WO2023112537A1 - 積層体 - Google Patents

積層体 Download PDF

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Publication number
WO2023112537A1
WO2023112537A1 PCT/JP2022/040963 JP2022040963W WO2023112537A1 WO 2023112537 A1 WO2023112537 A1 WO 2023112537A1 JP 2022040963 W JP2022040963 W JP 2022040963W WO 2023112537 A1 WO2023112537 A1 WO 2023112537A1
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WO
WIPO (PCT)
Prior art keywords
laminate
polyrotaxane
olefin
adhesive
layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2022/040963
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English (en)
French (fr)
Japanese (ja)
Inventor
篤 江幡
裕樹 田代
智啓 田口
成志 吉川
隆裕 安海
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toyo Seikan Group Holdings Ltd
Toyo Seikan Co Ltd
Original Assignee
Toyo Seikan Group Holdings Ltd
Toyo Seikan Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toyo Seikan Group Holdings Ltd, Toyo Seikan Co Ltd filed Critical Toyo Seikan Group Holdings Ltd
Priority to JP2023567606A priority Critical patent/JPWO2023112537A1/ja
Priority to CN202280081826.8A priority patent/CN118382534A/zh
Priority to EP22907070.1A priority patent/EP4450279A4/en
Publication of WO2023112537A1 publication Critical patent/WO2023112537A1/ja
Priority to US18/740,908 priority patent/US20240326395A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • 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
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/02—2 layers
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/03—3 layers
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/20—Inorganic coating
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/31—Heat sealable
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • 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
    • B32B2439/00—Containers; Receptacles
    • B32B2439/02—Open containers
    • B32B2439/06—Bags, sacks, sachets

Definitions

  • the present invention relates to a laminate, and more particularly to an olefin-based laminate containing a large amount of olefin-based resin and suitable for manufacturing pouches by pasting by heat sealing or ultrasonic sealing.
  • Olefin resins typified by propylene resins and ethylene resins, have long been used in the packaging field, and are particularly easy to heat seal. are widely produced.
  • the above unstretched olefin resin film is in the form of a laminate in which a reinforcing film such as a stretched film is laminated. used.
  • the reinforcing film is laminated to the unstretched olefinic resin film using a dry lamination adhesive or the like.
  • a laminate using an unstretched olefinic resin is required to be a monomaterial in which the content of the olefinic resin is increased as much as possible and materials other than the olefinic resin are eliminated as much as possible. This is because a laminate containing a large amount of olefinic resin and having a high monomaterial property can be reused as an olefinic resin.
  • pouches made from laminates containing a large amount of olefin resin have low impact resistance and drop strength, and often break when dropped from a certain height.
  • polymers with a molecular structure called polyrotaxane have been developed.
  • a chain-shaped axial molecule penetrates the rings of multiple cyclic molecules, and bulky groups are attached to both ends of the axial molecule, and the cyclic molecule cannot come off from the axial molecule due to steric hindrance.
  • Various uses have been proposed for this polyrotaxane.
  • Patent Literature 1 proposes a laminate for a vacuum heat insulating material in which a heat-sealable layer and a gas barrier layer are bonded together with a polyrotaxane-containing adhesive.
  • the adhesive since the polyrotaxane is blended in the adhesive, the adhesive follows the expansion and contraction of each layer. As a result, delamination does not occur and excellent gas barrier properties are exhibited.
  • Patent Document 2 proposes a cell packaging material having an outer layer made of polyrotaxane.
  • the outer layer is composed of polyrotaxane instead of PET or Ny, wear resistance and scratch resistance are improved.
  • Patent Document 3 proposes a thermoplastic elastomer composition comprising a thermoplastic urethane elastomer containing polyrotaxane. Since this elastomer composition contains polyrotaxane, it is possible to produce a molded article having excellent elongation and strength.
  • an object of the present invention is to provide an olefin laminate that contains a large amount of olefin resin, is suitable for recycling, and is suitable for producing pouches having excellent impact resistance and drop strength.
  • Another object of the present invention is to provide an olefin-based laminate mainly composed of an olefin-based resin obtained by using an adhesive compounded with polyrotaxane.
  • the adhesive layer is formed from an adhesive containing polyrotaxane
  • the olefin-based resin is an ethylene-based resin or a propylene-based resin.
