JP2000108262A - Polypropylene film for metal deposition and metal- deposited polypropylene film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve adhesive property between a metal-deposited film and a substrate and improve gas barrier property by a method wherein a coating layer, comprising a mixed coating agent of a polyester urethane base resin and water-soluble organic solvent while having a specified thickness, is provided on the surface of the base layer of a polypropylene resin to specify a bonding strength between the base layer and the coating layer. SOLUTION: A polypropylene resin forming a base layer is a crystalline isotactic polypropylene resin and the mesopented rate of the isotactic polypropylene resin is preferably 88% or more. The coating layer of this film is constituted of mixed coating agent of a polyester urethane base resin and water-soluble organic solvent while the coating layer can be formed by coating and drying the mixed coating agent or a water-soluble and/or water dispersive crosslinked polyester urethane base resin and a water soluble organic solvent. The thickness of the coating layer, formed on at least one side of the base layer, is 0.05-2 μm while a bonding strength between the base layer and the coating layer is 0.3 N/cm or more.

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 metal-deposited polypropylene film and a metal-deposited polypropylene film which are provided with a metal-deposited film on a metal-deposited polypropylene film and have excellent gas barrier properties and moisture-proof properties.

[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 widely deposited (metallized) for the purpose of improving the appearance at the time of display due to metallic luster, improving gas barrier performance, and suppressing deterioration of the contents due to external light such as ultraviolet rays. ing.

Japanese Patent Application Laid-Open No. 7-314612 discloses a thermoplastic resin film for packaging in which the surface carboxylic acid concentration of the coating is 0.005 or more and a metallized thermoplastic film for packaging having a metal layer on the coating. JP-A-266484 discloses a gas barrier laminate having a vapor-deposited layer made of an inorganic compound on a coating layer formed by applying and drying a mixed solution of a metal alkoxide and an isocyanate compound on a base layer, with the aim of improving gas barrier performance. Japanese Unexamined Patent Publication No. Hei 8-267637 discloses a gas barrier material having a vapor-deposited layer in which a metal alkoxide or a hydrolyzate is provided on a metal surface of a vapor-deposited film in which a vapor-deposited layer made of an inorganic compound is provided on a base layer. However, when the base layer is a polypropylene resin, the adhesive strength between 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, and the gas barrier performance deteriorates. Sometimes. Further, there is a problem that the vapor deposition layer of the vapor deposition film is damaged during the process of providing the coating layer off-line, resulting in poor appearance or deterioration of gas barrier performance.

[0004]

DISCLOSURE OF THE INVENTION In view of the above-mentioned circumstances, the present invention provides a polypropylene film for 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. And a metal-deposited polypropylene film.

[0005]

That is, the present invention provides a coating layer having a thickness of 0.05 μm to 2 μm comprising a mixed coating of a polyester urethane resin and a water-soluble organic solvent on at least one surface of a polypropylene resin base layer. Provided film, wherein the adhesive strength between the base layer and the coating layer is 0.3 N / cm
The above is a polypropylene film for metal vapor deposition as described above, and a metal vapor deposited film made thereof.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The polypropylene resin forming the base layer of the present invention is a crystalline isotactic polypropylene resin. The mesopentad fraction of the isotactic polypropylene resin is preferably at least 88%. The mesopentad fraction is the proportion of the isotactic tertiary structure measured by ¹³ C-NMR in the entire structure. When the meso pentad fraction is less than 88%, the effect on the mechanical properties of the biaxially oriented polypropylene film becomes large, causing a decrease in Young's modulus, and the polypropylene film for metal deposition tends to elongate under tension, resulting in poor workability. There are cases. More preferably, the mesopentad fraction is 90%.
That is all. The Young's modulus in the longitudinal direction of the polypropylene film for metal deposition of the present invention is preferably 1.3 GPa or more,
1.5 GPa or more is more preferable.

The mesopentad fraction of the polypropylene resin in the present invention 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. In general, 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)], etc., the ratio of the segment having each of the above conformations can be determined from ¹³ C-NMR. Among these, the ratio of the conformation of mmmm to the absorption intensity of all methyl groups, that is, the mesopentad fraction (hereinafter referred to as mm
mm) may be m (mmmm) m, m
It is defined as the sum of three heptad fractions of (mmmm) r and r (mmmm) r.

The isotacticity of the isotactic polypropylene resin of the base layer (hereinafter abbreviated as II)
Is preferably 85% or more. II is boiling n-
It is the weight ratio of the undissolved portion when extracted with hexane. I
If I is less than 85%, 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 1 to 15
It is desirably in the range of g / 10 minutes. By using such a polypropylene resin, film formation stability is improved.

