WO2012039259A1 - Composition de résine de polyuréthane, dispersion de polyuréthane, film de revêtement d'ancrage pour dépôt en phase vapeur et film ainsi déposé - Google Patents

Composition de résine de polyuréthane, dispersion de polyuréthane, film de revêtement d'ancrage pour dépôt en phase vapeur et film ainsi déposé Download PDF

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Publication number
WO2012039259A1
WO2012039259A1 PCT/JP2011/069932 JP2011069932W WO2012039259A1 WO 2012039259 A1 WO2012039259 A1 WO 2012039259A1 JP 2011069932 W JP2011069932 W JP 2011069932W WO 2012039259 A1 WO2012039259 A1 WO 2012039259A1
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Prior art keywords
polyurethane resin
polyol
film
vapor deposition
molecular weight
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PCT/JP2011/069932
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English (en)
Japanese (ja)
Inventor
内田　隆
辰也 柴田
増田　順一
洋一 石田
坂本　純
Original Assignee
三井化学株式会社
東レ株式会社
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Priority to JP2012534980A priority Critical patent/JP5597716B2/ja
Publication of WO2012039259A1 publication Critical patent/WO2012039259A1/fr

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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
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7628—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group
    • C08G18/7642—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group containing at least two isocyanate or isothiocyanate groups linked to the aromatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate groups, e.g. xylylene diisocyanate or homologues substituted on the aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
    • 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
    • B32B2250/244—All polymers belonging to those covered by group B32B27/36
    • 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
    • B32B2255/205—Metallic 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/28—Multiple coating on one surface
    • 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
    • B32B2307/518—Oriented bi-axially
    • 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
    • B32B2307/70—Other properties
    • B32B2307/716—Degradable
    • B32B2307/7163—Biodegradable
    • 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
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable

Definitions

  • the present invention relates to a polyurethane resin composition, a polyurethane dispersion, an anchor coat film for vapor deposition, and an anchor-coated vapor deposition film.
  • a gas barrier film is produced by treating the surface of a base film with an anchor coating agent and then depositing a metal and / or a metal oxide.
  • a film made of a biodegradable resin has been studied as a base film for such a gas barrier film from the viewpoint of reducing the environmental load.
  • an amorphous polylactic acid resin and a crystalline polylactic acid resin are coextruded into a sheet shape and stretched, and then the surface of the obtained sheet is composed of a copolymerized polyester resin, an isocyanate compound, toluene, and methyl ethyl ketone.
  • An aliphatic polyester film obtained by applying an anchor coat using an anchor coat agent and forming a vapor deposition layer on the surface to be treated of the anchor coat has been proposed (for example, Patent Document 1).
  • the anchor coating agent used in Patent Document 1 improves the adhesion between the film and the vapor deposition layer
  • the obtained aliphatic polyester film has an oxygen gas permeability of about 3 to 5 cc / m 2 ⁇ 24 hr.
  • gas barrier properties are insufficient.
  • An object of the present invention is to provide a polyurethane resin composition, a polyurethane dispersion, an anchor coat film for vapor deposition, and an anchor-coated vapor deposition film that have a good balance between adhesion and gas barrier properties.
  • the polyurethane resin composition of the present invention is a polyurethane resin composition containing a polyurethane resin (A), and the polyurethane resin (A) comprises xylylene diisocyanate and / or hydrogenated xylylene diisocyanate.
  • the polyurethane resin (A) comprises xylylene diisocyanate and / or hydrogenated xylylene diisocyanate.
  • the polyurethane dispersion of the present invention is a polyurethane dispersion containing the polyurethane resin composition described above, and the polyurethane resin (A) contains an isocyanate group-terminated urethane prepolymer (A ′) and a polyamine.
  • the isocyanate group-terminated urethane prepolymer (A ′) is obtained by reacting at least with a chain extender, and at least the xylylene diisocyanate and / or hydrogenated xylylene diisocyanate reacts with the polyol component (a-1).
  • the polyol component (a-1) comprises a polyurethane polyol obtained by reacting at least a polyisocyanate and a polyol component (a-2), and a low molecular weight polyol having 2 to 6 carbon atoms.
  • the all component (a-2) contains at least one high molecular weight polyol selected from the group consisting of polyether polyols, polyester polyols and polycarbonate polyols having a number average molecular weight of 300 to 1,500, and the polyol component (a-1 ) And / or the polyol component (a-2) contains polyhydroxyalkanoic acid.
  • the polyurethane dispersion further includes a polyurethane resin (B) dispersed in water, and the polyurethane resin (B) includes an isocyanate group-terminated urethane prepolymer (B ′) and The isocyanate group-terminated urethane prepolymer (B ′) is obtained by reacting at least the polyisocyanate and the polyol component (b-1).
  • the polyol component (b-1) preferably contains at least one high molecular weight polyol selected from the group consisting of polyether polyol, polyester polyol and polycarbonate polyol, and polyhydroxyalkanoic acid.
  • the content ratio of the polyurethane resin (A) is 60 to 95% by mass with respect to the total amount of the polyurethane resin (A) and the polyurethane resin (B). Is preferred.
  • the content of the high molecular weight polyol in the polyurethane resin (A) is 10 to 30% by mass with respect to the total amount of the polyurethane resin (A). is there.
  • the polyurethane dispersion of the present invention is preferably used as an anchor coating agent for depositing a deposition layer on at least one side of a film containing a biodegradable resin.
  • the biodegradable resin is polylactic acid.
  • the vapor deposition layer is made of aluminum or an oxide thereof.
  • the anchor coat film for vapor deposition of the present invention is characterized by comprising a film containing a biodegradable resin and an anchor coat layer made of the above polyurethane resin composition on at least one surface of the film.
  • the content of the high molecular weight polyol component is 10 to 10% relative to all the components of the polyurethane resin (A). It is suitable that it is 30 mass%.
  • the anchor coat layer further contains a polyurethane resin (B), and the polyurethane resin (B) is a polyether polyol, a polyester polyol, and a polycarbonate polyol as a copolymerization component. It is preferable to contain 30 to 80% by mass of at least one high molecular weight polyol selected from the group consisting of all components of the polyurethane resin (B).
  • the ratio of the polyurethane resin (A) in the total amount of the urethane resin of the polyurethane resin (A) and the polyurethane resin (B) in the anchor coat layer is 60 to It is suitable that it is 95 mass%.
  • the anchor coat layer is crosslinked with at least one crosslinking agent selected from the group consisting of a carbodiimide crosslinking agent, an epichlorohydrin crosslinking agent and an oxazoline crosslinking agent. It is preferable that
  • the biodegradable resin is polylactic acid.
  • the film has polylactic acid as a main constituent.
  • the film includes a skin layer made of amorphous polylactic acid on at least one surface, and the anchor coat layer is formed on the surface of the skin layer. It is.
  • the vapor deposition film of the present invention is characterized by comprising the above-mentioned anchor coat film for vapor deposition and a vapor deposition layer deposited on the surface of the anchor coat layer of the anchor coat film for vapor deposition.
  • the vapor deposition layer is made of aluminum or an oxide thereof.
  • the polyurethane resin composition of the present invention and the polyurethane dispersion of the present invention have both adhesion and gas barrier properties, and are suitable as an anchor coating agent for depositing a deposition layer on the surface of a film containing a biodegradable resin. Can be used.
  • the anchor coat layer is formed from the polyurethane resin composition of the present invention, so that it has excellent adhesion and gas barrier properties, and biodegradation Since a film containing a conductive resin is provided, the environmental load can be reduced.
  • the polyurethane resin composition of the present invention contains a polyurethane resin (A), and more specifically, a xylylene diisocyanate and / or a hydrogenated xylylene diisocyanate component, and a number average molecular weight of 300 to 1500.
  • a polyurethane resin (A) containing at least one high molecular weight polyol component selected from the group consisting of ether polyols, polyester polyols and polycarbonate polyols as a copolymerization component is included.
  • Examples of such a polyurethane resin composition include a polyurethane dispersion obtained by dispersing the polyurethane resin (A) in water.
  • the polyurethane resin (A) can be obtained by at least reacting an isocyanate group-terminated urethane prepolymer (A ′) with a chain extender.
  • the isocyanate group-terminated urethane prepolymer (A ′) is produced by reacting xylylene diisocyanate (XDI) and / or hydrogenated xylylene diisocyanate (H 6 XDI) with the polyol component (a-1). can get.
  • xylylene diisocyanate examples include 1,3-xylylene diisocyanate and 1,4-xylylene diisocyanate.
  • xylylene diisocyanates can be used alone or in combination of two or more.
  • Examples of the hydrogenated xylylene diisocyanate include 1,3-bis (isocyanatomethyl) cyclohexane and 1,4-bis (isocyanatomethyl) cyclohexane.
  • These hydrogenated xylylene diisocyanates can be used alone or in combination of two or more.
  • the polyol component (a-1) contains a polyurethane polyol and a low molecular weight polyol having 2 to 6 carbon atoms.
  • the polyurethane polyol can be obtained by reacting at least the polyisocyanate and the polyol component (a-2).
  • polyisocyanate examples include aromatic polyisocyanates, araliphatic polyisocyanates, aliphatic polyisocyanates (including alicyclic polyisocyanates), and the like.
  • Aromatic polyisocyanates include, for example, 4,4′-, 2,4′- or 2,2′-diphenylmethane diisocyanate or mixtures thereof (MDI), 2,4- or 2,6-tolylene diisocyanate or mixtures thereof (TDI), 4,4'-toluidine diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI), m- or p-phenylene diisocyanate or mixtures thereof, 4,4'-diphenyl diisocyanate, 4,4'-diphenyl ether Aromatic diisocyanates such as diisocyanates are mentioned.
  • MDI 4,4′-, 2,4′- or 2,2′-diphenylmethane diisocyanate or mixtures thereof
  • TDI 2,4- or 2,6-tolylene diisocyanate or mixtures thereof
  • TODI 4,4'-toluidine diisocyanate
  • NDI 1,5-naphthalene diis
  • araliphatic polyisocyanate examples include 1,3- or 1,4-xylylene diisocyanate or a mixture thereof (XDI), 1,3- or 1,4-tetramethylxylylene diisocyanate or a mixture thereof (TMXDI), Examples thereof include aromatic aliphatic diisocyanates such as ⁇ , ⁇ ′-diisocyanate-1,4-diethylbenzene.
  • aliphatic polyisocyanate examples include hexamethylene diisocyanate (HDI), trimethylene diisocyanate, tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,2-, 2,3- or 1,3-butylene diisocyanate, 2 , 4,4- or 2,2,4-trimethylhexamethylene diisocyanate.
  • HDI hexamethylene diisocyanate
  • trimethylene diisocyanate trimethylene diisocyanate
  • tetramethylene diisocyanate 1,5-pentamethylene diisocyanate
  • 1,2-, 2,3- or 1,3-butylene diisocyanate 2,4- or 2,2,4-trimethylhexamethylene diisocyanate.
  • examples of the aliphatic polyisocyanate include alicyclic polyisocyanates.
  • alicyclic polyisocyanate examples include 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), 4,4′-, 2,4′- or 2,2′-dicyclohexyl.
  • Methane diisocyanate or a mixture thereof H 12 MDI
  • 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane or a mixture thereof hydrogenated xylylene diisocyanate, H 6 XDI), bis (isocyanatomethyl) norbornane ( NBDI)
  • Alicyclic diisocyanate 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane or a mixture thereof (hydrogenated xylylene diisocyanate, H 6 XDI), bis (isocyanatomethyl) norbornane ( NBDI)
  • a modified product of the above-described polyisocyanate can be used.
