JP2001054939A - Polypropylene film for metal vapor deposition and metal vapor-deposited polypropylene film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polypropylene film for metal vapor deposition having excellent gas barrier capacity while improving the adhesiveness of a metal vapor deposition film and a film base material at the time of metal vapor deposition and a metal vapor-deposited polypropylene film. SOLUTION: A surface layer comprising a polypropylene type resin of which the main peak of heat absorption accompanying the fusion of a crystal is 155-163 deg.C and the crystal fusion calorie is 20-90 J/g is laminated to at least the single surface of a base layer comprising isotactic polypropylene with a mesopentad ratio of 90% or more and a coating layer with a thickness of 0.05-2 μm comprising a mixed coating agent of a polyester urethane resin and a water soluble org. solvent is provided on the surface layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metallized polypropylene film and a metallized polypropylene film. More specifically, the present invention relates to a metallized polypropylene film having excellent adhesion to a metallized film and a metallized polypropylene film provided with the metallized film and having excellent gas barrier properties and moisture resistance.

[0002]

2. Description of the Related Art Polypropylene films are widely used as packaging films because of their excellent moisture-proof properties, strength, transparency and surface gloss. Further, for the purpose of improving gas barrier properties and moisture proof properties of the film, a polypropylene film coated with polyvinylidene chloride is widely used as a transparent and excellent gas barrier film. However, it has been pointed out that polyvinylidene chloride has an adverse effect on the environment due to the generation of chlorine-based gas and toxic chlorine-based substances during waste incineration. In recent years, there has been a movement to convert all gas barrier packaging materials to polyolefin resins in order to reduce costs and recover gas barrier packaging materials. Therefore, metal such as aluminum is vapor-deposited on a polyolefin resin film for the purpose of improving the appearance of the display due to the metallic luster, improving the gas barrier performance, and suppressing deterioration of the contents due to external light such as ultraviolet rays (metallization). It is also widely practiced.

[0003] US Patent No. 4,345,005 discloses that
Biaxially metallized biaxially metallized corona-discharged ethylene-propylene copolymer resin layer containing about 2% to about 4% ethylene, formed by coextrusion on at least one side of an isotactic polypropylene resin base layer There is disclosure of an oriented polypropylene film. In addition, US Pat.
7,383 discloses that ethylene and carbon content of 3 to 3
There is disclosed a multilayer metallized packaging film in which a random copolymer layer of 0.25 to 15% by weight of α-olefin No. 6 is formed and a metal layer is formed thereon. Similarly, as a biaxially oriented polypropylene composite film for metal oxide deposition, Japanese Patent Application Laid-Open No. 9-94929 discloses a polyolefin resin having a surface layer to be deposited with a heat of fusion of 30 to 85 J / g. As a resin for this, polypropylene copolymer, syndiotactic polypropylene resin,
Copolymers of ethylene and α-olefin, and blend resins of these resins and isotactic homopolypropylene or polypropylene copolymers are mentioned.

[0004] By laminating a copolymer resin among these surface resins on the surface layer, the adhesiveness of the metal-deposited film is improved. However, since the copolymer resin generally has a low melting point, it adheres to a longitudinal stretching roll during film formation. There are great restrictions on film formation such as
The problem of gloss reduction due to sticking marks is a problem. In addition, when the metal is vapor-deposited due to its low melting point, the metal vapor-deposited film tends to be whitened due to the heat of aggregation of the metal or the radiation heat from the evaporation source, and it is difficult to obtain a metallic luster. Similarly, when the surface layer is made of syndiotactic polypropylene, the melting temperature is low as shown in JP-A-7-89022, and it is known that a problem of heat resistance occurs similarly to the copolymer resin.

Further, US Pat. No. 4,419,410 discloses that an oriented polypropylene film is formed by laminating a polypropylene having a relatively low stereoregularity on a polypropylene having a high stereoregularity, so that the organic lubricant and the antistatic agent can be expressed. Although there is a disclosure of a promoting technology, US Pat.
As shown in JP-A-83, it is known that the addition of an organic lubricant among these additives particularly deteriorates the adhesion to a vapor-deposited film, and this technique cannot be applied to a polypropylene film for metal vapor deposition. .

One of the important characteristics of a metal-deposited polypropylene film using the above-mentioned base material is that the permeability of oxygen and water vapor is lowered by metal vapor deposition, and the oxygen and water vapor when used as a part of a packaging material are reduced. There is a so-called gas barrier performance of suppressing the deterioration of the contents due to the gas barrier. Since the gas barrier performance largely depends on the preservability of foods, which are the contents, a metal-deposited polypropylene film having an even higher gas barrier performance is required. However, the above-mentioned metal-deposited polypropylene film has a low adhesive strength between a layer of a polypropylene resin, a polypropylene copolymer resin, a layer of an ethylene / α-olefin copolymer resin and a metal-deposited layer, and a polypropylene film coated with vinylidene chloride. Equivalent gas barrier performance has not been obtained, and when extruding and laminating metal-deposited surfaces with other materials using polyethylene etc., the resin has a low melting point,
There are problems that the metal vapor-deposited film loses metallic luster and the gas barrier performance is significantly reduced.

JP-A-7-314612 discloses a packaging thermoplastic resin film having a surface carboxylic acid concentration of 0.005 or more, a packaging metallized thermoplastic film having a metal layer provided on the coating layer, JP-A-7-266484
In Japanese Patent Application Laid-Open No. H08-214, there is disclosed a gas barrier laminate in which a base layer is coated with a mixed solution of a metal alkoxide and an isocyanate compound on a base layer, and a vapor-deposited layer made of an inorganic compound is provided on a coating layer. -267637
Japanese Patent Application Publication No. JP-A-2002-133873 discloses a barrier material having a deposition layer in which a metal alkoxide or a hydrolyzate coating layer is provided on a metal surface of a deposition film in which a deposition layer made of an inorganic compound is provided on a base layer. However, when the base layer and the surface layer are conventional polypropylene resins, the adhesive strength with the coating layer and the vapor deposition layer is low, and when processing into a packaging bag or the like that requires gas barrier properties, the coating layer and the vapor deposition layer are likely to peel off. There was a problem that the gas barrier performance deteriorated.

[0008]

SUMMARY OF THE INVENTION In view of the above circumstances, it is an object of the present invention to provide a metal vapor deposition having excellent gas barrier performance while improving the adhesion between a metal vapor deposited film and a substrate when metal is vapor deposited. It is to provide a polypropylene film and a metallized polypropylene film.

[0009]

In order to solve the above-mentioned problems, a polypropylene film for metal vapor deposition according to the present invention has at least one surface of a base layer made of isotactic polypropylene having a mesopentad fraction of 90% or more due to crystal melting. A main layer of endothermic heat is in the range of 155 to 163 ° C., and a surface layer of a polypropylene resin having a heat of crystal fusion in the range of 20 to 90 J / g is laminated, and a polyester urethane resin and a water-soluble organic layer are formed on the surface layer. It is characterized in that a coating layer having a thickness in the range of 0.05 μm to 2 μm, which is made of a mixed coating of a solvent, is provided.

[0010] The polypropylene film for metal deposition according to the present invention is obtained by providing a metal deposition film on the coating layer surface of such a polypropylene film for metal deposition.

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the polypropylene film for metal vapor deposition of the present invention, the resin forming the base layer must be an isotactic polypropylene resin having a mesopentad fraction of 90% or more. It is preferably at least 92%, more preferably at least 95%. If the mesopentad fraction of the base layer is less than 90%, the effect on the mechanical properties of the polypropylene film becomes large, causing a decrease in the Young's modulus, making the polypropylene film for metal vapor deposition easily stretchable with respect to tension and poor in workability. .

