JP2002301787A - Method for manufacturing vapor-deposited plastic film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a vapor-deposited plastic film excellent in the adhesiveness of a base material film and a vapor deposition layer and gas barrier properties after boiling treatment or printing. SOLUTION: The vapor-deposited plastic film is manufactured by coating at least one surface of a plastic film with a resin mixture containing an oxazoline group-containing water soluble polymer and subsequently stretching the coating film at least in one direction and further vapor-depositing a metal and/or a metal oxide on the surface of the formed coating layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a vapor-deposited plastic film (hereinafter sometimes referred to as "vapor-deposited film"), and more particularly, to a vapor-deposited plastic film formed by forming a thin film of metal or metal oxide. And a method for producing a vapor-deposited film having excellent adhesion and gas barrier properties after boil treatment.

[0002]

2. Description of the Related Art Deposition films are made of metal to be deposited and / or
Alternatively, by selecting a metal oxide, properties such as gas barrier properties, moisture impermeability, shielding property of visible / ultraviolet light, heat ray reflectivity, conductivity, transparent conductivity, and magnetic recording property can be variously changed. Therefore, it is used for various purposes. For example, it is used as a packaging material, a decoration material, a window glass blocking material, a gold / silver thread material, a capacitor material, a display material, a wiring board material, a magnetic recording material, and the like. Furthermore, in recent years, new applications such as a part of a transparent conductive sheet used for a liquid crystal display element, a solar cell, an electromagnetic wave shield, a touch panel, a substrate for an EL, a color filter, and the like have been attracting attention.

[0003] However, the vapor-deposited film has a problem in that the vapor-deposited film is partially peeled off during the processing step of the film or when it comes into contact with moisture, thereby deteriorating the characteristics of the vapor-deposited film, for example, gas barrier properties. is there.

Conventionally, in order to prevent the gas barrier property from being lowered, a coating layer (undercoat) made of various polyurethanes, various polyesters, or a mixture of polyurethane and polyester is provided between the base polyester film of the vapor-deposited polyester film and the vapor-deposited layer. Layer) is known (for example, JP-A-2-50837). Further, in order to improve water resistance and solvent resistance, a coating solution containing a special polyurethane, polyester and epoxy compound has been proposed (JP-A-4-176858).

However, many of the above-mentioned vapor-deposited films have insufficient water resistance (hot water resistance) and solvent resistance at high temperatures. For example, a vapor-deposited polyester film most likely to be used most commonly is used for food packaging. In this case, the gas barrier properties after the boil treatment or after printing with the solvent-based ink are not always sufficient. In particular, a vapor-deposited polyester film made of recycled polyester film waste has a disadvantage that the gas barrier properties are significantly reduced. Further, as the application of the vapor-deposited polyester film has been expanded, a vapor-deposited polyester film having stronger adhesiveness and highly reliable gas barrier properties has been demanded.

[0006] Further, the coating layer formed by the anchor coating agent is
It may be provided after film formation, but an in-line coating method provided in the film formation step is also possible. For example,
In the case where the film is a biaxially stretched film, a method of applying an anchor coating agent to a uniaxially stretched film, stretching the film in a dry or undried state in the horizontal direction, and then performing a heat treatment,
Since film formation, coating and drying can be performed simultaneously, a great advantage can be expected in terms of manufacturing cost. However, a suitable base film for vapor deposition provided with a coating layer by this in-line coating method is not known,
The vapor-deposited film obtained from the base film has insufficient solvent resistance and hot water resistance more than the vapor-deposited film obtained by a usual method, and has a gas barrier property after printing or after hot water treatment such as boil and retort. Is significantly reduced.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has as its object to improve the adhesiveness between a base film and a vapor deposited layer and the gas barrier properties after boil processing and printing. To provide a method for manufacturing a vapor-deposited film.

[0008]

The inventors of the present invention have conducted various studies to achieve the above object, and as a result, have used a coating solution containing a specific resin and adopted a specific coating method. As a result, it has been found that a vapor-deposited film having excellent characteristics can be obtained, and the present invention has been completed.

