Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
  • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
  • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
  • B65D65/38—Packaging materials of special type or form
  • B65D65/40—Applications of laminates for particular packaging purposes
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
  • Y02W30/00—Technologies for solid waste management
  • Y02W30/50—Reuse, recycling or recovery technologies
  • Y02W30/80—Packaging reuse or recycling, e.g. of multilayer packaging

Definitions

• the present invention relates to a laminate with excellent aroma retention and a packaging material using the laminate.
• the packaging materials used for packaging food and daily necessities are usually made by bonding a heat-sealable film such as polyethylene film or polypropylene film to a resin film with excellent heat resistance and strength such as polyester film or nylon film using an adhesive. It consists of a combined laminate (Patent Documents 1 and 2).
• Patent Documents 1 and 2 On the other hand, in recent years, attempts have been made to recycle and use packaging materials with the increasing demand for building a recycling-oriented society. However, it is difficult to separate the resins by type in the above-described laminated body in which different types of resin films are bonded together, and thus it is not suitable for recycling.
• JP 2014-004799 A Japanese Patent Application Laid-Open No. 2004-238050
• a biaxially oriented polyolefin film such as oriented polypropylene or oriented polyethylene film is used as the outer layer side when viewed from the contents, and an unoriented polypropylene film or the like is used as the inner layer side (sealant film). It is conceivable to use a low-density polyethylene film or the like. Since the olefin resin occupies most of the entire laminate, such a laminate is superior in recyclability compared to laminates using different base materials, while a low-polarity film such as an olefin film is laminated. The laminate is considerably inferior in fragrance retention compared to a laminate using a polar film such as a PET film.
• the present invention has been made in view of such circumstances, and aims to provide a laminate and a packaging material that are excellent in recyclability and aroma retention.
• the present invention comprises a stretched polyolefin film, a heat seal layer having a thickness of 1 to 10 ⁇ m, an aroma-retaining adhesive layer disposed between the stretched polyolefin film and the heat seal layer, the stretched polyolefin film and the heat seal layer. and a first cyclic polyolefin-based resin layer disposed between and, wherein the thickness of the first cyclic polyolefin-based resin layer is 1 to 15 ⁇ m, and a packaging material obtained using the laminate.
• the laminate of the present invention it is possible to obtain a laminate and a packaging material that are excellent in recyclability and aroma retention.
• Stretched polyolefin films include high-density polyethylene film (HDPE), uniaxially stretched polyethylene film (MDOPE), biaxially stretched polyethylene film (OPE), biaxially stretched polypropylene film (OPP), and the like.
• HDPE high-density polyethylene film
• MDOPE uniaxially stretched polyethylene film
• OPE biaxially stretched polyethylene film
• OPP biaxially stretched polypropylene film
• the stretched polyolefin film may contain additives as necessary. Specifically, it improves workability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slip properties, releasability, flame retardancy, mold resistance, electrical properties, strength, etc.
• plastic compounds and additives such as lubricants, cross-linking agents, antioxidants, ultraviolet absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents and pigments can be added. The amount of additive added is adjusted within a range that does not affect other performances.
• the stretched polyolefin film may be surface-treated. This can improve adhesion with adjacent layers.
• the method of surface treatment is not particularly limited, and examples include corona discharge treatment, ozone treatment, low-temperature plasma treatment using oxygen gas and/or nitrogen gas, physical treatment such as glow discharge treatment, and oxidation using chemicals. Chemical treatments such as treatments can be mentioned.
• the thickness of the stretched polyolefin film can be appropriately adjusted according to the purpose, but it is preferably 5 ⁇ m to 300 ⁇ m in terms of the balance between mechanical strength and workability. It is more preferably 7 ⁇ m to 100 ⁇ m.
• the heat-sealing layer is made of an olefin-based resin and has a heat-sealing property of being melted by heat and being mutually fused.
• polyethylene resins such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE), polypropylene (CPP), ethylene-propylene copolymer, and polymethylpentene, Ethylene-vinyl acetate copolymer (EVA), ethylene-methyl methacrylate copolymer (EMMA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methyl acrylate (EMA) copolymer, ethylene-ethyl acrylate- Maleic anhydride copolymer (E-EA-MAH), ethylene-acrylic acid copolymer (EAA), ethylene-based copolymer such as ethylene-methacrylic acid copolymer (EMAA); further ethylene-acryl
• Polyethylene resins such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE), polypropylene (CPP), ethylene-propylene copolymer, etc. can be preferably used, and linear low density polyethylene (LLDPE), polypropylene (CPP), ethylene-propylene copolymers are particularly preferred.
• the LDPE may be branched low-density polyethylene obtained by high-pressure radical polymerization, preferably branched low-density polyethylene obtained by homopolymerizing ethylene by high-pressure radical polymerization.
• LLDPE is produced by a low-pressure radical polymerization method using a single-site catalyst, with an ethylene monomer as a main component, and ⁇ -olefins such as butene-1, hexene-1, octene-1, and 4-methylpentene as comonomers. can be preferably used.
• the comonomer content in LLDPE is preferably in the range of 0.5 to 20 mol %, more preferably in the range of 1 to 18 mol %.
• Single-site catalysts include various single-site catalysts such as metallocene compounds of Group IV or V transition metals of the periodic table and metallocene catalyst systems such as combinations of organoaluminum compounds and/or ionic compounds.
• single-site catalysts have uniform active sites, the molecular weight distribution of the resulting resin is sharper than that of multi-site catalysts, which have heterogeneous active sites. is less likely to be precipitated, and a resin having physical properties excellent in stability of seal strength and anti-blocking suitability can be obtained.
• the density of the ethylene-based resin is preferably 0.880-0.970 g/cm 3 .
• the film has appropriate rigidity, excellent mechanical strength such as heat seal strength and pinhole resistance, and improved film formability and extrusion suitability.
• the melting point is generally preferably in the range of 60 to 130°C, more preferably in the range of 70 to 120°C. If the melting point is within this range, processing stability and coextrusion workability with the first cyclic polyolefin resin layer, which will be described later, are improved. Furthermore, since it also has flexibility, it has good pinhole resistance.
• the MFR (190° C., 21.18 N) of the ethylene resin is preferably 2 to 20 g/10 minutes, more preferably 3 to 10 g/10 minutes. If the MFR is within this range, the extrudability of the film is improved.
• propylene-based resins examples include propylene homopolymers, propylene/ ⁇ -olefin random copolymers such as propylene-ethylene copolymers, propylene-butene-1 copolymers, and propylene-ethylene-butene-1 copolymers. Coalescing, metallocene-catalyzed polypropylene, and the like. Each of these may be used alone or in combination.
• a propylene- ⁇ -olefin random copolymer is preferred, and a propylene- ⁇ -olefin random copolymer polymerized using a metallocene catalyst is particularly preferred.
• These polypropylene resins preferably have an MFR (230° C., 21.18 N) of 0.5 to 30.0 g/10 minutes and a melting point of 110 to 165° C. More preferably, MFR (230 °C, 21.18N) is 2.0 to 15.0 g/10 min, and the melting point is 115 to 162°C. When the MFR and the melting point are within this range, the resulting film has good dimensional stability and also improves the film formability of the film.
• the polyolefin resin used for the heat seal layer a cyclic olefin resin, which will be described later, may be used.
• the heat seal layer may be made of a cyclic olefin resin. It is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less.