As the resin for the base layer, an isotactic polypropylene resin alone is preferable, but a polypropylene-based copolymer resin or the like may be laminated on the base layer depending on the purpose, and these copolymer resins are collected in the base layer. In this case, another copolymer resin 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 coating layer and the metal deposition film. It is permissible to add a small amount of organic crosslinkable particles or inorganic particles in order to improve the particle size. 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 and calcium carbonate,
Examples include silicon oxide and aluminum silicate. The average particle size of these particles is preferably in the range of 0.5 to 5 [mu] m, since slipperiness can be imparted without greatly deteriorating the transparency of the film of the present invention.

The base 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 5 in order not to lower the heat resistance.
The temperature is preferably 0 ° C or higher, more preferably 76 ° C or higher. 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 (ie, substantially no crystal melting is observed when the petroleum resin is measured by a differential calorimeter) from the viewpoint of compatibilization with the isotactic polypropylene resin of the base layer. The number average molecular weight is preferably 1,000 or less.

The terpene resin substantially containing no polar group includes a hydroxyl group (—OH), an aldehyde group (—CHO), a ketone group (—CO—), a carboxyl group (—COOH),
Halogen group, sulfonic acid group (—SO ₃ Y, Y is H, Na
And terpene resins having no polar group, such as modified hydrocarbons having a composition of (C ₅ H ₈ ) _n and modified compounds 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 crosslinked 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.

The dicarboxylic acid component includes 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.

The diol component includes 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, they have a linear structure, but they have a tri- or higher valent 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, and hexamethylene diisocyanate and trimethylol. Ethane adducts and the like can be mentioned.

Examples of the chain extender include pendant carboxyl group-containing diols such as ethylene glycol, diethylene glycol, propylene glycol, and the like.
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.

Further, when forming the coating layer constituting the present invention, in order to improve the coating formability of the coating layer and the adhesive force between the coating layer and the polypropylene resin base layer, N- It is preferable to add at least one of methylpyrrolidone, ethyl cellosolve acetate, and dimethylformamide. In particular, N-methylpyrrolidone is preferable because it has a large effect of improving the film formability and the adhesion to the substrate. The amount of the polyester urethane resin 1
1 to 15 parts by weight based on 00 parts by weight is preferable from the viewpoint of the flammability of the coating agent and the prevention of odor deterioration, and more preferably 3 to 15 parts by weight.
10 parts by weight.

Further, as a method for obtaining a coating liquid in which a crosslinked structure is introduced into a water-dispersible polyester urethane resin, JP-A-63-15816, JP-A-63-256661, and JP-A-5-152159. There is a method. As the crosslinking 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 adhesiveness between the base layer and the metal deposition film. Examples of the isocyanate-based compound include the above-mentioned toluene diisocyanate, xylene diisocyanate, naphthalene diisocyanate, and hexamethylene diisocyanate. Diisocyanate,
Examples include, but are not limited to, isophorone diisocyanate.

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.

From the viewpoints of food hygiene and adhesion to a substrate, it is preferable to add an amine compound to the coating layer of the present invention.

The amount of the crosslinking agent selected from isocyanate compounds, epoxy compounds and amine compounds is as follows:
1 to 15 parts by weight per 100 parts by weight of the mixed coating agent of the water-soluble polyester urethane resin and the water-soluble organic solvent is preferable from the viewpoint of improving chemical resistance and preventing deterioration of water resistance, and more preferably 3 to 10 parts by weight. is there. If the amount of the crosslinking agent is too small, the effect of improving the adhesiveness may be insufficient,
If the amount is too large, there is a decrease in adhesiveness presumably due to the unreacted cross-linking agent.

Further, a small amount of a crosslinking accelerator may be added in order to completely cross-link and cure the above-mentioned coating layer composition within the speed of forming the film of the present invention. 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-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.

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 and a mixture thereof may be added.

In the polypropylene film for metal vapor deposition constituting the film of the present invention, it is necessary to provide a coating layer having a thickness of 0.05 to 2 μm on at least one surface of the base layer. If the coating layer is thinner than 0.05 μm, the adhesiveness to the base layer is deteriorated, causing 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-described crosslinking reaction may be incomplete and the gas barrier performance may deteriorate.When the coating layer is provided on the base 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 base layer is 0.1.
3 N / cm or more is required. 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 base layer is 0.5 N / cm or more, more preferably 1.0 N / cm.
cm or more.

The film surface in the present invention preferably has a center line average roughness Ra of 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm, from the viewpoint of handleability, slipperiness and anti-blocking properties. It is.

Further, the surface gloss of the metallized polypropylene film of the present invention is preferably 135% or more for the beautiful metallic luster after the deposition, more preferably 138%.
That is all.

