Out the Invention

[0008] The present invention relates to a fragrance-retaining coating composition containing a hydroxyl group-containing polyester resin having a glass transition temperature in the range of 40 to 120°C and an organic solvent. More preferably, it relates to a fragrance-retaining coating composition further containing a polyisocyanate curing agent as a curing agent. Note that the fragrance-retaining coating composition may or may not contain at least one of a compound having an active hydrogen group with a molecular weight of 100 or more and 250 or less and a compound having an active hydrogen group with a solubility parameter of 29.5 or less as a component that reacts with the curing agent. Also, it may or may not contain a polyester compound having an amino group at the terminal. Also, the fragrance-retaining coating composition may or may not contain a plate-like inorganic compound or a compound having a phosphate structure.

[0009] <Fragrance-retaining coating composition> (Hydroxyl group-containing polyester resin having a glass transition temperature in the range of 40 to 120°C) In the present invention, one or more hydroxyl group-containing polyester resins having a glass transition temperature in the range of 40 to 120°C can be used. As the hydroxyl group-containing polyester resin of the present invention, a hydroxyl group-containing polyester resin which is a condensate of a low molecular weight diol and a dibasic acid is preferable. As the low molecular weight diol, at least one of an aliphatic diol, an alicyclic diol, and an aromatic diol is preferable.

[0010] For example, one or more selected from low molecular weight diols with or without 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, tricyclodecanedimethanol, etc. are preferred. However, the low molecular weight diol may consist only of ethylene glycol, or other low molecular weight diols may be used in combination.

[0011] Examples of aromatic diols include hydroquinone, resorcinol, catechol, naphthalenediol, biphenol, bisphenol A, bisphenol F, tetramethylbiphenol, and ethylene oxide extensions and hydrogenated alicyclics thereof. Optionally, glycerin, trimethylolpropane, trimethylolethane, tris(2-hydroxyethyl)isocyanurate, 1,2,4-butanetriol, pentaerythritol, dipentaerythritol, etc. may be blended with the above low molecular weight diol as a polyhydric alcohol with a valence of three or more, but it is not necessary to blend them.

[0012] Examples of the dibasic acid include aliphatic dibasic acids 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, azelaic acid, etc., polyvalent carboxylic acids such as aromatic dibasic acids, or anhydrides thereof are preferred. Further, if necessary, trimellitic acid, pyromellitic acid or the like may be blended as a polybasic acid having three or more functional groups with the above dibasic acid, but it is not necessary to blend them. Note that the hydroxyl group-containing polyester resin having a glass transition temperature in the range of 40 to 120°C does not have to be a polyester polyol having an isocyanurate ring. In order to obtain a polyester polyol by reacting the above diol compound and dibasic acid in the present invention, these are reacted in the presence of a catalyst. As such a catalyst, a general one among the catalysts used for the reaction of the diol compound and dibasic acid can be employed.

[0013] The glass transition temperature of the hydroxyl group-containing polyester resin is the measured glass transition temperature determined by thermal analysis. As a method of thermal analysis, in accordance with JIS K7121 (Method for Measuring Transition Temperature of Plastics), for example, using Pyris1 DSC manufactured by PerkinElmer, the glass transition temperature can be measured under the conditions of a heating rate of 20°C / min and a nitrogen gas flow rate of 20 ml / min. The glass transition temperature of the hydroxyl group-containing polyester resin is in the range of 40 to 120°C. Preferably it is 50°C or higher, more preferably 55°C or higher, still more preferably 58°C or higher, and most preferably 62°C or higher. Also preferably it is 110°C or lower, more preferably 100°C or lower, still more preferably 95°C or lower, and most preferably 90°C or lower. When the glass transition temperature of the polyester resin is lower than 40°C, the fragrance retention tends to decrease, and when it is higher than 120°C, the coating film obtained from the resulting composition becomes hard, so the adhesion and fragrance retention tend to decrease.

[0014] (Hydroxyl value) The range of the hydroxyl value of the hydroxyl group-containing polyester resin is preferably in the range of 1 to 200 mgKOH / g, more preferably in the range of 1 to 100 mgKOH / g. The hydroxyl value can be determined by applying the method specified in JIS K1557-1:2007. That is, after acetylating the hydroxyl groups by dissolving the polyester resin sample in a pyridine solution containing an acetylating reagent (e.g., acetic anhydride), the excess acetylating reagent is hydrolyzed with water, and the amount of acetic acid produced is determined by titration with potassium hydroxide. At this time, 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 above titration result.