  • the olefin-based resin is a resin composition containing an ethylene-based resin and a propylene-based resin.
  • the adhesive layer contains polyrotaxane in an amount of less than 17% by mass.
  • the urethane-based adhesive is blended with polyrotaxane.
  • the functional group at the end of the side chain of the cyclic molecule is a hydroxyl group.
  • thermoplastic resin layer is an unstretched sealant film made of the olefin resin, and the other thermoplastic resin layer is formed from an unstretched or stretched film. is being done.
  • the other thermoplastic resin layer is formed of a stretched film, and the stretched film is provided with an inorganic coating or an organic coating.
  • An intermediate thermoplastic resin layer is provided between the one thermoplastic resin layer and the other thermoplastic resin layer.
  • the other thermoplastic resin layer is a stretched film, the intermediate thermoplastic resin layer is an unstretched or stretched film, and at least one of the other thermoplastic resin layer and the intermediate thermoplastic resin layer is composed of the olefin resin.
  • At least one of the stretched film forming the other thermoplastic resin layer and the stretched film forming the intermediate thermoplastic resin layer is provided with an inorganic coating or an organic coating.
  • a pouch obtained from the above olefin-based laminate.
  • the olefin-based laminate of the present invention has a basic structure in which an adhesive layer is provided between two thermoplastic resin layers. Contains olefin resin. Therefore, the olefin-based resin has a high monomaterial property and is excellent in recyclability.
  • the pouches (bag-like containers) formed from this laminate exhibit high drop strength even though they are mostly made of olefin resin, and are effectively prevented from being broken when dropped from a high place. ing.
  • the olefin-based laminate of the present invention improves various properties required for packaging materials such as pouches by adopting various layer structures suitable for packaging materials within the range that satisfies the above-mentioned basic structure and the like. can be made
  • FIG. 2 is a diagram for explaining the molecular structure of polyrotaxane used in the present invention.
  • Polyrotaxane is a known compound, and as shown in FIG. 1, a polyrotaxane molecule indicated as a whole by 1 has a composite molecular structure formed of a chain-shaped axial molecule 2 and a cyclic molecule 3. have. That is, it has a structure in which a chain-shaped axial molecule 2 is enclosed by a plurality of cyclic molecules 3 , and the axial molecule 2 penetrates the inside of the ring of the cyclic molecule 3 . Therefore, the cyclic molecule 3 can slide freely on the axial molecule 2, but bulky terminal groups 4 are formed at both ends of the axial molecule 2, so that the cyclic molecule 3 does not fall off from the axial molecule 2. is prevented.
  • the adhesive layer containing polyrotaxane since the cyclic molecules 3 can slide on the axial molecules 2, the adhesive layer containing polyrotaxane has a high degree of molecular freedom, and can follow expansion and contraction of adjacent layers and disperse stress when a load is applied. This is a factor in improving the impact resistance.
  • chain-like axial molecule 2 various types are known as the chain-like axial molecule 2.
  • chain-like axial molecule 2 As long as it can penetrate the ring of the cyclic molecule, it may be linear or branched. It is formed.
  • polymers forming such axial molecules 2 include polyvinyl alcohol, polyvinylpyrrolidone, cellulose-based resins (carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, etc.), polyacrylamide, polyethylene oxide, polyethylene glycol, polypropylene glycol, polyvinyl acetal, Polyvinyl methyl ether, polyamine, polyethyleneimine, casein, gelatin, starch, olefin resin (polyethylene, polypropylene, etc.), polyester, polyvinyl chloride, styrene resin (polystyrene, acrylonitrile-styrene copolymer resin, etc.), acrylic resin ( Poly(meth)acrylic acid, polymethyl methacrylate, polymethyl acrylate, acrylonitrile-methyl acrylate copolymer resin, etc.), polycarbonate, polyurethane, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral, polyacryl
  • suitable polymers forming the axial molecule 2 are polyethylene glycol, polyisoprene, polyisobutylene, polybutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, polypropylene, polyvinyl alcohol or polyvinyl methyl ether.
  • polyethylene glycol is most preferable in terms of affinity and reactivity with the adhesive in which the polyrotaxane is blended. In terms of monomaterial properties, polyethylene and polypropylene are suitable.
  • the bulky terminal groups 4 formed at both ends of the axial molecule 2 include an adamantyl group, a trityl group, a fluoresceinyl group, a dinitrophenyl group, and a pyrenyl group. and adamantyl groups are preferred.