That is, the gist of the present invention resides in that at least one surface of a plastic film is coated with a resin mixture containing 6 to 80% by weight of an oxazoline group-containing water-soluble polymer, and then stretched in at least one direction. The present invention resides in a method for producing a vapor-deposited plastic film, which comprises vapor-depositing a metal and / or a metal oxide on the surface of a formed coating layer.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The raw material (plastic raw material) of the plastic film in the present invention is not particularly limited as long as it is a plastic raw material used as a film. Specific examples include polyolefins such as homopolymers or copolymers such as ethylene, propylene and butene; amorphous polyolefins such as cyclic polyolefins; polyester resins such as polyethylene terephthalate and polyethylene-2,6-naphthalate; , Nylon 12, polyamide such as copolymer nylon, polyvinyl alcohol, ethylene-vinyl acetate copolymer partial hydrolyzate (EVOH), polyimide,
Polyetherimide, polysulfone, polyethersulfone, polyetheretherketone, polycarbonate (PC), polyvinylbutyral, polyarylate, ethylene-tetrafluoroethylene copolymer, ethylene trifluoride chloride, ethylene tetrafluoride-perfluoro Resin composition consisting of alkyl vinyl ether copolymer, polyvinylidene fluoride, polyvinyl fluoride, fluorinated resin such as perfluoroethylene-perfluoropropylene-perfluorovinyl ether terpolymer, and acrylate compound having radically reactive unsaturated compound Product, a resin composition comprising this acrylate compound and a mercapto compound having a thiol group, epoxy acrylate, urethane acrylate,
Examples include a photocurable resin such as a resin composition obtained by melting an oligomer such as polyester acrylate and polyether acrylate into a polyfunctional acrylate monomer, and a mixture thereof. Among them, polyester, polypropylene, polyamide, polyvinyl alcohol and ethylene-vinyl acetate copolymer partial hydrolyzate are preferable, and polyester is particularly preferable.

The polyester particularly preferable as a plastic raw material in the present invention is a polyethylene in which at least 80 mol% of its constituent units are ethylene terephthalate, and a polyethylene whose at least 80 mol% of its constituent units is ethylene naphthalate. Naphthalate, a poly-1,4-polysiloxane in which at least 80 mol% of its constituent units is 1,4-cyclohexane dimethylene terephthalate
And cyclohexane dimethylene terephthalate.

Examples of the copolymerization components other than the above-mentioned components include diol components such as diethylene glycol, propylene glycol, neopentyl glycol, polyethylene glycol and polytetramethylene glycol, isophthalic acid, and 2,6-naphthalenedicarboxylic acid. , 5-sodium sulfoisophthalic acid, adipic acid, azelaic acid, a dicarboxylic acid component of sebacic acid and its ester-forming derivative, and oxymonocarboxylic acid of oxybenzoic acid and its ester-forming derivative.

The plastic film according to the present invention comprises:
Depending on the use, additional particles forming the projections on the film surface, precipitated particles, and other catalyst residues may be contained in an amount commonly used by those skilled in the art. Further, as an additive other than the above-mentioned projection forming agent, as necessary, an antistatic agent, a stabilizer,
It may contain a lubricant, a cross-linking agent, an anti-blocking agent, an antioxidant, a coloring agent, a light-blocking agent, an ultraviolet absorber and the like.

The plastic raw material in the present invention is not particularly limited even if it is a recycled raw material. For example, recycled polyester processed into a chip shape of scrap film generated in the process of manufacturing a polyester film product may be used from the viewpoint of resource saving. . The proportion of such recycled polyester used is
Although not particularly limited, the ratio in the raw material polyester is preferably in the range of 10 to 100% by weight.

The resin mixture (coating solution) used for forming the coating layer in the present invention must contain 6 to 80% by weight of the oxazoline group-containing water-soluble polymer. Specific examples of the coating liquid include a resin mixture containing 10 to 80% by weight of an oxazoline group-containing water-soluble polymer, 10 to 80% by weight of an aqueous acrylic resin, and 10 to 70% by weight of an aqueous polyurethane resin. Is exemplified.

The above oxazoline group-containing water-soluble polymer is defined as any one of the addition-polymerizable oxazolines (a) represented by the following general formulas (I) to (III) and, if necessary, at least one other type of oxazoline. It is a polymer obtained by polymerizing the monomer (b).

[0017]

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The above-mentioned polymer is used by dissolving it in a mixed solvent of water and a water-soluble organic solvent. Since it does not usually contain an emulsifier, the effects of water resistance and solvent resistance due to crosslinking of oxazoline groups are sufficient. Can be demonstrated.

In the above formula, R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group,
It is an aralkyl group, a phenyl group or a substituted phenyl group, and R5 is a noncyclic organic group having an addition-polymerizable unsaturated bond.

The above-mentioned halogen atom usually includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, but is preferably a chlorine atom or a bromine atom.
Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group,
Examples thereof include an isobutyl group, a pentyl group, and a hexyl group. Examples of the aralkyl group include an aralkyl group having 1 to 5 carbon atoms in the alkyl chain, such as a benzyl group, a phenethyl group, a benzhydryl group, and a naphthylmethyl group. Examples of the substituted phenyl group include a chlorophenyl group, a bromophenyl group, a methoxyphenyl group, an ethoxyphenyl group, a methylaminophenyl group, an ethylaminophenyl group, a dimethylaminophenyl group, a methylethylaminophenyl group, a diethylaminophenyl group, and the like. Is mentioned. Examples of the acyclic organic group having an addition-polymerizable unsaturated bond include a vinyl group and an isopropenyl group.