• the content of the polyolefin resin in the heat seal layer is preferably 90% by mass or more, particularly preferably 95% by mass or more, and more preferably substantially made of polyolefin resin.
• the content of the polyethylene resin is preferably 90% by mass or more, more preferably 95% by mass or more, and further preferably substantially composed of the polyethylene resin.
• the film thickness of the heat-sealing layer can be appropriately adjusted according to the purpose, but from the viewpoint of aroma retention and heat-sealing properties, it is, for example, 1 ⁇ m to 10 ⁇ m, more preferably 3 ⁇ m to 10 ⁇ m.
• the first cyclic polyolefin resin layer is a resin layer containing a cyclic polyolefin resin.
• the first cyclic polyolefin-based resin layer can be arranged at any position between the stretched polyolefin film and the heat seal layer. It may be arranged between the stretched polyolefin film and the aroma-retaining adhesive layer described below, or may be arranged between the aroma-retaining adhesive layer and the heat seal layer.
• the first cyclic polyolefin-based resin layer can be produced by co-extrusion with the heat seal layer, and from the viewpoint of production efficiency, it is preferred that the first cyclic polyolefin resin layer is arranged between the aroma-retaining adhesive layer and the heat seal layer. preferable.
• the structure of the cyclic olefin-based resin is not particularly limited, and examples thereof include norbornene-based polymers, vinyl alicyclic hydrocarbon polymers, and cyclic conjugated diene polymers. Among these, norbornene-based polymers are preferred.
• a ring-opening polymer of a norbornene-based monomer hereinafter referred to as "COP"
• COP norbornene-based copolymer obtained by copolymerizing a norbornene-based monomer and an olefin such as ethylene
• COC hydrogenates are particularly preferred.
• the weight average molecular weight of the cyclic olefin resin is preferably 5,000 to 500,000, more preferably 7,000 to 300,000.
• the norbornene-based monomer which is the raw material of the norbornene-based polymer, is an alicyclic monomer having a norbornene ring.
• Examples of such norbornene-based monomers include norbornene, tetracyclododecene, ethylidenenorbornene, vinylnorbornene, ethylidetetracyclododecene, dicyclopentadiene, dimethanotetrahydrofluorene, phenylnorbornene, methoxycarbonylnorbornene, methoxy carbonyltetracyclododecene and the like. These norbornene-based monomers may be used alone or in combination of two or more.
• olefins used in norbornene-based copolymers obtained by copolymerizing norbornene-based monomers with copolymerizable olefins include olefins having 2 to 20 carbon atoms, such as ethylene, propylene, and 1-butene; cycloolefins such as cyclobutene, cyclopentene and cyclohexene; and non-conjugated dienes such as 1,4-hexadiene. These olefins may be used alone or in combination of two or more.
• cyclic polyolefin resins examples include ring-opening polymers (COP) of norbornene-based monomers such as “ZEONOR” manufactured by Nippon Zeon Co., Ltd. Norbornene-based copolymers Examples of (COC) include “APEL” manufactured by Mitsui Chemicals, Inc., and “TOPAS” manufactured by Polyplastics.
• cyclic polyolefin resins it is preferable to use 60% by mass or more, more preferably 80% by mass or more, of cyclic polyolefin resins having a glass transition temperature of 100°C or less. By setting it as the said range, it becomes easy to make fragrance retention property, the intensity
• the cyclic olefin resin having a glass transition temperature of 100 ° C. or less is contained in the mass% or more, when the first cyclic polyolefin resin layer and the heat seal layer are produced by a coextrusion method, these interlayers The strength is improved, and high seal strength can be obtained.
• cyclic polyolefin resin having a glass transition temperature of 100° C. or less for example, an amorphous cyclic polyolefin resin having a norbornene monomer content of 75% by mass or less can be preferably used, and more preferably the monomer is is a cyclic polyolefin resin having a content ratio of 70% by mass or less.
• the Tg of the first cyclic polyolefin-based resin layer is 200 from the viewpoints of production feasibility and industrial availability of raw materials. °C or less, more preferably 60°C to 180°C.
• the content ratio of the norbornene monomer in the total amount of the cyclic polyolefin resin used is preferably in the range of 20 to 90% by mass, and more It is preferably 25 to 90% by mass, more preferably 30 to 85% by mass. If the content ratio is within this range, heat resistance, rigidity, moisture resistance, and processing stability are improved.
• the glass transition temperature Tg in the present invention is a value obtained by measuring with DSC.
• the first cyclic polyolefin resin layer may contain the olefin resin exemplified as the material for the heat seal layer in addition to the cyclic polyolefin resin described above.
• the first cyclic polyolefin resin layer preferably contains 70% by mass or more of the cyclic polyolefin resin. Since it becomes easier to obtain suitable straight cutting properties, it becomes easier to improve easy tearability.
• the content of the cyclic polyolefin resin in the first cyclic polyolefin resin layer is preferably 80% by mass or more, more preferably 90% by mass or more. It may be a layer substantially made of a cyclic polyolefin resin.
• the film thickness of the first cyclic polyolefin-based resin layer is 1 to 15 ⁇ m from the viewpoint of balance between aroma retention, strength of correlation with other layers, and recyclability. It is preferably 10 ⁇ m or less, more preferably 1 to 8 ⁇ m, particularly preferably 1 to 6 ⁇ m.
• the laminate of the present invention may further include another cyclic polyolefin resin layer (second cyclic polyolefin resin layer) in addition to the first cyclic polyolefin resin layer.
• second cyclic polyolefin resin layer can be arranged at any position between the stretched polyolefin film and the heat seal layer. It may be arranged between the stretched polyolefin film and the aroma-retaining adhesive layer described below, or may be arranged between the aroma-retaining adhesive layer and the heat seal layer.
• the second cyclic polyolefin resin layer can be produced by co-extrusion with the heat seal layer and the first cyclic polyolefin resin layer. is preferably located between
• the same material as the first cyclic polyolefin resin layer can be used for the second cyclic polyolefin resin layer.
• the film thickness of the second cyclic polyolefin-based resin layer is preferably 1 to 15 ⁇ m from the viewpoints of balance between aroma retention properties and correlation strength with other layers, and recyclability. It is preferably 10 ⁇ m or less, more preferably 1 to 8 ⁇ m, particularly preferably 1 to 6 ⁇ m.
• the scent-retaining adhesive layer is a cured coating of a scent-retaining adhesive and is disposed between the oriented polyolefin film and the heat seal layer.
• the fragrance-retaining adhesive is one having an oxygen barrier property of 300 cc/m 2 /day/atm or less at 23° C. and 0% RH in a coating film applied at 3 g/m 2 (solid content).
• the aroma retention property and the oxygen barrier property are different in properties, since there is a correlation between the aroma retention property and the oxygen barrier property, the oxygen barrier property is substituted for the index of the aroma retention property in this specification.
• the aroma-retaining adhesive preferably used in the present invention includes a polyol composition (X) containing at least one polyester polyol (A) of the following (A1) to (A3) and at least two isocyanates per molecule. and a polyisocyanate composition (Y) containing a compound having a group (hereinafter also simply referred to as an isocyanate compound (B)).
