JP5375255B2 - Deposition film and gas barrier film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a film for vapor deposition that has a well-balanced combination of adhesion properties and gas barrier properties. <P>SOLUTION: The film for vapor deposition has an anchor coat layer formed from a urethane resin formed on at least one side of a film formed from a thermoplastic resin. In the film, the polyurethane resin is a polyurethane dispersion prepared by dispersing in water an aqueous polyurethane resin produced by reacting an isocyanate group-terminated urethane prepolymer with a chain extender and the isocyanate group-terminated urethane prepolymer includes an adhesive urethane prepolymer for imparting adhesion properties and a gas-barrier urethane prepolymer for imparting gas barrier properties. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

The present invention relates to a vapor deposition film and a gas barrier film. In particular, the present invention relates to a vapor deposition film and a gas barrier film using a urethane resin as an anchor coat layer.

Conventionally, it is widely known that 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 or the like.
For example, in Patent Document 1, a first coating layer mainly composed of a polyurethane polymer is provided on at least one surface of a base film made of a thermoplastic resin, and one or more metals or A gas barrier film obtained by forming a second coating layer made of a metal oxide has been proposed, but the gas barrier properties are not sufficient.

  Further, Patent Document 2 discloses a polyester film for easy adhesion transparent vapor deposition in which a polyurethane-based resin layer that is crosslinked and cured with a melamine-based or epoxy-based crosslinking agent is formed on at least one surface of a polyester film. Not enough.

Japanese Patent Laid-Open No. 2001-10003 JP-A-11-300197

  An object of the present invention is to eliminate the above-described problems of the prior art. That is, the anchor coating agent used for the film for vapor deposition improves the adhesion between the base film and the vapor deposition film, but the gas barrier property is not sufficient for the recent demand for high barrier market. Therefore, it is providing the film for vapor deposition which has adhesiveness and gas-barrier property in a good balance.

The above-mentioned subject is a film for vapor deposition formed by forming an anchor coat layer made of a urethane resin on at least one surface of a film made of a thermoplastic resin, wherein the polyurethane resin comprises an isocyanate group-terminated urethane prepolymer and a chain extender. A polyurethane dispersion obtained by water-dispersing an aqueous polyurethane resin obtained by a reaction, wherein the isocyanate group-terminated urethane prepolymer has an adhesive urethane prepolymer for imparting adhesion, and a gas barrier property. It can be achieved by a vapor deposition film characterized by containing a gas barrier urethane prepolymer.
As a more preferable aspect,
(1) The water-based polyurethane resin contains an adhesive-gas barrier resin obtained by a reaction between the adhesive urethane prepolymer and the gas barrier urethane prepolymer, and a chain extender,
(2) The water-based polyurethane resin is obtained by a reaction between the adhesive urethane prepolymer and the chain extender obtained by a reaction between the adhesive urethane prepolymer and the gas barrier urethane prepolymer and the chain extender. Including a gas barrier resin,
(3) The adhesive urethane prepolymer is obtained by a reaction between a polyisocyanate component and a polyol component, and the polyol component contains a polyester polyol,
(4) The polyol component contains polyhydroxyalkanoic acid, and the polyester polyol has a ring structure in the molecule.
(5) The polyester polyol is obtained by a reaction between a polybasic acid and a polyhydric alcohol, and the polybasic acid contains terephthalic acid and / or isophthalic acid and / or orthophthalic acid,
(6) The gas barrier urethane prepolymer is obtained by a reaction between a polyisocyanate component and a polyol component, and the polyol component is composed of a low molecular weight polyol.
(7) The polyisocyanate component contains an araliphatic diisocyanate and / or an alicyclic diisocyanate, and the low molecular weight polyol is an alkane polyol having 2 to 6 carbon atoms and / or a polyoxyalkylene glycol having 2 to 6 carbon atoms. And polyhydroxyalkanoic acid,
(8) The polyisocyanate component contains xylylene diisocyanate and / or hydrogenated xylylene diisocyanate,
(9) A vapor deposition polyester film in which the thermoplastic resin is polyester,
(10) A gas barrier film in which a layer made of metal and / or metal oxide is laminated on the anchor coat layer.

  The film for vapor deposition of the present invention is not only excellent in adhesion to the vapor deposition layer, but also excellent in gas barrier properties after vapor deposition, so that it is suitable for packaging applications or industrial material applications that require very high gas barrier properties. Can also be suitably used.

It is the schematic of peel strength measurement.

  In the present invention, an anchor coat layer is provided on at least one surface of a film (base film) made of a thermoplastic resin to form a vapor deposition film. As the thermoplastic resin constituting the base film, polyolefin resin, nylon resin, or polyester resin can be used. Of these, polyester resins are preferred from the viewpoint of heat resistance.

  Here, the polyester resin is a general term for polymer compounds in which the main bond in the main chain is an ester bond, and can usually be obtained by polycondensation reaction of a dicarboxylic acid component and a glycol component.

  The dicarboxylic acid component used here is mainly terephthalic acid. As long as the effects of the present invention are not impaired, other dicarboxylic acid components such as naphthalenedicarboxylic acid, isophthalic acid, diphenyldicarboxylic acid, diphenylsulfonedicarboxylic acid, diphenoxyethanedicarboxylic acid, 5-sodiumsulfoisophthalic acid, phthalic acid and the like Aromatic dicarboxylic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, dimer acid, maleic acid, fumaric acid and other aliphatic dicarboxylic acids, cyclohexyne dicarboxylic acid and other alicyclic dicarboxylic acids, p-oxybenzoic acid An oxycarboxylic acid such as can be used in combination.

  On the other hand, the glycol component is mainly ethanediol. As long as the effects of the present invention are not inhibited, other glycol components, for example, glycerides such as propanediol, pentanediol, hexanediol and neopentylglycol, alicyclic glycols such as cyclohexanedimethanol, bisphenol A and bisphenol S Aromatic glycols such as can be used in combination.

  Furthermore, polyethers such as polyethylene glycol and polytetramethylene glycol may be copolymerized. These dicarboxylic acid components and glycol components may be used in combination of two or more, or two or more polyesters may be blended and used. Further, two or more layers may be used as a co-extruded laminated film.

  Examples of polyester polymerization catalysts include alkali metal compounds, alkaline earth metal compounds, zinc compounds, lead compounds, manganese compounds, cobalt compounds, aluminum compounds, antimony compounds, and titanium compounds, among which germanium compounds and antimony compounds. And titanium compounds are particularly preferably used. Moreover, when manufacturing polyester, coloring inhibitors, such as a phosphorus compound, can be used.

  The polyester subjected to the polycondensation reaction under high temperature and reduced pressure is further subjected to a solid phase polymerization reaction under reduced pressure or in an inert gas atmosphere at a temperature lower than its melting point to reduce the acetaldehyde content, The amount of carboxyl end groups can be adjusted.

  In the present invention, the film made of the thermoplastic resin as the base film may be an unoriented (unstretched) film or an oriented (stretched) film, but biaxial from the viewpoint of mechanical properties and the like. An oriented (biaxially stretched) film is preferred.

  In this invention, it is preferable that a base film contains a particle | grain with an average particle diameter of 0.01-5 micrometers from a viewpoint of workability, such as handleability and lamination, printing, etc. The particles may be known particles for film addition. For example, internal particles, inorganic particles, and organic particles are preferable. Preferably it is 0.01 to 3 weight%, More preferably, 0.03 to 3 weight% is contained.

  Examples of inorganic particles include wet and dry silica, colloidal silica, aluminum silicate, titanium oxide, calcium carbonate, calcium phosphate, barium sulfate, aluminum oxide, mica, kaolin, clay, and organic particles include styrene, silicone, acrylic Particles containing as constituents acids, methacrylic acids, polyesters, divinyl compounds and the like can be used. Among them, it is preferable to use inorganic particles such as wet and dry silica and alumina, and particles containing styrene, silicone, acrylic acid, methacrylic acid, polyester, divinylbenzene and the like as constituent components. Furthermore, these internal particles, inorganic particles, and organic particles may be used in combination of two or more.