  • the molecular weight of the above-mentioned axial molecule is not particularly limited, but if it is too large, the affinity with the adhesive component tends to be poor, and if it is too small, the mobility of the cyclic molecule is reduced, resulting in poor impact resistance. The improvement effect tends to decrease. From this point of view, the weight average molecular weight Mw of the axial molecule 2 is preferably in the range of about 1,000 to 100,000.
  • the cyclic molecule 3 may have a ring large enough to enclose the axial molecule 2.
  • rings include cyclodextrin ring, crown ether ring, benzocrown ring, dibenzocrown ring and dicyclohexanone ring.
  • a crown ring can be mentioned, and a cyclodextrin ring is particularly preferred.
  • a plurality of cyclic molecules 3 as described above are included in one axial molecule 2.
  • the cyclic molecule The inclusion number of 3 is preferably in the range of 0.001 to 0.6, more preferably 0.002 to 0.5, still more preferably 0.003 to 0.4. If the number of clathrates of the cyclic molecules 3 is too large, the cyclic molecules 3 are densely present with respect to one axial molecule, so that the mobility tends to decrease and the effect of improving the impact resistance tends to decrease. On the other hand, if the number of clathrates is too small, the gap between the axial molecules 2 becomes narrower, which tends to reduce the mobility and the effect of improving the impact resistance.
  • the maximum number of inclusions of the cyclic molecules 3 with respect to one axial molecule 2 can be calculated from the length of the axial molecule 2 and the thickness of the ring of the cyclic molecule 3 .
  • the maximum inclusion number is calculated as follows. That is, two repeating units [ --CH.sub.2 -- CH.sub.2 O--] of polyethylene glycol approximate the thickness of one ⁇ -cyclodextrin ring.
  • the number of repeating units is calculated from the molecular weight of this polyethylene glycol, and 1/2 of this number of repeating units is obtained as the maximum inclusion number of the cyclic molecule. Assuming that the maximum number of clathrates is 1.0, the number of clathrates of the cyclic molecule is adjusted within the range described above.
  • a side chain may be introduced into the ring of the cyclic molecule 3 described above.
  • This side chain is indicated at 5 in FIG. That is, by introducing such a side chain 5 into the ring, it is possible to more reliably form an appropriate space between adjacent axial molecules 2, which is advantageous for improving impact resistance.
  • the introduction of the side chain 5 can impart reactivity to the adhesive component in which the polyrotaxane is blended, forming a crosslinked structure with the adhesive, thereby forming a pouch. Strength can be further improved.
  • the side chains 5 are preferably formed by repeating organic chains having 3 to 20 carbon atoms, and the average weight molecular weight of such side chains is about 300 to 10,000.
  • the side chain 5 as described above is introduced by utilizing the functional group of the ring of the cyclic molecule 3 and modifying this functional group.
  • the ⁇ -cyclodextrin ring has 18 hydroxyl groups as functional groups, through which side chains are introduced. That is, up to 18 side chains can be introduced into one ⁇ -cyclodextrin ring. For example, if 9 out of 18 hydroxyl groups of the ⁇ -cyclodextrin ring have side chains attached, the degree of modification is 50%. Such a degree of modification is set within an appropriate range according to the adhesive component used in combination.
  • the side chain 5 (organic chain) as described above may be linear or branched as long as the characteristic of the polyrotaxane that the cyclic molecule 3 slides on the axial molecule 2 is not impaired.
  • ring-opening polymerization, radical polymerization, cationic polymerization, anionic polymerization, RAFT polymerization, NMP polymerization, etc. by reacting an appropriate compound with the functional group of the ring to form an appropriate size.
  • Side chains can be introduced.
  • ring-opening polymerization can introduce side chains derived from cyclic compounds such as cyclic lactones, cyclic ethers, cyclic acetals, cyclic amines, cyclic carbonates, cyclic iminoethers, and cyclic thiocarbonates.
  • cyclic compounds such as cyclic lactones, cyclic ethers, cyclic acetals, cyclic amines, cyclic carbonates, cyclic iminoethers, and cyclic thiocarbonates.
  • Cyclic ethers, cyclic siloxanes, lactones, and cyclic carbonates are preferred from the viewpoints of easy availability, high reactivity, and easy adjustment of size (molecular weight).