The mesopentad fraction of the polypropylene resin in the present invention is the proportion of the isotactic steric structure as measured by ¹³ C-NMR in the entire structure. The mesopentad fraction reflects the stereoregularity of polypropylene. The stereoregularity of the polypropylene film can be evaluated by the pentad fraction due to the absorption of the methyl group measured by ¹³ C-NMR. Generally, the conformation of five repeating units (pentads) in a polypropylene molecular chain is mmmm, mmmr, rmm
r, mmrr, mmrm, rmrr, rmrm, rrr
r, mrrr, mrrm, and the like. Here, m is meso, r is racem (racem).
o) shows the conformation. The pentad fraction of the polypropylene film is, for example, T.D. HAYASHHI et al. [P
OLYMER, Vol. 29, 138-143 (198
8)] and the like, the ratio of the segments having each of the above conformations can be determined from ¹³ N-NMR. Among these, the ratio of the conformation of mmmm to the absorption intensity of all methyl groups, that is, the isotactic pentad fraction (hereinafter sometimes abbreviated as mmmm) is m (mmm
m) defined as the sum of three heptad fractions, m, m (mmmm) r, and r (mmmm) r.

The isotactic polypropylene resin of the base layer preferably has an isotacticity (hereinafter abbreviated as II) of 90% or more. II is the weight ratio of the undissolved portion when extracted with boiling n-hexane. If II is less than 90%, the amount of eluted by a solvent such as xylene or n-hexane becomes too large, which may be unsuitable as a packaging film.

Further, the melt flow index (hereinafter, abbreviated as MFI) of the base layer is preferably in the range of 1 to 15 g / 10 minutes. By using such a polypropylene resin, film formation stability is improved.

As the resin of the base layer, an isotactic polypropylene resin alone is preferable, but a polypropylene copolymer resin or the like may be laminated on the other surface of the surface of the polypropylene resin laminated on the base layer according to the purpose. When these copolymer resins are collected in the base layer, other copolymer resins may be contained as far as the characteristics allow.

It is preferable that an organic lubricant such as fatty acid amide is not added to the base layer resin of the present invention for the adhesiveness of the metal deposition film. However, it imparts slipperiness and improves workability and winding property. Therefore, it is permissible to add a small amount of organic crosslinkable particles or inorganic particles. Examples of the organic cross-linkable particles for this purpose include cross-linked silicone particles, cross-linked polymethyl methacrylate particles, cross-linked polystyrene particles, and the like, and inorganic particles include zeolite, calcium carbonate, silicon oxide,
Examples thereof include aluminum silicate. The average particle diameter of these particles is preferably in the range of 0.5 to 5 μm, since the sliding properties can be imparted without greatly deteriorating the transparency and gas barrier performance of the film of the present invention.

An important point of the present invention is that the melting temperature of the polypropylene resin of the surface layer is relatively high, and the main peak of the crystal melting temperature of the polypropylene resin of the surface layer of the present invention is 155 to 163. It is important that the temperature is in ° C. The upper limit of the melting temperature is defined as a characteristic value specific to polypropylene, but the lower limit of the melting temperature is defined by the heat resistance during the processing of the metallized film. There is.

The main peak of the crystal melting temperature of the polypropylene resin of the surface layer of the present invention is preferably from 157 to 162 ° C, more preferably from 158 to 162 ° C. In this case, the main peak is a single endothermic peak when only a single endothermic peak is observed, and when a plurality of resin melting peaks are present when a plurality of resins are mixed and used for a surface layer, The one with the largest peak area. Further, it is preferable that all the peaks of the melting temperature are in the range of 100 ° C. to 163 ° C. for the film forming property and the heat resistance at the time of metal deposition, and the sum of the heats of fusion of the peaks below 155 ° C. It is preferably less than 1/3 of the sum of the calories. If the sum of the heats of fusion of peaks lower than 155 ° C. is 1/3 or more, the metal vapor-deposited layer may cause blocking on the opposite surface to cause pick-off, thereby greatly deteriorating the gas barrier properties.

The heat of crystal fusion of the polypropylene resin of the surface layer of the present invention is 20 to 90 J / g, more preferably 20 to 80 J / g. When a plurality of resins are used and there are a plurality of peaks, the sum of the heat of crystal fusion falls within the above range.

While the heat of crystal fusion of a normal isotactic polypropylene resin is 100 J / g or more,
The point is that the heat of crystal fusion of the polypropylene resin used as the surface resin of the present invention is small. If the heat of crystal fusion is too large, the adhesiveness to the coating layer described later may be poor. If the heat of crystal fusion is too small, the heat resistance during metal deposition may be poor. The heat of crystal fusion of the polypropylene resin of the surface layer of the present invention is more preferably 40 to 70 J / g, and further preferably 45 to 65 J / g.

In order to make the peak value of the melting temperature and the heat of fusion of the polypropylene resin in the surface layer within the range of the present invention, it is important to select the resin. In the case of a polypropylene-based copolymer resin as in the prior art, for example, in the case of an ethylene / propylene random copolymer, the heat of fusion decreases with the amount of ethylene copolymerized. However, at the same time, the melting temperature is also rapidly lowered, so that it is difficult to fall within the scope of the present invention, but it can be achieved depending on the polymerization conditions, and the polypropylene copolymer resin is not excluded from the scope of the present invention. .

In the present invention, an isotactic polypropylene resin having a pentad fraction of 60 to 88% is preferable as the surface resin. If the meso pentad fraction is less than 60%, the rubber component of the resin increases,
The surface layer may not be glossy and may have whitening due to poor heat resistance during metal deposition. If the mesopentad fraction exceeds 88%, the adhesion to the coating layer will be poor. The mesopentad fraction of the isotactic polypropylene of the surface resin of the present invention is preferably from 65 to 85%, more preferably from 68 to 80%. The mesopentad fraction can be set to such a value by selecting an isotactic polypropylene having a mesopentad fraction of the present invention or by mixing two or more isotactic polypropylene resins having different mesopentad fractions. . The mesopentad fraction in the case of mixing can be approximately approximated by a value measured by ¹³ C-NMR, which is calculated by a mixing ratio of two or more mesopentad fractions.

The polypropylene resin used as the surface resin of the present invention preferably has an MFI of 1 to 20 g / 10 minutes for lamination with the base layer.

The thickness of the surface layer of the present invention is preferably not less than 0.25 μm and not more than half the thickness of the base layer. If the thickness of the surface layer is less than 0.25 μm, uniform lamination becomes difficult due to film breakage or the like, and the effect of improving the adhesiveness may be reduced. If the thickness is too large, the contribution of the surface layer to the mechanical properties increases, causing a decrease in the Young's modulus, and the polypropylene film for metal deposition tends to be stretched with respect to tension, resulting in poor workability.

It is preferable that an organic lubricant such as fatty acid amide is not added to the surface resin of the present invention for adhesion of the metal film. However, in order to impart lubricity and improve workability and winding property. It is permissible to add a small amount of organic crosslinkable particles or inorganic particles. Organic crosslinkable particles for this purpose include:
Examples include crosslinked silicone and crosslinked polymethyl methacrylate particles, and inorganic particles include zeolite, calcium carbonate, silicon oxide, and aluminum silicate.

The surface resin according to the present invention comprises at least one resin selected from petroleum resins substantially free of polar groups and terpene resins substantially free of polar groups per 100 parts by weight of the base resin. It is preferable to add 20 parts by weight to the upper limit because the adhesion to the coating layer can be further strengthened.