• Polyester polyol (A1) obtained by polycondensation of a polyhydric carboxylic acid containing an ortho-oriented polycarboxylic acid and a polyhydric alcohol (2) Polyester polyol having an isocyanuric ring (A2) (3) Polyester polyol (A3) having a polymerizable carbon-carbon double bond
• the ortho-oriented polycarboxylic acid used in the synthesis of the polyester polyol (A1) includes orthophthalic acid or its acid anhydride, naphthalene 2,3-dicarboxylic acid or its acid anhydride, naphthalene 1,2-dicarboxylic acid or its acid anhydrides, anthraquinone 2,3-dicarboxylic acid or its acid anhydride, 2,3-anthracenecarboxylic acid or its acid anhydride, and the like. These compounds may have a substituent at any carbon atom of the aromatic ring.
• the substituents include chloro, bromo, methyl, ethyl, i-propyl, hydroxyl, methoxy, ethoxy, phenoxy, methylthio, phenylthio, cyano, nitro, amino, phthalimido group, carboxyl group, carbamoyl group, N-ethylcarbamoyl group, phenyl group, naphthyl group and the like.
• the polyvalent carboxylic acid used for synthesizing the polyester polyol (A1) may contain a polyvalent carboxylic acid other than the ortho-oriented polyvalent carboxylic acid.
• Polycarboxylic acids other than ortho-oriented polycarboxylic acids include aliphatic polycarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, and dodecanedicarboxylic acid; maleic anhydride, maleic acid, fumaric acid, and the like.
• unsaturated bond-containing polycarboxylic acids alicyclic polycarboxylic acids such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid; terephthalic acid, isophthalic acid, pyromellitic acid, trimellitic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid and these acid anhydrides or ester-forming derivatives of dicarboxylic acids, aromatic polycarboxylic acids such as p-hydroxybenzoic acid, p-(2-hydroxyethoxy)benzoic acid and ester-forming derivatives of these dihydroxycarboxylic acids; can be used alone or in combination of two or more. Among them, succinic acid,
• the ratio of the ortho-oriented polycarboxylic acid to the total amount of the polycarboxylic acid is preferably 40 to 100% by mass.
• the polyhydric alcohol used to synthesize the polyester polyol (A1) preferably contains at least one selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexanedimethanol, and ethylene glycol. It is more preferable to include
• Polyhydric alcohols other than the above may be used in combination, such as 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, methylpentanediol, and dimethylbutanediol.
• butylethylpropanediol diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol; glycerin, trimethylolpropane, trimethylolethane, tris(2-hydroxyethyl) isocyanurate, 1 , 2,4-Butanetriol, pentaerythritol, dipentaerythritol and other polyhydric alcohols having a valence of 3 or more, hydroquinone, resorcinol, catechol, naphthalenediol, biphenol, bisphenol A, hisphenol F, tetramethylbiphenol, and these and aromatic polyhydric phenols such as hydrogenated alicyclic aromatic polyhydric phenols.
• polyester polyol (A1) has 3 or more hydroxyl groups (referred to as polyester polyol (a1) for convenience), some of the hydroxyl groups may be modified with acid groups.
• polyester polyols are hereinafter also referred to as polyester polyols (A1').
• the polyester polyol (A1') is obtained by reacting the polyester polyol (a1) with a polyvalent carboxylic acid or an acid anhydride thereof.
• the ratio of hydroxyl groups to be modified with polycarboxylic acid is preferably 1/3 or less of the hydroxyl groups provided in the polyester polyol (a1).
• Polyvalent carboxylic acids used for modification include succinic anhydride, maleic acid, maleic anhydride, fumaric acid, 1,2-cyclohexanedicarboxylic anhydride, 4-cyclohexene-1,2-dicarboxylic anhydride, and 5-norbornene.
• the polyester polyol (A2) is obtained, for example, by reacting a triol having an isocyanuric ring, a polyhydric carboxylic acid containing an ortho-oriented aromatic polyhydric carboxylic acid, and a polyhydric alcohol.
• triols having an isocyanuric ring include alkylene oxide adducts of isocyanuric acid such as 1,3,5-tris(2-hydroxyethyl)isocyanuric acid and 1,3,5-tris(2-hydroxypropyl)isocyanuric acid. etc.
• the ortho-oriented aromatic polycarboxylic acid, polycarboxylic acid, and polyhydric alcohol those similar to the polyester polyol (A1) can be used.
• triol compound having an isocyanuric ring 1,3,5-tris(2-hydroxyethyl)isocyanuric acid or 1,3,5-tris(2-hydroxypropyl)isocyanuric acid is preferably used.
• ortho-oriented aromatic polycarboxylic acid ortho-phthalic anhydride is preferably used.
• Ethylene glycol is preferably used as the polyhydric alcohol.
• the polyester polyol (A3) is obtained by using a component having a polymerizable carbon-carbon double bond as a polyhydric carboxylic acid or polyhydric alcohol.
• polyvalent carboxylic acids having polymerizable carbon-carbon double bonds examples include maleic anhydride, maleic acid, fumaric acid, 4-cyclohexene-1,2-dicarboxylic acid and its acid anhydrides, and 3-methyl-4-cyclohexene. -1,2-dicarboxylic acids and acid anhydrides thereof.
• Maleic anhydride, maleic acid, and fumaric acid are preferable because it is presumed that the smaller the number of carbon atoms, the less flexible the molecular chain becomes and the more difficult it is for oxygen to permeate.
• polyhydric alcohols having a polymerizable carbon-carbon double bond examples include 2-butene-1,4-diol.
• polyhydric carboxylic acids and polyhydric alcohols that do not have a polymerizable carbon-carbon double bond may be used in combination.
• polyhydric carboxylic acid and polyhydric alcohol those similar to polyester polyols (A1) and (A2) can be used.
• Polyvalent carboxylic acid is preferably at least one selected from the group consisting of succinic acid, 1,3-cyclopentanedicarboxylic acid, orthophthalic acid, acid anhydride of orthophthalic acid and isophthalic acid, and orthophthalic acid and acid anhydride thereof.
• At least one polyhydric alcohol selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexanedimethanol is preferably used, and ethylene glycol is more preferably used.
• the hydroxyl value of the polyester polyol (A) is preferably 20 mgKOH/g or more and 250 mgKOH/g or less.
• the hydroxyl value is less than 20 mgKOH/g, the viscosity of the polyol composition (A) is increased due to the excessive molecular weight, and the coating temperature must be increased when applied as a solventless adhesive, for example. If the hydroxyl value exceeds 250 mgKOH/g, the crosslink density of the cured coating film may become too high and the adhesive strength may decrease.
• the acid value is preferably 200 mgKOH/g or less. If the acid value exceeds 200 mgKOH/g, the reaction between the polyol composition (X) and the polyisocyanate composition (Y) will be too fast, possibly deteriorating the coatability.
• the lower limit of the acid value is not particularly limited, it is 20 mgKOH/g or more as an example. When the acid value is 20 mgKOH/g or more, good aroma retention and initial cohesion can be obtained due to intermolecular interactions.
• the hydroxyl value of the polyester polyol (A) can be measured by the hydroxyl value measuring method described in JIS-K0070, and the acid value can be measured by the acid value measuring method described in JIS-K0070.
• the polyester polyol (A) has a number average molecular weight of 300 to 5000, since a crosslink density with an excellent balance between adhesiveness and aroma retention can be obtained. More preferably, the number average molecular weight is 350-3000. The number average molecular weight is obtained by calculation from the obtained hydroxyl value and the designed number of hydroxyl functional groups.