  • the compound used for introducing the side chain 5 using radical polymerization is a radically polymerizable compound, but the ring possessed by the cyclic molecule 3 of the polyrotaxane 1 is an active site that serves as a radical initiation point. does not have Therefore, prior to reacting the radical polymerizable compound, the functional group (hydroxyl group) of the ring is reacted with a compound for forming a radical initiation point, such as an organic halogen compound, to form a radical initiation point. It is necessary to form a different active site.
  • the radically polymerizable compound used for introducing the side chain by radical polymerization includes at least one group having an ethylenically unsaturated bond, for example, a (meth)acrylic group, a vinyl group, a styryl group, or the like. compounds (hereinafter referred to as ethylenically unsaturated monomers) are preferably used.
  • the side chain 5 introduced into the ring of the cyclic molecule 3 has repeating units such as —O— bonds, —NH— bonds, or —S— bonds, depending on the method of introduction. It may be introduced or may have substituents such as hydroxyl group, carboxyl group, acyl group, phenyl group, halogen atom, silyl group, mercapto group, vinyl group, NCO group and NCS group. Furthermore, depending on the type of functional group possessed by the compound used to introduce the side chain 5, a portion of this side chain may be bonded to the ring functional group of the cyclic molecule possessed by another axial molecule. However, it may also form a pseudo-crosslinked structure.
  • the most preferably used polyrotaxane 1 has a polyethylene glycol to which an adamantyl group is bonded as a terminal group 4 as an axial molecule 2, and a cyclic molecule 3 is a cyclic molecule having an ⁇ -cyclodextrin ring. 3, and a side chain 5 (terminal OH group) such as polycaprolactone is introduced.
  • the olefin-based laminate 10 of the present invention using the above-described polyrotaxane contains 80% by mass or more of olefin-based resin, particularly 90% by mass or more of ethylene-based resin or polypropylene-based resin. It has a basic structure in which an adhesive layer 15 is provided between the two thermoplastic resin layers 11 and 13 on the condition that it is included.
  • the laminate 10 of the present invention contains an extremely large amount of olefin resin, it has high monomaterial property and excellent recyclability. For example, when it is collected as waste after use, it can be reused as an olefin resin either alone or mixed with virgin olefin resin after pulverization, washing, drying, etc. as appropriate. , it is possible to suppress deterioration of physical properties due to recycling.
  • thermoplastic resin layers 11 and 13 are usually formed using an olefinic resin in order to realize the olefinic resin content described above.
  • the olefin-based resin include ethylene-based resins such as low-density polyethylene, high-density polyethylene, and copolymer resins of ethylene and other olefins; propylene-based resins such as polypropylene and copolymer resins of propylene and other olefins; can be mentioned.
  • ethylene-based resins and propylene-based resins which are widely used in the field of packaging materials, are suitable.
  • the olefin-based resin may be a resin composition containing an ethylene-based resin and a propylene-based resin
  • the thermoplastic resin layer 11 is formed of an ethylene-based resin or a propylene-based resin
  • 13 can be formed from a propylene-based resin or an ethylene-based resin.
  • the laminate 10 uses one thermoplastic resin layer 11 as a sealant resin layer, and as shown in FIG. suitable for manufacturing the pouch 20 by gluing.
  • one thermoplastic resin (olefin-based resin) layer 11 used as a sealant resin layer is formed of an unstretched olefin-based material.
  • the other thermoplastic resin (olefin resin) layer 13 laminated by the adhesive layer 15 is preferably stretched in order to improve strength and heat resistance. It is most preferable to use a propylene-based resin as the olefin-based resin from the viewpoint of obtaining a pouch that exhibits excellent heat resistance even in heat treatment such as retort sterilization and has high strength.
  • the unstretched olefin-based resin layer 11 (cast film) usually has a thickness of 30 to 150 ⁇ m.
  • the other stretched olefin resin layer 13 (stretched film) is stretched and heat-set to such an extent that its strength and heat resistance are improved, and its thickness is usually about 10 to 30 ⁇ m.
  • the adhesive layer 15 is formed of the adhesive containing the aforementioned polyrotaxane. That is, since one olefin-based resin layer 11 (unstretched film) and the other olefin-based resin layer 13 (stretched film) are attached with such an adhesive, heat resistance, impact resistance, etc. A superior pouch 20 can be obtained.