Examples of the above addition-polymerizable oxazoline (a) include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, and 2-vinyl-5.
-Methyl-2-oxazoline, 2-isopropenyl-2
-Oxazoline, 2-isopropenyl-4-methyl-2
-Oxazoline, 2-isopropenyl-5-ethyl-2
-Oxazoline and the like, and these may be used in combination of two or more. In particular, 2-isopropenyl-2-oxazoline is easily available industrially and is preferably used.

The monomer (b) is not limited as long as it is a monomer copolymerizable with the addition-polymerizable oxazoline (a). Examples of the monomer (b) include methyl methacrylate, butyl methacrylate, and 2-ethylhexyl methacrylate. Methacrylic esters, methacrylic acid, itaconic acid, unsaturated carboxylic acids such as maleic acid, unsaturated nitriles such as methacrylonitrile, methacrylamide, unsaturated amides such as N-methylolated methacrylamide, vinyl acetate,
Vinyl esters such as vinyl propionate, vinyl ethers such as methyl vinyl ether and ethyl vinyl ether, α-olefins such as ethylene and propylene, and halogen-containing α and β-unsaturated monomers such as vinyl chloride, vinylidene chloride and vinyl fluoride , Styrene, α, β-unsaturated aromatic monomers such as α-methylstyrene and the like,
These may be used in combination of two or more.

Examples of the polymerization method of the oxazoline group-containing water-soluble polymer include, for example, the above-mentioned addition-polymerizable oxazoline (a) and, if necessary, at least one of the above-mentioned monomers (b), benzoyl peroxide, azobisisobutyrate and the like. A method in which a polymerization initiator such as lonitrile and the like are dissolved in a water-soluble organic solvent and heated. The water-soluble paint of the oxazoline group-containing polymer can be obtained by adding water to the obtained polymer solution and subjecting it to heat distillation to remove a part or all of the solvent. Further, the above-mentioned method of polymerizing a water-soluble polymer may be an anionic polymerization method using n-butyllithium or the like as a catalyst.

As described above, the ratio of the oxazoline group-containing water-soluble polymer in the coating solution is 6 to 80% by weight.
It is preferably from 10 to 80% by weight, particularly preferably from 15 to 6%.
0% by weight. When the blending ratio of the oxazoline group-containing water-soluble polymer is less than 6% by weight, crosslinking with the oxazoline group is insufficient, and when it exceeds 80% by weight, the hot water resistance and solvent resistance of the coating layer are insufficient. In addition, the oxazoline group content in the oxazoline group-containing water-soluble polymer is usually 0.4 to 5.0 mmol / g, particularly 0.5 to 5.0 mmol / g.
4.0 mmol / g, and the amount of the oxazoline group-containing water-soluble polymer in the coating solution is usually 10 to 80 mmol / g.
%, But the oxazoline group content is 8 to 9 m
If the water-soluble polymer increased to about mol / g can be prepared, the ratio of the oxazoline group-containing water-soluble polymer can be reduced to about 6% by weight.

The above-mentioned aqueous acrylic resin is a resin containing alkyl acrylate and / or alkyl methacrylate as a main component. Specifically, the content of the alkyl acrylate and / or alkyl methacrylate component is usually 40 to 95 mol. %, The content of the copolymerizable vinyl monomer component having a functional group is usually 5 to 60 mol%.
Is a water-soluble or water-dispersible resin.

The functional group in the above vinyl monomer includes, for example, a carboxyl group, an acid anhydride group, a sulfonic acid group or a salt thereof, an amide group or an alkylated amide group, and an amino group (substituted amino group). ), An alkylolated amino group or a salt thereof, a hydroxyl group, an epoxy group and the like, and particularly preferably a carboxyl group, an acid anhydride group and an epoxy group. Two or more of these groups may be contained in the resin.

When the content of the alkyl acrylate and / or the alkyl methacrylate in the aqueous acrylic resin is 40 mol% or more, the coatability, the strength of the coating film and the blocking resistance are particularly improved. The content of the alkyl acrylate and / or the alkyl methacrylate is 95 mol% or less, and the compound having a specific functional group as a copolymer component is added to the aqueous acrylic resin in an amount of 5 mol%.
By the introduction as described above, water-solubilization or water-dispersion can be facilitated and the state can be stabilized for a long time. As a result, the adhesion between the coating layer and the polyester film layer can be improved, and the strength, water resistance and chemical resistance of the coating layer due to the reaction in the coating layer can be improved.