  • a modified product include a multimer of the above-described polyisocyanate (for example, dimer, trimer, pentamer). Body, heptamer, etc.), for example, biuret modified product formed by reaction of the above polyisocyanate or multimer with water, monool or polyalcohol (described later) allophanate modified product, Examples include oxadiazine trione modified products produced by reaction with carbon dioxide gas, and polyol modified products produced by reaction with low molecular weight polyols (described later).
  • These polyisocyanates can be used alone or in combination of two or more.
  • polyisocyanate examples include araliphatic polyisocyanates and aliphatic polyisocyanates (more preferably, alicyclic polyisocyanates), and specific examples include XDI, IPDI, H 12 MDI, and H 6 XDI. It is done.
  • the polyol component (a-2) contains at least one high molecular weight polyol selected from the group consisting of polyether polyols, polyester polyols and polycarbonate polyols having a number average molecular weight of 300 or more and 1500 or less.
  • polyether polyol examples include polyoxyalkylene polyol and polytetramethylene ether glycol.
  • the polyoxyalkylene polyol is, for example, an alkylene oxide addition polymer starting from a low molecular weight polyol or a low molecular weight polyamine.
  • alkylene oxide examples include propylene oxide, ethylene oxide, butylene oxide, and styrene oxide. These alkylene oxides can be used alone or in combination of two or more. Of these, propylene oxide and ethylene oxide are preferable.
  • the low molecular weight polyol is a polyol having a number average molecular weight of less than 300, for example, ethylene glycol, propylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 2-methyl-1 , 3-propanediol, 1,5-pentanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexanediol, 2, 6-dimethyl-1-octene-3,8-diol, alkane (carbon number 7 to 18) diol, cyclohexanedimethanol, hydrogenated bisphenol A, 1,4-dihydroxy-2-butene, bishydroxyethoxybenzene, xylene glycol , Bishydroxyethylene terephthalate, bisph Nord A, diethylene glycol, trioxyethylene
  • Dihydric alcohols such as glycerin, 2-methyl-2-hydroxymethyl-1,3-propanediol, 2,4-dihydroxy-3-hydroxymethylpentane, 1,2,6-hexanetriol, trimethylolpropane, 2 , 2-bis (hydroxymethyl) -3-butanol and other aliphatic triols (8 to 24 carbon atoms) such as tetramethylo Tetrahydric alcohols such as methane (pentaerythritol), diglycerin, for example, pentahydric alcohols such as xylitol, for example, hexahydric alcohols such as sorbitol, mannitol, allitol, iditol, dulcitol, altritol, inositol, dipentaerythritol, And 7-valent alcohols such as Perseitol.
  • the low molecular weight polyol also includes an addition polymer obtained by adding an alkylene
  • examples of the low molecular weight polyamine include aliphatic diamines such as ethylenediamine, and aromatic diamines such as tolylenediamine.
  • the number average molecular weight of the polyoxyalkylene polyol is preferably 300 to 1500, and more preferably 400 to 1000.
  • polytetramethylene ether glycol examples include a ring-opening polymer obtained by cationic polymerization of tetrahydrofuran, and an amorphous (room temperature liquid) polytetramethylene ether glycol obtained by copolymerizing the above-described dihydric alcohol with a polymerization unit of tetrahydrofuran. Is mentioned.
  • the number average molecular weight of polytetramethylene ether glycol is preferably 300 to 1500, and more preferably 400 to 1000.
  • polyester polyol examples include polycondensates obtained by reacting the above-described low molecular weight polyol and polybasic acid under known conditions.
  • polybasic acid examples include oxalic acid, malonic acid, succinic acid, methyl succinic acid, glutaric acid, adipic acid, 1,1-dimethyl-1,3-dicarboxypropane, 3-methyl-3-ethylglutaric acid , Azelaic acid, sebacic acid, other aliphatic dicarboxylic acids (having 11 to 13 carbon atoms), suberic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, octadecanedioic acid, nonadecanedioic acid Carboxylic acids such as acid, eicosane diacid, methylhexane diacid, citraconic acid, hydrogenated dimer acid, maleic acid, fumaric acid, itaconic acid, orthophthalic acid, isophthalic acid,
  • polycondensation product of the low molecular weight polyol and the polybasic acid examples include poly (ethylene butylene adipate) polyol, poly (ethylene adipate) polyol, poly (ethylene propylene adipate) polyol, and poly (propylene adipate) polyol.
  • adipic acid-based polyester polyols such as poly (butylene hexane adipate) polyol and poly (butylene adipate) polyol.
  • polyester polyol examples include castor oil polyol, or a modified castor oil polyol obtained by reacting castor oil polyol and polypropylene glycol.
  • polyester polyol for example, polycaprolactone polyol, polyvalerolactone polyol obtained by ring-opening polymerization of lactones such as ⁇ -caprolactone and ⁇ -valerolactone, using the above-described low molecular weight polyol as an initiator, Furthermore, the lactone type
  • the number average molecular weight of the polyester polyol is preferably 300 to 1500, and more preferably 400 to 1000.
  • polycarbonate polyol examples include a ring-opening polymer of ethylene carbonate using the above dihydric alcohol as an initiator, and examples thereof include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1 Polycarbonate diol obtained by condensation reaction of a dihydric alcohol such as 1,6-hexanediol and a carbonate such as dimethyl carbonate, diethyl carbonate or diphenyl carbonate, and amorphous (room temperature liquid) polycarbonate polyol.
  • a dihydric alcohol such as 1,6-hexanediol
  • carbonate such as dimethyl carbonate, diethyl carbonate or diphenyl carbonate
  • amorphous (room temperature liquid) polycarbonate polyol room temperature liquid
  • the number average molecular weight of the polycarbonate polyol is preferably 300 to 1500, and more preferably 400 to 1000.
  • the number average molecular weight of the high molecular weight polyol can be calculated by combining a known hydroxyl value measurement method such as an acetylation method or a phthalation method and the number of functional groups of the initiator or the raw material.
  • the content of these high molecular weight polyols is, for example, 5 to 35% by mass, preferably 10 to 30% by mass, and more preferably 15 to 25% by mass with respect to the total amount of the polyurethane resin (A) to be obtained. As such, it is blended.
  • the adhesion may be lowered.
  • the content of the high molecular weight polyol exceeds the above upper limit, the gas barrier property may be lowered.
  • content of the high molecular weight polyol with respect to the total amount of a polyurethane resin (A) can be calculated from the preparation amount of the raw material component in manufacture of a polyurethane resin (A).
  • the polyol component (a-2) can further contain other high molecular weight polyols (high molecular weight polyols excluding polyether polyols, polyester polyols, and polycarbonate polyols) as necessary.
  • high molecular weight polyols excluding polyether polyols, polyester polyols, and polycarbonate polyols
  • polyols are polyols (excluding polyether polyols, polyester polyols, and polycarbonate polyols) having a number average molecular weight of 300 or more.
  • acrylic polyols, epoxy polyols, and natural oils having a number average molecular weight of 300 to 1,500.
  • examples include polyols, silicone polyols, fluorine polyols, and polyolefin polyols.
  • acrylic polyol examples include a copolymer obtained by copolymerizing a polymerizable monomer having one or more hydroxyl groups in the molecule and another monomer copolymerizable therewith. It is done.
  • examples of the polymerizable monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2,2-dihydroxymethylbutyl (meth) acrylate, poly Examples thereof include hydroxyalkyl maleate and polyhydroxyalkyl fumarate.
  • monomers copolymerizable with these include, for example, (meth) acrylic acid, alkyl (meth) acrylate (C1-12), maleic acid, alkyl maleate, fumaric acid, fumaric acid Alkyl, itaconic acid, alkyl itaconate, styrene, ⁇ -methylstyrene, vinyl acetate, (meth) acrylonitrile, 3- (2-isocyanato-2-propyl) - ⁇ -methylstyrene, trimethylolpropane tri (meth) acrylate, Examples include pentaerythritol tetra (meth) acrylate.
  • the acrylic polyol can be obtained by copolymerizing these monomers in the presence of a suitable solvent and a polymerization initiator.
  • epoxy polyol examples include an epoxy polyol obtained by a reaction between a low molecular weight polyol (described later) and a polyfunctional halohydrin such as epichlorohydrin or ⁇ -methylepichlorohydrin.
  • Examples of the natural oil polyol include hydroxyl group-containing natural oils such as castor oil and palm oil.
  • silicone polyol for example, in the copolymerization of the acrylic polyol described above, a vinyl group-containing silicone compound such as ⁇ -methacryloxypropyltrimethoxysilane is used as another copolymerizable monomer.
  • a vinyl group-containing silicone compound such as ⁇ -methacryloxypropyltrimethoxysilane is used as another copolymerizable monomer. Examples include coalesced and terminal alcohol-modified polydimethylsiloxane.
  • fluorine polyol for example, in the copolymerization of the acrylic polyol described above, a vinyl group-containing fluorine compound such as tetrafluoroethylene or chlorotrifluoroethylene is used as another copolymerizable monomer. Examples include coalescence.
  • polyolefin polyols examples include polybutadiene polyol and partially saponified ethylene-vinyl acetate copolymers.
  • These other high molecular weight polyols can be used alone or in combination of two or more.
  • the content ratio is appropriately set according to the purpose and application.
  • the polyol component (a-2) can also contain the above-described low molecular weight polyol.
  • the content ratio is appropriately set according to the purpose and application.
  • the polyol component (a-2) can contain polyhydroxyalkanoic acid.
  • the polyol component (a-2) is reacted with the polyisocyanate described above at a ratio in which the equivalent ratio of hydroxyl group to isocyanate group (OH / NCO) exceeds 1.
  • the polyurethane polyol can be obtained as a polyester polyurethane polyol, a polyether polyurethane polyol, a polycarbonate polyurethane polyol, or a polyester polyether polyurethane polyol.
  • Examples of the low molecular weight polyol having 2 to 6 carbon atoms in the polyol component (a-1) include those having a total carbon number of 2 to 6 among the above low molecular weight polyols. More specifically, for example, ethylene Glycol, propylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 3- Dihydric alcohols such as methyl-1,5-pentanediol, 1,6-hexanediol, 1,4-dihydroxy-2-butene, diethylene glycol, trioxyethylene glycol, dipropylene glycol, such as glycerin, 2-methyl- 2-hydroxymethyl-1,3-propanediol, 2,4-dihy Trivalent alcohols such as loxy-3-hydroxymethylpentane, 1,2,6-he
  • These low molecular weight polyols having 2 to 6 carbon atoms can be used alone or in combination of two or more.
  • Preferred examples of the low molecular weight polyol having 2 to 6 carbon atoms include dihydric alcohols and trihydric alcohols.
  • the content ratio of the low molecular weight polyol having 2 to 6 carbon atoms is, for example, 5 to the total amount of the high molecular weight polyol and the low molecular weight polyol having 2 to 6 carbon atoms in the polyurethane polyol. -50 mass%, preferably 8-40 mass%.
  • polyol component (a-1) can further contain other high molecular weight polyols (high molecular weight polyols excluding polyurethane polyols) if necessary.
  • polystyrene resins include the above-described polyether polyol, the above-described polyester polyol, the above-described polycarbonate polyol, the above-described acrylic polyol, the above-described epoxy polyol, the above-described natural oil polyol, the above-described silicone polyol, the above-described fluorine polyol, Examples include the polyolefin polyols described above.