[0015] Examples of such polyesters include Ester UE9800 (Unitika Ltd.) (a copolymerized polyester containing ethylene glycol and propylene glycol as diol copolymerization components and terephthalic acid as a dicarboxylic acid copolymerization component), Ester UE-9200 (Unitika Ltd.), DYNAPOL L 912 (Evonik), Plascote RZ-105 (Mutual Chemical Co., Ltd.), and the like.

[0016] (Hardener) As the hardener, a hardener containing a polyisocyanate compound can be used. Or it may not be used. Examples of the polyisocyanate compound include aromatic aliphatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, etc. Among them, an isocyanate hardener having three or more functional groups is preferable. Specific examples of the aromatic aliphatic diisocyanate 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, α,α,α’,α’-tetramethylxylylene diisocyanate, and the like.

[0017] Specific examples of the aliphatic diisocyanate include 1,6 - hexamethylene diisocyanate, tetramethylene diisocyanate, 2 - methyl - pentane - 1,5 - diisocyanate, 3 - methyl - pentane - 1,5 - diisocyanate, lysine diisocyanate, trioxyethylene diisocyanate, etc. Specific examples of the alicyclic diisocyanate include isophorone diisocyanate, cyclohexane diisocyanate, hydrogenated diphenylmethane diisocyanate, norbornane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated tetramethylxylene diisocyanate, etc. In addition, two or more of such isocyanate compounds may be mixed and used.

[0018] Further, the above diisocyanate compound is reacted with low - molecular - weight active hydrogen compounds such as ethylene glycol, propylene glycol, metaxylylene alcohol, 1,3 - bis(hydroxyethyl)benzene, 1,4 - bis(hydroxyethyl)benzene, trimethylolpropane, glycerol, pentaerythritol, erythritol, sorbitol, ethylenediamine, monoethanolamine, diethanolamine, triethanolamine, metaxylylenediamine and their alkylene oxide adducts, various polyester resins, polyether polyols, polyamide high - molecular - weight active hydrogen compounds, etc., and adducts obtained therefrom, biuret bodies obtained by trimerizing the above diisocyanate compounds, isocyanurate bodies obtained by isocyanurating the above diisocyanate compounds, etc. are preferably employed as components.

[0019] From the environmental aspect, the curing agent is preferably a biomass curing agent containing a biomass polyol compound and a biomass polyisocyanate compound. However, a curing agent that is not biomass may also be used. As the biomass curing agent, a trifunctional isocyanate compound having an isocyanurate ring obtained by nurating a biomass diisocyanate may also be used. Biomass isocyanate can also obtain an isocyanate compound derived from plants by converting the amino group into an isocyanate group using plant-derived amino acids as raw materials. For example, lysine diisocyanate (LDI) can be obtained by methyl esterifying the carboxyl group of lysine and then converting the amino group into an isocyanate group. Also, 1,5-pentamethylene diisocyanate can be obtained by decarboxylating the carboxyl group of lysine and then converting the amino group into an isocyanate group. Moreover, a polymer or oligomer formed by polymerizing the above isocyanate compound and a diol compound so that the terminal becomes an isocyanate group can also be used.

[0020] 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 and the isocyanate group of the polyisocyanate compound in the curing agent is preferably 1:1 to 1:5.

[0021] (Solvent) As the solvent, an organic solvent and / or water can be used. Examples of the organic solvent 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, methyl cyclohexane, etc.).

[0022] (Other components) Other components that the fragrance retention coating composition may contain, as long as they do not impair the effects of the present invention, include hydroxyl group-containing polyester resins other than those having a glass transition temperature in the range of 40 to 120 °C, and other polyol compounds. Further, it may contain pigments such as known extender pigments and coloring pigments, pigment dispersants, dyes, and the like. In addition, a catalyst can be used during the reaction of the polyester polyol and the isocyanate curing agent. Among them, it is preferable to use an organometallic compound. Such organometallic compounds include titanium compounds such as dibutyltitanium dichloride, tetrabutyl titanate, and butoxytitanium trichloride; tin compounds such as dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate, dibutyltin diacetate, dioctyltin dilaurate, tributyltin acetate, tributyltin chloride, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin trichloroacetate, and tin 2-ethylhexanoate; lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate; and further, iron 2-ethylhexanoate, iron acetylacetonate, cobalt benzoate, cobalt 2-ethylhexanoate, zinc naphthenate, zinc 2-ethylhexanoate, zirconium naphthenate, and the like. Among these, titanium compounds such as tetrabutyl titanate are preferable. Tertiary amine compounds can also be used. For example, triethylamine, triethylenediamine, 1,4-diazabicyclo(2,2,2)octane, and 1,8-diazabicyclo(5,4,0)-undecene-7 (DBU) can be used.