The petroleum resin substantially free of polar groups is
A hydroxyl group (-OH), a carboxyl group (-COOH), a sulfonic acid group (-SO ₃ Y, Y is H, Na, etc.) and a petroleum resin having no polar group made of their modified product, i.e. petroleum It is a resin mainly composed of a cyclopentadiene-based or higher olefin-based hydrocarbon using an unsaturated hydrocarbon directly as a raw material. When these resins are added to the surface resin in the present invention, the glass transition temperature measured by a differential calorimeter is preferably 50 ° C. or higher, more preferably 76 ° C. or higher, so as not to lower the heat resistance. Hydrogenated petroleum resin is particularly preferable, in which hydrogen is added to the petroleum resin so that the degree of hydrogenation is 80% or more, preferably 95% or more. Further, the petroleum resin is preferably amorphous (that is, substantially no crystal melting is observed when the petroleum resin is measured by a differential calorimeter) from the viewpoint of compatibilization with the polypropylene resin of the surface layer, and The number average molecular weight is preferably 1,000 or less.

The terpene resin having substantially no polar group includes a hydroxyl group (—OH), an aldehyde group (—CHO), a ketone group (—CO—), a carboxyl group (—COOH), a halogen group, and a sulfonic acid group. (-SO ₃ Y, Y is H, Na and the like) and terpene resins having no polar group, such as modified products thereof,
That is, a hydrocarbon having a composition of (C ₅ H ₈ ) _n and a modified compound derived therefrom. Note that n is a natural number of about 2 to 20. Terpene resins are sometimes referred to as terpenoids. Representative compound names include pinene, dipentene, kalen, myrcene, ocimene, limonene, tervinolene, terpion, sapinene, tricyclene, pisapolene, zingiperene, santalen, camphorene, millen, totalene, and the like.
%, Preferably 90% or more, particularly preferably hydrogenated β-pinene and hydrogenated dipentene.

Next, in order to obtain excellent gas barrier properties after metal deposition, it is necessary that the coating layer of the film of the present invention comprises a mixed coating of a polyester urethane resin and a water-soluble organic solvent. The coating layer can be formed by applying and drying a mixed coating of a water-soluble and / or water-dispersible polyester urethane resin and a water-soluble organic solvent.

The polyester urethane resin comprises a polyester polyol obtained by esterifying a dicarboxylic acid and a diol component, a polyisocyanate, and if necessary, a chain extender.

As the dicarboxylic acid component, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid,
Adipic acid, trimethyladipic acid, sebacic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, pimelic acid, 2,2-dimethylglutaric acid, azelaic acid, fumaric acid, maleic acid, itaconic acid, 1,3 -Cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid,
1,4-naphthalic acid, diphenic acid, 4,4′-oxybenzoic acid, 2,5-naphthalenedicarboxylic acid, and the like can be used.

As the diol component, ethylene glycol, 1,4-butanediol, diethylene glycol,
Aliphatic glycols such as triethylene glycol, 1,
Examples thereof include aromatic diols such as 4-cyclohexanedimethanol, and poly (oxyalkylene) glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

In addition to the dicarboxylic acid component and the diol component, oxycarboxylic acids such as p-oxybenzoic acid and the like may be copolymerized. Further, these have a linear structure, but have a trivalent or higher ester formation. Branched polyesters can also be formed using the components.

Examples of polyisocyanates include hexamethylene diisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, isophorone diisocyanate, tetramethylene diisocyanate, xylylene diisocyanate, lysine diisocyanate, adducts of tolylene diisocyanate and trimethylol propane, hexamethylene diisocyanate and trimethylol Ethane adducts and the like can be mentioned.

As the chain extender, pendant carboxyl group-containing diols such as ethylene glycol, diethylene glycol, propylene glycol,
1,4-butanediol, hexamethylene glycol,
Glycols such as neopentyl glycol, or ethylenediamine, propylenediamine, hexamethylenediamine, phenylenediamine, tolylenediamine,
Examples include diamines such as diphenyldiamine, diaminodiphenylmethane, diaminodiphenylmethane, and diaminocyclohexylmethane.

When forming a coating layer constituting the present invention, a water-soluble organic solvent is used as a coating agent in order to improve the coating formability of the coating layer and the adhesive strength between the polypropylene resin layer and the surface layer. It is preferable to add and mix at least one of N-methylpyrrolidone, ethyl cellosolve acetate, and dimethylformamide. In particular, N-methylpyrrolidone is preferable because it has a large effect of improving film formability and adhesion to the surface layer. The addition amount is preferably 1 to 15 parts by weight based on 100 parts by weight of the polyester urethane resin in view of preventing the flammability and odor deterioration of the coating agent and reducing the residual solvent in the coating layer, and more preferably 3 to 10 parts by weight. Department.

Further, as a method for obtaining a coating agent in which a crosslinked structure is introduced into a water-soluble and / or water-dispersible polyester urethane resin, JP-A-63-15816, JP-A-63-256651, and JP-A-5-25651. No. 152159. As the crosslinkable component, addition of at least one crosslinking agent selected from isocyanate compounds, epoxy compounds, and amine compounds can be mentioned. These cross-linking agents cross-link with the above-mentioned polyester urethane resin to enhance the adhesion between the surface layer and the metal vapor-deposited film.
For example, the above-mentioned toluene diisocyanate, xylene diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and the like are exemplified, but not limited thereto.

As the epoxy compound, for example,
Diglycidyl ether of bisphenol A and its oligomers, diglycidyl ether of hydrogenated bisphenol A and its oligomers, diglycidyl ether of orthophthalic acid, diglycidyl ether of isophthalic acid, diglycidyl ether of terephthalic acid, diglycidyl ether of adipic acid, and the like. Yes, but not limited to this.

Examples of the amine compound include amine compounds such as melamine, urea and benzoguanamine;
Formaldehyde or a compound having 1 to 6 carbon atoms in the amino compound
Examples include, but are not limited to, amino resins obtained by addition condensation of the above alcohol, hexamethylenediamine, triethanolamine, and the like.

The amount of the crosslinking agent selected from isocyanate compounds, epoxy compounds and amine compounds is
1 to 15 parts by weight of the water-soluble and / or water-dispersible polyester urethane-based resin and the water-soluble organic solvent in an amount of 1 to 15 parts by weight makes the coating layer hard and smooth, thereby improving the adhesion of the metal deposition film. And more preferably 3
To 10 parts by weight. If the amount of the crosslinking agent is too small,
In some cases, the effect of improving the adhesiveness is insufficient, and when it is too large, there is a decrease in the adhesiveness presumably due to the unreacted and remaining crosslinking agent.

In order to completely crosslink and cure the above-mentioned coating layer composition, a small amount of a crosslinking accelerator may be added.
As the cross-linking accelerator, a water-soluble acidic compound is preferable since the cross-linking accelerating effect is large. For example, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, trimethyladipic acid, sebacic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, sulfonic acid, pimelic acid, 2,2-dimethyl Glutaric acid, azelaic acid, fumaric acid, maleic acid, itaconic acid, 1,
3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,4-naphthalic acid, diphenic acid, 4,4′-
Oxybenzoic acid, 2,5-naphthalenedicarboxylic acid, and the like can be used.

Inert particles may be added to the coating layer of the present invention. Examples of the inert particles include inorganic fillers such as silica, alumina, calcium carbonate, barium sulfate, magnesium oxide, zinc oxide and titanium oxide. Organic polymer particles such as cross-linked polystyrene particles, cross-linked acryl particles, cross-linked silicon particles, and the like. In addition to the inert particles, a wax-based lubricant, a mixture thereof, and the like may be added as long as the adhesiveness to the surface layer and the metal deposition layer is not deteriorated.

It is necessary to provide a coating layer having a thickness of 0.05 to 2 μm on at least one surface of the surface layer of the polypropylene film for metal deposition constituting the film of the present invention. If the thickness of the coating layer is less than 0.05 μm, the adhesion to the surface layer is deteriorated, resulting in fine film detachment, and the gas barrier performance after metal deposition is deteriorated. When the thickness is more than 2 μm, it takes time to cure the coating layer, and the above-mentioned crosslinking reaction may be incomplete and the gas barrier performance may deteriorate.When the coating layer is provided on the surface layer in a film forming process, Recoverability of the film debris to the base layer is deteriorated, many internal voids are formed around the resin of the coating layer, and the mechanical properties are reduced.