• the glass transition temperature of the polyester polyol (A) is preferably ⁇ 30° C. or higher and 80° C. or lower, more preferably 0° C. or higher and 60° C. or lower, from the viewpoint of the balance between the adhesion to the substrate and the aroma retention property. More preferably, the temperature is 25°C or higher and 60°C or lower.
• the polyester polyol (A) may be a polyester polyurethane polyol obtained by subjecting the polyester polyols (A1) to (A3) to a number average molecular weight of 1,000 to 15,000 by urethane extension through reaction with a diisocyanate compound. Since the urethane-extended polyester polyol has a certain molecular weight component or more and a urethane bond, it has excellent initial cohesive strength and is excellent as an adhesive for lamination.
• the isocyanate compound (B) conventionally known ones can be used without particular limitation, and tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, Isophorone diisocyanate or trimers of these isocyanate compounds, and excess amounts of these isocyanate compounds, such as ethylene glycol, propylene glycol, metaxylylene alcohol, 1,3-bishydroxyethylbenzene, 1,4-bishydroxyethylbenzene, Low-molecular-weight active hydrogen compounds such as trimethylolpropane, glycerol, pentaerythr
• a polyester polyisocyanate obtained by reacting the polyester polyols (A1) to (A3) with a diisocyanate compound in such a manner that the ratio of hydroxyl groups to isocyanate groups is in excess of isocyanate may be used. These can be used alone or in combination of two or more.
• a blocked isocyanate may also be used as the isocyanate compound.
• isocyanate blocking agents include phenols such as phenol, thiophenol, methylthiophenol, ethylthiophenol, cresol, xylenol, resorcinol, nitrophenol and chlorophenol; oximes such as acetoxime, methylethylketoxime and cyclohexanone oxime; alcohols such as ethanol, propanol and butanol; halogen-substituted alcohols such as ethylene chlorohydrin and 1,3-dichloro-2-propanol; tertiary alcohols such as t-butanol and t-pentanol; Lactams such as caprolactam, ⁇ -valerolactam, ⁇ -butyrolactam and ⁇ -propyrolactam, and active methylene compounds such as aromatic amines, imides, acetylacetone, aceto
• the blocked isocyanate can be obtained by addition reaction of the above isocyanate compound and an isocyanate blocking agent by a known and commonly used appropriate method.
• an isocyanate compound having a skeleton derived from xylylene diisocyanate, hydrogenated xylylene diisocyanate, toluene diisocyanate, or diphenylmethane diisocyanate since good aroma retention can be obtained.
• isocyanate compounds examples include trimers of diisocyanate, biuret compounds synthesized by reaction with amines, and adduct compounds formed by reaction with alcohols.
• the adhesive is a solvent type
• the adduct an adduct obtained by reacting with an alcohol appropriately selected from the above low-molecular-weight active hydrogen compounds can be used. Adducts with substances are preferred.
• the polyisocyanate composition (Y) contains an epoxy compound.
• epoxy compounds include diglycidyl ether of bisphenol A and its oligomers, diglycidyl ether of hydrogenated bisphenol A and its oligomers, diglycidyl orthophthalate, diglycidyl isophthalate, diglycidyl terephthalate, and di-p-oxybenzoate.
• glycidyl ester diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate, diglycidyl succinate, diglycidyl adipate, diglycidyl sebacate, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1 ,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether and polyalkylene glycol diglycidyl ethers, trimellitic acid triglycidyl ester, triglycidyl isocyanurate, 1,4-diglycidyloxybenzene, diglycidyl Examples include propylene urea, glycerol triglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol
• epoxy curing accelerator When an epoxy compound is used, a commonly known epoxy curing accelerator may be appropriately added for the purpose of accelerating curing as long as the object of the present invention is not impaired.
• the carbon-carbon double bond is A known polymerization catalyst can be used in combination, an example of which is a transition metal complex.
• the transition metal complex is not particularly limited as long as it is a compound capable of oxidatively polymerizing a polymerizable double bond.
• cobalt, manganese, lead, calcium, cerium, zirconium, zinc, iron, copper and other metals, octylic acid, naphthenic acid, neodecanoic acid, stearic acid, resin acid, tall oil fatty acid, tung oil fatty acid, linseed oil fatty acid, A salt with soybean oil fatty acid or the like can be used.
• the blending amount of the transition metal complex is preferably 0 to 10 parts by mass, more preferably 0 to 3 parts by mass based on the resin solid content contained in the polyol composition (X).
• the polyol composition (X) and the polyisocyanate composition (Y) are such that the equivalent ratio between the hydroxyl groups contained in the polyol composition (X) and the isocyanate groups contained in the polyisocyanate composition (Y) is 1/0. It is preferable to mix 5 to 1/10, more preferably 1/1 to 1/5. If the amount of the isocyanate compound is excessive, the excessive isocyanate compound remaining in the cured coating film of the adhesive may bleed out from the adhesive layer. On the other hand, if the reactive functional groups contained in the polyisocyanate composition (Y) are insufficient, the adhesive strength may be insufficient.
• additives may be added to the aroma-retaining adhesive as long as the adhesiveness and aroma-retaining properties are not impaired.
• An inorganic filler may be used as such an additive.
• Inorganic fillers include silica, alumina, aluminum flakes, glass flakes and the like.
• Plate-like inorganic compounds include hydrous silicates (phyllosilicate minerals, etc.), kaolinite-serpentine clay minerals (halloysite, kaolinite, endellite, dickite, nacrite, etc., antigorite, chrysotile, etc.), pyrophyllite Light-talc group (pyrophyllite, talc, kerorai, etc.), smectite group clay minerals (montmorillonite, beidellite, nontronite, saponite, hectorite, sauconite, stevensite, etc.), vermiculite group clay minerals (vermiculite, etc.), mica or Mica group clay minerals (mica such as muscovite and phlogopite, margarite, tetrasilylic mica, teniolite, etc.), chlorite group (cookieite, sudoite, clinochlore, chamosite, nimite,
• the plate-like inorganic compound may be an ionic compound having an electric charge between layers, or may be a nonionic compound having no electric charge.
• the presence or absence of an electric charge between layers does not directly affect the fragrance retaining property of the adhesive layer.
• ionic plate-like inorganic compounds and inorganic compounds that swell with water have poor dispersibility in solvent-based adhesives, and when the amount added increases, the adhesive becomes thicker and thixotropic. As a result, the coating suitability may deteriorate. For this reason, it is preferable that the plate-like inorganic compound is non-ionic with no interlayer electrification.
• the average particle diameter of the plate-like inorganic compound is not particularly limited, it is preferably 0.1 ⁇ m or more, more preferably 1 ⁇ m or more, as an example. If it is smaller than 0.1 ⁇ m, the detour path of oxygen molecules will not be long, and a sufficient improvement in aroma retention cannot be expected.
• the upper limit of the average particle size is not particularly limited, but if the particle size is too large, defects such as streaks may occur on the coated surface depending on the coating method. Therefore, as an example, the average particle diameter is preferably 100 ⁇ m or less, and preferably 20 ⁇ m or less.
• the average particle size of the plate-like inorganic compound means the particle size with the highest appearance frequency when the particle size distribution of the plate-like inorganic compound is measured with a light scattering type measuring device.
• the aspect ratio of the plate-like inorganic compound is high in order to improve the aroma retention due to the labyrinthine effect of oxygen. Specifically, it is preferably 3 or more, more preferably 10 or more, and most preferably 40 or more.