  • These other high molecular weight polyols can be used alone or in combination of two or more.
  • the content ratio is appropriately set according to the purpose and application.
  • the polyol component (a-1) and / or the polyol component (a-2) contains polyhydroxyalkanoic acid.
  • polyhydroxyalkanoic acid is blended in one or both of the polyol component (a-1) and the polyol component (a-2).
  • polyhydroxyalkanoic acid examples include dimethylolacetic acid, dimethylollactic acid, dimethylolpropionic acid, and dimethylolbutanoic acid.
  • polyhydroxyalkanoic acids can be used alone or in combination of two or more.
  • the polyhydroxyalkanoic acid is preferably dimethylolpropionic acid.
  • the polyurethane resin (A) can be prepared as an anionic internal emulsion aqueous polyurethane resin.
  • the content ratio of the polyhydroxyalkanoic acid is, for example, 5 to 35% by mass with respect to the total amount of the low molecular polyol having 2 to 6 carbon atoms and the polyol component (a-2) in the polyol component (a-1), preferably 10 to 25% by mass.
  • each component is an isocyanate group terminal urethane prepolymer (A') of the isocyanate group of all the polyisocyanate components in an isocyanate group terminal urethane prepolymer (A ').
  • the equivalent ratio (NCO / OH) to the hydroxyl groups of all polyol components in () is, for example, 1.1 to 2.5, preferably 1.2 to 2.3, and more preferably 1.2 to 2.0. It mix
  • the isocyanate group-terminated urethane prepolymer (A ′) can be produced by a polymerization method such as bulk polymerization or solution polymerization, for example.
  • the polyol component (a-1) is added thereto, for example, 50 to 130 ° C., preferably The reaction is performed at 50 to 100 ° C., for example, for 1 to 15 hours, preferably 3 to 12 hours.
  • xylylene diisocyanate and / or hydrogenated xylylene diisocyanate and a polyol component (a-1) are added to an organic solvent, for example, 50 to 130 ° C., preferably 50 to The reaction is carried out at 80 ° C. for 3 to 15 hours, preferably 5 to 12 hours, for example.
  • the organic solvent is a solvent that is inert to the isocyanate group and rich in hydrophilicity, for example, ketones such as acetone and methyl ethyl ketone, for example, esters such as ethyl acetate, butyl acetate, and isopropyl acetate, And ethers such as tetrahydrofuran, nitriles such as acetonitrile, and amides such as N, N-dimethylformamide and N-methylpyrrolidone.
  • ketones are used.
  • a known urethanization catalyst such as amine, tin, lead, or bismuth may be added as necessary, and the resulting isocyanate group-terminated urethane prepolymer (A ')
  • a known removal means such as distillation or extraction.
  • the resulting isocyanate group-terminated urethane prepolymer (A ′) contains an anionic group due to the blending of the polyhydroxyalkanoic acid. Therefore, preferably, a neutralizing agent is added to the anionic group. A salt is formed.
  • Examples of the neutralizing agent include amines such as trimethylamine, triethylamine, tri-n-propylamine, tributylamine, triethanolamine, triisopropanolamine, N, N′-dimethylethanolamine, such as potassium hydroxide, water
  • examples thereof include inorganic alkali salts such as sodium oxide and lithium hydroxide, and ammonia.
  • amines and ammonia are used.
  • the amount of neutralizing agent added is, for example, 0.4 to 1.2 equivalents, preferably 0.6 to 1.0 equivalents per equivalent of anionic group.
  • the isocyanate group content of the isocyanate group-terminated urethane prepolymer (A ′) thus obtained is, for example, 2 to 20% by mass, preferably 3 to 15% by mass.
  • the average number of functional groups of the isocyanate group in the isocyanate group-terminated urethane prepolymer (A ′) is, for example, 1.1 to 3.5, preferably 1.5 to 2.5.
  • the number average molecular weight of the isocyanate group-terminated urethane prepolymer (A ′) is, for example, 400 to 5000, preferably 500 to 3000.
  • the obtained isocyanate group-terminated urethane prepolymer (A ′) is dispersed in water and reacted with a chain extender.
  • Examples of a method for dispersing the isocyanate group-terminated urethane prepolymer (A ′) in water include, for example, a method of gradually adding water to the isocyanate group-terminated urethane prepolymer (A ′) while stirring the water. On the other hand, a method of gradually adding an isocyanate group-terminated urethane prepolymer (A ′) can be used.
  • an aqueous dispersion containing the isocyanate group-terminated urethane prepolymer (A ′) is prepared.
  • the stirring is preferably performed using a homodisper or the like so as to impart high shear.
  • the amount of water added is, for example, 20 to 1000 parts by mass with respect to 100 parts by mass of the total amount of the isocyanate group-terminated urethane prepolymer (A ′).
  • a chain extender is added to an aqueous dispersion containing an isocyanate group-terminated urethane prepolymer (A ′), and a chain extension reaction is performed.
  • the chain extender contains a polyamine.
  • Polyamines include, for example, aromatic polyamines such as 4,4′-diphenylmethanediamine, araliphatic polyamines such as 1,3- or 1,4-xylylenediamine or mixtures thereof, such as 3-aminomethyl- 3,5,5-trimethylcyclohexylamine, 4,4'-dicyclohexylmethanediamine, 2,5 (2,6) -bis (aminomethyl) bicyclo [2.2.1] heptane, 1,3- or 1, Alicyclic polyamines such as 4-bis (aminomethyl) cyclohexane or mixtures thereof, 1,3- or 1,4-cyclohexanediamine or mixtures thereof, such as ethylenediamine, 1,3-propanediamine, 1,4- Butanediamine, 1,6-hexamethylenediamine, diethylenetriamine, Tetraethylenepentamine, and aliphatic polyamines such as tetraethylene pentamine and the like.
  • aromatic polyamines such as 4,4′-
  • examples of polyamines include polyamino alcohols.
  • examples of polyamino alcohols include N- (2-aminoethyl) ethanolamine and N- (3-aminopropyl) ethanolamine.
  • polyamines can be used alone or in combination of two or more.
  • the polyamine is preferably polyamino alcohol.
  • chain extender can further contain a low molecular weight polyol, hydrazine, and derivatives thereof.
  • Examples of the low molecular weight polyol include the low molecular weight polyol described above.
  • hydrazine and derivatives thereof include hydrazine (including hydrates), succinic dihydrazide, adipic dihydrazide, and the like.
  • the chain extender contains a low molecular weight polyol, hydrazine and a derivative thereof, the content ratio is appropriately set according to necessity and application.
  • a chain extender is added to an aqueous dispersion of an isocyanate group-terminated urethane prepolymer (A ′).
  • the blending ratio of the chain extender is, for example, the equivalent ratio of the isocyanate group of the isocyanate group-terminated urethane prepolymer (A ′) to the active hydrogen group (hydroxyl group and amino group) of the chain extender (NCO / active hydrogen group).
  • the ratio is about 1, preferably 0.8 to 1.2.
  • a chain extender is added dropwise to an aqueous dispersion containing an isocyanate group-terminated urethane prepolymer (A ′) while stirring the aqueous dispersion. Stirring is preferably performed using a homodisper or the like so as to impart high shear.
  • the chain extender to be dropped can be prepared in advance as a chain extender aqueous solution by diluting with water in advance.
  • this chain extension reaction is carried out by subjecting the isocyanate group-terminated urethane prepolymer (A ′) and the chain extender to, for example, 5 to 30 ° C., preferably 5 to 25 at normal pressure and, if necessary, in a nitrogen atmosphere.
  • the reaction is performed at a temperature of 10 minutes to 5 hours, preferably 30 minutes to 3 hours.
  • reaction is completed at room temperature, for example, with further stirring.
  • the polyurethane dispersion of the present invention can be obtained as an aqueous dispersion containing the polyurethane resin (A).
  • the polyurethane dispersion thus obtained has a solid content of, for example, 5 to 60% by mass, preferably 10 to 50% by mass, and an average particle size of, for example, 10 to 500 nm, preferably 20 ⁇ 300 nm.
  • the resin acid value is, for example, 5 to 50 mgKOH / g, preferably 10 to 40 mgKOH / g, and the urethane / urea group concentration (total amount) is, for example, 15 to 50% by mass, preferably 20 to 45%. % By mass.
  • the polyurethane dispersion of the present invention has both adhesiveness and gas barrier properties, which will be described in detail later, but is suitably used as an anchor coating agent for depositing a vapor deposition layer on the surface of a film containing a biodegradable resin. be able to.
  • a polyurethane resin (B) (a polyurethane resin different from the above-mentioned polyurethane resin (A)) is further dispersed in water. Yes.
  • an aqueous dispersion containing the polyurethane resin (A) described above and an aqueous dispersion containing the polyurethane resin (B) are used. Can be mixed.
  • the polyurethane resin (B) reacts at least a chain extender with an isocyanate group-terminated urethane prepolymer (B ′) (an isocyanate group-terminated urethane prepolymer different from the above-mentioned isocyanate group-terminated urethane prepolymer (A ′)). Can be obtained.
  • the isocyanate group-terminated urethane prepolymer (B ′) can be obtained by reacting at least the polyisocyanate and the polyol component (b-1).
  • the above-described polyisocyanate that is, the above-described aromatic polyisocyanate, the above-described araliphatic polyisocyanate, the above-described aliphatic polyisocyanate (including the above-described alicyclic polyisocyanate), and those.
  • examples include modified products.
  • Preferred examples include araliphatic polyisocyanates and alicyclic polyisocyanates (more preferably, alicyclic polyisocyanates), and specific examples include XDI, IPDI, H 12 MDI, and H 6 XDI.
  • the polyol component (b-1) contains at least one high molecular weight polyol selected from the group consisting of polyether polyols, polyester polyols and polycarbonate polyols having a number average molecular weight of, for example, 300 or more and 3000 or less.
  • polyether polyols examples include the polyether polyols described above.
  • polyester polyol examples include the polyester polyols described above.
  • polycarbonate polyol examples include the polycarbonate polyols described above.
  • the content of these high-molecular-weight polyols is, for example, 30 to 80% by mass, preferably 35 to 75% by mass, and more preferably 40 to 70% by mass with respect to the total amount of the polyurethane resin (B) to be obtained. As such, it is blended.
  • the adhesion may be lowered.
  • the content of the high molecular weight polyol exceeds the above upper limit, the gas barrier property may be lowered.
  • content of the high molecular weight polyol with respect to the total amount of a polyurethane resin (B) can be computed from the preparation amount of the raw material component in manufacture of a polyurethane resin (B).
  • the polyol component (b-1) can further contain other high molecular weight polyols (high molecular weight polyols excluding polyether polyols, polyester polyols, and polycarbonate polyols) as necessary.
  • high molecular weight polyols excluding polyether polyols, polyester polyols, and polycarbonate polyols
  • Examples of the other high molecular weight polyol include the above-described polyurethane polyol, the above-described acrylic polyol, the above-described epoxy polyol, the above-described natural oil polyol, the above-described silicone polyol, the above-described fluorine polyol, and the above-described polyolefin polyol.
  • the content ratio is appropriately set according to the purpose and application.
  • the polyol component (b-1) can also contain the above-described low molecular weight polyol.
  • the content ratio is appropriately set according to the purpose and application.
  • the polyol component (b-1) further contains polyhydroxyalkanoic acid.