The adhesive strength between the coating layer and the surface layer is not more than 0.1.
3 N / cm or more is preferable. When it is less than 0.3 N / cm, the coating layer is easily peeled off in the processing step, and the restriction on use is increased. Preferably, the adhesive strength between the coating layer and the surface layer is 0.1.
5 N / cm or more, more preferably 1.0 N / cm
That is all.

The surface roughness of the polypropylene film for metal vapor deposition of the present invention is defined as a center line surface roughness (Ra) of 0.0 from the viewpoint of handleability, slipperiness and anti-blocking properties.
It is preferably from 1 to 0.2 μm, more preferably from 0.05 to
0.1 μm.

The Young's modulus in the longitudinal direction of the polypropylene film for metal vapor deposition of the present invention is preferably at least 1.3 GPa, more preferably at least 1.5 GPa. When the Young's modulus in the longitudinal direction is less than 1.3 GPa, wrinkles are likely to be formed in the film during secondary processing such as vapor deposition processing and lamination processing, and gas barrier performance may be deteriorated.

The surface gloss of the metal-deposited polypropylene film of the present invention is preferably at least 135%, and more preferably at least 138%, for the beautiful metal gloss after vapor deposition.

Next, as a method of providing a coating layer in the present invention, a coating material for the coating layer is applied to the surface layer using a reverse roll coater, a gravure coater, a rod coater, an air doctor coater or a coating device other than these, outside the polypropylene film manufacturing process. Method of application, preferably,
As a method of applying in the film manufacturing process, a coating layer coating agent is applied to the surface layer of the polypropylene unstretched film, a method of sequentially or simultaneously biaxially stretching, applying to the surface layer of the uniaxially stretched polypropylene film, and further applying For example, there is a method of stretching in a direction perpendicular to the uniaxial stretching direction. Of these methods, the method of applying to the surface layer of the uniaxially stretched polypropylene film and further stretching in the direction perpendicular to the direction of the uniaxial stretching is particularly preferable since the thickness of the coating layer is made uniform and the productivity is improved.

The polypropylene film for metal deposition of the present invention has the above-mentioned surface layer laminated on at least one surface of the base layer,
The coating layer is laminated on at least one surface of the surface layer, but a third layer may be laminated on the other surface where the surface layer is not laminated on one surface of the base layer, if necessary. As the resin of the third layer, for example, a polypropylene-based copolymer resin is laminated in order to impart heat sealability. Further, in order to impart slipperiness, the same organic crosslinked particles or inorganic particles as described above added to the polypropylene-based copolymer resin,
It is preferable that an ethylene-propylene block copolymer, a mixture of the ethylene-propylene block copolymer and high-density polyethylene, and the like are laminated. The third layer surface on the opposite side is activated by corona discharge treatment or the like as necessary.

Next, an example of a method for producing the polypropylene film for metallization of the present invention will be described, but the present invention is not limited by the following production method.

The isotactic polypropylene resin of the base layer and the polypropylene resin of the surface layer according to the present invention and / or
Alternatively, a resin for the third layer is prepared, supplied to a separate extruder, melted at a temperature of 200 to 290 ° C., passed through a filter, and then merged in a short tube or a mouthpiece.
It is extruded from a slit-shaped die at the desired lamination thickness, wound around a metal drum, and cooled and solidified into a sheet to obtain an unstretched laminated film. In this case, the temperature of the cooling drum is preferably set to 30 to 90 ° C. to crystallize the film. The surface layer of this unstretched laminated film is coated with the above-mentioned coating agent for the coating layer (the surface layer is subjected to corona discharge treatment if necessary), and is simultaneously biaxially stretched at 150 to 165 ° C., or in the case of the sequential biaxial stretching method. , 1 unstretched film
The coating is heated to a temperature of 20 to 145 ° C., stretched 4 to 7 times in the longitudinal direction, cooled, and coated with a coating material on the surface of the above-described uniaxially stretched laminated film (the surface of the surface is corona-discharged if necessary). Then, after introducing into a tenter type stretching machine and stretching in the width direction by 7 to 11 times at 150 to 170 ° C., it is subjected to relaxation heat treatment at 155 to 170 ° C. and cooled. Further, the third layer laminated on the opposite side of the base layer provided with the coating layer, if necessary, is subjected to corona discharge treatment in an atmosphere of air, nitrogen, or a mixture of carbon dioxide and nitrogen, and then wound up. For use as a polypropylene film.

The aging of the polypropylene film for metal evaporation obtained in the present invention at 40 to 60 ° C. promotes the reaction of the coating layer, thereby improving the adhesive strength with the surface layer, Is also preferred since the adhesive strength of the resulting material is also improved and the gas barrier performance is improved. The time for aging is preferably 12 hours or more from the viewpoint of improving the adhesive strength between the surface layer and the metal deposition layer and improving the chemical resistance, and more preferably 24 hours or more.

Next, metal evaporation is performed by vacuum evaporation of metal, and metal is evaporated from an evaporation source to form a metal evaporation layer on the coating layer surface of the polypropylene film for metal evaporation in the present invention.

As the evaporation source, a boat type of a resistance heating system, a crucible type by radiation or high frequency heating,
There is a method using electron beam heating, but there is no particular limitation.

As the metal used for the vapor deposition, it is preferable to provide an aluminum vapor-deposited layer on at least one side from the viewpoints of durability, productivity and cost of the metal vapor-deposited layer. At this time, other metal components such as nickel, copper, gold, silver, chromium, zinc, tin, silicon, and magnesium can be deposited simultaneously or sequentially with aluminum. These metals have a purity of 99% or more, preferably 99.5%.
What has been processed into the above granular, rod, tablet, wire or crucible shape is preferred.

The thickness of the metal deposition film is preferably 10 nm or more in order to exhibit a high gas barrier performance. More preferably, it is 20 nm or more. Although there is no particular upper limit for the deposited film, 100 n
Less than m is more preferred.

The glossiness of the metal deposition layer is preferably at least 600%, more preferably at least 700%.

Further, a vapor-deposited film of a metal oxide is provided, and is suitably used as a transparent packaging film and the like as a transparent gas barrier film having excellent gas barrier properties. Here, as the metal oxide deposited film, aluminum oxide is preferable in terms of durability, productivity, and cost of the deposited layer. These vapor deposition methods can be performed by a known method. For example, in the case of an aluminum oxide film, the film is run in a high-vacuum apparatus having a degree of vacuum of 10 ⁻⁴ Torr or less, and the aluminum metal is heated and melted to evaporate. Then, a small amount of oxygen gas is supplied to the evaporating point, and aluminum is oxidized to be agglomerated and deposited on the film surface to form an evaporated film. The thickness of the metal oxide film is preferably in the range of 10 to 50 nm, more preferably in the range of 10 to 30 nm. Oxidation of a metal oxide vapor-deposited film proceeds after vapor deposition, and the light transmittance of the metal oxide vapor-deposited film changes.
The range is 0%. If the light transmittance is less than 70%, the content is difficult to see through in a packaging bag, which is not preferable. Further, when the light transmittance exceeds 90%, gas barrier performance tends to be insufficient when used as a packaging bag, which is not preferable.

The adhesive strength between the coating layer of the polypropylene film for metal evaporation and the metal and metal oxide films is preferably 0.3 N / cm or more, more preferably 0.5 N / cm or more. If the adhesive strength is less than 0.3 N / cm, the vapor-deposited film may be peeled off when the vapor-deposited film is rolled up into a roll and unwound during the secondary processing, and the gas barrier performance may deteriorate.