• the amount of the plate-like inorganic compound is arbitrary, as an example, when the total solid content of the polyol composition (X), the polyisocyanate composition (Y), and the plate-like inorganic compound is 100 mass, the plate-like inorganic compound The blending amount of the inorganic compound is 5 to 50 parts by mass.
• the fragrance-retaining adhesive may contain an adhesion promoter.
• adhesion promoters include silane coupling agents such as hydrolyzable alkoxysilane compounds, titanate-based coupling agents, aluminum-based coupling agents, epoxy resins, and the like. Silane coupling agents and titanate-based coupling agents are expected to have the effect of improving adhesion to various film materials.
• the aroma-retaining adhesive layer may contain a known acid anhydride.
• acid anhydrides include phthalic anhydride, succinic anhydride, het acid anhydride, hymic acid anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydraphthalic anhydride, and tetrabromophthalic acid.
• anhydride tetrachlorophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenotetracarboxylic anhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 5-(2 ,5-oxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, styrene maleic anhydride copolymer and the like.
• a compound or the like having an oxygen scavenging function may be added.
• compounds having an oxygen-scavenging function include hindered phenols, vitamin C, vitamin E, organophosphorus compounds, gallic acid, pyrogallol, and other low-molecular-weight organic compounds that react with oxygen, cobalt, manganese, nickel, iron, Examples include transition metal compounds such as copper.
• the fragrance-retaining adhesive may contain a compound represented by the following general formula (1) or (2).
• R 1 to R 3 are a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a (meth)acryloyl group, a phenyl group which may have a substituent, a (meth)acryloyloxy group, is a group selected from alkyl groups having 1 to 4 carbon atoms, at least one of which is a hydrogen atom, and n represents an integer of 1 to 4.
• R 4 to R 5 are a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a (meth)acryloyl group, a phenyl group which may have a substituent, a (meth)acryloyloxy group is a group selected from alkyl groups having 1 to 4 carbon atoms, m and l are integers of 1 to 4, p is an integer of 0 to 30, and q is an integer of 0 to 30, but p and q are Except when both are 0.)
• Specific examples of the compounds represented by the general formulas (1) and (2) include phosphoric acid, pyrophosphoric acid, triphosphoric acid, methyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, dibutyl phosphate, and 2-ethylhexyl acid phosphate. , bis(2-ethylhexyl) phosphate, isododecyl acid phosphate, butoxyethyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, 2-hydroxyethyl methacrylate acid phosphate, polyoxyethylene alkyl ether phosphate and the like.
• the compounding amount of the compound represented by the general formula (1) or (2) is preferably 0.005 to 10% by mass, more preferably 0.01 to 1% by mass, of the total solid content of the fragrance-retaining adhesive. is more preferable.
• a tackifier such as xylene resin, terpene resin, phenol resin, rosin resin, etc. may be added as necessary in order to improve the adhesiveness to various film materials immediately after application.
• the amount to be added is preferably in the range of 0.01 to 5 parts by weight per 100 parts by weight of the total solid content of the polyol composition (X) and the polyisocyanate composition (Y).
• an active energy ray can also be used as a method of reacting the polymerizable carbon-carbon double bond.
• a known technique can be used as the active energy ray, and curing can be performed by irradiating ionizing radiation such as an electron beam, ultraviolet rays, or ⁇ rays.
• a known ultraviolet irradiation apparatus equipped with a high-pressure mercury lamp, an excimer lamp, a metal halide lamp, or the like can be used.
• a photo (polymerization) initiator that generates radicals by irradiation with ultraviolet rays is added in an amount of 0.1 to 20 parts by weight with respect to 100 parts by weight of the polyester polyol (A2). It is preferable to add a certain amount.
• radical-generating photo (polymerization) initiators include hydrogen abstraction types such as benzyl, benzophenone, Michler's ketone, 2-chlorothioxanthone, and 2,4-diethylthioxanthone; Photocleavable types such as cyclohexylphenyl ketone, 2-hydroxy-2-methylphenyl ketone and the like are included. It is possible to use one or more of these in combination.
• the aroma-retaining adhesive contains stabilizers (antioxidants, heat stabilizers, ultraviolet absorbers, etc.), plasticizers, antistatic agents, lubricants, antiblocking agents, coloring agents, crystal nucleating agents, etc. good.
• stabilizers antioxidants, heat stabilizers, ultraviolet absorbers, etc.
• plasticizers antistatic agents, lubricants, antiblocking agents, coloring agents, crystal nucleating agents, etc.
• antiblocking agents coloring agents, crystal nucleating agents, etc. good.
• the fragrance-retaining adhesive used in the present invention may be in the form of either a solvent type or a non-solvent type.
• the solvent-based adhesive refers to a method in which the adhesive is applied to a base material, heated in an oven or the like to volatilize the organic solvent in the coating, and then laminated to another base material, a so-called dry adhesive. Refers to the form used in the lamination method.
• Solvents used include toluene, xylene, methylene chloride, tetrahydrofuran, methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, acetone, methyl ethyl ketone (MEK), cyclohexanone, toluol, xylol, n-hexane, cyclohexane, and the like. is mentioned.
• Either one or both of the polyol composition (X) and the polyisocyanate composition (Y) contain the organic solvent described above. In the case of a solvent type, the solvent used as the reaction medium during the production of the constituents of the polyol composition (X) or the polyisocyanate composition (Y) may also be used as a diluent during coating.
• Solvent-free adhesives are used in the so-called non-solvent lamination method, in which the adhesive is applied to the base material and then laminated to another base material without going through the process of heating in an oven or the like to volatilize the solvent. It refers to the form that can be Neither the polyol composition (X) nor the polyisocyanate composition (Y) substantially contains the organic solvent described above. The constituent components of the polyol composition (X) or the polyisocyanate composition (Y) and the organic solvent used as the reaction medium during the production of the raw materials cannot be completely removed, resulting in the polyol composition (X) or the polyisocyanate composition ( If a small amount of organic solvent remains in Y), it is understood that the organic solvent is not substantially contained.
• the polyol composition (X) contains a low-molecular-weight alcohol
• the low-molecular-weight alcohol reacts with the polyisocyanate composition (Y) and becomes part of the coating film, so it is not necessary to volatilize after coating. Therefore, such a form is also treated as a non-solvent type adhesive.
• the adhesive when the fragrance-retaining adhesive used in the present invention is solvent-based, the adhesive preferably contains a drying aid. This makes it possible to suppress the organic solvent from remaining on the fragrance-retaining adhesive layer. Drying aids include isosorbide, isomannide, isoidide, triacetin and the like, and isosorbide is preferably used. The blending amount of the drying aid can be adjusted as appropriate, but as an example, it is 0.5% by mass or more and 50% by mass or less of the adhesive.
• the adhesive preferably contains a reactive diluent.
• a reactive diluent examples include isosorbide, isoidide, isomannide, furandimethanol, trans-tetrahydrofuran-3,4-diol, sorbitol, erythritol, etc. Isosorbide is preferably used.
• the amount of the reactive diluent to be blended can be appropriately adjusted according to the desired aroma retention property. It is preferably 80% by mass or less, more preferably 70% by mass or less.