  In addition, the base film contains, for example, an antistatic agent, a heat stabilizer, an antioxidant, a crystal nucleating agent, a weathering agent, an ultraviolet absorber, a pigment, and a dye as long as the effects of the present invention are not hindered. It is possible.

  The film for vapor deposition of the present invention requires that an anchor coat layer made of urethane resin is formed on at least one side of the film made of the thermoplastic resin. The polyurethane resin needs to be a polyurethane dispersion in which an aqueous polyurethane resin obtained by a reaction between an isocyanate group-terminated urethane prepolymer and a chain extender is dispersed in water.

That is, the polyurethane dispersion used as the anchor coating agent in the vapor deposition film of the present invention can be obtained by dispersing an aqueous polyurethane resin in water. The aqueous polyurethane resin contains an isocyanate group-terminated urethane prepolymer and a chain extension. It can be obtained by reaction with an agent.
In the present invention, the isocyanate group-terminated urethane prepolymer includes an adhesive urethane prepolymer and a gas barrier urethane prepolymer. Here, the adhesive urethane prepolymer is used for imparting adhesiveness, and the gas barrier urethane prepolymer is used for imparting gas barrier property.

  The adhesive urethane prepolymer is an isocyanate group-terminated urethane prepolymer for imparting adhesiveness to the polyurethane dispersion used as an anchor coating agent in the film for vapor deposition of the present invention, comprising a polyisocyanate component, a polyol component, Can be obtained by reacting the isocyanate group of the polyisocyanate component in an excess ratio with respect to the hydroxyl group of the polyol component.

  In the following, when the polyisocyanate component used for the synthesis of the adhesive urethane prepolymer is distinguished from the polyisocyanate component used for the synthesis of the gas barrier urethane prepolymer, it is used for the synthesis of the adhesive urethane prepolymer. The polyisocyanate component used is an adhesive polyisocyanate component, and the polyisocyanate component used for the synthesis of the gas barrier urethane prepolymer is a gas barrier polyisocyanate component (described later).

  Moreover, when distinguishing the polyol component used for the synthesis of the adhesive urethane prepolymer and the polyol component used for the synthesis of the gas barrier urethane prepolymer, the polyol component used for the synthesis of the adhesive urethane prepolymer, The polyol component used for the synthesis of the gas barrier urethane prepolymer as the adhesive polyol component is the gas barrier polyol component (described later).

  Examples of the adhesive polyisocyanate component include aromatic polyisocyanate, araliphatic polyisocyanate, alicyclic polyisocyanate, and aliphatic polyisocyanate.

  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.

  Examples of the araliphatic polyisocyanate 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 include araliphatic diisocyanates such as ω, ω′-diisocyanate-1,4-diethylbenzene.

  Examples of the alicyclic polyisocyanate include 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), 4,4′-, 2,4′- or 2,2′-dicyclohexyl. Methane diisocyanate or mixtures thereof (H12MDI), 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane or mixtures thereof (hydrogenated xylylene diisocyanate, H6XDI), bis (isocyanatomethyl) norbornane (NBDI), 1 , 3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate. It includes alicyclic diisocyanate is.

Examples of the aliphatic polyisocyanate include hexamethylene diisocyanate (HDI), trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, 1,2-, 2,3- or 1,3-butylene diisocyanate, 2,4,4. -Or aliphatic diisocyanates such as 2,2,4-trimethylhexamethylene diisocyanate.
Examples of the adhesive polyisocyanate component include a multimer (for example, dimer, trimer, pentamer, heptamer, etc.) of the above-mentioned adhesive polyisocyanate component, for example, the above-mentioned adhesive polyisocyanate. Modified biuret produced by reaction of components or multimers with water, modified allophanate produced by reaction with monool or polyhydric alcohol (described later), modified oxadiazine trione produced by reaction with carbon dioxide gas Furthermore, a polyol modified product produced by a reaction with a low molecular weight polyol (described later) can be mentioned.

These adhesive polyisocyanate components can be used alone or in combination of two or more.
Preferred examples of the adhesive polyisocyanate component include araliphatic polyisocyanates and alicyclic polyisocyanates, and more preferred examples include XDI, IPDI, H12MDI, and H6XDI.

Examples of the adhesive polyol component include macro polyols and low molecular weight polyols.
The macropolyol is a polyol having a number average molecular weight of 400 to 10,000, for example, polyester polyol, polyether polyol, polycarbonate polyol, polyurethane polyol, acrylic polyol, epoxy polyol, natural oil polyol, silicone polyol, fluorine polyol, polyolefin polyol, etc. Is mentioned.

  The polyester polyol can be obtained by a known esterification reaction, that is, a condensation reaction between a polybasic acid and a polyhydric alcohol, a transesterification reaction between an alkyl ester of a polybasic acid and a polyhydric alcohol, or the like.

  Examples of the polybasic acid or its alkyl ester include aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid and dimer acid, for example, fatty acids such as hexahydrophthalic acid and tetrahydrophthalic acid. Cyclic dicarboxylic acids such as aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid and naphthalenedicarboxylic acid, or dialkyl esters thereof (for example, C 1-6 alkyl esters) or acid anhydrides thereof Or a mixture thereof.

The polybasic acid preferably includes an aromatic dicarboxylic acid such as isophthalic acid, terephthalic acid, or orthophthalic acid, and more preferably includes the combined use of an aromatic dicarboxylic acid and an aliphatic dicarboxylic acid.
Examples of the polyhydric alcohol include 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, alkane (carbon number 7 to 22) diol, 2, 6-dimethyl-1-octene-3,8-diol, cyclohexanedimethanol, hydrogenated bisphenol A, 1,4-dihydroxy-2-butene, bishydroxyethoxybenzene, xylene glycol, bishydroxyethylene terephthalate, bisphenol A or water Alkylated bisphenol A Oxide adducts, diethylene glycol, trioxyethylene glycol, tetraoxyethylene glycol, pentaoxyethylene glycol, hexaoxyethylene glycol, dipropylene glycol, trioxypropylene glycol, tetraoxypropylene glycol, pentaoxypropylene glycol, hexaoxypropylene glycol, etc. Diols such as glycerin, 2-methyl-2-hydroxymethyl-1,3-propanediol, 2,4-dihydroxy-3-hydroxymethylpentane, 1,2,6-hexanetriol, trimethylolpropane, 2, Triols such as 2-bis (hydroxymethyl) -3-butanol and other aliphatic triols (8 to 24 carbon atoms), for example, tetramethylol Tan, D- sorbitol, xylitol, D- mannitol, polyols having four or more hydroxyl groups, such as D- mannitol, or mixtures thereof, and the like.

  Examples of the polyhydric alcohol also include polyhydroxy compounds containing an anionic group. Examples of the anionic group include a betaine structure-containing group such as a carboxyl group, a sulfonyl group, a phosphate group, and a sulfobetaine. Preferably, a carboxyl group is mentioned. Examples of such a polyhydroxy compound containing a carboxyl group as an anionic group include polyhydroxyalkanoic acids such as dimethylolacetic acid, dimethylollactic acid, dimethylolpropionic acid, and dimethylolbutanoic acid.

  The polyhydric alcohol is preferably a diol.

  Preferably, the polyester polyol includes a polyester polyol having a ring structure in the molecule, such as a polyester polyol obtained by a reaction between a polybasic acid containing an aromatic dicarboxylic acid and an aliphatic dicarboxylic acid and a polyhydric alcohol containing a diol. It is done.

  The polyether polyol is, for example, an alkylene oxide having a low molecular weight polyol (described later) as an initiator (for example, ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, 3-methyltetrahydrofuran, oxetane compound or the like having 2 to 5 carbon atoms). Alkylene oxide) can be obtained by ring-opening homopolymerization or ring-opening copolymerization. Specific examples include polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethylene-propylene copolymer, and polyoxytetramethylene glycol (polytetramethylene ether glycol).

  The polycarbonate polyol can be obtained, for example, by reacting phosgene, dialkyl carbonate, diallyl carbonate, alkylene carbonate, or the like in the presence or absence of a catalyst using a low molecular weight polyol (described later) as an initiator. it can.