The gas barrier performance of the polypropylene film for metal vapor deposition of the present invention on which a metal vapor deposition film and a metal oxide vapor deposition were applied was found to have a water vapor transmission rate of 4 g /
m ² . d, the oxygen transmission rate is 200 ml / m ² . d.
It is preferable that it is not more than MPa when used for food packaging.

[Measurement Method of Physical Properties] The characteristic values of the present invention were measured by the following methods. (1) Mesopentad fraction (mmmm) A sample was dissolved in o-dichlorobenzene / benzene-D6, and ¹³ C-NMR was measured at a resonance frequency of 67.93 MHz using a JNM-GX270 apparatus manufactured by JEOL. For the assignment of the obtained spectra and the calculation of the pentad fraction, see T.W. The method performed by Hayashi et al. [Poly
mer, 29, 138-143 (1988)], the peak derived from the methyl group was assigned as 21.855 ppm for the spectrum derived from the methyl group, the peaks were assigned, the peak area was determined, and the ratio to the total peak area derived from the methyl group was calculated as a percentage. Displayed with. Detailed measurement conditions are as follows. Measurement solvent: o-dichlorobenzene (90 wt%) / benzene-D ₆ (10 wt%) Sample concentration: 15 to 20 wt% Measurement temperature: 120 to 130 ° C. Resonance frequency: 67.93 MHz Pulse width: 10 μsec (45 ° pulse) Pulse Repetition time: 7.091 sec Data point: 32K Integration count: 8168 Measurement mode: Noise decoupling

(2) Degree of Isotacticity (II) The sample is vacuum dried at 130 ° C. for 2 hours. Thereafter, the temperature is returned to room temperature, and a sample having a weight of W (mg) is taken therefrom, placed in a Soxhlet extractor, and extracted with boiling n-hexane for 12 hours.
Next, the sample was taken out and sufficiently washed with acetone.
Vacuum dried at 30 ° C. for 6 hours and then weighed W ′ (m
g) is measured and determined by the following equation. II = (W ′ / W) × 100 (%)

(3) Melt flow index (MF)
I) Polypropylene test method according to JIS K-6758 (23
0 ° C, 2.16 kgf).

(4) Crystal melting endothermic peak temperature (° C.) and heat of crystal melting (J / g) Thermal analyzer R manufactured by Seiko Instruments
A DC220 type was charged with 5 mg of a surface layer resin sealed in an aluminum pan, and heated at a rate of 20 ° C./min to determine a peak temperature of heat of crystal fusion. The heat of crystal fusion was calculated from the area of the endothermic peak by using a built-in program of the company's thermal analysis system SSC5200. When a mixture of two or more resins has a plurality of endothermic peaks, the sum of the respective heats of crystal fusion is defined as the heat of crystal fusion. The main peak at this time refers to a single endothermic peak itself when only a single endothermic peak is observed, and a peak having the largest peak area when a plurality of endothermic peaks are observed. The peak temperature and the heat of fusion of the crystal below 155 ° C. are calculated in the same manner. The peak temperature and the heat of fusion are calculated for each peak by the built-in program, and the heats of fusion are totaled.

(5) Surface Layer Thickness, Coating Layer Thickness, Thickness of Metal Deposited Film and Metal Oxide Deposited Layer The cross-sectional structure of the film was observed using a transmission electron microscope (TEM), and the surface layer thickness, the coating layer thickness, and the metal deposition were observed. The thickness of the layer and the metal oxide deposited layer was measured.

(6) Center line average roughness (Ra) As described in JIS B-0601-1976, the center line average roughness R measured on the film surface by the stylus method
Represented by a.

(7) Young's Modulus of Film The film wound into a roll is cut into a 10 mm-width strip, and the length is measured at 50 mm, and the film is mounted on a Tensilon (manufactured by Toyo Sokki) at a tensile speed of 20 mm / min. A rising curve is recorded on chart paper at a chart speed of 500 m / min. After drawing a tangent to the rising curve from the base point of the chart paper, a perpendicular line is drawn at a point 25 mm from the base point, and the intersection of the tangent line and the perpendicular line is read as strong. Then, the Young's modulus (GPa) is calculated by the following equation. Young's modulus (GPa) = [Strength (kg) x Test length (mm) x
Chart speed (mm / min)] ÷ [Pull speed (mm / min)
min) × 25 mm × film thickness (mm) × film width (mm)] × 9.807 × 10 ⁻³

(8) Surface Gloss of Film (%) Based on JIS Z8741 method, it was determined as 60 ° specular gloss using a digital variable angle gloss meter UGV-5D manufactured by Suga Test Instruments.

(9) Surface Gloss (%) of Metal-Deposited Film A polypropylene film for metal-deposition is loaded into a continuous vacuum evaporation apparatus, aluminum is evaporated from an electron beam heating type evaporation source, and the film is continuously run. While
The optical density (-log (light transmittance)) measured using an optical densitometer (TR927) manufactured by Macbeth is 1.9.
Aluminum was deposited in the range of ２．１2.1. The metal-deposited surface of this metal-deposited polypropylene film is
The measurement was performed based on Z8741 to determine the surface gloss.

(10) Adhesive strength (N / cm) The adhesive strength between the coating layer and the surface layer of the polypropylene film for metal deposition was determined by applying a 20 μm thick biaxially oriented polypropylene film (S645, manufactured by Toray Industries, Inc.) to the coating layer surface. After bonding with a polyurethane-based adhesive and standing at 40 ° C. for 48 hours, measurement was performed by 90 ° peeling at a peeling speed of 10 cm / min using a 15 mm width Tensilon made by Toyo Baldwin. The adhesion strength between the metal-deposited film and the metal-oxide-deposited film and the metal-deposited polypropylene film was 20 μm
Thick biaxially oriented polypropylene film (S by Toray Industries, Inc.)
645) was bonded using a polyurethane-based adhesive and measured in the same manner as above.

(11) Oxygen permeability (ml / m ² .dm)
Pa) Adhesive film made of polypropylene (Scotchmark, 40 μm thickness, manufactured by 3M) on the surface on which metal deposition was performed.
Were bonded, and the measurement was carried out using an oxygen transmittance measuring device Oxtran 2/20 manufactured by Modern Controls, Inc., at a temperature of 73 ° F. (22.8 ° C.) and a humidity of 0%.

(12) Water vapor transmission rate (g / m ² .d) A pressure-sensitive adhesive film made of polypropylene (Scotchmark, 40 μm thickness, manufactured by 3M) was applied to the surface on which metal deposition was performed.
Were bonded, and the measurement was carried out under the conditions of a temperature of 100 ° F. (37.8 ° C.) and a humidity of 100% RH using an oxygen transmittance measuring apparatus Oxtran 2/20 manufactured by Modarn Controls.

(13) Pickoff 10 cm × 10 cm of metal-deposited polypropylene film
A minute omission of the metal-deposited thin film in the area of No. was visually observed.

[0073]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below based on embodiments. Example 1 A coating material for a coating layer was obtained by the following method. First, "Hydran" A is a polyester urethane water-dispersible resin.
100 parts by weight of P-40F (manufactured by Dainippon Ink and Chemicals, Inc., solid content 20%) and N- as a water-soluble organic solvent
10 parts by weight of a melamine compound "Beckamine" APM (manufactured by Dainippon Ink and Chemicals, Inc.) as a cross-linking agent is added to a coating composition containing 5 parts by weight of methylpyrrolidone, and a water-soluble acidic compound " Catalyst "PT
S (manufactured by Dainippon Ink and Chemicals, Inc.) was added to 2 parts by weight of the mixed coating agent, and the solid content was diluted to 10% with distilled water.