• the fragrance-retaining adhesive is a solvent type
• the fragrance-retaining adhesive is applied to one substrate using a roll such as a gravure roll, and after heating in an oven or the like to evaporate the organic solvent, the other substrate is
• the laminate of the present invention is obtained by laminating the substrates. It is preferable to perform an aging treatment after lamination.
• the aging temperature is preferably room temperature to 80° C.
• the aging time is preferably 12 to 240 hours.
• the fragrance-retaining adhesive is a non-solvent type
• the fragrance-retaining adhesive that has been preheated to about 40° C. to 100° C. is applied to one substrate using a roll such as a gravure roll, and then immediately applied.
• the laminate of the present invention is obtained by laminating the other base material. It is preferable to perform an aging treatment after lamination.
• the aging temperature is preferably room temperature to 70° C.
• the aging time is preferably 6 to 240 hours.
• the amount of the fragrance-retaining adhesive to be applied is appropriately adjusted.
• the solid content is adjusted to 1 g/m 2 or more and 10 g/m 2 or less, preferably 1 g/m 2 or more and 5 g/m 2 or less.
• the coating amount of the adhesive is, for example, 1 g/m 2 or more and 10 g/m 2 or less, preferably 1 g/m 2 or more and 5 g/m 2 or less.
• the laminate of the present invention may further contain one or more polyolefin resin layers.
• the polyolefin-based resin the same polyolefin-based resin as used for the heat seal layer can be preferably used. It is preferable to use polyethylene resins such as very low density polyethylene (VLDPE), linear low density polyethylene (LLDPE) and low density polyethylene (LDPE). In particular, it is preferable to use polyolefin-based resins with different melting points for the heat-sealing layer and the polyolefin-based resin layer, because the suitability for packaging machines is improved.
• VLDPE very low density polyethylene
• LLDPE linear low density polyethylene
• LDPE low density polyethylene
• the polyolefin-based resin layer may contain a resin other than the polyolefin-based resin, but even in that case, the content of the polyolefin-based resin is preferably 50% by mass or more, more preferably 60% by mass or more.
• the polyolefin-based resin layer can be formed, for example, by a coextrusion method together with the heat seal layer and the first and/or second cyclic polyolefin-based resin layers.
• the film thickness of the polyolefin-based resin layer is, for example, 1 ⁇ m or more and 40 ⁇ m or less.
• the laminate of the present invention may be provided with a printed layer.
• the printed layer is a layer on which characters, figures, symbols, and other desired patterns are printed using liquid ink.
• liquid ink is a general term for solvent-based inks used for gravure printing or flexographic printing. It may contain a resin, a colorant, and a solvent as essential components, or it may be a so-called clear ink that contains a resin and a solvent but does not substantially contain a colorant.
• the printed layer is provided, for example, on either side of the stretched polyolefin film either directly or via a layer such as a primer layer having liquid ink receptivity.
• the printed layer may be provided all over the stretched polyolefin film, or may be provided only partially.
• Resins used in liquid inks are not particularly limited, and examples include acrylic resins, polyester resins, styrene resins, styrene-maleic acid resins, maleic acid resins, polyamide resins, polyurethane resins, vinyl chloride-vinyl acetate copolymer resins, Vinyl chloride-acrylic copolymer resin, ethylene-vinyl acetate copolymer resin, vinyl acetate resin, polyvinyl chloride resin, chlorinated polypropylene resin, cellulose-based resin, epoxy resin, alkyd resin, rosin-based resin, rosin-modified maleic acid resin , ketone resins, cyclized rubbers, chlorinated rubbers, butyrals, petroleum resins, etc., and may be used alone or in combination of two or more. At least one, or two or more selected from polyurethane resins, vinyl chloride-vinyl acetate copolymer resins, and cellulose resins are preferred.
• Colorants used in liquid inks include inorganic pigments such as titanium oxide, red iron oxide, antimony red, cadmium red, cadmium yellow, cobalt blue, Prussian blue, ultramarine blue, carbon black, graphite, soluble azo pigments, insoluble azo pigments, and azo lakes.
• Extender pigments such as pigments, condensed azo pigments, copper phthalocyanine pigments, organic pigments such as condensed polycyclic pigments, calcium carbonate, kaolin clay, barium sulfate, aluminum hydroxide and talc.
• the organic solvent used for liquid ink preferably does not contain an aromatic hydrocarbon-based organic solvent. More specifically, alcohol-based organic solvents such as methanol, ethanol, n-propanol, isopropanol and butanol, ketone-based organic solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, methyl acetate, ethyl acetate, propyl acetate and butyl acetate.
• alcohol-based organic solvents such as methanol, ethanol, n-propanol, isopropanol and butanol
• ketone-based organic solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, methyl acetate, ethyl acetate, propyl acetate and butyl acetate.
• ester organic solvents n-hexane, n-heptane, n-octane and other aliphatic hydrocarbon organic solvents, cyclohexane, methylcyclohexane, ethylcyclohexane, cycloheptane, cyclooctane and other alicyclic hydrocarbon organic solvents etc., and can be used alone or in combination of two or more.
• the laminate of the present invention may contain layers other than those described above.
• the layer having gas barrier properties may include an inorganic deposition layer or a coating layer having gas barrier properties.
• the inorganic deposition layer is a layer having gas barrier properties to prevent permeation of oxygen gas and water vapor gas, and is a deposition layer made of an inorganic material or an inorganic oxide.
• examples of inorganic substances or inorganic oxides include aluminum, alumina, silica, and the like, and these may be used alone, or two or more of them may be used in combination, such as binary vapor deposition of silica and alumina.
• Two or more inorganic deposition layers may be provided. When two or more inorganic deposition layers are provided, they may have the same composition or may have different compositions.
• the inorganic deposition layer can be provided on the resin layer described above by a conventionally known method.
• methods for forming the inorganic deposition layer include physical vapor deposition methods (PVD methods) such as vacuum deposition, sputtering, and ion plating; plasma chemical vapor deposition; A chemical vapor deposition method (Chemical Vapor Deposition method (CVD method)) such as a chemical vapor deposition method and a photochemical vapor deposition method can be used.
• PVD methods physical vapor deposition methods
• CVD method Chemical Vapor Deposition method
• the film thickness of the inorganic deposition layer is, for example, 1 to 200 nm.
• the film thickness is, for example, 1 to 100 nm
• the film thickness is, for example, 1 to 100 nm.
• laminates containing an inorganic vapor deposition layer often have sufficient fragrance retaining properties due to the effect of the inorganic vapor deposition layer. Therefore, it is preferable to apply the present invention to a laminate that does not contain an inorganic deposition layer.
• the laminate of the present invention further includes polyamide resins such as nylon 6 and nylon 66, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, resin films such as cellophane, paper, paperboard, woven and nonwoven fabrics such as textiles, or aluminum.
• Metal foil such as foil may be included. The thickness of these substrates may be appropriately adjusted according to the mode of use, and is, for example, 5 to 30 ⁇ m.
• a coating layer with gas barrier properties is provided, for example, by applying and drying a coating agent containing a resin with polyvinyl gas barrier properties.
• Conventionally known coating agents can be used as such a coating agent, and examples thereof include those containing a vinyl alcohol polymer such as polyvinyl alcohol, ethylene vinyl alcohol, polyvinyl butyral, etc., and an aqueous solvent.