[0023] <Fragrance Retention Laminate Using the Fragrance Retention Coating Composition and Method for Producing the Same> (Fragrance Retention Laminate) The fragrance-retaining laminate of the present invention can be used for applications considering its excellent fragrance-retaining properties. Such an application is a sealed container, at least a part of which is formed by the fragrance-retaining laminate of the present invention, and which is a container that can be sealed after storing the contents. And the contents sufficiently contain a fragrance component and can be in the form of a solid or a liquid without limitation. The fragrance-retaining laminate of the present invention is based on a layer formed by sequentially laminating a base material, a layer composed of a fragrance-retaining coating composition, and, if necessary, a sealant layer. A printing layer, a primer layer, or the like can also be provided between the layer composed of the fragrance-retaining coating composition and the base material layer, and / or between the layer composed of the fragrance-retaining coating composition and the sealant layer. Note that the fragrance-retaining laminate may or may not have a metal vapor deposition layer, a vapor deposition layer of other inorganic compounds, or thin layers thereof. When not having these layers, it is preferable in that a step of removing these layers is not required in the process of reusing the fragrance-retaining laminate after use.

[0024] (Base material layer) The above-mentioned base material layer used in the fragrance-retaining laminate of the present invention may be a known one, and as a packaging material for foods, daily necessities, etc. having a fragrance component, it can be used as a layer located on the innermost layer or the outermost layer of the packaging container in a state where these are packaged. Such a base material layer is not particularly limited as long as it is a layer having no fragrance-retaining property. Examples of the base material layer include polyolefins such as polyethylene, polypropylene, and ethylene-propylene copolymer, polyesters such as polyethylene terephthalate, unstretched films, uniaxially stretched films, biaxially stretched films, etc. of polyamides, paper, woven fabrics or non-woven fabrics within a range capable of forming a layer composed of a fragrance-retaining coating composition, and these can be selected and used.

[0025] (Fragrance-retaining coating composition layer) With the fragrance-retaining coating composition of the present invention, a coating layer can be formed by known means. Such known means include roll coating methods using a gravure cylinder or the like, doctor knife methods, air knife / nozzle coating methods, bar coating methods, spray coating methods, dip coating methods, and coating methods combining these methods. If necessary, an anchor coating agent (AC agent) such as a urethane-based or acrylic-based one may be previously applied to the surface of the base material layer by a known method. In the case of a packaging container obtained by printing printing ink by surface printing, from the viewpoint that the fragrance-retaining coating composition layer does not directly contact the content, it is preferably applied to the surface that becomes the outside when processed on the container, similar to the printing ink. Also, in the case of a packaging container obtained by printing printing ink by reverse printing, from the viewpoint of protecting the fragrance-retaining coating composition layer, it is also preferably applied to the surface that becomes the inside when processed on the container, similar to the printing ink.

[0026] The coating amount after drying of the fragrance-retaining coating composition layer in the laminate of the present invention varies depending on the above-mentioned base material layer and the target fragrance-retaining level, but is preferably 0.08 to 5.0 g / m 2 Also, from the viewpoint of reducing the residual solvent in the fragrance-retaining coating composition layer and obtaining fragrance retention, it is preferably 1.5 g / m 2 or less. When the coating amount is less than 0.08 g / m 2 , the target fragrance retention may not be obtained, and even if it exceeds 5.0 g / m 2 , it is difficult to further improve the fragrance retention, and moreover, a large amount of residual solvent may remain in the fragrance-retaining coating composition layer. Preferably it is 0.08 g / m 2 or more, more preferably 0.15 g / m 2 or more, and still more preferably 0.2 g / m 2 or more. Also, the fragrance-retaining coating composition layer may be a layer formed by impregnating paper, woven fabric or non-woven fabric with the fragrance-retaining coating composition. The laminate of the present invention has a coating amount of the fragrance retention coating composition of 0.15 to 1.0 g / m 2 Even if it is a very thin film, it is a laminate having sufficient fragrance retention and excellent processability.