Next, as a resin for the base layer of the present invention, isotactic polypropylene having a mesopentad fraction of 98% (isotactic index: 98.5, MF
I: 2.3 g / 10 min.), And isotactic polypropylene having a mesopentad fraction of 74% (isotactic index: 85) as a surface resin.
%, MFI: 2.8 g / 10 min, endothermic peak temperature accompanying crystal melting: 162 ° C., heat of crystal fusion: 52 J / g)
0.05% of crosslinked polymethyl methacrylate particles (crosslinked PMMA particles) having an average particle size of 2 μm as an organic crosslinked particle lubricant.
A resin composition added in parts by weight, and an ethylene-propylene-butene copolymer (ethylene copolymerization amount: 2.5% by weight, butene copolymerization amount: 12%) as a heat seal layer resin on the surface opposite to the base layer where the surface layer is not laminated %) As an organic crosslinked particle lubricant, crosslinked silicone particles (crosslinked S) having an average particle size of 4 μm.
i) Each of which was added with 0.15% by weight was supplied to a separate extruder, melt-extruded at 270 ° C., passed through a filter, and then turned into a surface layer / base layer / heat seal layer in a three-layered die. And then extruded from a slit-shaped die and wound around a metal drum heated to 60 ° C. to form a sheet. This sheet was heated to a temperature of 132 ° C., stretched 5 times in the longitudinal direction, cooled, and then exposed to 12 W. After applying a corona discharge treatment with a treatment intensity of min / m ² and applying the mixed coating agent for the coating layer in the foreground to the surface layer,
Subsequently, it is led to a tenter type stretching machine and preheated at 170 ° C.
Subsequently, the film was stretched 9 times in the width direction at 160 ° C., heat-treated at 165 ° C. while giving 10% relaxation in the width direction, and cooled. The thickness configuration of the film was a coating layer / surface layer / base layer / heat seal layer: a polypropylene film for metal deposition having a thickness of 0.1 μm / 1 μm / 15 μm / 2 μm. The coating composition of the coating layer at this time is shown in Table 1, the film composition is shown in Table 2, and the characteristics evaluation results of the film are shown in Table 3. The adhesive strength between the coating layer and the surface layer of the film of the present invention is 2.0 N
/ Cm, and the center line average roughness Ra of the coating layer is 0.1.
At 03 μm, the gloss was 140%.

Next, aluminum metal is heated and melted and evaporated in the vacuum evaporation apparatus so that the light transmittance becomes 90% on the polypropylene film for metal evaporation, and a small amount of oxygen gas is supplied to the evaporation point. Then, aluminum was coagulated and deposited on the film surface while incompletely oxidizing aluminum, and a vapor-deposited film was attached to obtain a metal oxide-deposited polypropylene film. Table 3 shows the evaluation results. The metal oxide-deposited polypropylene film has no pick-off, and its gas barrier performance is such that the oxygen permeability is 80 ml / m ² . d. MPa, water vapor transmission rate 1.2 g / m ² . d. The adhesive strength between the coating layer and the metal oxide vapor-deposited layer was 1.7 N / cm.

Examples 2 and 3 A film was formed under the same conditions as in Example 1 except that the surface layer resin had a mesopentad fraction, a melting temperature and a heat of fusion as shown in Table 2, and a polypropylene for metal deposition was prepared. To obtain a film and a metal oxide-deposited polypropylene film,
evaluated. Table 1 shows the composition of the coating layer at that time, and Table 3 shows the results of evaluating the properties of the film.

Example 4 Hydrogenated dicyclopentadiene resin ("Escolets" 5320HC manufactured by Tonex) was used as the petroleum resin containing substantially 90% by weight of the isotactic polypropylene of the surface layer used in Example 1 and having substantially no polar group. Of 10% by weight, and further, as inorganic particles, a crosslinked PMM having an average particle size of 2 μm.
A polypropylene film for metal deposition and a metal oxide-deposited polypropylene film were obtained in the same manner as in Example 1, except that 0.10 parts by weight of the A particles was used as the surface layer resin composition. Table 1 shows the coating composition of the coating layer at this time, Table 2 shows the film composition, and Table 3 shows the evaluation results of the film properties.

Example 5 70% by weight of the isotactic polypropylene of the surface layer used in Example 1 and syndiotactic polypropylene 3
Except that the mixture of 0% by weight was used as the surface layer resin composition.
In the same manner as in Example 1, a polypropylene film for metal deposition and a polypropylene film for metal oxide deposition were obtained.
Table 1 shows the coating composition of the coating layer at this time, Table 2 shows the film composition, and Table 3 shows the evaluation results of the film properties. The ratio of the melting peak area of the surface layer was 130 ° C. and 162 ° C., the main peak temperature at that time was 162 ° C., and the ratio of the heat of fusion was 130 ° C./162° C. = 3/7.

Example 6 An isotactic polypropylene having a mesopentad fraction of 90% (isotactic index:
96.5, MFI: 2.3 g / 10 min.), And a film was formed under the same conditions as in Example 1 to obtain a metallized polypropylene film and a metal oxide-deposited polypropylene film. Table 1 shows the composition of the coating layer, Table 2 shows the composition of the film, and Table 3 shows the results of evaluating the properties of the film.

Examples 7 and 8 The laminate structure was changed to cover layer / surface layer / base layer / heat seal layer:
A film was formed under the same conditions as in Example 1 except that 0.1 μm / 0.5 μm / 17 μm / 2 μm (Example 7) and 0.1 μm / 3 μm / 15 μm / 2 μm (Example 8) were used for metal deposition. A polypropylene film and a metal oxide-deposited polypropylene film were obtained and evaluated. The composition of the coating layer at that time is shown in Table 1, the composition of the film is shown in Table 2, and the results of the property evaluation are shown in Table 3.

Example 9 The composition of the coating layer was determined based on 100 parts by weight of "Hydran" (a polyester urethane-based water-dispersible resin) AP-70 (manufactured by Dainippon Ink and Chemicals, Inc., solid content: 35%).
Ethyl cellosolve acetate as a water-soluble organic solvent
0 parts by weight, 5 parts by weight of an isocyanate compound hexamethylene diisocyanate as a crosslinking agent, 1.5 parts by weight of "Catalyst" PTS (manufactured by Dainippon Ink and Chemicals, Inc.) as a crosslinking accelerator, and The same conditions as in Example 1 were used, except that 0.1 part by weight of water-dispersed silica particles having an average particle size of 0.05 μm was added to the surface of the film after diluting to a solid content of 10% with distilled water. Films were formed, and a polypropylene film for metal deposition and a polypropylene film for metal oxide deposition were obtained and evaluated. The coating composition at this time is shown in Table 1, the film composition is shown in Table 2, and the property evaluation results are shown in Table 3.

Example 10 Instead of the water-soluble organic solvent N-methylpyrrolidone of the mixed coating composition for the coating layer of Example 1, dimethylformamide was mixed, and 5 parts by weight of diglycidyl ether isophthalate was used as a crosslinking agent. A polypropylene film for metal deposition and metal oxidation were prepared in the same manner as in Example 1 except that 0.05 parts by weight of water-dispersed silica particles having a particle diameter of 0.1 μm were mixed and applied to the surface layer to form a coating layer. A product-deposited polypropylene film was obtained. Table 1 shows the coating composition of the coating layer at this time.
Table 2 shows the film composition, and Table 3 shows the evaluation results of the film properties.

Examples 11 and 12 As shown in Table 2, except that the thickness of the coating layer was 0.05 μm (Example 11) and 2 μm (Example 12).
The film was formed under the same conditions as described above, and a polypropylene film for metal deposition and a metal oxide-deposited polypropylene film were obtained and evaluated. Table 1 shows the coating composition of the coating layer at that time, Table 2 shows the film composition, and Table 3 shows the evaluation results of the film properties.