• the vinyl alcohol polymer may have reactive functional groups other than hydroxyl groups, such as acetoacetyl groups, carboxyl groups, anionic carboxyl groups, sulfonic acid groups, and anionic sulfonic acid groups. These may be used individually by 1 type, and may use 2 or more types together.
• Water-based solvents include water, glycols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, polyethylene glycol and polypropylene glycol; diols such as butanediol, pentanediol and hexanediol; propylene glycol laurate; diethylene glycol ethers such as diethylene glycol monoethyl, diethylene glycol monobutyl, diethylene glycol monohexyl, carbitol; glycol ethers such as cellosolve, including propylene glycol ether, dipropylene glycol ether, and triethylene glycol ether; methanol, ethanol , isopropyl alcohol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, butyl alcohol, pentyl alcohol; sulfolane, esters, ketones, lactones such as ⁇ -butyrolactone,
• the coating agent further contains a layered inorganic compound, a cross-linking agent capable of reacting with the functional group of the vinyl alcohol polymer, an inorganic filler, an antifoaming agent, a stabilizer (antioxidant, heat stabilizer, ultraviolet absorber, etc.), and a plasticizer. agents, antistatic agents, lubricants, antiblocking agents, coloring agents, leveling agents, and the like.
• a coating agent for forming a coating layer having gas barrier properties As a coating agent for forming a coating layer having gas barrier properties, commercially available products can be used. Takelac WPB (registered trademark) series manufactured by Kagaku Co., Ltd., and the like.
• laminates containing films made of polyester resin for example, often have sufficient aroma retention properties by themselves. Therefore, the present invention is preferably applied to laminates that do not contain these substrates.
• the laminate of the present invention can be used as a multilayer packaging material for the purpose of protecting foods, medicines, and the like.
• the layer structure may vary depending on the contents, usage environment, and usage pattern.
• the packaging material of the present invention can be obtained, for example, by stacking the heat-sealable layers of the laminate of the present invention facing each other and then heat-sealing the peripheral edges.
• the laminate of the present invention is folded or overlapped so that the inner layer surface (sealant film surface) faces each other, and the peripheral edge is sealed, for example, by a side seal type, a two-sided seal type, There are three-sided seal type, four-sided seal type, envelope pasted seal type, palm pasted seal type, pleated seal type, flat bottom seal type, square bottom seal type, gusset type, and other heat seal methods. be done.
• the packaging material of the present invention can take various forms depending on the contents, environment of use, and form of use. A self-supporting packaging material (standing pouch) or the like is also possible.
• As a heat sealing method known methods such as bar sealing, rotary roll sealing, belt sealing, impulse sealing, high frequency sealing and ultrasonic sealing can be used.
• the opening is heat-sealed to manufacture a product using the packaging material of the present invention.
• Contents to be filled include rice crackers, bean confections, nuts, biscuits, cookies, wafer confections, marshmallows, pies, half-baked cakes, candies, snacks, bread, snack noodles, instant noodles, dried noodles, and pasta.
• aseptic packaged rice, rice porridge, rice porridge, packaged mochi, staples such as cereal foods, pickles, boiled beans, natto, miso, frozen tofu, tofu, mushrooms, konjac, processed wild plants, jams, peanut cream, salads, frozen Vegetables, processed agricultural products such as processed potatoes, processed hams, bacon, sausages, processed chicken products, processed livestock products such as corned beef, fish hams and sausages, fish paste products, kamaboko, seaweed, tsukudani, bonito flakes, salted fish, Processed marine products such as smoked salmon and cod roe, fruits such as peaches, mandarin oranges, pineapples, apples, pears and cherries, vegetables such as corn, asparagus, mushrooms, onions, carrots, radishes, and potatoes, hamburgers, and meat.
• Frozen and chilled prepared foods such as bowls, fried seafood, gyoza, and croquettes, prepared foods such as chilled side dishes, butter, margarine, cheese, cream, instant creamy powder, dairy products such as infant formula powder, liquid seasonings, and retort pouches Examples include foods such as curry and pet food.
• the packaging material of the present invention can also be used as a packaging material for cigarettes, disposable body warmers, medicines such as infusion packs, cosmetics, and vacuum insulation materials.
• the packaging material of the present invention may be a lid material using the laminate of the present invention.
• Polyisocyanate composition (Y-1) Mitsui Chemicals "Takenate D-110N” (trimethylolpropane adduct of meta-xylylene diisocyanate non-volatile component 75.0% NCO% 11.5%) was used as a polyisocyanate composition (Y-1).
• Adhesive 2 Polyisocyanate composition (Y-2) 36 parts of 4,4-diphenylmethane diisocyanate and 19 parts of 2,4'-diphenylmethane diisocyanate were charged into a reaction vessel equipped with a stirrer, a thermometer and a nitrogen gas inlet tube, stirred under nitrogen gas, and heated to 60°C. .
• PPG polypropylene glycol having a number average molecular weight of 400
• 22 parts of PPG having a number average molecular weight of 1000 and 11 parts of PPG having a number average molecular weight of 2000 were added dropwise in several portions, The mixture was stirred for 5 to 6 hours to complete the urethanization reaction.
• the NCO group content of the obtained polyisocyanate was 13.5%. This was designated as polyisocyanate composition (Y-2).
• Adhesive 3 Polyol composition (X-3) 28.98 parts of ethylene glycol, 0.16 parts of glycerin, 84.56 parts of 1,3,5-tris(2-hydroxyethyl)isocyanuric acid were placed in a polyester reaction vessel equipped with an agitator, nitrogen gas inlet tube, Snyder tube, and condenser. and 57.54 parts of phthalic anhydride were charged, and the inside temperature was maintained at 220°C by gradually heating so that the temperature at the top of the rectifying tube did not exceed 100°C. When the acid value became 1 mgKOH/g or less, the esterification reaction was terminated to obtain a polyester polyol having a number average molecular weight of 420. The hydroxyl value was 378.3 mgKOH/g.
• a polyol composition (X-3) was prepared by adding 100 parts by mass of isosorbide to 100 parts by mass of the obtained polyester polyol.
• Polyisocyanate composition (Y-3) 48.56 parts of ethylene glycol, 0.12 parts of glycerin, 16.54 parts of 1,3,5-tris(2-hydroxyethyl)isocyanuric acid were added to a polyester reaction vessel equipped with a stirrer, nitrogen gas inlet tube, Snyder tube, and condenser. and 66.88 parts of phthalic anhydride were charged, and the inside temperature was maintained at 220°C by gradually heating so that the temperature at the top of the rectifying tube did not exceed 100°C.
• Adhesive 4 Polyol composition (X-4) (Polyol composition (X-4)) 79.10 parts of ethylene glycol, 74.06 parts of phthalic anhydride, 73.07 parts of adipic acid and 0.01 part of titanium tetraisopropoxide were placed in a polyester reaction vessel equipped with an agitator, nitrogen gas inlet tube, Snyder tube and condenser. was charged, and the inside temperature was maintained at 220°C by gradually heating so that the temperature at the top of the rectifying tube did not exceed 100°C.
• polyester polyol having a number average molecular weight of 800.
• the hydroxyl value was 143.2 mgKOH/g.
• the obtained polyester polyol was used as a polyol composition (X-4).
• Polyisocyanate composition (Y-4) 79.27 parts of ethylene glycol, 59.25 parts of phthalic anhydride, 87.68 parts of adipic acid and 0.02 parts of titanium tetraisopropoxide are placed in a polyester reaction vessel equipped with an agitator, nitrogen gas inlet tube, Snyder tube and condenser. was charged, and the inside temperature was maintained at 220°C by gradually heating so that the temperature at the top of the rectifying tube did not exceed 100°C.