Examples of the alkyl group of the above-mentioned alkyl acrylate and alkyl methacrylate include a methyl group, an n-propyl group, an isopropyl group, an n-butyl group,
Examples include an isobutyl group, a 2-ethylhexyl group, a lauryl group, a stearyl group, and a cyclohexyl group. Examples of the compound having a carboxyl group or an acid anhydride include, for example, acrylic acid, methacrylic acid, itaconic acid, maleic acid, and the like, alkali metal salts thereof, alkaline earth metal salts, ammonium salts, and the like. And maleic acid. Examples of the compound having a sulfonic acid group or a salt thereof include vinyl sulfonic acid, styrene sulfonic acid, metal salts of these sulfonic acids such as sodium, and ammonium salts.

Examples of the compound having an amide group or an alkylolated amide group include acrylamide, methacrylamide, N-methylmethacrylamide, methylolated acrylamide, methylolated methacrylamide, ureido vinyl ether, and β-ureidoisobutyl. Vinyl ether, ureidoethyl acrylate and the like.

Examples of the compound having an amino group or an alkylolated amino group or a salt thereof include, for example, diethylaminoethyl vinyl ether, 2-aminoethyl vinyl ether, 3-aminopropyl vinyl ether, 2-aminobutyl vinyl ether, dimethyl Aminoethyl methacrylate, dimethylaminoethyl vinyl ether, those amino groups of which are methylolated,
Examples thereof include those quaternized with an alkyl halide, dimethyl sulfate, sultone and the like.

Examples of the compound having a hydroxyl group include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate,
Examples include β-hydroxyvinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monoacrylate, and polypropylene glycol monomethacrylate. Examples of the compound having an epoxy group include glycidyl acrylate and glycidyl methacrylate.

Compounds which can be used in combination include, for example, acrylonitrile, styrenes, butyl vinyl ether, mono or dialkyl maleate, mono or dialkyl fumarate, mono or dialkyl itaconate, methyl vinyl ketone, vinyl chloride,
Vinylidene chloride, vinyl acetate, vinylpyridine, vinylpyrrolidone, vinyltrimethoxysilane and the like can be mentioned.

As the aqueous acrylic resin, any type of acrylic resin may be used, but an acrylic resin containing no emulsifier is preferably used.
The reason is that the water resistance of the oxazoline group-containing water-soluble polymer is not inhibited by the emulsifier.

Accordingly, the water-based acrylic resin is a self-dispersion type water-based acrylic resin synthesized using a reactive emulsifier or a water-based acrylic resin synthesized using a high molecular weight surfactant. Is also good. The reason is that the water resistance of the oxazoline group-containing water-soluble polymer is not inhibited by the reacted emulsifier or high molecular weight surfactant.

The mixing ratio of the aqueous acrylic resin in the coating solution is usually in the range of 10 to 80% by weight, preferably 20 to 60% by weight. The mixing ratio of the water-based acrylic resin is 1
If the amount is less than 0% by weight, the effects of water resistance and solvent resistance tend not to be sufficiently exhibited, and if it exceeds 80% by weight, the adhesion of the barrier layer tends to deteriorate. The aqueous acrylic resin is preferably used together with an aqueous polyurethane resin described below.

The water-based acrylic resin prevents a decrease in water resistance and solvent resistance of the oxazoline group-containing water-soluble polymer. It is considered that the above-described reduction preventing effect is due to the following reason. The acrylic resin film has an effect of preventing oligomers from depositing on the polyethylene terephthalate surface. The effect of preventing the oligomer precipitation prevents the moisture and the solvent that have entered the defect barrier layer formed by the oligomer mass from attacking the coating layer. Therefore, the water-based acrylic resin is considered to sufficiently exhibit the water resistance and the solvent resistance of the oxazoline group-containing water-soluble polymer.

The aqueous polyurethane resin is not particularly limited, but those not containing a low-molecular hydrophilic dispersant or the like are preferably used. The aqueous polyurethane resin is
It is a water-soluble or water-dispersible resin produced by reacting a polyhydroxy compound with a polyisocyanate compound according to a conventional method. The aqueous polyurethane resin is
In order to increase the affinity with an aqueous medium, those containing a carboxyl group or a salt thereof (hereinafter simply abbreviated as a carboxyl group) are preferable.

Examples of the above polyhydroxy compound include polyethylene glycol, polypropylene glycol, polyethylene propylene glycol, polytetramethylene glycol, hexamethylene glycol, tetramethylene glycol, 1,5-pentanediol,
Examples thereof include diethylene glycol, triethylene glycol, polycaprolactone, polyhexamethylene adipate, polyhexamethylene sebacate, polytetramethylene adipate, polytetramethylene sebacate, trimethylolpropane, trimethylolethane, pentaerythritol, and glycerin.

Examples of the above polyisocyanate compounds include hexamethylene diisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, isophorone diisocyanate, adducts of tolylene diisocyanate and trimethylolpropane, and adducts of hexamethylene diisocyanate and trimethylolethane. No.