  • polyhydroxyalkanoic acid examples include the polyhydroxyalkanoic acid described above.
  • the content ratio of the polyhydroxyalkanoic acid is, for example, 3 to 30% by mass, preferably 5 to 5% by weight of the polyhydroxyalkanoic acid with respect to the total amount of the polyol component (b-1). 25% by mass.
  • the isocyanate group-terminated urethane prepolymer (B ′) is reacted with the polyisocyanate and the polyol component (b-1) by the same synthesis method as that for the isocyanate group-terminated urethane prepolymer (A ′). Can be obtained.
  • the resulting isocyanate group-terminated urethane prepolymer (B ′) preferably contains an anionic group due to the blending of polyhydroxyalkanoic acid.
  • the above-described neutralizing agent is added in the above ratio to form an anionic group salt.
  • the isocyanate group content of the isocyanate group-terminated urethane prepolymer (B ′) thus obtained is, for example, 0.5 to 10% by mass, preferably 1 to 8% by mass.
  • the average number of functional groups of the isocyanate groups in the isocyanate group-terminated urethane prepolymer (B ′) is, for example, 1.1 to 3.5, preferably 1.5 to 2.5.
  • the number average molecular weight of the isocyanate group-terminated urethane prepolymer (B ′) is, for example, 700 to 15000, preferably 1000 to 8000.
  • the obtained isocyanate group-terminated urethane prepolymer (B ′) is then dispersed in water and reacted with a chain extender.
  • a method for water-dispersing the isocyanate group-terminated urethane prepolymer (B ′) for example, a method similar to the method for water-dispersing the isocyanate group-terminated urethane prepolymer (A ′) can be employed.
  • the chain extender contains a polyamine.
  • polyamine examples include the above-described polyamine, more specifically, the above-described aromatic polyamine, the above-described araliphatic polyamine, the above-described alicyclic polyamine, the above-described aliphatic polyamine, and the above-mentioned polyaminoalcohol.
  • polyamines can be used alone or in combination of two or more.
  • the polyamine is preferably polyamino alcohol.
  • the chain extender may further contain the above-described low molecular weight polyol, the above-described hydrazine and its derivatives, and the like.
  • the chain extender contains a low molecular weight polyol, hydrazine and a derivative thereof, the content ratio is appropriately set according to necessity and application.
  • the isocyanate group-terminated urethane prepolymer (B ′) and the chain extender can be reacted in the same manner as in the reaction between the isocyanate group-terminated urethane prepolymer (A ′) and the chain extender.
  • An aqueous dispersion containing the resin (B) can be obtained.
  • the aqueous dispersion containing the polyurethane resin (A) and the aqueous dispersion containing the polyurethane resin (B) are mixed and stirred by a known method.
  • a polyurethane dispersion can be obtained as an aqueous dispersion in which the polyurethane resin (A) and the polyurethane resin (B) are dispersed in water.
  • the polyurethane dispersion thus obtained has a solid content of, for example, 5 to 60% by mass, preferably 10 to 50% by mass, and an average particle size of, for example, 10 to 500 nm, preferably 20 ⁇ 300 nm.
  • the resin acid value is, for example, 5 to 50 mgKOH / g, preferably 10 to 40 mgKOH / g, and the urethane / urea group concentration is, for example, 15 to 50% by mass, preferably 20 to 45% by mass. is there.
  • the main component as the solid content is the polyurethane resin (A), and more specifically, the content ratio (solid content) of the polyurethane resin (A) and the polyurethane resin (B) is
  • the polyurethane resin (A) is, for example, 60% by mass or more, preferably 60 to 95% by mass with respect to the total amount of the polyurethane resin (A) and the polyurethane resin (B), and the polyurethane resin (B) For example, it is 40% by mass or less, preferably 5 to 40% by mass.
  • Isocyanate group-terminated urethane prepolymer (A ′), polyurethane resin (A), isocyanate group-terminated urethane prepolymer (B ′), polyurethane resin (B), etc. It is distilled off by heating at an appropriate temperature.
  • the adhesion in addition to the polyurethane resin (A), if the polyurethane resin (B) is further dispersed in water, the adhesion can be further improved.
  • the polyurethane dispersion of the present invention includes, for example, a cross-linking agent (described later), a silane coupling agent, a plasticizer, an antifoaming agent, a leveling agent, an antifungal agent, and an antirust, as long as the effects of the present invention are not impaired.
  • additives such as water swellable inorganic layered compounds such as additives, heat stabilizers, dyes, inorganic pigments, organic pigments, extender pigments, curing agents, anti-tacking agents, inorganic particles, montmorillonite, and synthetic mica, and organic particles can do.
  • the mixing ratio of various additives is appropriately selected depending on the purpose and application.
  • the polyurethane resin (A) is excellent in adhesion and gas barrier properties, and the polyurethane resin (B) can further improve the adhesion,
  • it can be used as an adhesive material such as an adhesive, a primer, and an anchor coat agent.
  • it can be used in fields requiring adhesion and gas barrier properties, for example, gas barrier laminate films.
  • a vapor deposition film in which a vapor deposition layer is formed on a film containing a biodegradable resin as an anchor coating agent for depositing the vapor deposition layer on the surface (at least one side) of the film containing the biodegradable resin, Can be used.
  • the anchor coat film for vapor deposition of the present invention may be abbreviated as a base film containing a biodegradable resin (hereinafter simply referred to as (the present invention) base film). ) And an anchor coat layer.
  • biodegradable resin for example, microbial production resins such as polyhydroxybutyrate and poly (hydroxybutyrate / hydroxyhexanoate), for example, esterified starch, cellulose acetate, chitosan / cellulose / starch , Starch / chemical synthetic biodegradable plastic (green plastic) and other natural resins such as polylactic acid, (polylactic acid / polybutylene succinate) block copolymer, polycaprolactone, poly (caprolactone / butylene succinate) , Polybutylene succinate, poly (butylene succinate / adipate), poly (butylene succinate / carbonate), poly (ethylene terephthalate / succinate), poly (butylene adipate / terephthalate), polyethylene succinate), poly Neil alcohols), such as chemical synthetic resins such as polyglycolic acid and the like can be used in combination with single component or two or more components.
  • microbial production resins such as polyhydroxybuty
  • the biodegradable resin contained in the base film of the present invention (hereinafter sometimes simply referred to as the biodegradable resin of the present invention) is excellent in moldability and increases the plant degree of the obtained base film.
  • Polylactic acid is preferable because it can be obtained at a relatively low cost.
  • the biodegradable resin of the present invention is preferably contained in an amount of 50% by mass or more with respect to all polymer components constituting the film from the viewpoint of reducing the environmental impact of the film on the natural environment. Since the speed may be increased, the content is more preferably 70% by mass or more, and still more preferably 90% by mass or more.
  • the base film of the present invention preferably contains polylactic acid as a main constituent.
  • the film containing polylactic acid as a main constituent is defined in the present invention as having 70% by mass or more of polylactic acid with respect to all the components constituting the base film.
  • the biodegradation rate of the resulting film may be increased, and the plant degree may be increased.
  • the base film of the present invention contains polylactic acid as a main constituent, the content of polylactic acid is more preferably 80% by mass or more, and still more preferably 90% by mass with respect to all polymer components constituting the film. That's it.
  • the upper limit of the content of polylactic acid is 100% by mass or less, preferably 99.5% by mass or less with respect to 100% by mass of the polymer constituting the base film of the present invention.
  • polylactic acid is polylactic acid containing L-lactic acid and / or D-lactic acid as a main constituent.
  • the polylactic acid may contain a comonomer component other than lactic acid.
  • the comonomer include ethylene glycol, propylene glycol, butanediol, heptanediol, hexanediol, octanediol, nonanediol, decanediol, 1,4-cyclohexanedimethanol, neopentylglycol, glycerin, and pentane.
  • Glycol compounds such as erythritol, bisphenol A, polyethylene glycol, polypropylene glycol and polytetramethylene glycol, oxalic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, malonic acid, glutaric acid, cyclohexanedicarboxylic acid, terephthalic acid , Isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4'-diphenyl ether di Dicarboxylic acids such as rubonic acid, 5-sodium sulfoisophthalic acid and 5-tetrabutylphosphonium isophthalic acid, glycolic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxybenzoic acid and other hydroxycar
  • the amount of copolymerization of these comonomers is not particularly limited as long as the effects of the present invention are exhibited.
  • the total monomer units in the polylactic acid contained in the film are 100 mol%.
  • the content is preferably 1 to 30 mol%.
  • L-lactic acid-rich polylactic acid (poly L-lactic acid) is preferably used from the viewpoint of resin availability.
  • poly L-lactic acid the content of L-lactic acid unit in 100 mol% of total lactic acid units of poly L-lactic acid (the content of L-lactic acid unit in 100 mol% of total lactic acid units of poly L-lactic acid is referred to as A substance having an L content of 50 to 100 mol% is used.
  • the amount of L-form of poly-L-lactic acid is more preferably 80 to 100 mol%, further preferably 95 to 100 mol%, and most preferably 97 to 100 mol%.
  • the content of D-lactic acid units in 100 mol% of total lactic acid units in the poly-D-lactic acid (total 100 lactic acid units in poly-D-lactic acid) % D-lactic acid unit content (hereinafter referred to as D-form amount) is 50 to 100 mol%.
  • the D-form amount of poly-D-lactic acid is more preferably 80 to 100 mol%, further preferably 95 to 100 mol%, and most preferably 97 to 100 mol%.
  • the crystallinity of polylactic acid varies depending on the content of L-lactic acid units or D-lactic acid units. That is, the higher the amount of D-form in poly L-lactic acid, the lower the crystallinity of poly L-lactic acid and the closer it is to amorphous. On the other hand, the lower the D-form amount in poly L-lactic acid, the higher the crystallinity of poly L-lactic acid. Similarly, the crystallinity of poly-D-lactic acid varies with the amount of L-form. In other words, the higher the L-form amount in poly-D-lactic acid, the lower the crystallinity of poly-D-lactic acid approaches the amorphous state.
  • the lower the L-form amount in poly-D-lactic acid the lower the poly-D-lactic acid.
  • the crystallinity of lactic acid is increased.
  • polylactic acid with low crystallinity is blended with polylactic acid with high crystallinity, it is preferable from the viewpoint of stretchability.
  • 4032D having high crystallinity is preferably used.
  • additive scattering / bleed-out suppression, coating film / deposition film adhesion, easy printability, heat sealability, print lamination, gloss, slipperiness, release For various purposes such as moldability, easy peelability, surface hardness, smoothness, surface roughness, hand cutting, surface hydrophilicity, optical property control, surface heat resistance, and concealment Accordingly, other resins may be added as appropriate, and one or more other resin layers may be laminated.
  • the base film of the present invention preferably has a skin layer made of amorphous polylactic acid on at least one side.
  • evaluation using a differential scanning calorimeter (DSC) method described below is used. That is, polylactic acid collected from a polylactic acid resin chip or a skin layer of the base film of the present invention was heat-treated at 130 ° C. for 10 hours, and rapidly cooled to 10 ° C./minute from 20 ° C. to 220 ° C.
  • DSC differential scanning calorimeter
  • the polylactic acid is defined as amorphous polylactic acid.
  • amorphous polylactic acid in order to make polylactic acid substantially amorphous, it is preferable to control its D-form amount to 9 to 91 mol%.
  • the amount of the D form is more preferably 10 to 90 mol%, still more preferably 11 to 89 mol%.