[0027] (Heat seal layer) When the fragrance retention laminate of the present invention has a heat seal layer, the heat seal layer may be a dried coating film layer of a heat sealant or a sealant layer. The heat seal layer that may be used can be formed by applying and drying a heat sealant. The heat sealant used for forming the heat sealant is not particularly limited, and may be any form such as a type in which a thermoplastic resin having heat sealability is dissolved in an organic solvent, a type dissolved in water or an aqueous organic solvent, or an emulsion type dispersed in water or an aqueous organic solvent. The sealant layer that may be used can be formed by extrusion lamination or dry lamination. As the extrusion lamination method, after applying the above-mentioned anchor coating agent to the surface of the layer made of the fragrance retention coating composition provided on one surface of the base film as needed, the above-mentioned polyethylene, polypropylene, ethylene-vinyl acetate copolymer, etc. for forming a sealant film in a molten state are extruded and laminated by a known extrusion laminator. The method can be used. Further, the molten resin can be laminated in a sandwich shape with other materials using the intermediate layer.

[0028] As the dry lamination method, after applying a known adhesive to the surface of the layer made of the fragrance retention coating composition provided on one surface of the base film of the base film, a sealant film made of polyolefin such as uniaxially stretched polyethylene, uniaxially stretched polypropylene, biaxially stretched polyethylene, biaxially stretched polypropylene, unstretched polyethylene, unstretched polypropylene, ethylene-vinyl acetate copolymer, etc. is laminated by a known dry laminator. The method can be used.

[0029] (Anchor coating agent used as needed in the extrusion lamination process) When the laminate layer of the fragrance-retaining laminate of the present invention is formed by extrusion lamination, as the anchor coating agent that can be used as needed, imine-based anchor coating agents, isocyanate-based anchor coating agents, etc. can be preferably used. Specifically, commercially available anchor coating agents include A-3210 / A-3070, A-3210 / A3072, A-3210 / A-3075 (all manufactured by Mitsui Chemicals), Sekadine 2710A / Sekadine 2810C(T), Sekadine 2730A / Sekadine 2730B, Sekadine 2710A / Sekadine 2710C (all manufactured by Dainichi Seika Kogyo Co., Ltd.), Deck Dry LX-500, Deck Dry LX-901, Deck Dry LX747A (all manufactured by DIC Graphic Co., Ltd., Deck Dry is a registered trademark of DIC Graphics).

[0030] (Adhesive used as needed in the dry lamination process) When the laminate layer of the fragrance-retaining laminate of the present invention is formed by extrusion dry lamination, as the adhesive that can be used as needed, laminate adhesives conventionally used in the production of packaging composite laminate films can be appropriately selected. For example, adhesives such as urethane resin-based, imino group-containing resin-based, and butadiene resin-based adhesives can be mentioned. Among them, urethane resin-based adhesives are preferred. A two-component adhesive composed of a combination of an isocyanate group-terminated urethane prepolymer composed of a polyol component and an excess of an aliphatic polyisocyanate component and a polyol component, or a two-component adhesive composed of a combination of a hydroxyl group-terminated urethane prepolymer composed of an excess of a polyol component and an aliphatic polyisocyanate component and a polyisocyanate component can be used. As needed, it can also contain an epoxy compound or a silane coupling agent.

[0031] Examples of commercially available adhesives include Deck Dry LX-401A, 75A, 719, 703VL, 500, 510, etc. (all manufactured by DIC Graphics Co., Ltd., Deck Dry is a registered trademark of DIC Graphics), Takelac / Takenate A-969 / A-5, A-977 / A-92, A-606 / A-50, A-515 / A-50, A-626 / A-50, A-525 / A-52, A-666 / A-65, etc. (all manufactured by Mitsui Chemicals, Inc.), RU-77, 771, 3600, 3900, etc. (all manufactured by Rock Paint Co., Ltd.), and the like.