The introduction of a carboxyl group into the side chain of the polyurethane may be carried out, for example, by using a carboxyl group-containing polyhydroxy compound as one of the starting polyhydroxy compounds during the synthesis of the polyurethane, or by introducing a polyurethane having an unreacted isocyanate group. React hydroxyl group-containing carboxylic acid or amino group-containing carboxylic acid with isocyanate group,
Next, the reaction can be easily performed by adding the reaction product to an aqueous alkali solution under high-speed stirring and neutralizing the solution.

The carboxyl group-containing polyhydroxy compound includes, for example, dimethylolpropionic acid,
Examples include dimethylolacetic acid, dimethylolvaleric acid, and bis (ethylene glycol) trimellitate. Examples of the hydroxyl group-containing carboxylic acid include, for example, 3
-Hydroxypropionic acid, γ-hydroxybutyric acid, p-
Examples of amino group-containing carboxylic acids such as (2-hydroxyethyl) benzoic acid and malic acid include β-aminopropionic acid, γ-aminobutyric acid, p-aminobenzoic acid and the like.

The carboxyl group of the aqueous polyurethane resin may have a counter ion. Examples of the counter ion include monovalent ions, preferably hydrogen ions or amine ions containing ammonium ions.

The mixing ratio of the aqueous polyurethane resin in the coating solution is usually 10 to 70% by weight, preferably 20 to 50% by weight.
% By weight. When the mixing ratio of the aqueous polyurethane resin is less than 10% by weight, the barrier layer tends to peel off together with the coating layer.
It tends to deteriorate water resistance. The aqueous polyurethane resin is preferably used together with the aqueous acrylic resin.

The coating solution in the present invention may contain an aqueous polyester resin in addition to the oxazoline group-containing water-soluble polymer, aqueous acrylic resin and aqueous polyurethane resin. The aqueous polyester resin is not particularly limited, but preferably any of a water-soluble or water-dispersible saturated or unsaturated polyester containing no low-molecular hydrophilic dispersant or the like can be used.

The dicarboxylic acid component of the above-mentioned saturated polyester includes, for example, terephthalic acid, isophthalic acid,
Examples include aromatic dicarboxylic acids such as 2,5-naphthalenedicarboxylic acid, aliphatic dicarboxylic acids such as adipic acid, azelaic acid, and sebacic acid; oxycarboxylic acids such as oxybenzoic acid; and ester-forming derivatives thereof. As the glycol component, for example, ethylene glycol, 1,4-butanediol, diethylene glycol, aliphatic glycols such as triethylene glycol,
Examples include alicyclic glycols such as 1,4-cyclohexanedimethanol, aromatic diols such as p-xylene diol, and poly (oxyalkylene) glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

Although the above-mentioned saturated polyester has a linear structure, it can be made into a branched polyester by using a trivalent or higher valent ester-forming component. On the other hand, examples of the unsaturated polyester include those shown in the following (1) and (2).

(1) JP-B No. 45-2201, 46
-2050, 44-7134, JP-A-48
As is known in JP-A-78233 and JP-A-50-58123, a resin skeleton obtained by reacting a raw material component containing a copolymerizable unsaturated group with another raw material component is contained in the resin skeleton. Unsaturated polyester having a saturated group.

(2) JP-B-49-47916, 5
As known in Japanese Patent Application Laid-Open No. 0-6223 and the like, after obtaining a saturated polyester having no copolymerizable unsaturated group, it has reactivity with a functional group such as a hydroxyl group or a carboxyl group present in the saturated polyester. An unsaturated polyester obtained by adding a vinyl monomer having a functional group and a vinyl group to a saturated polyester.

Examples of the above-mentioned vinyl monomers include compounds having an epoxy group and a vinyl group such as glycidyl methacrylate, compounds having an alkoxysilanol group and a vinyl group such as vinylmethoxysilane and methacryloxyethyltrimethoxysilane, and maleic anhydride. Examples thereof include a compound having an acid anhydride group such as an acid and tetrahydrophthalic anhydride and a vinyl group, and a compound having an isocyanate group and a vinyl group such as an adduct of 2-hydroxypropyl methacrylate-hexamethylene diisocyanate.

The aqueous polyester resin preferably contains a carboxyl group in order to increase the affinity with an aqueous medium. The introduction of a carboxyl group into the side chain of a saturated or unsaturated polyester is carried out by reacting a dioxane compound having a carboxylic acid with the polyester (Japanese Patent Laid-Open No. 61-2 / 1986).
No. 28030), a method of radically grafting an unsaturated carboxylic acid to a polyester (JP-A-62-225).
No. 510), a method of introducing a substituent into an aromatic ring by reacting a polyester with halogenoacetic acid (Japanese Patent Application Laid-Open No. Sho 62-2).
No. 25527), a method of reacting a polyester with a polyvalent carboxylic anhydride compound (Japanese Patent Application Laid-Open No. 62-24031).
No. 8) or the like.