  • the skin layer made of amorphous polylactic acid may contain other components (other resins, additives, etc.) as long as the amount is small. That is, the content of amorphous polylactic acid in the skin layer is preferably 80% by mass or more, more preferably 90% by mass or more, and 95% by mass with respect to all components of the skin layer. % Or more is more preferable.
  • the anchor coat layer of the present invention is provided on the skin layer made of amorphous polylactic acid.
  • the adhesion of the vapor deposition layer of the vapor deposition film can be enhanced and the gas barrier property can be enhanced.
  • an anchor coat layer and a vapor deposition layer are formed on one side in this order to express gas barrier properties.
  • the core layer (inner layer) of the base film of the present invention is preferably made of crystalline polylactic acid.
  • the core layer is made of crystalline polylactic acid, practical flatness and dimensional stability can be imparted to the resulting film, and characteristics such as gas barrier properties and solvent resistance can be improved in some cases.
  • the above-described DSC technique is used. That is, in the above method, when at least one of a cold crystallization peak derived from polylactic acid having a calorific value of 5 J / g or a melting peak is observed, the polylactic acid is defined as crystalline polylactic acid.
  • the base film of the present invention preferably contains inorganic particles and / or organic particles (hereinafter sometimes simply referred to as “particles”) from the viewpoints of improving handling properties during secondary processing and improving blocking resistance. .
  • the particles are preferably prepared and used, for example, as a resin masterbatch used as a component of the base film of the present invention.
  • the slipperiness when the films are stacked is improved, so when the film is wound up in the film forming process or in the processing process such as printing, laminating, coating, bag making, vapor deposition, etc.
  • the roll-up property is excellent without causing wrinkles, stretching, or film edge misalignment.
  • blocking resistance may be excellent.
  • the vapor deposition film is excellent in slipperiness, so that the vapor deposition layer is peeled off, so-called pick-off defects, etc. It is difficult to generate and may exhibit excellent gas barrier properties.
  • the average particle size of the particles (inorganic particles and / or organic particles) added to the base film of the present invention is too small, the handling property and blocking resistance are poor. Moreover, since defects, such as a pinhole, are easy to generate
  • the said average particle diameter is measured using the TEM image of a film cross section as shown below.
  • the average particle size of the particles added to the base film of the present invention is preferably 0.5 to 4 ⁇ m, and more preferably 0.5 to 3 ⁇ m.
  • the content of the particles is more preferably 0.02 to 5% by mass, still more preferably 0.03 to 3% by mass.
  • the substrate film of the present invention is a laminated film having a skin layer on at least one side (configuration example: skin layer made of amorphous polylactic acid 1 / made of crystalline polylactic acid. Core layer / Skin layer made of amorphous polylactic acid 2) Since the surface of the film can be appropriately roughened without greatly detracting from the transparency of the film, the particles should be added only to the skin layer. Is preferred. As described below, when the waste film produced when the film of the present invention or other film is produced in the core layer is reused, the presence of a small amount of particles in the core layer is allowed.
  • the content of the particles in the skin layer is preferably 0.02 to 0.5% by mass, more preferably based on all components constituting the skin layer. Is 0.03 to 0.3% by mass.
  • the thickness of the skin layer is preferably 0.1 to 4 ⁇ m.
  • a radial defect generally referred to as a flow mark
  • the skin layer has particles.
  • the particles may fall off in the subsequent stretching step, and the film forming machine may be soiled.
  • the thickness of the skin layer is more preferably 0.2 to 2 ⁇ m, still more preferably 0.3 to 1 ⁇ m.
  • the inorganic particles used in the base film of the present invention are not particularly limited as long as the effects of the present invention are exhibited.
  • examples of the organic particles include particles made of polymers of polystyrene, organic silicone, polyacrylic acids, polymethacrylic acids, polyesters, polymethoxysilane compounds, polyurethane compounds, fluorine compounds, divinyl compounds, and the like.
  • These particles can be used alone or in combination of two or more.
  • the particles preferably used in the base film of the present invention have excellent affinity with polylactic acid, and when the film is produced, the particles are not dropped off easily, making the film difficult to stain, and the surface roughness can be easily controlled.
  • inorganic particles such as wet and dry silica, aluminum silicate (aluminum silicate), aluminosilicate (aluminosilicate), talc, polystyrene, organic silicone, polyacrylic acid, polymethacrylic acid, polyester, divinylbenzene It is preferable to use organic particles such as a polymer.
  • the film of the present invention may have, for example, a flame retardant, a heat stabilizer, a light stabilizer, an antioxidant, a weathering agent, a moisture proof agent, and a water repellent as long as the effects of the present invention are not impaired.
  • a flame retardant for example, a heat stabilizer, a light stabilizer, an antioxidant, a weathering agent, a moisture proof agent, and a water repellent as long as the effects of the present invention are not impaired.
  • Low molecular weight materials, organic lubricants such as wax, antifoaming agents such as polysiloxane, and coloring agents such as pigments and dyes may be included.
  • These additives can be contained in an amount of 0 to 30% by mass with respect to 100% by mass of all components of
  • the waste film produced when the film of the present invention is produced and other films are produced within a range that does not impair the effects of the present invention. You may blend and use the waste film produced in the case.
  • the anchor coat film for vapor deposition of the present invention includes an anchor coat layer made of a polyurethane resin composition containing a polyurethane resin (A).
  • a polyurethane resin composition containing a polyurethane resin (A).
  • the anchor coat layer of the film of the present invention (hereinafter sometimes simply referred to as the anchor coat layer of the present invention) is a polyurethane dispersion containing the above-described polyurethane resin (A) dispersed in water.
  • the anchor coating agent is preferably a polyurethane resin composition formed by applying and drying on at least one side of the base film of the present invention.
  • the polyurethane resin (A) contained in the anchor coat layer of the present invention is a xylylene diisocyanate component and / or a hydrogenated xylylene diisocyanate.
  • the component is a copolymerization component, excellent gas barrier properties can be imparted to the obtained anchor coat film for vapor deposition and the vapor deposited film.
  • the polyurethane resin (A) of the present invention contains at least one high molecular weight polyol component selected from the group consisting of a polyether polyol, a polyester polyol and a polycarbonate polyol having a number average molecular weight of 300 or more and 1500 or less as a copolymer component. .
  • the polyurethane resin (A) of the present invention contains the polyether polyol of the above aspect as a high molecular weight polyol as a copolymer component
  • the polyurethane of the present invention contains the polyurethane resin (A) in the base film of the present invention.
  • the resulting anchor coat layer tends to firmly adhere to the base film containing the biodegradable resin described above. Yes. As a result, the adhesion of the deposited layer of the resulting deposited film can be increased.
  • the content of the high molecular weight polyol component in the polyurethane resin (A) of the present invention is preferably 10 to 30% by mass with respect to all the components of the polyurethane resin (A).
  • the content of the high molecular weight polyol component is less than 10% by mass, the adhesion of the deposited layer may be insufficient in the obtained deposited film.
  • the content of the high molecular weight polyol component exceeds 30% by mass, the gas barrier property of the obtained vapor deposition film may be lowered.
  • the content of the high molecular weight polyol is more preferably 15 to 25% by mass.
  • the anchor coat layer of the present invention further contains a polyurethane resin (B).
  • the anchor coat layer of the present invention is a polyurethane having at least one high molecular weight polyol selected from the group consisting of polyether polyols, polyester polyols and polycarbonate polyols as a copolymerization component in order to further improve the adhesion of the deposited layer. It is preferable to further contain the resin (B).
  • the resin (B) As a polyurethane resin (B) here, the preferable aspect of an above-mentioned polyurethane resin (B) is quoted also about the thing except having described below.
  • the content of the high molecular weight polyol component contained in the polyurethane resin (B) as a copolymerization component is preferably 30 to 80% by mass with respect to all the components of the polyurethane resin (B).
  • the content of the high molecular weight polyol is less than 30% by mass, the deposited layer adhesion of the obtained deposited film may be insufficient.
  • the content of the high molecular weight polyol exceeds 80% by mass, the gas barrier property of the obtained deposited film may be insufficient.
  • the content of the polymer polyol is more preferably 35 to 75% by mass, still more preferably 40 to 70% by mass.
  • the ratio of the polyurethane resin (A) to the total amount of the urethane resin (A) and the polyurethane resin (B) is preferably 60 to 95% by mass.
  • the ratio of the polyurethane resin (A) is less than 60% by mass, the gas barrier property of the obtained vapor deposition film may be insufficient.
  • the proportion of the polyurethane resin (A) exceeds 95% by mass, the adhesion of the deposited layer of the resulting film may be insufficient.
  • the proportion of the polyurethane resin (A) is more preferably 70 to 90% by mass.
  • the anchor coat layer of the present invention is preferably crosslinked by a crosslinking agent. That is, the polyurethane resin composition constituting the anchor coat layer of the present invention is preferably crosslinked by a crosslinking agent.
  • the crosslinking agent used for the anchor coat layer of the present invention includes a carbodiimide crosslinking agent, an epichlorohydrin crosslinking agent and an oxazoline crosslinking agent. More preferably, it is at least one selected from the group consisting of: Further, as the cross-linking agent, it is more preferable to use a water-soluble cross-linking agent because the adhesion of the vapor deposition layer can be effectively enhanced. That is, it is most preferable to use a water-soluble carbodiimide-based crosslinking agent, epichlorohydrin-based crosslinking agent, or oxazoline-based crosslinking agent. In addition, these crosslinking agents can be used independently or can use 2 or more types together.
  • the carbodiimide-based crosslinking agent is a crosslinking agent having a carbodiimide structure, and examples thereof include a high molecular weight polycarbodiimide obtained by subjecting the above polyisocyanate to decarboxylation condensation reaction in the presence of a carbodiimidization catalyst.
  • the epichlorohydrin-based crosslinking agent is a crosslinking agent having an epichlorohydrin structure, and examples thereof include bisphenol A-epichlorohydrin type epoxy resins.
  • the oxazoline-based crosslinking agent is a crosslinking agent having an oxazoline structure, such as 2,2′-bis- (2-oxazoline), 2,2′-methylene-bis- (2-oxazoline), 2,2 ′.
  • crosslinking agent used in the anchor coat layer of the present invention examples include a carbodiimide-based crosslinking agent “Carbodilite” (for example, V-02-L2) manufactured by Nisshinbo Chemical, and an oxazoline-based crosslinking agent “Epocross” (for example, WS- 500), epichlorohydrin-based crosslinking agent “Polycup” (for example, 3160) manufactured by Hercules, and the like.
  • Carbodilite for example, V-02-L2
  • Epocross for example, WS- 500
  • epichlorohydrin-based crosslinking agent “Polycup” for example, 3160 manufactured by Hercules, and the like.
  • the content of the crosslinking agent used in the anchor coat layer of the present invention is preferably 1 to 30% by mass with respect to all components of the anchor coat layer.
  • the content of the crosslinking agent is less than 1% by mass, the improvement effect by the crosslinking agent described above may be small / not seen. If it is 30% by mass or more, even if it is added more than that, the improvement effect is not seen, and the economic superiority may be significantly impaired.
  • the content of the crosslinking agent is more preferably 2 to 20% by mass, and further preferably 3 to 10% by mass.