  In addition, the polyurethane polyol is a polyester polyol, polyether polyol and / or polycarbonate polyol obtained as described above, in a ratio in which the equivalent ratio of hydroxyl group to isocyanate group (OH / NCO) exceeds 1, By making it react, it 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 acrylic polyol 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. Moreover, as another monomer copolymerizable with these, for example, (meth) acrylic acid, alkyl (meth) acrylate (1 to 12 carbon atoms), maleic acid, alkyl maleate, fumaric acid, fumaric acid Alkyl, itaconic acid, alkyl itaconate, styrene, α-methylstyrene, vinyl acetate, (meth) acrylonitrile, 3- (2-isocyanato-2-propyl) -α-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.

  Examples of the epoxy polyol include an epoxy polyol obtained by a reaction between a low molecular weight polyol (described later) and a polyfunctional halohydrin such as epichlorohydrin or β-methylepichlorohydrin.

  Examples of the natural oil polyol include hydroxyl group-containing natural oils such as castor oil and coconut oil.

  As the silicone polyol, for example, in the copolymerization of the acrylic polyol described above, a vinyl group-containing silicone compound such as γ-methacryloxypropyltrimethoxysilane is used as another copolymerizable monomer. Examples include coalesced and terminal alcohol-modified polydimethylsiloxane.

As the 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.
Examples of the polyolefin polyol include polybutadiene polyol, partially saponified ethylene-vinyl acetate copolymer, and the like.

  The hydroxyl equivalent of the macropolyol is, for example, 200 to 5000, and preferably 250 to 4000.

  Moreover, the number average molecular weight of a macropolyol is 400-10000, for example, Preferably it is 500-8000.

The number average molecular weight of the macropolyol can be calculated from 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 low molecular weight polyol is a polyol having a number average molecular weight of less than 400, and examples thereof include the polyhydric alcohols described above. 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, alkane (carbon number 7 to 22) diol, diethylene glycol, trioxyethylene glycol, tetra Oxyethylene glycol, pentaoxyethylene glycol, hexaoxyethylene glycol, dipropylene glycol, trioxypropylene glycol, tetraoxypropylene glycol, pentaoxypropylene glycol, hexaoxypropylene glycol Low molecular weight diols such as Le, such as polyhydroxy acids such as dimethylolpropionic acid.

  These adhesive polyol components can be used alone or in combination of two or more.

  The adhesive polyol component preferably includes a combination of a macro polyol and a low molecular weight polyol, and more preferably a combination of a polyester polyol, a low molecular weight diol and a polyhydroxyalkanoic acid.

  In order to obtain an adhesive urethane prepolymer, the adhesive polyisocyanate component and the adhesive polyol component are reacted by a known polymerization method such as bulk polymerization or solution polymerization.

  In this reaction, if an adhesive polyol component contains a polyhydroxy compound containing an anionic group such as polyhydroxyalkanoic acid, an aqueous polyurethane resin is prepared as an anionic internal emulsion type aqueous polyurethane resin. Can do.

  The polyhydroxy compound containing an anionic group can be contained, for example, as a polyhydric alcohol of a polyester polyol or as a low molecular weight polyol.

  In the synthesis of the adhesive urethane prepolymer, each component has an equivalent ratio (NCO / OH) of the isocyanate group of the adhesive polyisocyanate component to the hydroxyl group of the adhesive polyol component, for example, 1.1 to 2.5. The blending ratio is preferably 1.2 to 2.3, more preferably 1.2 to 2.0. If the equivalent ratio is within this range, the dispersion stability of the adhesive urethane prepolymer can be improved.

  In bulk polymerization, for example, the adhesive polyol component is added to this while stirring the adhesive polyisocyanate component in a nitrogen atmosphere, for example, at 50 to 130 ° C., preferably at 50 to 100 ° C., for example, The reaction is carried out for 1 to 15 hours, preferably 3 to 12 hours.

  In solution polymerization, for example, in a nitrogen atmosphere, an adhesive polyisocyanate component and an adhesive polyol component are added to an organic solvent, and the temperature is, for example, 50 to 130 ° C., and preferably 50 to 80 ° C., for example, 3 to 15 The reaction is performed for a time, preferably 5 to 12 hours.

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. Preferably, ketones and acetonitriles are used.
Further, in the above-described reaction, for example, a known urethanization catalyst such as amine, tin, lead, bismuth and the like may be added as necessary, and free from the resulting adhesive urethane prepolymer. The (unreacted) adhesive polyisocyanate component may be removed by a known removing means such as distillation or extraction.

  In the obtained adhesive urethane prepolymer, when an anionic group is contained, a neutralizing agent is preferably added to form a salt of the anionic group.

  Examples of the neutralizing agent include amines such as trimethylamine, triethylamine, tri-n-propylamine, tributylamine, triethanolamine, triisopropanolamine, N, N′-dimethylethanolamine, for example, potassium hydroxide, water Examples thereof include inorganic alkali salts such as sodium oxide and lithium hydroxide, and ammonia. Preferably, amines and ammonia are used.

  The addition amount of the neutralizing agent 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 adhesive urethane prepolymer thus obtained is, for example, 0.5 to 10% by weight, preferably 1 to 8% by weight.

  Moreover, the average functional group number of the isocyanate group of the adhesive urethane prepolymer is, for example, 1.1 to 3.5, preferably 1.5 to 2.5, and the number average molecular weight is, for example, 700 to 15000. , Preferably, it is 1000-8000.

  The gas barrier urethane prepolymer is an isocyanate group-terminated urethane prepolymer for imparting gas barrier properties to the polyurethane dispersion used as an anchor coating agent in the film for vapor deposition of the present invention, comprising a gas barrier polyisocyanate component and a gas barrier. The reactive polyol component can be obtained by reacting the isocyanate group of the gas barrier polyisocyanate component in an excess ratio with respect to the hydroxyl group of the gas barrier polyol component.

  Examples of the gas barrier polyisocyanate component include the same polyisocyanate component as the above-mentioned adhesive polyisocyanate component. For example, aromatic polyisocyanates such as MDI, TDI, TODI, NDI, for example, araliphatic polyisocyanates such as XDI, TMXDI, alicyclic polyisocyanates such as IPDI, H12MDI, H6XDI, NBDI, fats such as HDI Group polyisocyanate and the like.

  These gas barrier polyisocyanate components can be used alone or in combination of two or more.

  Preferred examples of the gas barrier polyisocyanate component include araliphatic diisocyanates and alicyclic diisocyanates, and more preferred examples include XDI and H6XDI.

  Examples of the gas barrier polyol component include the same polyol component as the above-described adhesive polyol component. For example, a macro polyol, a low molecular weight polyol, etc. are mentioned.

  These gas barrier polyol components can be used alone or in combination of two or more.

  The gas barrier polyol component is preferably a low molecular weight polyol, more preferably a combination of an alkane polyol having 2 to 6 carbon atoms and / or a polyoxyalkylene glycol having 2 to 6 carbon atoms and a polyhydroxyalkanoic acid. Is mentioned.

  Specifically, as the alkane polyol having 2 to 6 carbon atoms, for example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1, Examples include 2-butylene glycol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, and the like. Preferably, ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,6-hexanediol and the like are mentioned.

  Examples of the polyoxyalkylene glycol having 2 to 6 carbon atoms include diethylene glycol, trioxyethylene glycol, tetraoxyethylene glycol, pentaoxyethylene glycol, hexaoxyethylene glycol, dipropylene glycol, trioxypropylene glycol, tetraoxypropylene glycol, Examples thereof include pentaoxypropylene glycol and hexaoxypropylene glycol. Preferably, diethylene glycol, trioxyethylene glycol, dipropylene glycol, and trioxypropylene glycol are used.

  Examples of the polyhydroxyalkanoic acid include dimethylolacetic acid, dimethylollactic acid, dimethylolpropionic acid, and dimethylolbutanoic acid. Preferably, dimethylolpropionic acid is used.