The carboxyl group of the aqueous polyester resin may have a counter ion. Examples of the counter ion include a monovalent ion, preferably an amine onium ion containing a hydrogen ion or an ammonium ion.

The mixing ratio of the aqueous polyester resin in the coating solution is usually 10 to 70% by weight, preferably 20 to 50% by weight.
% By weight. When the mixing ratio of the aqueous polyester resin is less than 10% by weight, the barrier layer tends to peel off together with the coating layer, and when it exceeds 70% by weight,
It tends to deteriorate water resistance.

The coating solution of the present invention may be used as a crosslinking agent, for example, epoxy, methylol or alkylol as a crosslinking agent in order to improve the adhesion (blocking property), water resistance, solvent resistance and mechanical strength of the coating layer. Urea-based, melamine-based, guanamine-based, acrylamide-based, polyamide-based compounds, aziridine compounds, block polyisocyanate compounds, silane coupling agents, titanium coupling agents, zircoaluminate coupling agents, peroxides, light A small amount of a reactive vinyl compound, a photosensitive resin, or the like may be contained as long as the adhesiveness is not deteriorated. In particular, it is preferable to use an epoxy compound such as glycidyl acrylate or glycidyl methacrylate in combination, since crosslinking to a side chain such as a carboxyl group in the resin compound can enhance the adhesiveness to the deposited film.

The coating liquid of the present invention may be used as inorganic fine particles such as silica,
Silica sol, alumina, alumina sol, zirconium sol, kaolin, talc, calcium carbonate, titanium oxide,
It may contain barium salt, carbon black, molybdenum sulfide, antimony oxide sol, etc., and if necessary, furthermore, an antifoaming agent, a coating improver, a thickener, an antistatic agent, an organic lubricant, an organic lubricant. It may contain system polymer particles, an antioxidant, an ultraviolet absorber, a foaming agent, a dye, a pigment, and the like.

As a method of applying the coating solution to the polyester film, a reverse roll coater, a gravure coater, a rod coater, an air doctor coater, or any other method described in “Coating System” (written by Yuji Harazaki, Maki Shoten, 1979) is used. Is applied in the film manufacturing process using the coating device of (1). That is, in the present invention,
The coating layer must be provided in the film forming process. When the film is a biaxially stretched film, it is preferable to apply the coating solution to a film that has been stretched uniaxially in the longitudinal direction, stretch it in the dry or undried state in the transverse direction, and then perform heat treatment.

As described above, the method of applying a coating solution and then stretching it in at least one direction (in-line coating method) has a great advantage in terms of manufacturing cost since film formation, coating and drying can be performed simultaneously. The coating layer can be provided on one side or both sides, and when provided on both sides, the coating layers may be the same or different. In order to improve the applicability and adhesiveness to the film, the film surface may be subjected to a chemical treatment, a discharge treatment or the like before the application.

Although the thickness of the plastic film is not particularly limited, it is usually 2 to 500 μm, especially 5 to 200 μm. The thickness of the coating layer is usually in the range of 0.01 to 5 μm,
Preferably, it is in the range of 0.02 to 1 μm. If the thickness of the resin layer is less than 0.01 μm, it tends to be difficult to obtain a uniform resin layer, and if it exceeds 5 μm, the slipperiness tends to decrease and the handling of the film tends to be difficult.

The water droplet contact angle of the coating layer formed as described above is preferably 60 ° or more. In general, a water-soluble resin coating layer having a large amount of an emulsifier, a hydrophilic compound, and a hydrophilic group tends to reduce the contact angle of water droplets and deteriorate water-resistant adhesion to a metal-deposited thin film, so care must be taken.

In the present invention, the metal and / or metal oxide to be deposited include, for example, aluminum, silicon, magnesium, palladium, zinc, tin, nickel,
Examples include metals such as silver, copper, gold, indium, stainless steel, chromium, and titanium, oxides of these metals, and mixtures thereof. The method of vapor deposition is generally vacuum deposition, but ion plating, sputtering, CV
D or the like may be used. The deposition film is formed on the surface of the coating layer. The thickness of the deposited film is appropriately selected depending on the final use of the deposited film, but is usually 5 to 500 nm, preferably 10 to 200 nm. In addition, in order to impart adhesiveness after vapor deposition, particularly, water resistance and scratch resistance,
A resin protective layer may be provided on the deposition surface.

[0060]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist. The evaluation method in each of the following examples is as follows.

(1) Evaluation of adhesiveness: A polyester film having the same thickness as the base polyester film was laminated on the vapor-deposited surface of the vapor-deposited film by an ordinary dry lamination method, and then subjected to an aging treatment. The obtained laminated body has a width of 15
mm, and the end portion was partially peeled off, and T-peeling was performed at a speed of 100 mm / min with a peeling tester. The evaluation of adhesiveness was determined based on the criteria shown in Table 1 below.