[0032] (Printing layer) Regardless of whether it is dry lamination or extrusion lamination, even when there is no sealant layer or when no laminate layer is formed, the aroma-retaining laminate of the present invention may have a printing layer. The printing layer can be obtained by printing using a gravure printing method, a flexographic printing method, or the like. As described above, in the case of surface printing, a printing layer of printing ink is provided on the surface that becomes the outside when processed into a container, and in the case of reverse printing, a printing layer of printing ink is provided on the surface that becomes the inside when processed into a container. The order of the aroma-retaining coating composition layer and the printing layer with respect to the base material layer can be arbitrarily determined. However, in order to obtain a uniform aroma-retaining coating composition layer, it is preferable to provide the aroma-retaining coating composition layer on the surface of the base material layer.

[0033] (Other functional layers) Furthermore, in the laminate of the present invention, for the purpose of improving gas barrier properties, reinforcing strength, etc., one or more various functional layers may be provided between the base material film and the sealant film. Examples of such functional layers include vapor deposition layers of silica, alumina, metal, and other resin layers for the purpose of improving gas barrier properties such as oxygen, a stretched nylon film layer for the purpose of improving the strength reinforcement of the laminate film, and a nylon-based metaxylene diamine resin film layer for the purpose of improving both functions. These various functional layers can be formed by vapor deposition on any layer, formation of a coating film, lamination of films, or the like. Incidentally, the laminate of the present invention may or may not have a layer made of ethylene-vinyl alcohol copolymer, polyvinyl alcohol or polyamide, an inorganic compound layer such as a metal layer or a metal oxide layer, and a layer containing a metal-containing pigment.

[0034] (Use of the laminate of the present invention) The laminate of the present invention is used for containers such as bags for airtightly packaging solids or liquids containing fragrance components, such as foods originally containing fragrance components such as coffee powder, coffee beans and tea leaves, foods with added fragrances, cosmetics, detergents, shampoos, rinses, etc. For this purpose, the laminate is sealed by heating or the like between sealant layers, etc., so that the packaged product is sealed and the fragrance component alone is not released outside the container. Therefore, when a container that can use the laminate of the present invention and be airtightly sealed is used, at least the laminate of the present invention can prevent the fragrance from leaking outside the container due to penetration or permeation of the fragrance component. Further, by providing another layer for preventing the permeation of, for example, oxygen, carbon dioxide, water, etc. in the laminate, it is possible to achieve both prevention of the permeation of the fragrance component and prevention of the permeation of oxygen, carbon dioxide, water, etc. as a whole laminate. It may also have a layer for shielding ultraviolet rays. The laminate having these layers can protect, seal and package the contents without having a metal layer or a metal oxide layer. In addition, it is possible to package the contents of the packaging target that previously required a metal layer or the like for the purpose of not allowing the fragrance component to permeate. The form 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 can be used as a member such as a lid that adheres to a container body having fragrance retention properties such as a bag, a glass container, an injection molded product or an extrusion molded product of resin.

[0035] (Fragrance component) The fragrance component whose permeation is prevented by the layer formed by the fragrance retention coating composition of the present invention is the fragrance component contained in the above-mentioned solid or liquid packaged by a container formed using a packaging material having this layer. Such fragrance components are fragrance components derived from raw materials for obtaining the solid or the liquid (for example, if the solid or the liquid is food, etc., materials such as spices, meat, vegetables, fruits, fish, dairy products, seasonings, oils, etc.), and natural or synthetic fragrance components added for the purpose of scenting or the like during product manufacturing, such as food, fabric softeners, liquid detergents, shampoos, rinses, antiperspirants, wet wipes, cosmetics, room and car air fresheners, scented stationery, etc. Further, the fragrance components of these articles are not limited thereto. And preventing the permeation of the fragrance component is not directly intended to prevent the permeation of substances other than the fragrance component such as oxygen and nitrogen.

Examples

[0036] <Preparation of laminate> (Examples 1 to 11 and Comparative Examples 1 to 5) As the base material layer, OPP (biaxially oriented polypropylene film (P2161, thickness 25 μm, Toyobo Co., Ltd.)) or MDOPE (uniaxially oriented polyethylene film (PE3K-H, thickness 25 μm, Futamura Chemical Co., Ltd.)) was prepared. Then, the coating compositions of the examples and comparative examples were applied with a wire bar and dried. In Example 2, MDOPE was used as the base material, and in the examples other than Example 2 and the comparative examples, OPP was used. The coating amounts after drying were 1.0, 0.5, 0.2, 0.1 g / m 2 So that the compositions of the examples and comparative examples shown in Tables 1 to 3 were diluted in advance with the solvents described in the corresponding tables, and the above coating was performed. After aging the coated samples at 40°C for 3 days, an adhesive (Take lacquer A-969 / Takenate A-5 (Mitsui Chemicals, Inc.), solid content 30%) was applied to the coating composition-coated surface with a wire bar so that the coating amount after drying was 3.0 g / m 2 was applied. The results of the following Examples 1 to 11 and Comparative Examples 1 to 5 are the results when the coating amount after drying is 1.0 g / m 2 However, the same results were obtained in any case of the above coating amounts.