  • the adhesive layer 15 may be present between the thermoplastic resin layers 11 and 13 and does not necessarily have to be adjacent to these resin layers 11 and 13 .
  • the adhesive in which polyrotaxane is blended is not particularly limited, and dry laminate adhesives such as urethane adhesives and epoxy adhesives can be used. , it is preferable to use a urethane-based adhesive.
  • Urethane-based adhesives are particularly effective when epoxy groups, episulfide groups, thietanyl groups, OH groups, SH groups, NH2 groups, NCO groups, or NCS groups are introduced as functional groups into the side chains 5 of the polyrotaxane. target.
  • polyurethanes are formed by the reaction of polyols and polyisocyanates. That is, when the above functional groups are introduced into the side chains 5 of the polyrotaxane, the side chains 5 of the polyrotaxane are incorporated into the polymerization chain of the polyurethane formed by the reaction of the polyol and the polyisocyanate to form a crosslinked structure. is formed, it is most suitable for improving the strength of the pouch.
  • Polyols used for forming polyurethane adhesives are compounds having two or more OH groups in one molecule, such as di-, tri-, tetra-, penta-, hexa-hydroxy compounds, 1 Polyester containing two or more OH groups in the molecule (polyester polyol), polyether containing two or more OH groups in one molecule (hereinafter referred to as polyether polyol), two or more OH in one molecule group-containing polycarbonate (polycarbonate polyol), polycaprolactone containing two or more OH groups in one molecule (polycaprolactone polyol), acrylic polymer containing two or more OH groups in one molecule (poly acrylic polyol) is typical.
  • the most preferred polyols in the present invention are polyester polyols because of their high affinity with polyrotaxanes.
  • the above polyester polyol is a polymer obtained by a condensation reaction between a polybasic acid such as adipic acid and phthalic acid and a polyol.
  • Polyols to be reacted with polybasic acids include aliphatic polyols such as ethylene glycol, propylene glycol, neopentyl glycol and pentaerythritol; aromatic alcohols such as dihydroxynaphthalene, trihydroxynaphthalene and bisphenol A; sulfur-containing polyols such as ethoxy)phenyl]sulfide; and the like.
  • the polyisocyanate to be reacted with the polyol is a compound having two or more NCO groups in one molecule.
  • Specific examples include, but are not limited to, aliphatic isocyanates such as ethylene diisocyanate, trimethylene diisocyanate and tetramethylene diisocyanate; isophorone diisocyanate, norbornane diisocyanate, bis(isocyanatomethyl)cyclohexane, 2-isocyanatomethyl Alicyclic isocyanates such as 3-(3-isocyanatopropyl)-5-isocyanatomethyl-bicyclo[2,2,1]-heptane; xylylene diisocyanate, bis(isocyanatoethyl)benzene, bis(isocyanatomethyl)naphthalene, bis Aromatic isocyanates such as (isocyanatomethyl) diphenyl ether; sulfur-containing aliphatic isocyanates such as thiodieth
  • the above-mentioned polyisocyanate is usually used in an amount such that the isocyanate group (NCO group) is about 0.8 to 1.2 mol per 1 mol of the hydroxyl group possessed by the above-mentioned polyol.
  • polyrotaxane is less than 17% by mass, particularly less than 10% by mass in the adhesive layer 15 formed from the above adhesive (for example, a urethane-based adhesive obtained from polyester polyol and polyisocyanate).
  • a urethane-based adhesive obtained from polyester polyol and polyisocyanate.
  • the adhesive coating film containing the polyrotaxane in the above amount has improved loss tangent (tan ⁇ ) and improved vibration absorption in a dynamic viscoelasticity test (10 Hz) at 5 ° C. , which is confirmed in Examples described later.
  • loss tangent tan ⁇
  • vibration absorption in a dynamic viscoelasticity test (10 Hz) at 5 ° C.
  • polyrotaxane is blended in the urethane adhesive.
  • the tangent (tan ⁇ ) shows a value of 0.21 or more, particularly 0.23 or more, and the vibration absorbability is improved.
  • an adhesive coating film containing polyrotaxane in the above amount and having improved vibration absorption is equivalent to an adhesive coating film that does not contain polyrotaxane in order to work to firmly bond films together.
  • the elastic modulus of As in Example 1 the storage modulus E' in the dynamic viscoelasticity test (10 Hz) at 5°C exceeds 1 GPa.