  And a gas barrier urethane prepolymer is obtained by making a gas barrier polyisocyanate component and a gas barrier polyol component react by the synthesis method similar to the synthesis method of the adhesive urethane prepolymer described above.

  In this reaction, if a polyhydroxy compound containing an anionic group such as polyhydroxyalkanoic acid is contained in the gas barrier polyol component, the aqueous polyurethane resin is prepared as an anionic internal emulsion type aqueous polyurethane resin. Can do.

  The polyhydroxy compound containing an anionic group can be contained, for example, as a low molecular weight polyol.

  Thereby, similarly to the above-described adhesive urethane prepolymer, the gas barrier urethane prepolymer can be well dispersed (described later).

  The isocyanate group content of the gas barrier urethane prepolymer thus obtained is, for example, 2 to 20% by weight, preferably 3 to 15% by weight.

  Moreover, the average functional group number of the isocyanate group of the gas barrier urethane prepolymer is, for example, 1.1 to 3.5, preferably 1.5 to 2.5.

  The number average molecular weight of the gas barrier urethane prepolymer is, for example, 400 to 5000, preferably 500 to 3000.

  In order to obtain a polyurethane dispersion used as an anchor coating agent in the vapor deposition film of the present invention, the obtained adhesive urethane prepolymer and gas barrier urethane prepolymer are then dispersed in water and reacted with a chain extender.

  In this reaction, for example, a mixed liquid of an adhesive urethane prepolymer and a gas barrier urethane prepolymer is reacted with a chain extender. Alternatively, for example, the adhesive urethane prepolymer and the chain extender are reacted, and the gas barrier urethane prepolymer and the chain extender are separately reacted, and then they are mixed.

  In the following, first, a method for reacting a mixture of an adhesive urethane prepolymer and a gas barrier urethane prepolymer with a chain extender will be described.

  In this method, first, the adhesive urethane prepolymer and the gas barrier urethane prepolymer are dispersed in water.

  As a method of dispersing the adhesive urethane prepolymer and the gas barrier urethane prepolymer in water, for example, stirring the adhesive urethane prepolymer and the gas barrier urethane prepolymer, gradually adding water to them, While stirring water, a method of gradually adding an adhesive urethane prepolymer and a gas barrier urethane prepolymer to this, while stirring an adhesive urethane prepolymer, gradually a gas barrier urethane prepolymer and Examples thereof include a method of adding water or a method of gradually adding an adhesive urethane prepolymer and water to the gas barrier urethane prepolymer while stirring the gas barrier urethane prepolymer.

  As a result, an aqueous dispersion containing the adhesive urethane prepolymer and the gas barrier urethane prepolymer 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 weight with respect to 100 parts by weight of the total amount of the adhesive urethane prepolymer and the gas barrier urethane prepolymer.

  Next, in this method, a chain extender is blended in an aqueous dispersion containing an adhesive urethane prepolymer and a gas barrier urethane prepolymer to cause a chain extension reaction.

  In the present invention, examples of the chain extender include low molecular weight polyols, low molecular weight polyamines, amino alcohols and the like.

  Examples of the low molecular weight polyol include the low molecular weight polyol described above.

  Low molecular weight 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-amino Methyl-3,5,5-trimethylcyclohexylamine, 4,4'-dicyclohexylmethanediamine, 2,5 (2,6) -bis (aminomethyl) bicyclo [2.2.1] heptane, 1,3- or Alicyclic polyamines such as 1,4-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, Examples thereof include aliphatic polyamines such as triethylenetetramine and tetraethylenepentamine, such as hydrazine (including hydrates), hydrazine and hydrazine derivatives such as succinic dihydrazide and adipic dihydrazide.

  Examples of amino alcohols include N- (2-aminoethyl) ethanolamine and N- (3-aminopropyl) ethanolamine.

  These chain extenders can be used alone or in combination of two or more.

  Preferred chain extenders include low molecular weight polyamines, hydrazines, and amino alcohols.

  In the chain extension reaction, for example, a chain extender is added to an aqueous dispersion of the adhesive urethane prepolymer and the gas barrier urethane prepolymer.

  The blending ratio of the chain extender is, for example, the equivalent ratio (NCO / active hydrogen group) of the isocyanate group of the adhesive urethane prepolymer and the gas barrier urethane prepolymer to the active hydrogen group (hydroxyl group and amino group) of the chain extender. , A ratio of about 1, preferably a ratio of 0.8 to 1.2.

  Specifically, in the chain extension reaction, a chain extender is dropped while stirring an aqueous dispersion containing an adhesive urethane prepolymer and a gas barrier urethane prepolymer. 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.

  Further, this chain extension reaction is carried out by subjecting the adhesive urethane prepolymer and the gas barrier urethane prepolymer and the chain extender to, for example, 5 to 30 ° C., preferably 5 to 5 ° C. under normal pressure and, if necessary, in a nitrogen atmosphere. The reaction is carried out at 25 ° C., for example, for 10 minutes to 5 hours, preferably 30 minutes to 3 hours.

  By setting the reaction conditions in this manner, the reaction between the isocyanate groups of the adhesive urethane prepolymer and the gas barrier urethane prepolymer and water can be suppressed.

  Moreover, after completion | finish of dripping of a chain extender, reaction is completed, for example at normal temperature, stirring further.

  By the above reaction, an aqueous polyurethane resin in which the adhesive urethane prepolymer and the gas barrier urethane prepolymer have reacted with the chain extender (hereinafter referred to as an adhesive-gas barrier resin) can be obtained. And the polyurethane dispersion used as an anchor coating agent in the film for vapor deposition of this invention can be obtained as an aqueous dispersion containing adhesiveness-gas barrier resin.

Next, a method of reacting the adhesive urethane prepolymer and the chain extender, separately reacting the gas barrier urethane prepolymer and the chain extender, and then mixing them will be described.
In this method, first, an aqueous dispersion containing an adhesive urethane prepolymer is prepared.

  The preparation of the aqueous dispersion containing the adhesive urethane prepolymer employs, for example, the same preparation method as the above-described preparation method of the aqueous dispersion containing the adhesive urethane prepolymer and the gas barrier urethane prepolymer.

  Next, in this method, a chain extender is blended in the aqueous dispersion containing the obtained adhesive urethane prepolymer, and a chain extension reaction is performed by the same method as the chain extension reaction described above.

  By the above reaction, an aqueous polyurethane resin (hereinafter referred to as an adhesive resin) in which the adhesive urethane prepolymer and the chain extender have reacted can be obtained.

In this method, an aqueous dispersion containing a gas barrier urethane prepolymer is separately prepared.
The preparation of the aqueous dispersion containing the gas barrier urethane prepolymer employs, for example, the same preparation method as the above-described preparation method of the aqueous dispersion containing the adhesive urethane prepolymer and the gas barrier urethane prepolymer.

  Next, in this method, a chain extender is blended in the aqueous dispersion containing the obtained gas barrier urethane prepolymer, and a chain extension reaction is performed by the same method as the chain extension reaction described above.

  By the above reaction, an aqueous polyurethane resin (hereinafter referred to as a gas barrier resin) in which a gas barrier urethane prepolymer and a chain extender have reacted can be obtained.

  Thereafter, in this method, the aqueous dispersion containing the obtained adhesive resin and the aqueous dispersion containing the gas barrier resin are mixed and stirred. Thereby, the polyurethane dispersion used as an anchor coating agent in the film for vapor deposition of the present invention is obtained as an aqueous dispersion containing an adhesive resin and a gas barrier resin.

  The polyurethane dispersion thus obtained has a solid content of, for example, 5 to 60% by weight, preferably 10 to 50% by weight, 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 weight, preferably 20 to 45% by weight. is there.

  In the synthesis of the adhesive urethane prepolymer and the gas barrier urethane prepolymer, when an organic solvent is used, after completion of the synthesis reaction of the adhesive urethane prepolymer and the gas barrier urethane prepolymer, or chain extension After completion of the reaction, the organic solvent is distilled off by heating at an appropriate temperature, for example, under reduced pressure.