[0037] On the adhesive-coated surface, CPP (unstretched polypropylene film (P1128, thickness 25 μm, Toyobo Co., Ltd.)) or LLDPE (unstretched polyethylene film of linear low-density polyethylene (Unilax LS-711C, thickness 50 μm, Idemitsu Unilax Co., Ltd.)) was laminated, and aged at 40 °C for 3 days to obtain each laminate. In Example 2, LLDPE was laminated. In Examples and Comparative Examples other than Example 2, the above CPP was laminated. For the obtained laminates, the aroma retention, oxygen barrier property, and peel strength were measured.

[0038] (Examples 12 to 18) In Example 1 above, a layer (coating layer) made of an aroma retention coating composition was provided with a blue ink layer and an adhesive layer in this order, and further, on the adhesive-coated surface, the above CPP was provided as Example 12. Similarly, a layer made of an aroma retention coating composition was provided with a white ink layer and an adhesive layer in this order, and further, on the adhesive-coated surface, the above CPP was provided as Example 13. On the base material layer, a blue ink layer, a layer made of an aroma retention coating composition layer, and an adhesive layer were provided in this order, and further, on the adhesive-coated surface, the above CPP was provided as Example 14. Also, the same example as Example 1 was taken as Example 15. For Example 15, the coating amount of the layer made of the aroma retention coating composition was 0.5 g / m 2 , 0.2 g / m 2 , 0.1 g / m 2 Examples in which the amount was changed were taken as Examples 16 to 18, respectively.

[0039] Materials, glass transition temperature (Tg), and hydroxyl value used in Examples and Comparative Examples Eter UE-9800: polyester resin (Unitika Ltd.) Tg: 85 °C, hydroxyl value 4 mgKOH / g, acid value 3 mgKOH / g, viscosity-average molecular weight 13000 Eter UE-9200: polyester resin (Unitika Ltd.) Tg: 65 °C, hydroxyl value 6 mgKOH / g, acid value 1 mgKOH / g, viscosity-average molecular weight 15000 DYNAPOL L912: Polyester resin (Evonik) Tg: 105°C, hydroxyl value 5 mg KOH / g, acid value 3 mg KOH / g, number average molecular weight 15000 Plascoat RZ - 105: Hydroxyl - containing polyester resin (Gohsei Chemical) Tg: 53°C, hydroxyl value unknown, acid value 5 mg KOH / g

[0040] Nichigo Polyester LP - 033: Polyester resin (Mitsubishi Chemical) Tg: 15°C, hydroxyl value 4 - 8 mg KOH / g Nichigo Polyester LP - 035: Polyester resin (Mitsubishi Chemical) Tg: 20°C, hydroxyl value 2 - 8 mg KOH / g TEGOVariPlus CA: Ketone - aldehyde resin (Evonik) Tg: 70°C, hydroxyl value 110 mg KOH / g Kuraray Poval 5 - 98: Polyvinyl alcohol resin (Kuraray) Tg unknown, hydroxyl value unknown Duránate 24A - 90E: HDI - biuret (Asahi Kasei) Tg unknown, no hydroxyl group Takenate D - 110N: XDI - TMP adduct (Mitsui Chemicals) Tg unknown, no hydroxyl group Desmodur ultra Z4470BA: IPDI - isocyanurate (Sumika Covestro) Tg unknown, no hydroxyl group MEK: Methyl ethyl ketone IPA: Isopropyl alcohol Blue ink: Belflow R Blue 800 (Sakata Inx) White ink: Belflow R White 115 (Sakata Inx)

[0041] <Fragrance retention test method> The above laminate was cut into a 7 cm square, and with one side bent in half, the long side and the short side were heat-sealed one by one. As the contents, the following curry powder (1 g) or coffee powder (1 g), or softener (4 g) or liquid shampoo (4 g) was put in, and the remaining one side was heat-sealed. The prepared pouch was put into a glass bottle and sealed, and the leakage of fragrance after storage at 40 °C for 7 days was evaluated as follows. When 5 testers familiar with the evaluation of fragrance confirmed the fragrance of the atmosphere in the glass bottle and judged according to the following criteria, the leakage of fragrance evaluated by the largest number of the above testers is shown in the following table.