• a fragrance-retaining adhesive 4 was obtained by mixing 50 parts of the polyol composition (X-4) and 100 parts of the polyisocyanate composition (Y-4).
• Polyisocyanate composition (Y-5) 114.00 parts of Millionate MN (mixture of 4,4'-diphenylmethane diisocyanate and 2,4'-diphenylmethane diisocyanate) was placed in a reaction vessel equipped with a stirrer, nitrogen gas inlet tube, Snyder tube, cooling condenser and dropping funnel. While stirring while heating to 70° C., 28.16 parts of polypropylene glycol (molecular weight: about 400) and 58.44 parts of polypropylene glycol (molecular weight: about 1000) were added dropwise using a dropping funnel over 2 hours, followed by further stirring for 4 hours. to obtain a polyisocyanate composition (Y-5).
• the NCO% measured according to JIS-K1603 was 13.5%.
• LLDPE (1) linear low-density polyethylene
• COC (1) norbornene copolymer
• a 20 ⁇ m thick OPP film (Pylon P2161, manufactured by Toyobo Co., Ltd.) was coated with white ink (Finert R794 White G3, manufactured by DIC) so that the thickness of the dry coating film would be 1 ⁇ m to form a printed layer.
• Adhesive 1 is applied to the printed layer using a bar coater so that the coating amount is 3.0 g/m 2 (solid content), and the diluted solvent is volatilized with a dryer set at a temperature of 70 ° C. to dry and adhere. formed a layer.
• aging was performed at 40° C. for 2 days to obtain a laminate of Example 1.
• Example 2 80 parts by mass of LLDPE (1) and high-density polyethylene (density: 0.960 g/cm 3 , MFR: 8.0 g/10 min (190° C., 21.18 N), hereinafter referred to as HDPE (A laminate 2' was obtained in the same manner as in Example 1, except that a mixture with 20 parts by mass of 1) was used and LLDPE (1) was used as the material of the heat seal layer.
• Example 2 a laminate of Example 2 was obtained in the same manner as in Example 1 except that the laminate 2' was used instead of the laminate 1'.
• Example 3 A laminate 3' was obtained in the same manner as in Example 2, except that a mixture of 90 parts by mass of LLDPE (1) and 10 parts by mass of HDPE (1) was used as the material for the polyolefin resin layer 2. Next, a laminate of Example 3 was obtained in the same manner as in Example 1 except that the laminate 3' was used instead of the laminate 1'.
• Example 4 Norbornene-based copolymer (manufactured by Mitsui Chemicals, Inc., "APEL APL8008T", MFR: 15 g/10 min (260° C., 21.18 N), hereinafter referred to as COC (2) as a material for the first cyclic polyolefin resin layer. ), and linear medium density polyethylene (density: 0.930 g/cm 3 , MFR: 5 g/10 min (190° C., 21.18 N), hereinafter referred to as LMDPE) is used as the polyolefin resin layer 1.
• LMDPE linear medium density polyethylene
• COC (3) as a material for the second cyclic polyolefin resin layer
• LLDPE (3) linear low-density polyethylene
• the first cyclic polyolefin resin layer (6) / polyolefin resin layer 1 (15) / second cyclic polyolefin resin layer (6) / heat seal layer (3) lamination Body 4' was obtained.
• the values in parentheses are the average film thickness ( ⁇ m) of each layer.
• the surface wetting tension of the first cyclic polyolefin resin layer was 40 mN/m.
• Example 4 a laminate of Example 4 was obtained in the same manner as in Example 1 except that the laminate 4' was used instead of the laminate 1'.
• Example 5 A mixture of 60 parts by mass of COC (3) and 40 parts by mass of COC (2) was used as the material for the first cyclic polyolefin resin layer, LLDPE (3) was used as the material for the polyolefin resin layer, and the second 60 parts by mass of a norbornene-based copolymer (“APEL AP6013T” manufactured by Mitsui Chemicals, Inc., MFR: 15 g/10 min (260° C., 21.18 N), hereinafter referred to as COC (4)) as a material for the cyclic polyolefin resin layer and 40 parts by mass of COC (2), and a propylene- ⁇ -olefin random copolymer (density: 0.900 g/cm 3 , melting point: 135 ° C., MFR: 4 g/10 min (230° C., 21.18 N), hereinafter referred to as MRCP).
• APEL AP6013T manufactured by Mitsui Chemicals, Inc., M
• the values in parentheses are the average film thickness ( ⁇ m) of each layer.
• the surface of the first cyclic polyolefin resin layer was subjected to corona discharge treatment to adjust the wetting tension of the surface to 40 mN/m.
• Example 5 a laminate of Example 5 was obtained in the same manner as in Example 1 except that the laminate 5' was used instead of the laminate 1'.
• Example 6 A mixture of 50 parts by mass of COC (3) and 50 parts by mass of COC (4) is used as the material for the first cyclic polyolefin resin layer and the second cyclic polyolefin resin layer, and LMDPE is used as the material for the polyolefin resin layer. and low-density polyethylene (density: 0.920 g/cm 3 , melting point: 115° C., MFR: 8 g/10 min (190° C., 21.18 N)) is used as the material for the heat seal layer.
• a laminate 6' of the first cyclic polyolefin resin layer (6)/polyolefin resin layer 1 (12)/second cyclic polyolefin resin layer (6)/heat seal layer (6) was obtained.
• the values in parentheses are the average film thickness ( ⁇ m) of each layer.
• the surface of the first cyclic polyolefin resin layer was subjected to corona discharge treatment to adjust the wetting tension of the surface to 40 mN/m.
• Example 6 a laminate of Example 6 was obtained in the same manner as in Example 1 except that the laminate 6' was used instead of the laminate 1'.
• Example 7 A laminate of Example 7 was obtained in the same manner as in Example 3, except that the adhesive 2 was used instead of the adhesive 1.
• Example 8 A laminate of Example 8 was obtained in the same manner as in Example 3 except that Adhesive 3 was used instead of Adhesive 1.
• Example 9 A 20 ⁇ m-thick OPP film (Pylon P2161, manufactured by Toyobo Co., Ltd.) was coated with white ink (Finert R794 White G3, manufactured by DIC) so that the thickness of the dry coating film would be 1 ⁇ m to form a printed layer.
• the adhesive 4 is applied to the printed layer using a solventless test coater so that the coating amount is 2.4 g/m 2 , and then the olefin resin layer 1 and the printed layer of the laminate 3 ′ are applied via the adhesive layer. After bonding, aging was performed at 40° C. for 2 days to obtain a laminate of Example 9.
• Comparative example 1 A laminate of Comparative Example 1 was obtained in the same manner as in Example 3, except that the adhesive 5 was used instead of the adhesive 1.
• Comparative example 2 A laminate of Comparative Example 2 was obtained in the same manner as in Example 1 except that a 25 ⁇ m-thick CPP film (manufactured by Toyobo Co., Ltd., Pylen P1128) was used instead of the laminate 1′.
• the laminate of the present invention exhibited excellent fragrance retention.

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• 2022
  • 2022-12-08 WO PCT/JP2022/045219 patent/WO2023120203A1/ja not_active Ceased
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