  • the adhesive containing the polyrotaxane as described above is obtained by adding the polyrotaxane to the reaction component forming the adhesive (for example, a coating composition in which a polyester polyol and a polyisocyanate are dispersed in an organic solvent).
  • the coating composition containing polyrotaxane is applied onto a film forming one olefin resin layer, then the film forming the other olefin resin layer is pressure-bonded, heated to an appropriate temperature, polymerized and cured, and By removing the solvent, the adhesive layer 15 is formed, and the olefinic laminate 10 shown in FIG. .
  • the thickness of the adhesive layer 15 is very thin and, of course, the thickness is within a range that satisfies the above-mentioned olefinic resin content in the laminate 10 .
  • the thickness is generally about 2 to 5 g/m 2 .
  • ⁇ Bag making of olefin laminate The above-described olefin-based laminate 10 of the present invention can be used for various purposes as a packaging material. and used as a pouch (bag-like container) 20.
  • Bag making is performed by a well-known means.
  • an empty pouch is prepared by three-way sealing using two olefinic laminates 10, 10, the contents are filled from the opening, and finally the opening is closed by heat sealing.
  • An empty pouch can also be produced by folding one sheet of the olefin-based laminate 10 and heat-sealing both side ends. In this case, there is no need to heat seal the bottom.
  • empty pouches can be manufactured using the olefinic laminate 10 exclusively for the sides or bottom. Such a method is advantageous in enlarging the volume of the pouch 20 or imparting standing properties.
  • the pouch made from the olefin-based laminate 10 of the present invention and filled with contents in this way has excellent monomaterial properties with respect to olefin-based resins such as polypropylene and polyethylene, and contains a large amount of these olefin-based resins. Since it contains olefin resin, it has excellent recyclability as an olefin resin. Furthermore, although it contains a large amount of olefinic resin, it has high impact resistance, high drop strength, and effectively suppresses bag breakage due to dropping from a high place.
  • olefin-based laminate 10 of the present invention has the above-described olefin-based resin content and basic structure, various aspects can be employed to improve properties required for packaging materials such as packaging bags. .
  • one or more stretched olefin resin layers can be laminated on the olefin resin layer 13 (stretched olefin resin layer) via an adhesive layer 15 containing polyrotaxane. Therefore, it is possible to achieve higher strength.
  • an inorganic coating is provided on at least one surface of the olefin resin layer 13 (stretched olefin resin layer) and the stretched olefin resin layer laminated thereon via the adhesive layer 15. , the gas barrier property against oxygen and the like can be improved.
  • Such inorganic coatings are formed by deposition films of various metals or metal oxides, coating films mainly composed of silicon oxide, coating films of condensates of metal alkoxides, and cross-linking reactions between carboxylic acids and metals.
  • There is a coating film in which metal oxide is dispersed and a coating film in which metal oxide is dispersed.
  • the above vapor deposition film is an inorganic vapor deposition film formed by physical vapor deposition such as sputtering, vacuum vapor deposition, ion plating, etc., or chemical vapor deposition such as plasma CVD, and includes various metals and metal oxides. It is a film formed by Since such a deposited film is formed of an inorganic substance, it exhibits higher oxygen barrier properties than gas barrier resins such as ethylene-vinyl alcohol copolymers.
  • the vapor deposition film formation may be performed directly on the surface of the thermoplastic resin film described above. It is preferable to form a vapor deposition film on the coating film (so-called anchor coat layer) by coating with a hydrophilic resin such as acrylic resin, polyamide, or polyurethane.
  • a hydrophilic resin such as acrylic resin, polyamide, or polyurethane.
  • the formed film is dense, and from the viewpoint of ensuring particularly high oxygen barrier properties, an inorganic film is formed by a deposited film formed of silicon oxide, aluminum oxide, silica-alumina composite oxide, or the like. Formation is preferable, and in particular transparency is ensured (cloudiness of 5% or less) and good visibility is exhibited, so it is most preferable that an inorganic film is formed by a deposited film of silicon oxide. preferred.
  • the above-described inorganic coating film is provided as a protective film layer (topcoat layer) on the vapor deposition film.
  • a coating film penetrates fine defects (cracks) generated in the vapor deposition film described above, prevents the growth of defects, and functions as a protective film that prevents the generation of new defects.