  In addition, the polyurethane dispersion used as the anchor coating agent in the vapor deposition film of the present invention is a water containing an adhesive-gas barrier resin, an adhesive resin, and a gas barrier resin by appropriately combining the two chain elongation reactions described above. It can also be prepared as a dispersion.

  In addition, the polyurethane dispersion used as the anchor coating agent in the vapor deposition film of the present invention is, for example, a plasticizer, an antifoaming agent, a leveling agent, a fungicide, and a rust preventive agent as long as the effects of the present invention are not impaired. , Matting agent, flame retardant, thixotropic agent, tackifier, thickener, lubricant, antistatic agent, surfactant, reaction retarder, antioxidant, UV absorber, hydrolysis inhibitor, weathering stabilizer , Heat stabilizers, dyes, inorganic pigments, organic pigments, extender pigments, curing agents, anti-tacking agents, inorganic particles, water-swelling inorganic layered compounds such as montmorillonite and synthetic mica, and additives such as organic particles are appropriately blended be able to. The mixing ratio of various additives is appropriately selected depending on the purpose and application.

  As described above, if a polyhydroxy compound containing an anionic group is contained as a raw material component of the adhesive urethane prepolymer and / or the gas barrier urethane prepolymer, the aqueous polyurethane resin is converted into an anionic property. Although it can be obtained as an internal emulsification type aqueous polyurethane resin, for example, a polyhydroxy compound containing a nonionic group such as polyoxyethylene glycol is contained as a raw material component, and the aqueous polyurethane resin is converted into a nonionic internal emulsification type aqueous resin. It can also be obtained as a polyurethane resin.

  Furthermore, in the polyurethane dispersion used as an anchor coating agent in the film for vapor deposition of the present invention, as a raw material component, neither a polyhydroxy compound containing an anionic group nor a polyhydroxy compound containing a nonionic group is contained. When the adhesive urethane prepolymer and the gas barrier urethane prepolymer are dispersed in water, the aqueous polyurethane resin can be dispersed in water as an externally emulsified aqueous polyurethane resin by blending and forcibly emulsifying a surfactant.

And the polyurethane dispersion used as an anchor coating agent in the film for vapor deposition of the present invention thus obtained has both adhesiveness (particularly water-resistant adhesiveness) and gas barrier properties. It can be used as an adhesive material such as an agent, a primer, and an anchor coating agent. In particular, it can be used in fields requiring adhesion and gas barrier properties, for example, gas barrier laminate films. Preferably, in a gas barrier laminate film in which a polyester film and an inorganic vapor deposition film are laminated, it can be used as an anchor coating agent for adhering the polyester film and the inorganic vapor deposition film.
The gas barrier laminate film includes, for example, a base film, an anchor coat layer formed on the surface of the base film, and an inorganic vapor deposition film formed on the surface of the anchor coat layer.

  Examples of the method for laminating the anchor coat layer on the base film include a hot melt coating method, an in-line coating method, and an offline coating method. When using the in-line coating method or offline coating method, prepare a coating solution in which the resin or compound constituting the anchor coating layer is dissolved and / or dispersed in water or an organic solvent, and apply the coating solution to the base film. It is preferable to apply.

  In addition, an anchor coating layer may be provided by applying a coating liquid to the base film by an off-line coating method or the like, but when using a polyester film as the base film, at least the polyester film before the orientation crystallization is completed. An in-line coating method in which a coating liquid for forming an anchor coat layer is applied on one side and heat-treated to complete orientation crystallization of the polyester film and the anchor coat layer is formed is preferable in that the anchor coat layer can be formed uniformly. . The in-line coating method can be performed according to a known method. However, the crystal orientation is different in that it prevents ink or vapor deposition film pinholes due to adhesion of dust in the process, or forms a thin anchor coat layer uniformly. A method in which a coating liquid for forming an anchor coat layer is applied onto a polyester film before completion, followed by drying, stretching, and heat treatment to complete oriented crystals of the polyester film, that is, anchor coating in the manufacturing process of a biaxially oriented polyester film An in-line coating method for forming a layer is more preferable. When the anchor coat layer is formed by an in-line coating method, it is preferable to use a water-soluble and / or water-dispersible resin or compound that is advantageous in terms of explosion-proof equipment and environmental pollution. Thereby, water can be used as a solvent for the coating agent, which is preferable.

  Moreover, a water-soluble organic compound, surfactant, etc. may be added to a coating liquid, and if it was manufactured by the conventionally well-known method, it can be used arbitrarily. When the anchor coat layer is formed by the in-line coating method, the adhesion with the metal and / or metal oxide layer, the gloss of the coating film, and the adhesion with the printing ink are excellent.

  The film for vapor deposition of the present invention has an anchor coat layer formed on at least one surface thereof, and the surface free energy of the film on which the anchor coat layer is formed is preferably 45 to 60 mN / m. Also, on the surface where the anchor coat layer is not provided, the film on that surface can be easily applied to the film surface by bonding with other materials as a packaging material, coating such as an adhesive, printing or vapor deposition of a metal compound, etc. The surface free energy of is preferably 45 to 60 mN / m.

  Examples of the method for setting the surface free energy to such a preferable range include a method of performing a surface treatment by corona discharge or the like on the film surface in air or a nitrogen gas atmosphere, a method of performing a surface treatment by a flame, and the like.

  The thickness of the anchor coat layer is not particularly limited, but is usually 0.001 μm or more and 1 μm or less, preferably 0. It is desirable that it is 005 μm or more and 0.3 μm or less, more preferably 0.01 μm or more and 0.1 μm or less, and particularly preferably 0.02 μm or more and 0.07 μm or less. If the anchor coat layer is too thick, the deposited film may be whitened when receiving heat of about 200 ° C. and the gloss may be reduced. If it is too thin, the adhesion between the metal and / or metal oxide layer and the anchor coat layer may be reduced. May be inferior. Moreover, the said thickness range is preferable also from the point of the collection | recovery point which uses a film by rechiping.

  In addition, various additives such as inorganic and organic particles, lubricants, antistatic agents, weathering agents, heat resistance agents, dyes, pigments and the like may be added to the anchor coat layer within a range that does not impair the effects of the present invention. Good.

  Moreover, it is one of the preferable usage aspects that the film for vapor deposition of this invention laminate | stacks the layer which consists of a metal and / or a metal oxide on an anchor coat layer, and uses it as a gas barrier film. Examples of metals or metal oxides include magnesium, calcium, barium, group 4, titanium, zirconium, group 13, aluminum, indium, group 14, silicon, germanium, tin, and oxides thereof, which are group 2 of the periodic table. Can be mentioned. Among these, aluminum, silicon and oxides thereof are particularly preferable. These metals and oxides thereof may be combined to form a layer made of metal and / or metal oxide.

  As a method for laminating the layers made of such metals and / or metal oxides, the layers may be formed by vacuum deposition, EB deposition, sputtering, ion plating, lamination, plasma vapor deposition (CVD), or the like. it can. However, in view of productivity, the vacuum deposition method is the best at present. As the heating means of the vacuum deposition apparatus by the vacuum deposition method, an electron beam heating method, a resistance heating method and an induction heating method are preferable. The thickness of the layer made of metal and / or metal oxide is appropriately selected depending on the type and configuration of the metal and / or metal oxide to be used, but is generally in the range of 2 to 300 nm. More preferably, it is the range of 3-100 nm, More preferably, it is the range of 5-50 nm. If the layer thickness exceeds 300 nm, the flexibility (flexibility) of the vapor-deposited thin film will decrease, and cracks or pinholes may occur in the thin film due to external forces such as bending and pulling after film formation (in post-processing steps, etc.) Gas barrier properties may be significantly impaired. Further, not only the transparency is lowered and the color is deteriorated, but also the productivity is remarkably lowered. On the other hand, when the layer thickness is less than 2 nm, it is difficult to obtain a uniform film with good transparency, the layer thickness may not be sufficient, and the gas barrier function may not be fully exhibited.

  Below, although the manufacturing method of the film for vapor deposition of this invention which used the polyester film for the base film is demonstrated concretely, this invention is not restricted to the following manufacturing methods.