Example 13 A metal-deposited polypropylene film was obtained in the same manner as in Example 1, except that aluminum metal was deposited on the coating layer of the polypropylene film for metal deposition of Example 1. The film composition at this time is shown in Table 2, and the evaluation results of the film properties are shown in Table 3. As for the gas barrier performance of the metal-deposited polypropylene film, the oxygen permeability was 49 (ml / m ² .
d. MPa), and the water vapor transmission rate was 0.6 (g / m ² .d). The glossiness of the surface of the vapor deposition layer was 780%, and the adhesive strength between the coating layer and the metal vapor deposition layer was 1.3 N / cm.

As shown in Table 3, the polypropylene film for metal deposition and the metallized polypropylene film of the present invention have excellent Young's modulus and excellent heat resistance of the surface resin, and thus have excellent vapor deposition workability. In addition, it has the characteristics of excellent adhesive strength between the coating layer and the metal deposition layer, and excellent gas barrier performance against oxygen and water vapor.

As is evident from Examples 2 and 3, when the crystal melting temperature and the heat of fusion of the surface resin are reduced, the adhesive strength is improved and the gas barrier performance is increased. When the crystal melting temperature and the heat of fusion are increased, the adhesive strength is increased. Although the strength tends to decrease and the gas barrier performance tends to decrease, within the scope of the claims of the present invention, there is no pick-off of the metal oxide deposited layer, and the gas barrier performance is excellent in practice. As is apparent from Example 4, when a petroleum resin is added to the surface resin, the adhesive strength is further improved, and this is more preferable.

In Example 5, the surface resin composition was such that isotactic polypropylene and syndiotactic polypropylene were mixed, and the peak of the crystal melting temperature was 100 to 16;
There are two points in the range of 3 ° C., the main peak temperature is 162 ° C., and the sum of the heats of fusion is 43 J / g. It can be seen that the adhesive strength is increased, and there is no pick-off of the metal oxide deposited layer, and as a result, the gas barrier performance is also improved.

As is apparent from Example 6, when the mesopentad fraction of the isotactic polypropylene in the base layer decreases, the Young's modulus tends to decrease, and the gas barrier performance tends to decrease. However, within the scope of the claims of the present invention, There is no pick-off of the metal oxide deposited layer, and it has excellent gas barrier performance.

Further, as is apparent from Example 7, when the thickness of the surface layer is small, the adhesive strength and gas barrier performance tend to decrease, but there is no pick-off of the metal oxide vapor deposited layer, and excellent gas barrier performance is obtained. Have. As is apparent from Example 8, when the lamination thickness of the surface layer is too large,
Although the Young's modulus tends to decrease and the gas barrier performance after metal deposition tends to decrease, there is no pick-off of the metal oxide vapor deposition layer, and the gas barrier performance is excellent.

As is apparent from Examples 9 and 10,
If the coating layer composition falls within the range of the present invention, the adhesive strength between the surface layer and the metal deposition layer is excellent, the metal oxide deposition layer is not picked off, and the gas barrier performance after metal deposition is excellent.
As is clear from Examples 11 and 12, when the thickness of the coating layer is small, the adhesive strength and gas barrier performance tend to decrease, and when it is large, the adhesive strength and gas barrier performance tend to decrease. Within the scope of the invention, there is no pick-off of the metal oxide vapor-deposited layer, and the gas oxide layer has practically excellent gas barrier performance.

As apparent from Example 13, the metallized polypropylene film of the present invention exhibits excellent adhesion strength and excellent gas barrier performance even in metallization without pick-off of the metallized layer.

Comparative Example 1 A metal-deposited polypropylene film was prepared in the same manner as in Example 1 except that a polypropylene film having only a base layer film was obtained without providing a coating layer in Example 1, and aluminum was deposited on the base layer. Obtained. Table 5 shows the film composition at this time, and Table 6 shows the results of evaluating the properties of the film. The adhesive strength between the base layer and the metal deposition layer is 0.25 N / cm
Therefore, the adhesive strength between the coating layer and the metal oxide deposited layer could not be measured, the pick-off occurred frequently in the metal oxide deposited layer, the oxygen permeability was 470 (ml / m ² .dMPa),
The water vapor transmission rate was 3.4 (g / m ² .d), and the gas barrier performance was poor.

Comparative Example 2 In Example 1, the coating composition for the coating layer was changed only to “Hydran” (a polyester urethane-based water-dispersible resin) AP-40F (manufactured by Dainippon Ink and Chemicals, Inc.). 0.
A metal oxide-deposited polypropylene film was obtained in the same manner as in Example 1 except that the film was laminated at 1 μm. The resin composition of the coating layer at this time is shown in Table 4, the composition of the film is shown in Table 5, and the evaluation results of the film properties are shown in Table 6. This film has a water-soluble organic solvent, a cross-linking agent and a cross-linking catalyst which are not added to and mixed with the coating composition for the coating layer, and the curing of the coating layer is insufficient, and the adhesive strength with the surface layer is as low as 0.1 N / cm. Therefore, the adhesion strength between the coating layer and the metal oxide deposition layer could not be measured,
Pickoff frequently occurs in the metal oxide deposited layer, the oxygen permeability is 670 (ml / m ² .dMPa), and the water vapor permeability is 3.
5 (g / m ² .d), which was inferior in gas barrier performance.

Comparative Example 3 0.12 mol of terephthalic acid, 0.84 mol of isophthalic acid, 0.33 mol of diethylene glycol and 0.65 mol of neopentyl glycol were used as coating materials for the coating layer.
under a catalyst at a temperature of 190 to 220 ° C. for 6 hours while removing water distilled off, and then a condensation reaction at 250 ° C. under reduced pressure for 1 hour to obtain a prepolymer.
Dioxotetrahydrofurfuryl) -3-methyl-3-
Cyclohexene 1,2-dicarboxylic anhydride 0.13m
and a selective monoesterification reaction at 140 ° C. for 3 hours to obtain a polymer. This polymer has an oxidation of 65K
OH mg / g. The polymer was neutralized with ammonia to obtain a polyester resin. Next, 10 parts by weight of an isocyanate compound, hexamethylene diisocyanate, was added as a crosslinking agent to 100 parts by weight of the active ingredient of the polyester resin, and "Catalyst" PTS (manufactured by Dainippon Ink and Chemicals, Inc.) was used as a crosslinking catalyst. )
1.5 parts by weight of N-methylpyrrolidone for improving the adhesion to the base layer and the metal deposition layer, and water-dispersed silica having an average particle diameter of 0.05 μm for improving the sliding property. A metal oxide-deposited polypropylene film was obtained in the same manner as in Example 1, except that 0.1 parts by weight of the particles were mixed. The coating composition of the coating layer at this time is shown in Table 4, the film composition is shown in Table 5, and the film properties are shown in Table 6. For polyester resin, the adhesive strength to the surface layer is 0.17
N / cm, so that the adhesion strength between the coating layer and the metal oxide deposited layer could not be measured, the pick-off frequently occurred in the metal oxide deposited layer, and the oxygen permeability was 415 (ml / m ² .d.MP).
a), the water vapor transmission rate was 3.3 (g / m ² .d), and the gas barrier performance was poor.

Comparative Examples 4 and 5 As Comparative Example 4, the coating layer thickness of Example 1 was set to 0.02 μm, and as Comparative Example 5, the coating layer thickness of Example 1 was set to 3 μm.
A polypropylene film for metal vapor deposition and a metal oxide vapor-deposited polypropylene film were obtained in the same manner as in Example 1 except that the above conditions were adopted. Table 4 shows the coating composition of the coating layer at this time.
Table 5 shows the film composition, and Table 6 shows the film properties. If the thickness of the coating layer is thin, the adhesive strength between the surface layer and the coating layer is reduced, so that the adhesive strength between the coating layer and the metal oxide deposited layer cannot be measured. did. When the thickness of the coating layer is as thick as 3 μm, the curing of the coating layer becomes insufficient, the adhesive strength with the surface layer is reduced, and the gas barrier performance is also reduced.