  • a preferable coating film includes a metal alkoxide such as alkoxysilane or alkoxytitanium, and a partially condensed one is preferable from the viewpoint of adhesion to the deposited film.
  • the thickness of the above-mentioned inorganic coating varies depending on the required level of oxygen barrier properties. In that case, the thickness should be such that an oxygen permeability of 1 cc/m 2 /day/atom or less can be ensured, and the thickness is generally about 1000 to 10 nm, particularly about 100 to 10 nm.
  • the thickness and constituent elements of the inorganic coating can be specified by depth direction analysis by X-ray photoelectron spectroscopy (XPS) or Auger electron spectroscopy (AES), energy dispersive X-ray analysis (EDX), and the like.
  • XPS X-ray photoelectron spectroscopy
  • AES Auger electron spectroscopy
  • EDX energy dispersive X-ray analysis
  • an organic coating may be provided to ensure gas barrier properties, and there are coating films mainly composed of polyvinyl alcohol or ethylene-vinyl alcohol copolymer.
  • the film may be formed directly on the surface of the thermoplastic resin film described above. It is preferable to form an organic film on the coating film (so-called anchor coat layer) by coating with a hydrophilic resin such as polyamide or polyurethane.
  • the olefinic resin content is within the above-described large amount range, it is possible to provide a layer containing a resin other than the olefinic resin.
  • a resin other than the olefinic resin for example, in order to suppress the decrease in impact resistance due to the relaxation of the orientation of the stretched layer due to heat treatment, the stretched film of a resin with a higher melting point than the olefin resin such as polyamide or ethylene-vinyl alcohol copolymer is used.
  • the layer can also be provided as a strength reinforcing layer. Polyamide is the most suitable high melting point resin for such a strength reinforcing layer.
  • nylon 6, nylon 6,6, nylon 11, nylon 12, nylon 13, nylon 6/nylon 6,6 copolymers, aromatic nylons (eg, polymetaxylylene adipamide), amorphous nylons (eg, nylon 6I/nylon 6T), etc. are preferably used.
  • the stretched film forming the strength reinforcing layer described above is added with an olefin resin (for example, a propylene resin) as a high-melting resin. ) may be blended within a range that does not impair the increase in strength, or a multilayer stretched film of a stretched film of an olefin resin and a stretched film of a high melting point resin may be provided as a strength reinforcing layer.
  • an olefin resin for example, a propylene resin
  • a multilayer stretched film of a stretched film of an olefin resin and a stretched film of a high melting point resin may be provided as a strength reinforcing layer.
  • the unstretched layer of the propylene-based resin most suitably used as the olefin-based resin is CPP
  • the stretched layer is OPP
  • the polyrotaxane-containing adhesive layer is AD
  • the inorganic coating is INOR
  • a strength reinforcing layer is expressed as PP/Ny
  • the preferred layer structure of the olefin-based laminate 10 is shown below.
  • CPP/AD/(INOR) OPP CPP/AD/(INOR)OPP/AD/OPP CPP/AD/OPP/AD/(INOR)OPP CPP/AD/(PP/Ny)/AD/(INOR)OPP (INOR) means that the inorganic coating may or may not be present, and the inorganic coating may be formed on either side of the OPP.
  • PP is a propylene resin
  • Ny is nylon.
  • a printed layer can be laminated between each layer or on the outside of the stretched layer.
  • thermoplastic resin layer (unstretched sealant film)> CPP film: Toray Advanced Film Co., Ltd. TORAYFAN ZK500 Thickness; 70 ⁇ m resin composition of the film; Polypropylene (PP) component 80% by mass Polyethylene (PE) component 20% by mass
  • thermoplastic resin layer Gas-barrier oriented polypropylene film with an inorganic film formed on one side: BAOPP film thickness; 20 ⁇ m Composition: OPP/coating film (anchor coat)/inorganic coating Inorganic coating: deposited film mainly composed of silicon oxide and protective film (topcoat) mainly composed of silicon or silicon oxide
  • a laminate was obtained by laminating an unstretched sealant film (CPP film) and a gas barrier stretched film (BAOPP film) by a dry lamination method. At this time, the adhesive was applied using a bar coater. The coating amount was adjusted with ethyl acetate so that the solid component was about 3 to 3.5 g/m 2 . Also, the CPP film was laminated so as to face the inorganic coating of the BAOPP film. After lamination, it was cured at 50° C. for 4 to 5 days.