  First, a commercially available polyethylene terephthalate resin can be used as it is as the polyester resin using polyethylene terephthalate used in the polyester film, but it may be produced through a polycondensation reaction as follows.

  To a mixture of 100 parts by weight of dimethyl terephthalate and 70 parts by weight of ethylene glycol, 0.09 parts by weight of magnesium acetate and 0.03 parts by weight of antimony trioxide are added and gradually heated, finally at 220 ° C. Transesterification is performed while distilling methanol to synthesize a polyethylene terephthalate precursor. Next, 0.02 part by weight of an 85% aqueous solution of phosphoric acid is added to the precursor, and the mixture is transferred to a polycondensation reaction kettle. The reaction system is gradually depressurized while being heated and heated in a polycondensation reaction kettle, and a polycondensation reaction is performed at 290 ° C. under a reduced pressure of 1 hPa to obtain a polyethylene terephthalate resin having a desired molecular weight. In addition, when adding particles, it is preferable to add a slurry in which particles are dispersed in ethylene glycol to a polycondensation reaction kettle so as to have a predetermined particle concentration to perform a polycondensation reaction.

  Next, although the manufacturing method of the polyester film which concerns on this invention is demonstrated, it is not limited to this example. The dried polyester resin chip is supplied to an extruder, heated to a temperature equal to or higher than the melting point of the polyester resin, and melted. Next, the molten polyester resin is extruded as a molten sheet from a T-die having slit-like discharge ports, and is tightly solidified on a cooling roll to obtain a cast film (unoriented film (unstretched film)). In order to improve the adhesion between the molten sheet and the cooling roll, it is usually preferable to employ an electrostatic application adhesion method and / or a liquid surface application adhesion method. The cast film is further stretched biaxially.

  First, it is preferably stretched 2.3 to 7 times in the MD direction (film longitudinal direction) with a roll group heated to a glass transition temperature of the polyester resin or higher, for example, 40 to 130 ° C., and a uniaxially oriented film (uniaxially stretched film) is obtained. obtain.

  Next, a coating liquid for forming an anchor coat layer is applied to at least one surface of the uniaxially oriented film.

  Next, the film is stretched 3 to 7 times at 45 to 130 ° C. in the TD direction (film width direction). In addition, although the method of extending | stretching one direction in two steps or more can be used, it is preferable that the final draw ratio also falls in the said range also in that case. The cast film can be simultaneously biaxially stretched so that the area magnification is 6 to 30 times. Here, the area ratio means a value obtained by multiplying the MD stretch ratio by the TD stretch ratio. In this case, the application of the coating liquid for forming the anchor coat layer is preferably performed before simultaneous biaxial stretching (that is, applied to a cast film).

  Thereby, the polyester film for vapor deposition of this invention is obtained. Further, the film thus obtained may be subsequently heat-treated in-line and / or offline. Furthermore, you may extend | stretch in MD and / or TD direction again before or after performing heat processing as needed. The heat treatment temperature is 150 to 250 ° C., preferably 200 to 240 ° C., and the heat treatment time is usually 1 second to 5 minutes. The heat shrinkage characteristics can be adjusted under these heat treatment conditions. In addition, the cooling rate of the film after heat treatment also affects the heat shrink characteristics. For example, after the heat treatment, the heat shrinkage stress can be adjusted by providing the film with rapid cooling or slow cooling, or by providing an intermediate cooling zone. Further, in particular, in order to impart specific heat shrinkage characteristics, relaxation may be performed in the MD direction and / or TD direction during the heat treatment or in the subsequent slow cooling zone.

  And the gas barrier film of this invention can be obtained by vapor-depositing aluminum oxide etc. on the anchor coat layer of this vapor deposition film.

  Hereinafter, the present invention will be described in detail by way of examples. The characteristics were measured and evaluated by the following methods.

(1) Oxygen transmission rate Oxygen transmission rate of gas barrier film under the conditions of a temperature of 23 ° C. and a humidity of 0% RH, an oxygen transmission rate measuring device (model name, “Oxytolan” (registered trademark) manufactured by MOCON, USA ("OXTRAN" 2/20)) and measured based on the method B (isobaric method) described in JIS K7126 (2000 version). Moreover, the measurement was performed twice and the average value of the two measured values was used as the value of oxygen permeability in each of the examples and the comparative examples. About each Example and the comparative example, the result of having performed with two test pieces was made into the value of oxygen permeability.

(2) Water vapor transmission rate The water vapor transmission rate of the gas barrier film under the conditions of a temperature of 40 ° C. and a humidity of 90% RH is a water vapor transmission rate measuring device (model name, “Permatran”, registered by MOCON, USA) (Trademark) W3 / 31) and measured based on the method B (infrared sensor method) described in JIS K7129 (2000 edition). Moreover, the measurement was performed twice and the average value of the two measured values was used as the value of the water vapor transmission rate in each example and comparative example. About each Example and the comparative example, the result performed with two test pieces was made into the value of the water-vapor-permeation rate.

(3) Measure the mass of 10 rectangular deposition films cut into a film thickness of 300 × 200 mm, and set the specific gravity of the film to 1.4 × 10 −3 (g / mm 3) according to the following formula: The film thickness was determined as the mass average thickness.
T = W / (1.4 × 10−3 × 300 × 200 × 10)
However, T: Film thickness (mm), W: Mass of 10 films (g).

(4) Aluminum oxide was vapor-deposited on the anchor coat layer side of the adhesion vapor deposition film by a continuous vacuum vapor deposition machine so that the vapor deposition layer thickness was 15 nm to obtain a gas barrier film. An unstretched polypropylene film (CPP) using a polyurethane adhesive (AD503 / CAT-10 = 20 parts by weight / 1 part by weight, solvent: ethyl acetate 20 parts by weight, manufactured by Toyo Morton Co., Ltd.) on the vapor deposition layer side of the gas barrier film. ) (Toray Synthetic Film Co., Ltd. T3501, 50 μm) pasted together, left standing at 40 ° C. for 48 hours, cut into strips of length 150 mm × width 15 mm, and the gas barrier film and CPP were folded at 90 ° The CPP and the gas barrier film are gripped so that a dry 90 ° peel test is performed using an Instron type tensile tester (Tensilon UCT-100 manufactured by Orientec Co., Ltd.) at 25 ° C. in an atmosphere of 50% RH. The peel strength was measured by pulling in the direction of the arrow in FIG. 1 at a speed of 300 mm / min. The average value of the strength between the measurement length of 50 mm and 100 mm was defined as the adhesion force.

(5) Aluminum oxide was vapor-deposited with a continuous vacuum vapor deposition machine on the anchor coat layer side of the water-resistant adhesion vapor deposition film so as to have a vapor deposition layer thickness of 15 nm to obtain a gas barrier film. An unstretched polypropylene film (CPP) using a polyurethane adhesive (AD503 / CAT-10 = 20 parts by weight / 1 part by weight, solvent: ethyl acetate 20 parts by weight, manufactured by Toyo Morton Co., Ltd.) on the vapor deposition layer side of the gas barrier film. ) (Toray Synthetic Film Co., Ltd. T3501, 50 μm) pasted together, left standing at 40 ° C. for 48 hours, cut into strips of length 150 mm × width 15 mm, and the gas barrier film and CPP were folded at 90 ° CPP and gas barrier film are gripped so that the release port is wetted with water droplets, and a wet 90 ° peel test is performed at 25 ° C. using an Instron type tensile tester (Tensilon UCT-100 manufactured by Orientec Co., Ltd.). Pulling in the direction of the arrow in FIG. 1 at a peeling rate of 300 mm / min in an atmosphere of% RH, the peel strength is measured. Was Tsu. The average value of the strength between the measurement lengths of 50 mm and 100 mm was defined as the water-resistant adhesion.