Comparative Example 6 An isotactic polypropylene polymer having a mesopentad fraction of 85% (isotactic index: 86%, MFI: 2.5 g / 10 minutes) was used as a resin for the base layer.
In the same manner as in Example 1, except that a resin composition was used in which 0.05 parts by weight of crosslinked polystyrene particles (crosslinked PS particles) having an average particle size of 4 μm were added as an organic crosslinked particle lubricant, a polypropylene film for metal deposition and a metal were used. An oxide-deposited polypropylene film was obtained. The coating composition of the coating layer at this time is shown in Table 4, the film composition is shown in Table 5, and the film properties are shown in Table 6. Since the mesopentad fraction of isotactic polypropylene in the base layer is low, the Young's modulus in the longitudinal direction of the film is reduced to 1.17 GPa, the film is stretched by the winding tension during metal deposition, and the gas barrier performance is reduced by oxygen permeation. Rate 252 (ml / m ² .d.MP
a), the water vapor permeability deteriorates to 4.2 (g / m ² .d).

Comparative Examples 7 and 8 In Comparative Example 7, an isotactic polypropylene polymer having a mesopentad fraction of 98.5% (isotactic index: 98%, MFI:
3.5 g / 10 min), crosslinked polystyrene particles (crosslinked PS particles) having an average particle size of 2 μm as an organic crosslinked particle lubricant.
In Comparative Example 8, ethylene resin was used as the surface layer resin. propylene. Butene random copolymer (ethylene: 4%, butene: 18%, M
FI: 6.9 g / 10 min), and 0.05 parts by weight of crosslinked polystyrene particles (crosslinked PS particles) having an average particle size of 2 μm as an organic crosslinked particle lubricant were added.
In the same manner as in Example 1, a polypropylene film for metal deposition and a polypropylene film for metal oxide deposition were obtained.
The coating composition of the coating layer at this time is shown in Table 4, the film composition is shown in Table 5, and the film properties are shown in Table 6. If the mesopentad fraction of the isotactic polypropylene in the surface layer is high, the adhesion strength between the surface layer and the coating layer is reduced, so that the adhesion strength between the coating layer and the metal oxide deposition layer cannot be measured, and the metal oxide deposition layer The pick-off frequently occurred, and the gas barrier performance also deteriorated. In addition, the main peak of endothermic heat due to crystal melting of the surface layer is low, and the heat of the deposited metal occurs during metal oxide deposition, and the deposited film whitens due to the heat of the deposited metal when the amount of heat of crystal fusion is low, and after being wound into a roll, Blocking causes peeling of the deposited film, and deteriorates gas barrier performance.

Comparative Examples 9 and 10 In Comparative Example 9, the surface layer thickness of Example 1 was reduced, and the film structure was changed to cover layer / surface layer / base layer / heat seal layer: 0.1 μm.
m / 0.2 μm / 15 μm / 2 μm. In Comparative Example 10, the surface layer thickness of Example 1 was increased, and the film configuration was changed to cover layer / surface layer / base layer / heat seal layer: 0.1 μm / 7 μm.
A polypropylene film for metal deposition and a metal oxide-deposited polypropylene film were obtained in the same manner as in Example 1 except that the thickness was changed to / 10 μm / 2 μm. The coating composition of the coating layer at this time is shown in Table 4, the film composition is shown in Table 5, and the film properties are shown in Table 6. If the surface layer thickness was too thin, partial film breakage occurred during the film formation, and the adhesive strength with the coating layer was reduced, so that pick-off frequently occurred in the metal oxide vapor-deposited layer and gas barrier performance was reduced. When the thickness of the surface layer is 以上 or more of the thickness of the base layer, the Young's modulus in the longitudinal direction of the film decreases, and the film elongates due to the winding tension during metal deposition, and the gas barrier performance deteriorates.

Comparative Example 11 As the surface resin, ethylene. propylene. Butene random copolymer (EPBC) (ethylene: 4%, butene: 1
8%, MFI: 6.9 g / 10 min, crystal melting temperature 135
Isotactic polypropylene (isotactic index: 90%, MFI: 3.5) with 80% by weight and a mesopentad fraction of 85%.
g / 10 min, Endothermic peak temperature accompanying crystal melting: 162
(C, heat of crystal fusion: 65 J / g) A polypropylene film for metal deposition and a polypropylene film for metal oxide deposition were obtained in the same manner as in Example 1, except that the mixture was 20% by weight. The coating composition of the coating layer at this time is shown in Table 4, the film composition is shown in Table 5, and the film properties are shown in Table 6. The peak of the crystal melting temperature of the surface layer is 135 ° C. and 162 ° C.
The sum of the heats of fusion is 27 J / g, and if it is less than the main peak of the crystal melting temperature of 155, blocking occurs on the opposite surface after metal deposition, and a large number of pickoffs occur to deteriorate the gas barrier performance.

[0100]

[Table 1]

[0101]

[Table 2]

[0102]

[Table 3]

[0103]

[Table 4]

[0104]

[Table 5]

[0105]

[Table 6]

[0106]

According to the polypropylene film for metal deposition and the metallized polypropylene film of the present invention,
A specific isotactic polypropylene resin as a base layer, a surface layer of a specific polypropylene resin is laminated on at least one surface thereof, and a coating layer comprising a mixed coating agent of a polyester urethane resin and a water-soluble organic solvent is provided on the surface layer, By performing metal deposition on the surface of the coating layer, it is possible to achieve excellent adhesion strength and gas barrier performance of the metal-deposited film after metal deposition, which cannot be achieved by conventional techniques.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 57/02 C08L 57/02 99/00 99/00

Claims (9)

[Claims] 1. A main endothermic peak due to crystal melting is 155 to 163 on at least one surface of a base layer made of isotactic polypropylene having a mesopentad fraction of 90% or more.
° C, a surface layer of a polypropylene-based resin having a heat of crystal fusion in the range of 20 to 90 J / g is laminated, and a mixture of a polyester urethane-based resin and a water-soluble organic solvent is formed on the surface layer. The thickness is 0.05μm ～ 2
A polypropylene film for metal deposition, provided with a coating layer in a range of μm. 2. The polypropylene film for metal vapor deposition according to claim 1, wherein all endothermic peaks associated with the crystal melting of the surface layer polypropylene-based resin are in the range of 100 to 163 ° C. 3. The polypropylene film for metal vapor deposition according to claim 1, wherein the polypropylene resin of the surface layer is a resin mainly composed of isotactic polypropylene having a mesopentad fraction of 60 to 88%. 4. The surface layer has a thickness of 0.25 μm or more,
The polypropylene film for metal deposition according to any one of claims 1 to 3, wherein the thickness is not more than half the thickness of the base layer. 5. A polypropylene resin having a mesopentad fraction of 60% to 88%, wherein at least one resin selected from a petroleum resin substantially free of a polar group and a terpene resin substantially free of a polar group is used as a surface resin. The polypropylene film for metal vapor deposition according to any one of claims 1 to 4, wherein 20 parts by weight is added to the upper limit with respect to 100 parts by weight of the resin. 6. A coating layer comprising at least one crosslinking agent selected from isocyanate compounds, epoxy compounds and amine compounds with respect to 100 parts by weight of a mixed coating of a polyester urethane resin and a water-soluble organic solvent. The polypropylene film for metal vapor deposition according to any one of claims 1 to 5, wherein 3 to 15 parts by weight is added. 7. The polypropylene film for metal deposition according to claim 1, wherein the water-soluble organic solvent comprises at least one of N-methylpyrrolidone, ethyl cellosolve acetate and dimethylformamide. 8. A metal-deposited polypropylene film, comprising a metal-deposited film provided on the surface of the coating layer of the metal-deposited polypropylene film according to claim 1. 9. The metallized polypropylene film according to claim 8, wherein the metallized film is aluminum and / or aluminum oxide.