  • anchor coat layer of the present invention does not inhibit the effects of the present invention in addition to the polyurethane resin composition described above, other resins, silane coupling agents, plasticizers, antifoaming agents, leveling agents, antifungal agents , Rust inhibitor, matting agent, flame retardant, thixotropic agent, tackifier, thickener, lubricant, antistatic agent, surfactant, reaction retarder, antioxidant, UV absorber, hydrolysis inhibitor , Weathering stabilizers, heat stabilizers, dyes, inorganic pigments, organic pigments, extender pigments, curing agents, anti-tacking agents, inorganic particles, water-swelling inorganic layered compounds such as montmorillonite, synthetic mica, various additives such as organic particles Etc.
  • the content of the polyurethane resin composition contained in the anchor coat layer of the present invention is preferably 70% by mass or more and 80% by mass or more with respect to all solid components forming the anchor coat layer. Is more preferable, and it is still more preferable that it is 90 mass% or more.
  • the thickness of the anchor coat layer of the present invention is not particularly limited, but from the viewpoints of the obtained anchor coat film for vapor deposition and gas barrier properties and biodegradability of the vapor deposited film, for example, 0.001 ⁇ m to 1 ⁇ m, preferably 0. 005 ⁇ m to 0.3 ⁇ m, more preferably 0.01 ⁇ m to 0.1 ⁇ m, and particularly preferably 0.02 ⁇ m to 0.07 ⁇ m. If the anchor coat layer is thicker than the above, the vapor deposition layer may be whitened by heat of about 200 ° C. to reduce the gloss, or the biodegradation rate of the resulting anchor coat film and vapor deposition film may be reduced.
  • the anchor coat layer has a tendency to increase the biodegradation rate if it is within the above range as long as desired gas barrier properties and adhesion of the deposited layer can be obtained.
  • the thickness of the film of the present invention is not particularly limited, but is preferably 5 to 100 ⁇ m, more preferably 8 to 50 ⁇ m, and still more preferably 10 to 25 ⁇ m, from the viewpoint of film handling properties and suitability for vapor deposition processing. .
  • the base film of the present invention is preferably biaxially oriented.
  • the biaxial orientation of the base film of the present invention is not particularly limited, but it is possible to use a known biaxial stretching method such as a sequential biaxial stretching method, a simultaneous biaxial stretching method, or a combination thereof. it can. Among these, it is preferable to use a sequential biaxial stretching method from the viewpoint of facility expandability.
  • a sequential biaxial stretching method from the viewpoint of facility expandability.
  • a resin composition containing a biodegradable resin (and an additive, if necessary) used for the base film of the present invention is made into a chip shape, melted and kneaded by an extruder or the like, and preferably removed by a filter. After optimizing the flow rate with a gear pump, it is extruded into a sheet shape from a die such as a T-die.
  • the base film of the present invention is produced as a multilayer film formed from a plurality of layers, the resin composition used for each layer of the base film of the present invention is melt-extruded from two or more extruders.
  • each is supplied to a multi-manifold base having a plurality of manifolds inside or a feed block installed on the top of the base.
  • the multi-manifold base or the feed block needs to be provided with a flow path having a required shape corresponding to the required number of layers in accordance with a required film layer configuration.
  • the molten resin extruded from each extruder is joined by a multi-manifold die or a feed block, and coextruded into a sheet form from a die such as a T die.
  • the biodegradable resin should just be contained in the at least 1 layer of the base film of this invention, and may be the main structural component of the at least 1 layer of a base film.
  • the other layer may be composed of the same biodegradable resin as the layer containing the biodegradable resin or the main component, or a known resin different from the biodegradable resin. You may be comprised from.
  • the base film of the present invention preferably comprises polylactic acid as a main component.
  • melt-extruded (multi-layer) sheet is preferably unstretched by being cooled and solidified while being in close contact with the casting drum using an air knife method and / or a pinning method (electrostatic application means) and / or a liquid surface coating adhesion method.
  • a film is preferably unstretched by being cooled and solidified while being in close contact with the casting drum using an air knife method and / or a pinning method (electrostatic application means) and / or a liquid surface coating adhesion method.
  • the unstretched sheet is preheated through a roll, and subsequently stretched in the longitudinal direction through a roll having a difference in peripheral speed.
  • the stretching ratio in the machine direction is preferably 2 to 5 times, and more preferably 2.5 to 4.5 times.
  • the stretching temperature in the longitudinal direction may be determined according to the resin composition of the base film of the present invention, and the quality of the base film obtained is within the range of the glass transition temperature (Tg) to the melting point (Tm) of the film. (Mechanical properties, dimensional stability, flatness, thickness unevenness, etc.) and productivity may be selected as appropriate. When a plurality of Tg and Tm are confirmed, the main constituent components Tg and Tm constituting the film may be used.
  • the longitudinal stretching temperature is preferably 60 to 85 ° C.
  • the longitudinal stretching temperature is 65 to 75 ° C. from the viewpoint of preventing the sheet from sticking to the longitudinal stretching roll. It is more preferable.
  • the obtained uniaxially stretched film is immediately cooled to room temperature, subsequently guided to a tenter and laterally stretched, and then heat-set while being relaxed at least in the lateral direction.
  • the stretching temperature in the transverse direction may be appropriately selected in the range of Tg or more and the melting point or less of the film, similarly to the longitudinal stretching temperature.
  • the stretching temperature in the direction is preferably 60 to 90 ° C, more preferably 65 to 85 ° C, and further preferably 70 to 80 ° C.
  • the transverse draw ratio is preferably 2 to 5 times, more preferably 2.5 to 4.5 times.
  • the heat setting temperature after transverse stretching is less than Tm of the film.
  • the base film is a single layer
  • the main constituent Tm is used.
  • the lower one of Tm may be used.
  • the heat setting temperature is preferably 120 to 160 ° C. from the viewpoint of improving dimensional stability, gas barrier properties, mechanical properties, and flatness. 130 to 150 ° C. is more preferable.
  • the relaxation rate during the relaxation treatment is preferably 0 to 10%, more preferably 1 to 6%, from the viewpoint of achieving both dimensional stability and flatness of the resulting film.
  • the relaxation treatment can be carried out in the longitudinal direction and / or the transverse direction during the heat treatment or in the subsequent slow cooling zone.
  • the cooling rate of the film after heat treatment may also affect the heat shrink characteristics.
  • the base film of the present invention biaxially oriented is obtained by winding the biaxially stretched film obtained as described above into a roll shape.
  • the stretching may be combined several times, that is, the film may be stretched in multiple stages, or may be stretched in the longitudinal direction and / or the transverse direction after the longitudinal-transverse stretching. Re-stretching may be performed more than once.
  • the wetting tension of the surface on which the anchor coat layer of the base film of the present invention is formed may be able to apply the anchor coat layer uniformly or may improve the interlayer adhesion between the anchor coat layer and the base film. Therefore, it is preferably 37 to 60 mN / m, and more preferably 39 to 50 mN / m.
  • surface treatment methods such as corona discharge treatment, flame treatment, and plasma treatment are preferably used. Among these, it is more preferable to use corona treatment from the viewpoints of economy, handling properties, and the like.
  • the atmospheric gas during the corona discharge treatment air, oxygen, nitrogen, carbon dioxide, or a mixed system of nitrogen / carbon dioxide is preferable. From the viewpoint of economy, the corona discharge treatment is particularly preferred in the air.
  • the anchor coat layer of the present invention (the anchor coat layer formed by applying and drying the coating agent of the present invention (polyurethane dispersion of the present invention) on at least one surface of the film) is a single layer.
  • a plurality of the polyurethane dispersions of the present invention or other coating agents may be combined to form a multilayer of two or more layers.
  • at least the outermost layer is preferably the anchor coat layer of the present invention.
  • Examples of the method for forming the anchor coat layer include an in-line coating method and an offline coating method, and can be appropriately selected depending on the resin composition of the base film and the composition of the coating agent.
  • the anchor coat layer is formed within the manufacturing process of the base film of the present invention.
  • the coating agent of the present invention polyurethane dispersion of the present invention
  • the oriented crystal of the anchor coat film for vapor deposition is completed.
  • the anchor coat film for vapor deposition of the present invention is produced by a sequential biaxial stretching method, after longitudinal stretching, at least one surface of the uniaxially stretched film is preferably subjected to corona discharge treatment to obtain a desired composition.
  • the coating agent (polyurethane dispersion) adjusted to 1 is applied to the surface.
  • the uniaxially stretched film after application is subsequently introduced into a tenter, and after the anchor coat layer is dried, it is transversely stretched and heat-set.
  • the anchor coat film for vapor deposition of the present invention is produced by the simultaneous biaxial stretching method, before the simultaneous biaxial stretching, at least one surface of the unstretched film is preferably subjected to corona treatment by an inline coating method. Then, an anchor coat layer is formed on the surface.
  • the anchor coat layer is formed by the off-line coating method
  • at least one surface of the film is preferably subjected to corona treatment, and then a known method is used for the surface.
  • a known method is used for the surface.
  • the coating agent of the present invention when considering the explosion-proof property of the apparatus and environmental pollution, it is preferable to prepare the coating agent of the present invention as a water-soluble and / or water-dispersible resin.
  • the anchor coat film for vapor deposition of the present invention can remarkably improve the gas barrier property by providing a vapor deposition layer on at least one anchor coat layer.
  • the anchor-coated vapor deposition film of the present invention (hereinafter sometimes simply referred to as the vapor deposition film of the present invention) is mainly composed of a biodegradable resin
  • the biodegradable resin is the vapor deposition of the present invention.
  • the content is 90% by mass or more, preferably 95% by mass or more, based on all components of the anchor coat film for use, the obtained deposited film may exhibit a practical biodegradation rate.
  • the said vapor deposition layer can also be formed in both surfaces of the anchor coat film for vapor deposition of this invention.
  • the anchor coat layer of the present invention needs to be formed on at least one side of the film, but is preferably formed on both sides.
  • Examples of inorganic materials (including metals) used for the vapor deposition layer include magnesium, calcium, barium, group 4 titanium, zirconium, group 13 aluminum, indium, group 14 silicon, which are group 2 of the periodic table, Examples thereof include germanium and tin. Further, for example, aluminum, aluminum oxide, magnesium oxide, titanium oxide, aluminum oxide, indium oxide, silicon oxide, silicon oxynitride, cerium oxide, calcium oxide, tin oxide, diamond-like carbon film Or a mixture thereof. Among these, aluminum, silicon and oxides thereof are preferable, and aluminum and oxides thereof are more preferable from the viewpoint of excellent gas barrier properties and production efficiency. Further, the vapor deposition layer may be formed in a multilayer shape by combining a plurality of layers.
  • the vapor deposition layer of the vapor deposition film of the present invention is formed on the surface of the anchor coat layer.
  • a vacuum process is used as a method for forming the vapor deposition layer.
  • a vacuum evaporation method, sputtering method, an ion plating method, a chemical vapor deposition method (CVD method) etc. are used preferably.
  • a reactive vapor deposition method is more preferably used from the viewpoint of productivity.
  • the vapor deposition layer of the vapor deposition film of the present invention is preferably formed by a vacuum vapor deposition method from the viewpoint of productivity.
  • an electron beam heating method, a resistance heating method, an induction heating method, or the like is preferably used as the heating method of the vacuum evaporation apparatus.
  • the surface of the film before vapor deposition (that is, the surface of the anchor coat layer of the present invention) to plasma treatment or corona treatment.
  • the treatment strength during the corona treatment is preferably 5 to 50 W ⁇ min / m 2 , more preferably 10 to 45 W ⁇ min / m 2 .
  • plasma discharge is preferably performed in an oxygen and / or nitrogen gas atmosphere, and copper is preferably used as the cored metal.