[Manufacture of anchor coating agent]
(1) Synthesis of adhesive urethane prepolymer (Synthesis Example 1)
In a four-necked flask equipped with a stirrer, thermometer, reflux tube, and nitrogen introduction tube, 190.7 parts by weight of ester A, 3.4 parts by weight of diethylene glycol, 21.3 parts by weight of dimethylolpropionic acid, 175.0 parts by weight of methyl ethyl ketone Parts were charged and mixed.
Next, 93.4 parts by weight of 4,4′-dicyclohexylmethane diisocyanate and 0.04 parts by weight of stanocto were added to a four-necked flask and reacted at 75 ° C. for 6 hours to obtain an isocyanate group-terminated urethane prepolymer (containing NCO groups). Rate 1.77% by weight).
Then, the reaction liquid of the obtained urethane prepolymer was cooled to 30 ° C. and neutralized by adding 16.1 parts by weight of triethylamine to obtain an adhesive urethane prepolymer.

(Synthesis Examples 2 to 5)
Except having made it react by the mixing | blending prescription shown in Table 1, the adhesive urethane prepolymer of the synthesis examples 2-5 was prepared by the method similar to the synthesis example 1. However, the reaction was performed at a reaction temperature of 75 ° C. for Synthesis Example 2, at a reaction temperature of 70 ° C. for Synthesis Example 3, at a reaction temperature of 70 ° C. for Synthesis Example 4, and at a reaction temperature of 70 ° C. for Synthesis Example 5.
Table 1 shows the formulation of Synthesis Examples 1-5.

(2) Preparation of gas barrier urethane prepolymer (Synthesis Example 6)
A four-necked flask equipped with a stirrer, thermometer, reflux tube, and nitrogen introduction tube was charged with 46.7 parts by weight of ethylene glycol, 20.7 parts by weight of dimethylolpropionic acid, and 175.0 parts by weight of methyl ethyl ketone and mixed. .
Next, 159.6 parts by weight of 1,3-xylylene diisocyanate and 82.3 parts by weight of 1,3-bis (isocyanatomethyl) cyclohexane were added to a four-necked flask and reacted at 70 ° C. for 6 hours. A base terminal urethane prepolymer (NCO group content: 6.3 wt%) was obtained.
Then, the reaction liquid of the obtained urethane prepolymer was cooled to 30 ° C. and neutralized by adding 15.6 parts by weight of triethylamine to obtain a gas barrier urethane prepolymer.

(Synthesis Example 7)
A gas barrier urethane prepolymer of Synthesis Example 7 was prepared in the same manner as in Synthesis Example 6 except that the reaction was carried out according to the formulation shown in Table 1. However, the reaction temperature was 65 ° C.
The formulation of Synthesis Examples 6 and 7 is shown in Table 1.

The abbreviations and product names in Table 1 are shown below.
H12MDI: 4,4′-dicyclohexylmethane diisocyanate H6XDI: 1,3-bis (isocyanatomethyl) cyclohexane (hydrogenated xylylene diisocyanate)
IPDI: 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate)
XDI: 1,3-xylylene diisocyanate ester A: polyester polyol ((terephthalic acid / isophthalic acid / adipic acid = 1/1/1 (molar ratio)) / (ethylene glycol / neopentyl glycol = 1/1 (molar ratio) )), Number average molecular weight: 3000)
Ester B: Polyester polyol ((isophthalic acid / sebacic acid = 1/1 (molar ratio)) / (ethylene glycol / neopentyl glycol = 1/3 (molar ratio)), number average molecular weight 2500)
Ester C: Polyester polyol (adipic acid / (neopentyl glycol / 1,6-hexanediol = 2/1 (molar ratio)), number average molecular weight 2000)
PTG2000: polytetramethylene ether glycol (number average molecular weight: 2000)
PC2000: Polycarbonate glycol (number average molecular weight: 2000)
EG: ethylene glycol DEG: diethylene glycol NPG: neopentyl glycol DMPA: dimethylolpropionic acid TEA: triethylamine MET: methyl ethyl ketone stannocto: stannous octylate In Table 1, the NCO group content conforms to JISK1556 (2006) And measured.

(3) Preparation of polyurethane dispersion (Preparation Example 1) (Aqueous dispersion of gas barrier resin)
415.6 parts by weight of the gas barrier urethane prepolymer obtained in Synthesis Example 6 was mixed with 700 parts by weight of ion-exchanged water, and the mixture was stirred for 5 minutes with a homodisper (manufactured by Primics) and dispersed in water.
Next, 29.9 parts by weight of N- (2-aminoethyl) ethanolamine was added to carry out a chain extension reaction. Thereafter, methyl ethyl ketone was distilled off, and an aqueous dispersion of gas barrier resin (pH 8.2, solid content 30). Polyurethane dispersion was prepared at a weight percent, an average particle diameter of 65 nm, a urethane / urea group concentration of 40.8 wt%, and a resin acid value of 24.0 mgKOH / g).

(Preparation Example 2) (Aqueous dispersion of adhesive resin)
447.7 parts by weight of the adhesive urethane prepolymer obtained in Synthesis Example 1 was mixed with 700 parts by weight of ion-exchanged water, and the mixture was stirred for 5 minutes with a homodisper and dispersed in water.
Subsequently, 9.0 parts by weight of N- (2-aminoethyl) ethanolamine was added to carry out a chain elongation reaction. Thereafter, methyl ethyl ketone was distilled off, and an aqueous dispersion of adhesive resin (pH 7.8, solid content 30). Polyurethane dispersion was prepared at a weight percent, an average particle size of 30 nm, a urethane / urea group concentration of 12.3% by weight, and a resin acid value of 26.6 mgKOH / g).
In addition, the solid content of the polyurethane dispersion obtained by Preparation Example 2 contained 56.9% by weight of the polyester component.

(Preparation Example 3) (Adhesion—Aqueous dispersion of gas barrier resin)
149.2 parts by weight of the adhesive urethane prepolymer obtained in Synthesis Example 1 and 277.0 parts by weight of the gas barrier urethane prepolymer obtained in Synthesis Example 6 were blended with 700 parts by weight of ion-exchanged water. The mixture was stirred with a disper for 5 minutes and dispersed in water.
Subsequently, 22.9 parts by weight of N- (2-aminoethyl) ethanolamine was added to carry out a chain extension reaction. Thereafter, methyl ethyl ketone was distilled off, and an aqueous dispersion of an adhesive-gas barrier resin (pH 7.8, A polyurethane dispersion was prepared with a solid content of 30% by weight, an average particle size of 80 nm, a urethane / urea group concentration of 31.3% by weight, and a resin acid value of 24.9 mgKOH / g.
The solid content of the polyurethane dispersion obtained in Preparation Example 3 contained 19.0% by weight of the polyester component.

(Preparation Examples 4 to 7) (Adhesiveness—Aqueous dispersion of gas barrier resin)
Except having made it react by the mixing | blending prescription shown in Table 2, the polyurethane dispersion of the preparation examples 4-7 was prepared by the method similar to the preparation example 3. FIG.
Table 2 shows the formulation of Preparation Examples 1-7.

[Production of polyester]
A polyester resin as a thermoplastic resin constituting the base film was prepared as follows.

(1) To a mixture of 100 parts by weight of polyester resin dimethyl terephthalate and 61 parts by weight of ethylene glycol, 0.04 parts by weight of magnesium acetate and 0.02 parts by weight of antimony trioxide are added, and the temperature is gradually raised. Finally, transesterification is carried out while distilling methanol at 220 ° C. Next, 0.020 part by weight of an 85% aqueous solution of phosphoric acid is added to the transesterification reaction product, and then transferred to a polycondensation reaction kettle. Further, the reaction system was gradually depressurized while being heated, and a polycondensation reaction was performed at 290 ° C. under a reduced pressure of 1 hPa by a conventional method. The amount of diethylene glycol was 1.2% by weight and the intrinsic viscosity was 0.65. A polyethylene terephthalate resin (hereinafter sometimes referred to as “PET”) in which 95 mol% or more of the component is made of terephthalic acid and 95 mol% or more of the glycol component is made of ethylene glycol was prepared.

(2) Particle master When producing the polyester of (1) above, an ethylene glycol slurry of agglomerated silica particles having an average particle size of 2.4 μm is added after the transesterification reaction, and then a polycondensation reaction is carried out to obtain a particle concentration of 2 mass% A particle master was obtained.