[0062]

[Table 1] A: 200 g or more B: 100 g or more and less than 200 g C: less than 100 g

(2) Contact angle of water droplet: A contact angle meter (Kyowa Interface Chemical Co., Ltd.)
The temperature was measured using a “CA-DT-A type contact angle meter” manufactured by
The contact angle between the sample film and distilled water was measured at 50 ° C. and a humidity of 50% RH. The contact angle was measured at two points on the left and right and a total of six points using three samples, and the average value was determined as the contact angle. In addition, the diameter of the water droplet was 2 mm, and the numerical value one minute after the drop was read.

(3) Gas barrier property: (a) Moisture permeability The moisture permeability of a sample after vapor deposition was measured with a moisture permeability measuring device (“W-1 type moisture permeability measuring device” manufactured by Modern Controls).
Was measured under the conditions of a temperature of 40 ° C. and a humidity of 90% RH. The evaluation of the moisture permeability (g / m ² · 24 hr) was determined based on the criteria shown in Table 2 below.

[0065]

[Table 2] A: less than 1 B: 1 or more and less than 2 C: 2 or more

(B) Oxygen Permeability Oxygen permeability was measured by applying gravure ink (“N” manufactured by Toyo Ink Co., Ltd.)
EW LP Super White ”) printed 2 μm thick,
As the sample 3, a sample obtained by boiling the sample 2 (90 ° C., 30 minutes) was used. For samples 1 to 3, use an oxygen permeability measuring device (“OX-TRN10 manufactured by Modern Controls”).
Oxygen permeability (cc / m ² · 24 h) at a temperature of 30 ° C. and a humidity of 90% RH.
r.atm) was measured. The oxygen permeability was evaluated based on the criteria shown in Table 3 below.

[0067]

[Table 3] A: less than 1 B: 1 or more and less than 10 C: 10 or more

Examples 1 to 8 and Comparative Examples 1 to 6 Polyethylene terephthalate containing 50% by weight of recycled polyethylene terephthalate and having an intrinsic viscosity of 0.62 was added to 28
It was extruded from a die of an extruder at a temperature of 0 to 300 ° C. and cast on a cooling drum while using an electrostatic adhesion method, to obtain an amorphous polyester sheet having a thickness of about 150 μm. After the above sheet was stretched 3.5 times in the longitudinal direction at 95 ° C., it contained the components shown in Tables 4 and 5 below, and the resin constituting the coating layer had the compounding ratio shown in Table 6 below. An aqueous medium coating solution is applied to one side of the film after the longitudinal stretching, and
The film was stretched 3.5 times in the transverse direction at 10 ° C. and heat-treated at 230 ° C. to obtain a biaxially stretched polyester film having a coating layer thickness of 0.1 μm and a base polyester film thickness of 12 μm. Next, a silicon oxide deposited film having a thickness of 500 ° was provided on the coating surface side of the above-mentioned film by a CVD method. Table 4 below shows the evaluation results of the obtained deposited film on the adhesiveness, the contact angle of water droplets, the moisture permeability, the oxygen permeability, and the like.

Resin A: 40 of oxazoline group-containing water-soluble polymer (oxazoline group content 4.5 mmol / g)
"Epocross WS-500" manufactured by Nippon Shokubai Co., Ltd. was used as a weight% solution (water / 1-methoxy-2-isopropanol = 1/2 volume ratio).

Resin B: Epocross K10 manufactured by Nippon Shokubai Co., Ltd. as an aqueous dispersion of an oxazoline group-containing water-insoluble polymer (oxazoline group content 0.9 mmol / g).
20 "was used.

Resin C: As the aqueous acrylic resin aqueous paint (non-emulsifier type), an aqueous acrylic resin aqueous paint obtained by the following method was used. That is, a mixture of 40 parts by weight of ethyl acrylate, 30 parts by weight of methyl methacrylate, 20 parts by weight of methacrylic acid, and 10 parts by weight of glycidyl methacrylate was subjected to solution polymerization in ethyl alcohol, and after polymerization, heating was performed while adding water to remove ethyl alcohol. did. The pH was adjusted to 7.5 with aqueous ammonia to obtain a water-based acrylic resin water-based coating (emulsifier-free type).

Resin D: As the aqueous acrylic resin aqueous coating (emulsifier-containing type), an aqueous acrylic resin aqueous coating obtained by the following method was used. That is, ethyl acrylate 40 parts by weight, methyl methacrylate 30 parts by weight, methacrylic acid 20 parts by weight, glycidyl methacrylate 10
A mixture of 1 part by weight of an emulsifier and 1 part by weight of sodium dodecylbenzenesulfonate was emulsion-polymerized in an aqueous medium, and the pH was adjusted to 7.5 with aqueous ammonia to obtain an aqueous acrylic resin aqueous paint (an emulsifier-containing type).