  • aluminum metal and alumina are evaporated by resistance heating boat method, crucible high frequency induction heating, electron beam heating method, and aluminum oxide is deposited on the film in an oxidizing atmosphere.
  • a method is preferably employed.
  • Oxygen is used as a reactive gas for forming an oxidizing atmosphere, but a gas mainly composed of oxygen and added with water vapor or a rare gas may be used. Further, ozone may be added or a method for promoting a reaction such as ion assist may be used in combination.
  • a method of evaporating Si metal, SiO or SiO 2 by an electron beam heating method and depositing silicon oxide on a film in an oxidizing atmosphere is employed.
  • the method described above is used as a method of forming the oxidizing atmosphere.
  • the thickness of the vapor deposition layer of the vapor deposition film of the present invention is appropriately selected depending on the composition of the vapor deposition layer, but is usually preferably 1 to 500 nm from the viewpoint of productivity, handling properties, and appearance of the vapor deposition film obtained. 100 nm is more preferable, and 5 to 50 nm is even more preferable. If the vapor deposition layer is less than the above range, it is difficult to form a uniform layer, and defects are easily generated in the vapor deposition layer, so that the gas barrier property may be significantly deteriorated. If the vapor deposition layer is thicker than 100 nm, the cost during vapor deposition increases, the coloration of the vapor deposition layer becomes significant, and the appearance may be inferior. In addition, the flexibility (flexibility) of the vapor deposition layer is lowered, and in the processing such as bending and pulling after film formation, the vapor deposition layer may be cracked, pinholes, etc., and the gas barrier property may be impaired.
  • the vapor permeability of the vapor deposition film of the present invention is preferably 1.5 g / m 2 / day or less.
  • the vapor barrier property is inferior, and when the vapor deposition film is processed into a package using the vapor deposition film as a packaging material, the freshness retention of the contents is inferior There is.
  • the water vapor permeability of the deposited film is more preferably 1.1 g / m 2 / day or less, and still more preferably 0.8 g / m 2 / day or less, most preferably for applications requiring better water vapor barrier properties.
  • steam barrier property is so preferable that it is preferable, and especially a minimum is not provided, but it is estimated that about 0.01 g / m ⁇ 2 > / day is a realizable lower limit.
  • the oxygen permeability of the vapor deposition film of the present invention is preferably 4 cc / m 2 / day / atm or less.
  • the oxygen barrier property is poor, and when the vapor deposition film is processed into a package using the packaging film as a packaging material, the freshness retention of the contents is poor There is.
  • Oxygen permeability of the deposited film is to use a more excellent oxygen barrier properties is desired, more preferably not more than 3cc / m 2 / day / atm , more preferably 2.5cc / m 2 / day / atm or less Most preferably, it is 2.0 cc / m 2 / day / atm or less.
  • oxygen barrier property is so preferable that it is favorable, especially a minimum is not provided, but about 0.01 cc / m ⁇ 2 > / day / atm is guessed as a feasible minimum.
  • the vapor deposition layer adhesion of the vapor deposition film of the present invention is preferably 20 g / 15 mm or more. Although there are uses that can be put into practical use even when the amount is less than 20 g / 15 mm, it can be used for a wide range of uses by satisfying the above range. When the adhesion of the deposited layer is less than 20 g / 15 mm, delamination between the base film of the present invention and the anchor coat layer becomes significant, and the workability and processing properties when processing the film of the present invention are inferior. The package after processing may be inferior in practicality.
  • the adhesion strength of the deposited layer is more preferably 30 g / 15 mm or more, still more preferably 50 g / 15 mm or more, and most preferably 80 g / 15 mm or more. The higher the adhesion of the deposited layer, the better.
  • the upper limit is not particularly set, but it is estimated that about 2000 g / 15 mm is an upper limit that can be realized.
  • an anchor coat film for vapor deposition of the present invention by forming an anchor coat layer using the above-described polyurethane dispersion, the adhesion of the vapor deposition layer and gas barrier properties are excellent, Since a film containing a biodegradable resin is provided, the environmental load can be reduced.
  • the anchor coat film is also preferably used in fields other than vapor deposition by taking advantage of its excellent gas barrier properties, interlayer adhesion, and the like.
  • the isocyanate-terminated polyurethane prepolymer (A′-1) was dispersed and emulsified in 808.4 g of ion-exchanged water with a homodisper, and stirred for 5 minutes.
  • the polyether polyol component In the solid content of the aqueous dispersion of the polyurethane resin (A-1), the polyether polyol component is contained in an amount of 23% by mass.
  • the resin acid value is 26.8 mgKOH / g, and the concentration of urethane / urea groups. (Total amount) was 31% by mass.
  • Synthesis Examples 2 to 10 Synthesis of Aqueous Dispersions of Polyurethane Resins (A-2) to (A-10) Synthesis was performed in the same manner as in Synthesis Example 1 except that they were reacted according to the formulation shown in Table 1. Water dispersions of polyurethane resins (A-2) to (A-10) of Examples 2 to 10 were prepared.
  • the isocyanate-terminated polyurethane prepolymer (B′-1) was dispersed and emulsified in 835.8 g of ion-exchanged water with a homodisper and stirred for 5 minutes.
  • the solid content of the aqueous dispersion of the polyurethane resin (B-1) contains 59.5% by mass of a polyester polyol component, and the resin acid value is 17.5 mg KOH / g, urethane / urea group. The concentration (total amount) was 12.3% by mass.
  • Synthesis Example 12 Synthesis of Aqueous Dispersion of Polyurethane Resin (B-2)
  • the polyurethane resin (B--) of Synthesis Example 12 was prepared in the same manner as in Synthesis Example 11 except that the reaction was carried out according to the formulation shown in Table 1.
  • the aqueous dispersion of 2) was prepared.
  • the solid content of the aqueous dispersion of the polyurethane resin (C-1) does not contain a high molecular weight polyol component, and the resin acid value is 27.3 mgKOH / g, the urethane / urea group concentration (total amount). ) was 39.4% by mass.
  • Synthesis of aqueous dispersion of polyurethane resin (D) (Synthesis Example 14) Synthesis of aqueous dispersion of polyurethane resin (D-1) Polyurethane polyol is produced using the same raw materials as polyurethane resin (A-1). The polyurethane resin (D-1) was synthesized without producing an isocyanate-terminated polyurethane prepolymer by batch charging of each component.
  • DIOL-400 manufactured by Mitsui Chemicals, polyether polyol
  • 19.2 g of dimethylolpropionic acid, ethylene glycol 14 0.2 g, 2.6 g of trimethylolpropane, and 136.3 g of methyl ethyl ketone were added and mixed.
  • the isocyanate-terminated polyurethane prepolymer (D′-1) was dispersed and emulsified in 808.4 g of ion-exchanged water with a homodisper and stirred for 5 minutes.
  • the solid content of the aqueous dispersion of this polyurethane resin (D-1) contains 23% by mass of a polyether polyol component, and the resin acid value is 26.8 mgKOH / g, urethane group / urea group. The concentration was 31% by mass.
  • DIOL400 Polyether polyol, number average molecular weight 400, manufactured by Mitsui Chemicals, Inc.
  • DIOL700 Polyether polyol, number average molecular weight 700, ester manufactured by Mitsui Chemicals, Inc.
  • A Polyester polyol A, 3-methyl-1,5-pentanediol / adipic acid Number average molecular weight 500, Kuraray ester B: polyester polyol B, 1,4-butanediol / adipic acid, number average molecular weight 1000
  • DMPA dimethylolpropion Acid
  • ME Methyl ethyl ketone H 12
  • MDI 4,4'-dicyclohexylmethane diisocyanate
  • IPDI 3- isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate)
  • XDI 1,3-xylylene diisocyanate
  • H 6 XDI: 1,3-bis (isocyanatomethyl) cyclohexane (hydrogenated xylylene diisocyanate)
  • EG Ethylene glycol
  • TMP Trimethylolpropane
  • TEA Triethylamine
  • KBM-603 N-2- (aminoethyl) -3-aminopropyltriethoxysilane, manufactured by Shin-Etsu Silicone Co.
  • MW-12LF, MX-730, MX-706 and MX-035 Melamine-based aqueous solution type cross-linking agent “Nicarac”, Nippon Carbide SV-02 and V-02-L2: Carbodiimide-based aqueous solution type cross-linking agent “Carbodilite”, Nisshinbo Chemical E-02: Carbodiimide emulsion type crosslinking agent “Carbodilite”, Nisshinbo Chemical K-2020E: Oxazoline type emulsion type crosslinking agent “Epocross”, Nippon Shokubai WS-500: Oxazoline type aqueous solution type crosslinking agent “Epocross”, BN-77 manufactured by Nippon Shokubai Co., Ltd .: Blocked isocyanate aqueous solution type cross-linking agent “Elastrone”, Daiichi Kogyo Seiyaku Co., Ltd.
  • aPLA amorphous polylactic acid
  • This polylactic acid was substantially amorphous, with no DSC curve according to the measurement method (7) shown below, exothermic peak derived from cold crystallization of polylactic acid, and endothermic peak derived from crystal melting. .
  • caPLA crystalline polylactic acid
  • the cPLA was blended by 85% by mass and the aPLA was blended by 15% by mass, supplied to a twin screw extruder having a cylinder temperature of 200 ° C., homogenized by melt kneading, and then extruded into a gut shape.
  • the gut-shaped molding was cooled with water and then pelletized into chips.
  • the obtained chip was dried at 100 ° C. for 4 hours in a rotary vacuum dryer.
  • PLA-MB1 After blending 95% by mass of the above aPLA and 5% by mass of Silton JC-30 (aluminosilicate, manufactured by Mizusawa Chemical), supplying it to a twin screw extruder with a cylinder temperature of 200 ° C. Extruded to.
  • the gut-shaped molding was cooled with water and then pelletized into chips.
  • the obtained chip was dried with a rotary vacuum dryer at 50 ° C. for 8 hours.
  • the produced chip was designated as PLA-MB1.
  • the chip was determined to be amorphous by the following measurement method (7).
  • PLA-MB2 After blending 98% by mass of the above aPLA and 2% by mass of Silton JC-20 (aluminosilicate, manufactured by Mizusawa Chemical), supplying it to a twin-screw extruder having a cylinder temperature of 200 ° C. Extruded to.
  • the gut-shaped molding was cooled with water and then pelletized into chips.
  • the obtained chip was dried with a rotary vacuum dryer at 50 ° C. for 8 hours.
  • the produced chip was designated as PLA-MB2.
  • the chip was determined to be amorphous by the following measurement method (7).
  • (6) PLA-MB3 After blending 98% by mass of the above cPLA and 2% by mass of Silton JC-20 (aluminosilicate, manufactured by Mizusawa Chemical), the mixture was supplied to a twin-screw extruder having a cylinder temperature of 200 ° C., homogenized by melt-kneading, and then gut-shaped. Extruded to.
  • Example 1 To the single screw extruder (a), caPLA was supplied as a resin composition of the core layer and extruded at 220 ° C., and the polymer was filtered with a filter obtained by sintering stainless steel fibers having an average opening of 65 ⁇ m, and B / A / C type 3 type 3 layer multi-manifold base.
  • a blend raw material premixed with 97% by mass of aPLA and 3% by mass of PLA-MB1 as a resin composition for the skin layer on one side is supplied to the single-screw extruder (b) and extruded at 220 ° C.