  Next, the present invention will be described based on examples, but is not necessarily limited thereto.

Example 1
Polyethylene terephthalate resin and particle master were mixed at a mass ratio of 98: 2.
The mixture of polyethylene terephthalate resin and particle master is vacuum dried, then supplied to an extruder, melt extruded at 280 ° C., filtered through an 8 μm cut stainless steel fiber sintered filter (FSS), and then sheet-shaped from a T-shaped die. This was cooled and solidified on a cooling drum having a surface temperature of 25 ° C. by an electrostatic contact method. The unstretched (unoriented) PET film thus obtained was heated to 105 ° C. for 2 seconds and then stretched 4.1 times at 115 ° C. in the MD direction to obtain a uniaxially oriented film. In order to form an anchor coat layer on one side of the uniaxially oriented film, corona discharge treatment was performed in air. Next, the polyurethane dispersions of Preparation Example 1 and Preparation Example 2 shown in Table 2 were prepared so that the weight ratio of the solid content of the polyurethane dispersion of Preparation Example 1 to the solid content of the polyurethane dispersion of Preparation Example 2 was 3. Next, it was blended in ion-exchanged water so that the solid content of the aqueous polyurethane resin was 5% by weight to prepare an anchor coating agent. The adjusted coating liquid was applied to the discharge treatment surface side with a rod coater. The coating thickness was set to 0.05 μm after completion of the oriented crystal of the polyester film, that is, after the heat treatment.

  This uniaxially oriented film was preheated at 105 ° C. for 2 seconds and then stretched 3.1 times in the TD direction while being heated to 115 ° C. This film was introduced into hot air at 233 ° C., heat-treated for 2 seconds without relaxing in the MD direction and TD direction, and then relaxed at 170 ° C. to 2.4% of the film width after TD stretching in the width direction. And cooled. After finally cooling to room temperature, the surface opposite to the anchor coat layer was subjected to a corona discharge treatment with a treatment strength of 20 W · min / m 2, and this was guided to a winder and wound up to obtain a mill roll. In this way, a film for vapor deposition having a thickness of 12 μm and finally having an anchor coat layer having a thickness of 0.05 μm was obtained.

  Next, aluminum oxide was vapor-deposited with a vapor deposition layer thickness of 15 nm on the anchor coat layer side of the polyester film by a continuous vacuum vapor deposition machine to obtain a gas barrier film PES1. The characteristics are shown in Table 3.

(Examples 2-6, Comparative Examples 1-2)
Except that the anchor coating agent was prepared according to the formulation shown in Table 3, the same conditions as in Example 1 were used, and vapor deposition films and gas barrier films PES2 to 8 were obtained. The characteristics are shown in Table 3.

  Table 3 shows the compounding formulations of the anchor coating agents of Examples 1 to 6 and Comparative Examples 1 and 2.

  From Table 3, each gas barrier film of an Example was excellent in gas barrier property and water-resistant adhesion. On the other hand, each gas barrier film of the comparative example is excellent in gas barrier properties but inferior in water-resistant adhesion, or inferior in water-resistant adhesion, but inadequate as a packaging material such as inferior in water barrier adhesion but poor in gas barrier properties. there were.

  The film for vapor deposition of the present invention is not only excellent in adhesion to the vapor deposition layer, but also excellent in gas barrier properties after vapor deposition, so that it is suitable for packaging applications or industrial material applications that require very high gas barrier properties. Can also be suitably used.

1: CPP film 2: Polyurethane adhesive 3: Gas barrier film

Claims (9)

A film for vapor deposition formed by forming an anchor coat layer using a urethane resin on at least one surface of a film made of a thermoplastic resin, wherein the polyurethane resin is reacted with an isocyanate group-terminated urethane prepolymer and a chain extender. resulting aqueous polyurethane resin is a polyurethane dispersion comprising a water-dispersible, the isocyanate group-terminated urethane prepolymer, seen containing an adhesion urethane prepolymer, and a gas-barrier urethane prepolymer, the adhesion urethane prepolymer For vapor deposition characterized in that it is obtained by a reaction between an adhesive polyisocyanate component and an adhesive polyol component, and a gas barrier urethane prepolymer is obtained by a reaction between a gas barrier polyisocyanate component and a gas barrier polyol component . F Lum.
(In the present invention, the adhesive polyisocyanate component represents a polyisocyanate component containing any of aromatic polyisocyanate, araliphatic polyisocyanate, alicyclic polyisocyanate, and aliphatic polyisocyanate,
The adhesion polyol component is a polyol component containing any of polyhydroxyalkanoic acid, polyester polyol, polyether polyol, polycarbonate polyol, polyurethane polyol, acrylic polyol, epoxy polyol, natural oil polyol, silicone polyol, fluorine polyol, and polyolefin polyol. Represents
The gas barrier polyisocyanate component represents a polyisocyanate component containing 1,3- or 1,4-xylylene diisocyanate or a mixture thereof and / or hydrogenated xylylene diisocyanate,
The gas barrier polyol component represents a polyol component containing an alkane polyol having 2 to 6 carbon atoms and / or a polyoxyalkylene glycol having 2 to 6 carbon atoms and polyhydroxyalkanoic acid. ) The water-based polyurethane resin contains an adhesive-gas barrier resin obtained by a reaction of the mixture of the adhesive urethane prepolymer and the gas barrier urethane prepolymer with a chain extender, according to claim 1. The film for vapor deposition as described. The water-based polyurethane resin is an adhesive resin obtained by a reaction between the adhesive urethane prepolymer and the chain extender, and a gas barrier property obtained by a reaction between the gas barrier urethane prepolymer and the chain extender. The film for vapor deposition according to claim 1, comprising a resin. The said adhesive polyol component contains polyester polyol, The film for vapor deposition in any one of Claims 1-3 characterized by the above-mentioned. The said polyester polyol has a ring structure in a molecule | numerator, The film for vapor deposition in any one of Claims 1-4 characterized by the above-mentioned. The polyester polyol is obtained by a reaction between a polybasic acid and a polyhydric alcohol, and the polybasic acid contains terephthalic acid and / or isophthalic acid and / or orthophthalic acid. The film for vapor deposition in any one of 5. Wherein the thermoplastic resin is a polyester resin, vapor deposition film according to any one of claims 1-6. Gas barrier film that is characterized in that laminated layers of metal and / or metal oxide on the anchor coat layer of the deposition film according to any one of claims 1-7. A film for vapor deposition formed by forming an anchor coat layer using a urethane resin on at least one surface of a film made of a thermoplastic resin, wherein the polyurethane resin is reacted with an isocyanate group-terminated urethane prepolymer and a chain extender. A polyurethane dispersion obtained by water-dispersing the obtained aqueous polyurethane resin, wherein the isocyanate group-terminated urethane prepolymer includes an adhesive urethane prepolymer and a gas barrier urethane prepolymer, It is obtained by a reaction between an adhesive polyisocyanate component and an adhesive polyol component, and a gas barrier urethane prepolymer is obtained by a reaction between a gas barrier polyisocyanate component and a gas barrier polyol component. Manufacturing method of Lum.
(In the present invention, the adhesive polyisocyanate component represents a polyisocyanate component containing any of aromatic polyisocyanate, araliphatic polyisocyanate, alicyclic polyisocyanate, and aliphatic polyisocyanate,
The adhesion polyol component is a polyol component containing any of polyhydroxyalkanoic acid, polyester polyol, polyether polyol, polycarbonate polyol, polyurethane polyol, acrylic polyol, epoxy polyol, natural oil polyol, silicone polyol, fluorine polyol, and polyolefin polyol. Represents
The gas barrier polyisocyanate component represents a polyisocyanate component containing 1,3- or 1,4-xylylene diisocyanate or a mixture thereof and / or hydrogenated xylylene diisocyanate,
The gas barrier polyol component represents a polyol component containing an alkane polyol having 2 to 6 carbon atoms and / or a polyoxyalkylene glycol having 2 to 6 carbon atoms and polyhydroxyalkanoic acid. )

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