[0042] Curry powder: Red can curry powder (Esbee Foods Co., Ltd.) Coffee powder: Blendy instant coffee (Ajinomoto AGF Co., Inc.) Softener: Soflan Aroma Rich Sweet Floral Aroma (LION Corporation) Liquid shampoo: Pantene Effortless Complete Night Repair Shampoo (Procter & Gamble Co.) ◎: No leakage of fragrance 〇: Slight leakage of fragrance △: Leakage of fragrance ×: Strong leakage of fragrance

[0043] <Oxygen barrier property evaluation method> For each laminate, in accordance with JIS K7126 Method B, using an oxygen permeability measuring device (manufactured by Mocon, product name: OX-TRAN1 / 50), the oxygen transmission rate (OTR value) was measured. The measurement was carried out at 25 °C in an atmosphere of 0% RH. 〇: Less than 100 cc / m 2 ·day·atm ×: 100 cc / m or more 2 ·day·atm

[0044] <Lamination strength evaluation method> Each laminate was cut into a width of 15 mm, and using a peel tester (manufactured by Yasuda Seiki Seisakusho Co., Ltd.), the T-peel strength (N / 15 mm) was measured as the peel strength.

[0045]

Table 1

[0046]

Table 2

[0047]

Table 3

[0048]

Table 4

[0049] According to each of the above examples, even if any of curry powder, coffee powder, softener, and shampoo is enclosed in a packaging bag provided with a layer made of the aroma-retaining coating composition of the present invention, these scents do not leak out of the packaging bag, and it was confirmed that the packaging bag has aroma-retaining properties. In these examples, however, the oxygen barrier property was insufficient. It can be seen that excellent aroma-retaining properties are not directly related to the degree of oxygen barrier property. Also, even when an ink layer was provided in the laminate, the aroma-retaining property did not change. And as the coating amount of the layer made of the aroma-retaining coating composition decreased to 0.5 g / m 2 , 0.2 g / m 2 , 0.1 g / m 2 , the aroma-retaining property tended to decrease, but even when it was 0.1 g / m 2 , it was still within the allowable range. On the other hand, Comparative Examples 1 to 3 adopted coating compositions containing resins with low glass transition temperatures. Among them, Comparative Examples 1 and 2 were examples where no curing agent was used. Further, Comparative Examples 4 and 5 were examples where ketone-aldehyde resins or polyvinyl alcohol resins were used. According to these Comparative Examples 1 to 4, the aroma-retaining property of the laminate was poor. Also, according to Comparative Example 5, although the gas barrier property was excellent, the aroma-retaining property was poor.

Claims

Claim 1: A fragrance-retaining coating composition for a laminate having a layer made of polypropylene or polyethylene as a base material layer and having an oxygen barrier property of 100 cc / m2·day / atm or more, the composition containing a hydroxyl group-containing polyester resin having a glass transition temperature in the range of 40 to 120°C and a solvent. (However, excluding the composition for coating a metal surface) Claim 2 The fragrance-retaining coating composition according to claim 1, further containing a polyisocyanate curing agent as a curing agent. Claim 3 The fragrance-retaining coating composition according to claim 2, wherein the polyisocyanate curing agent is a polyfunctional isocyanate curing agent having three or more functional groups. Claim 4: A laminate having at least a base material layer made of polypropylene, a layer made of the fragrance-retaining coating composition according to claim 1 or 2, and a heat-sealing layer, and having an oxygen barrier property of 100 cc / m2·day / atm or more. Claim 5: A laminate having at least a base material layer made of polyethylene, a layer made of the fragrance-retaining coating composition according to claim 1 or 2, and a heat-sealing layer, and having an oxygen barrier property of 100 cc / m2·day / atm or more. Claim 6 The coating amount after drying of the layer composed of the fragrance-retaining coating composition is in the range of 0.15 to 1.0 g / m ２ The laminate according to claim 4, which is in the range of. Claim 7: The laminate according to claim 5, wherein the coating amount after drying of the layer made of the fragrance-retaining coating composition is in the range of 0.15 to 1.0 g / m2.

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