  • the polymer was filtered through a filter obtained by sintering and compressing stainless steel fibers having an average opening of 65 ⁇ m in a flow path different from (a), and then supplied to the multi-manifold base while adjusting the flow rate with a gear pump.
  • the blend raw material in which 95% by mass of aPLA and 5% by mass of PLA-MB2 were mixed in advance as a resin composition for the other skin layer was supplied to the extruder (c) and extruded at 220 ° C. After the polymer is filtered through a filter in which stainless steel fibers with an average opening of 65 ⁇ m are sintered and compressed in a flow path different from a) and (b), the flow rate is adjusted with a gear pump and supplied to the multi-manifold base. did.
  • the manifold shape of the die is designed in advance so that the skin layers on both sides (formed by the extruder (b) and the extruder (c)) are not stacked up to the edge of the sheet.
  • the molten polymer from each extruder is merged in a multi-manifold die heated to 220 ° C. so as to be laminated in the order of extruder (b) / extruder (a) / extruder (c). More co-extruded into a sheet.
  • the thickness ratio of the skin layer (from the extruder (b)) / core layer (from the extruder (a)) / skin layer (from the extruder (c)) becomes 1/8/1.
  • the discharge amount of the extruder (a) and the extruder (b) and the peripheral speed of the cast drum were adjusted so that the thickness after axial orientation was 20 ⁇ m.
  • the obtained extruded sheet was cast on a mirror surface metal drum at 30 ° C. and cooled and solidified into a sheet shape. At this time, casting was performed so that the skin layer of the resin composition extruded by the extruder (c) was in contact with the drum.
  • the obtained unstretched sheet was stretched three times in the machine direction at 70 ° C. with a roll stretching machine, and immediately cooled to room temperature.
  • the skin layer surface of the resin composition extruded by the extruder (c) of the obtained longitudinally stretched film is subjected to corona discharge treatment in the atmosphere, and water is added so that the solid content concentration becomes 5% by mass in advance as described above.
  • the anchor coating agent A diluted in (1) was applied with a # 4 wire bar.
  • corona treatment and coating surface of the film is the surface in contact with the metal drum during casting.
  • this longitudinally stretched coated film was introduced into a tenter, dried and preheated at 70 ° C. while holding both edges with clips, then stretched 3.5 times in the transverse direction at 75 ° C., and subsequently 5% in the transverse direction.
  • the film was heat treated at 140 ° C. while being relaxed, and after cooling, it was wound up to obtain an anchor coat film for vapor deposition.
  • the obtained anchor coat film for deposition having a thickness of 20 ⁇ m (anchored biaxially oriented PLA film) was set in a vacuum deposition apparatus equipped with a film running apparatus. After a high pressure reduced state of 1.00 ⁇ 10 ⁇ 2 Pa, it was run on a cooled metal drum at 0 ° C. At this time, aluminum metal was heated and evaporated from an electron beam heating type evaporation source, and an inorganic adhesive film (deposition layer) made of aluminum was formed on the anchor coat layer of the film.
  • the aluminum vapor deposition film thus obtained was aged for 48 hours to obtain a vapor deposition film.
  • the optical density of the vapor deposition film was measured online during vapor deposition, and the vapor deposition thickness was controlled to be 2.5.
  • Tables 2 to 4 show the evaluation results of the crystallinity and appearance of the anchor-coated skin layer of the obtained vapor-deposited film, the gas barrier properties, and the adhesion of the vapor-deposited layer. (Examples 2 to 26, 29, Comparative Examples 1 to 4)
  • Example 1 an anchor coat film for vapor deposition and a vapor deposition film were produced under the same conditions except that each anchor coat agent shown in Tables 2 to 4 was applied on the longitudinally stretched film instead of the anchor coat agent A. .
  • Example 4 In Comparative Example 4, no anchor coat agent was applied.
  • Example 1 As a resin composition to be supplied to the extruder (c), a blend raw material in which 95% by mass of cPLA and 5% by mass of PLA-MB3 are premixed is used, and instead of the coating agent A, Table 4 shows An anchor coat film for vapor deposition and a vapor deposition film were produced under the same conditions except that each coating agent was applied onto the longitudinally stretched film.
  • the thin film section of the film cross section was photographed with 100 views of the film cross section photograph at a magnification of 10,000 using a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • grains of a skin layer was in the skin layer of the resin composition extruded by the extruder (c).
  • Particles 1.8 ⁇ m
  • particles in the skin layer of the resin composition extruded by the extruder (b) 3.0 ⁇ m.
  • Glass transition temperature (Tg), melting point (Tm) Based on JIS K 7121 (1987), a differential scanning calorimeter “Robot DSC-RDC220” manufactured by Seiko Denshi Kogyo was used, and a disk session “SSC / 5200” was used for data analysis.
  • a sample of the resin composition sampled from the base film was weighed in a sample pan at a rate of 5 mg, the heating rate was 10 ° C./min, and the temperature was raised from 20 ° C. to 220 ° C. in a nitrogen atmosphere.
  • Tg was determined. The measurement was performed three times for the same sample, and the average value of the obtained values was defined as Tg (° C.) of the sample.
  • Tm was determined from the peak of the exothermic peak accompanying melting of the differential scanning calorimetry chart obtained above. The measurement was performed three times for the same sample, and the average value of the obtained values was defined as Tm (° C.) of the sample.
  • the Tg of the base film used in Example 1 was 58 ° C. and Tm was 166 ° C.
  • Tg of the base film used in Example 27 was 63 ° C.
  • Tm was 166 ° C.
  • (7) Determination of crystallinity of polylactic acid
  • Polylactic acid collected from a raw material chip or film
  • the polylactic acid is not. Crystalline polylactic acid was obtained.
  • the polyurethane resin composition, polyurethane dispersion, vapor deposition anchor coat film and anchor-coated vapor deposition film of the present invention can be used in the field of gas barrier films.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition de résine de polyuréthane contenant une résine de polyuréthane (A) qui contient, comme composants de copolymérisation, un composant xylylènediisocyanate et/ou un composant xylylènediisocyanate hydrogéné et un composant polyol à poids moléculaire élevé. Ce composant polyol est constitué d'au moins un polyol sélectionné dans le groupe constitué par des polyols de polyéther, des polyols de polyester et des polyols de polycarbonate, et présente un poids moléculaire moyen de 300-1500 (inclus).
PCT/JP2011/069932 2010-09-22 2011-09-01 Composition de résine de polyuréthane, dispersion de polyuréthane, film de revêtement d'ancrage pour dépôt en phase vapeur et film ainsi déposé WO2012039259A1 (fr)

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KR20130139690A (ko) * 2012-06-13 2013-12-23 에스케이케미칼주식회사 폴리유산 수지 조성물 및 포장용 필름
WO2015107933A1 (fr) * 2014-01-15 2015-07-23 Dic株式会社 Agent de traitement de surface aqueux et produit l'utilisant
WO2016143889A1 (fr) * 2015-03-11 2016-09-15 三井化学株式会社 Stratifié, matériau d'emballage alimentaire et procédé de fabrication de stratifié
JP2017528541A (ja) * 2014-07-01 2017-09-28 ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツングＢＡＳＦ Ｃｏａｔｉｎｇｓ ＧｍｂＨ ポリエーテルを主体とした反応生成物、および前記反応生成物を含む水性ベースコート材料
JP2019034484A (ja) * 2017-08-17 2019-03-07 日本カーバイド工業株式会社 金属調積層体
JP2020083902A (ja) * 2018-11-15 2020-06-04 宇部興産株式会社 水性樹脂組成物及びそれを含有するコーティング剤組成物
JP2020105243A (ja) * 2018-12-26 2020-07-09 三井化学株式会社 アンカーコート剤および多層フィルム
JP2020163843A (ja) * 2019-03-27 2020-10-08 三井化学株式会社 ポリウレタン積層体
WO2020246593A1 (fr) * 2019-06-07 2020-12-10 三井化学株式会社 Agent de revêtement et corps stratifié
WO2021024701A1 (fr) * 2019-08-02 2021-02-11 東洋紡株式会社 Film de polyester stratifié blanc
CN112482045A (zh) * 2020-11-03 2021-03-12 安徽安利材料科技股份有限公司 一种聚乳酸生物可降解聚氨酯合成革及其制备方法
WO2022107660A1 (fr) * 2020-11-19 2022-05-27 中京油脂株式会社 Dispersion aqueuse
WO2023248600A1 (fr) * 2022-06-20 2023-12-28 Dic株式会社 Agent de revêtement pour film déposé par vaporisation, film barrière aux gaz et matériau d'emballage

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JPH04249249A (ja) * 1991-02-05 1992-09-04 Toray Ind Inc 水なし平版印刷用原版
WO1993008796A1 (fr) * 1991-11-02 1993-05-13 Takiron Co., Ltd. Autocollant pour preparation absorbable par voie percutanee
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KR20130139690A (ko) * 2012-06-13 2013-12-23 에스케이케미칼주식회사 폴리유산 수지 조성물 및 포장용 필름
WO2015107933A1 (fr) * 2014-01-15 2015-07-23 Dic株式会社 Agent de traitement de surface aqueux et produit l'utilisant
JPWO2015107933A1 (ja) * 2014-01-15 2017-03-23 Dic株式会社 水性表面処理剤及びそれを用いた物品
JP2017528541A (ja) * 2014-07-01 2017-09-28 ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツングＢＡＳＦ Ｃｏａｔｉｎｇｓ ＧｍｂＨ ポリエーテルを主体とした反応生成物、および前記反応生成物を含む水性ベースコート材料
WO2016143889A1 (fr) * 2015-03-11 2016-09-15 三井化学株式会社 Stratifié, matériau d'emballage alimentaire et procédé de fabrication de stratifié
JPWO2016143889A1 (ja) * 2015-03-11 2018-01-18 三井化学株式会社 積層体、食品包装材料および積層体の製造方法
US10434751B2 (en) 2015-03-11 2019-10-08 Mitsui Chemicals, Inc. Laminate, food packaging material, and method for producing laminate
JP2019034484A (ja) * 2017-08-17 2019-03-07 日本カーバイド工業株式会社 金属調積層体
JP2020083902A (ja) * 2018-11-15 2020-06-04 宇部興産株式会社 水性樹脂組成物及びそれを含有するコーティング剤組成物
JP2020105243A (ja) * 2018-12-26 2020-07-09 三井化学株式会社 アンカーコート剤および多層フィルム
JP7265352B2 (ja) 2018-12-26 2023-04-26 三井化学株式会社 アンカーコート剤および多層フィルム
JP2020163843A (ja) * 2019-03-27 2020-10-08 三井化学株式会社 ポリウレタン積層体
JP7461171B2 (ja) 2019-03-27 2024-04-03 三井化学株式会社 ポリウレタン積層体
WO2020246593A1 (fr) * 2019-06-07 2020-12-10 三井化学株式会社 Agent de revêtement et corps stratifié
WO2021024701A1 (fr) * 2019-08-02 2021-02-11 東洋紡株式会社 Film de polyester stratifié blanc
CN112482045A (zh) * 2020-11-03 2021-03-12 安徽安利材料科技股份有限公司 一种聚乳酸生物可降解聚氨酯合成革及其制备方法
WO2022107660A1 (fr) * 2020-11-19 2022-05-27 中京油脂株式会社 Dispersion aqueuse
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JP7435923B1 (ja) 2022-06-20 2024-02-21 Dic株式会社 蒸着フィルム用コーティング剤、ガスバリア性フィルム、及び、包装材

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