  • the adhesive has a coating amount of 3.25 g/m 2 , a thickness of 3.5 ⁇ m, and a density of 0.93 g/cm 3 .
  • Polypropylene (PP) is calculated assuming a density of 0.90 g/cm 3 .
  • polyethylene (PE) is calculated assuming a density of 0.93 g/cm 3 .
  • Example 1 Urethane adhesive (main agent A 44g, curing agent B 4g) and polyrotaxane-1 (0.48g) are mixed, and polyrotaxane-1 is added to the solid component of the combination of main agent A, curing agent B and polyrotaxane-1.
  • An adhesive containing 1.9% by mass was prepared, and the dynamic viscoelasticity of the adhesive coating was evaluated. (As explained earlier, the coating weight of this adhesive is adjusted with ethyl acetate so that the solid content is about 3-3.5 g/m 2 .)
  • the adhesive was applied to the CPP film, and the BAOPP film was laminated thereon by a dry lamination method to obtain a laminate.
  • the laminate was cured at 50° C. for 4 days, a pouch was made using this laminate (filled with 200 g of water), and the drop strength was evaluated. Also, the olefin resin content per total laminate weight was calculated. The above results are shown in Table 2.
  • Example 2 An adhesive (the content of polyrotaxane-1 was 5.6% by mass) was prepared in the same manner as in Example 1 except that the amount of polyrotaxane-1 was increased to 1.48 g, and the dynamic viscoelasticity of the adhesive coating film was measured. evaluated. A laminate and a pouch were produced in the same manner as in Example 1 except that this adhesive was used, and various properties were evaluated. The results are shown in Tables 1 and 2.
  • Example 3 An adhesive was prepared in the same manner as in Example 1 except that polyrotaxane-2 was used instead of polyrotaxane-1, a laminate and a pouch were produced, and various properties were evaluated. The results are shown in Tables 1 and 2.
  • Example 4 An adhesive was prepared in the same manner as in Example 2 except that polyrotaxane-2 was changed instead of polyrotaxane-1, a laminate and a pouch were produced, and various properties were evaluated. The results are shown in Tables 1 and 2.
  • AD means that polyrotaxane-1 is blended in the urethane-based adhesive
  • AD(PR2) means that polyrotaxane-2 is blended in the urethane-based adhesive
  • PO indicates an olefinic resin
  • Example 1 or Example 3 In the same manner as in Example 1 or Example 3 except that the amount of polyrotaxane-1 or polyrotaxane-2 was increased to 5.33 g, an adhesive having a polyrotaxane-1 or polyrotaxane-2 content of 17.7% by mass was prepared. A pouch was prepared in the same manner as in Example 1 or Example 3, and a drop bag test was performed. As a result, the number of unbroken bags was not much different from that of Comparative Example 1 in which polyrotaxane was not blended, and it was found that the optimum content of polyrotaxane in the adhesive was less than 17% by mass.
  • ⁇ Base polyethylene film> A biaxially stretched polyethylene film with a thickness of 25 ⁇ m was used.
  • a laminate was obtained by laminating a sealant polyethylene film and a biaxially oriented polyethylene film by a dry lamination method. At this time, the adhesive was applied using a bar coater. The coating amount was adjusted with ethyl acetate so that the solid component was about 3 to 3.5 g/m 2 . After lamination, it was cured at 50° C. for 4 to 5 days.
  • the laminate (laminate film) obtained above was formed into a bag having a width of 130 mm, a height of 175 mm, and a width of the folded bottom material of 36 mm, and filled with 330 g of water.
  • the sealing was performed using a heat plate heat sealer under the following conditions. Sealing conditions: Upper surface heating 200°C, 1.0 (s), 0.3 MPa Seal width: about 5mm
  • the adhesive was applied to a biaxially oriented polyethylene film (BAOPE), and a sealant polyethylene film (LLDPE) was laminated thereon by a dry lamination method to obtain a laminate.
  • BAOPE biaxially oriented polyethylene film
  • LLDPE sealant polyethylene film
  • Polyrotaxane 2 Axial molecule 3: Cyclic molecule 4: Terminal group 5: Side chain 10: Olefin-based laminate 11: Thermoplastic resin layer 13: Thermoplastic resin layer 15: Adhesive layer 20: Pouch

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