Resin E: The aqueous polyurethane resin aqueous coating obtained by the following method was used as the aqueous polyurethane resin aqueous coating. That is, first, terephthalic acid 66
A polyester polyol comprising 4 parts, 631 parts of isophthalic acid, 472 parts of 1,4-butanediol, and 447 parts of neopentyl glycol was obtained. Next, 321 parts of adipic acid and 268 parts of dimethylolpropionic acid were added to the obtained polyester polyol to obtain a pendant carboxyl group-containing polyester polyol A. Further, 160 parts of hexamethylene diisocyanate was added to 1880 parts of the above polyester polyol A to obtain a water-based polyurethane resin water-based paint.

Resin F: Water-based polyester resin water-based paint, "Polyester W" manufactured by Nippon Synthetic Chemical Industry Co., Ltd.
R-961 "was used.

[0075]

[Table 4]

Example 9 and Comparative Example 7 Nylon 6 having a recycled nylon 6 content of 50 wt.
And extruded from the T-die of the extruder at this temperature and quenched with a cooling drum to obtain an unstretched nylon sheet having a thickness of 144 μm.
After stretching the above sheet three times in the longitudinal direction at 60 ° C., an aqueous medium coating solution having a compounding ratio shown in Table 7 below was applied to one side of the sheet, and stretched three times in the longitudinal direction at 90 ° C. To obtain a biaxially stretched nylon film having a film thickness of 16 μm. An adhesive film, a gas barrier property, and a contact angle were measured for a film in which a silicon oxide vapor-deposited film was provided in the same manner as in Example 1, and a 50 μm-thick LLDPE film was adhered with an adhesive,
Table 5 shows the results.

Example 10 and Comparative Example 8 A polypropylene having a recycled polypropylene content of 50 weight was extruded from a T-die of an extruder at a temperature of 210 ° C. and rapidly cooled with a cooling drum to obtain an unstretched polypropylene sheet having a thickness of 1 mm. After stretching the above sheet in the longitudinal direction by 5 times at 150 ° C., an aqueous medium coating solution having a mixing ratio shown in Table 7 below was applied to one surface of the sheet, and stretched 10 times in the longitudinal direction at 155 ° C. To obtain a biaxially oriented polypropylene film having a film thickness of 20 μm. In the same manner as in Example 1, a film in which a silicon oxide vapor-deposited film was provided, and a 50 μm-thick LLDPE film was adhered with an adhesive was measured for adhesiveness, gas barrier property, and contact angle, and the results are shown in Table 5.

[0078]

[Table 5]

[0079]

According to the present invention described above, a vapor-deposited plastic film having excellent adhesiveness and gas barrier properties between a base film and a vapor-deposited layer, particularly excellent gas barrier properties after boil processing and printing. A manufacturing method is provided, and the industrial value of the present invention is very large.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Yuzo Otani 347 Inoguchi, Yamato-cho, Sakata-gun, Shiga Prefecture F-term in Central Research Laboratory, Mitsubishi Chemical Polyester Film Co., Ltd. (Reference) 4F100 AA17B AA20 AB01C AK01A AK01B AK07A AK21A AK25B AK41B AK51B AK68A AL05B BA03 BA06 BA07 BA10A CC00B EH66C GB15 GB41 JA20 JB09B JD02 JL11 JL16

Claims (8)

[Claims] 1. A plastic film containing a resin mixture containing 6 to 80% by weight of an oxazoline group-containing water-soluble polymer, applied to at least one surface of a plastic film, and then stretched in at least one direction. A method for producing a vapor-deposited plastic film, comprising vapor-depositing a metal and / or a metal oxide on a surface. 2. The method according to claim 1, wherein the proportion of the oxazoline group-containing water-soluble polymer in the resin mixture is 10 to 80% by weight. 3. The production method according to claim 1, wherein the oxazoline group content in the oxazoline group-containing water-soluble polymer is 0.4 to 5.0 mmol / g. 4. A resin mixture comprising 10 to 80% by weight of an oxazoline group-containing water-soluble polymer, 10 to 80% by weight of an aqueous acrylic resin, and 10 to 70% by weight of an aqueous polyurethane resin and / or an aqueous polyester resin. The method according to claim 1, further comprising a resin. 5. The production method according to claim 4, wherein the aqueous acrylic resin is an aqueous paint containing no emulsifier. 6. The method according to claim 1, wherein the plastic film is made of polyester. 7. The method according to claim 1, wherein the plastic film is made of any one of polypropylene, polyamide, polyvinyl alcohol, and a partially hydrolyzed ethylene-vinyl acetate copolymer. 8. The method according to claim 1, wherein a contact angle of a water droplet of the coating layer is 60 ° or more.