In the present invention, as a method for providing a coating layer, a method of applying a coating liquid outside a polypropylene film production step using a reverse roll coater, a gravure coater, a rod coater, an air doctor coater or any other coating apparatus, preferably As a method of applying in a film manufacturing process, a coating liquid is applied to an unstretched polypropylene film, and a method of sequentially or simultaneously biaxially stretching the same is applied to a uniaxially stretched polypropylene film. And the like. Of these, the method of applying to a uniaxially stretched polypropylene film and further stretching in a direction perpendicular to the uniaxial stretching direction is particularly preferable because the thickness of the coating layer is made uniform and the productivity is improved.

In the polypropylene film for metal vapor deposition of the present invention, the above-mentioned coating layer is laminated on at least one side of the base layer, but a third layer may be laminated on the other side of the base layer, if necessary. As the resin of the third layer, for example, a polypropylene-based copolymer is laminated to impart heat sealing properties. Further, in order to impart slipperiness, a polypropylene resin to which organic crosslinked particles or inorganic particles are added, an ethylene-propylene block copolymer,
It is preferable that a mixture of the ethylene-propylene block copolymer and the high-density polyethylene is laminated. The third layer surface on the opposite side is activated by corona discharge treatment or the like as necessary.

Next, an example of the 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 / or the resin of the third layer of the present invention were prepared, supplied to separate extruders, melted at a temperature of 200 to 290 ° C., and passed through a filter. Thereafter, they are merged in a short pipe or a die, extruded from a slit die with a 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. In the case of applying the above-mentioned coating agent to the base layer of the unstretched laminated film (the surface of the base layer is subjected to corona discharge treatment if necessary) and simultaneously biaxially stretching at 150 to 165 ° C, or in the case of the sequential biaxial stretching method ,
The unstretched film is heated to a temperature of 120 to 145 ° C., stretched 4 to 7 times in the longitudinal direction, cooled, and coated with the above-mentioned coating layer coating material which has been uniaxially stretched (the surface of the base layer is treated by corona discharge 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.

Aging the polypropylene film for metal vapor deposition obtained in the present invention at 40 to 60 ° C. promotes the reaction of the coating layer, thereby improving the adhesive strength with the base 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 the effect of improving the chemical resistance, and more preferably 24 hours or more.

Next, metal evaporation is performed by vacuum evaporation of the metal, and the metal is evaporated from an evaporation source to form an 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 resistance heating type, a crucible type by radiation or high frequency heating,
There is a method using electron beam heating, but there is no particular limitation.

The metals used for this deposition are Al, Z
Metals such as n, Mg, Sn, and Si are preferred, but Ti,
In, Cr, Ni, Cu, Pb, Fe and the like can also be used. These metals are preferably processed into granules, rods, tablets, wires, or crucibles having a purity of 99% or more, preferably 99.5% or more.

In particular, among the deposited metals, it is preferable to provide an aluminum deposited layer on at least one side from the viewpoints of durability, productivity and cost of the metal deposited layer. At this time, other metal components such as nickel, copper, gold, silver, chromium, and zinc can be deposited simultaneously or sequentially with aluminum.

The thickness of the metal deposition film is preferably 10 nm or more in order to exhibit high gas barrier performance. More preferably, it is 20 nm or more. The upper limit of the deposited film is not particularly set, but is 50 nm from the viewpoint of economy and productivity.
Less than is more preferable.

The gloss 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, the metal oxide deposited film is a film of a metal oxide such as incomplete aluminum oxide or incomplete silicon oxide. In particular, incomplete aluminum oxide is used in view of durability, productivity, and cost of the deposited layer. preferable. These deposition methods can be performed by a known method. For example, in the case of an incomplete 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. 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 a vapor deposition film. The thickness of the deposited metal oxide film is 10 to 5
The range is preferably 0 nm, more preferably 10 to 30.
nm range. The imperfectness of the metal oxide deposited film is
Oxidation proceeds after the deposition, and the light transmittance of the metal oxide deposited film changes, and the light transmittance is preferably 70 to 90%.
Range. 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 metallized polypropylene film and the metallized film and the metallized oxide film is preferably at least 0.3 N / cm, more preferably at least 0.5 N / cm. 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.

Further, the gas barrier performance of the polypropylene film for metal vapor deposition of the present invention, in which a metal vapor deposition film and a metal oxide vapor deposition were provided, was found to have a water vapor transmission rate of 4 g / g.
m ² · d or less and oxygen permeability is 200 ml / m ² · d · M
It is preferably Pa or less when used as a food packaging bag.

[0047]

[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 JEOL JNM-GX270 apparatus. For the assignment of the obtained spectra and the calculation of the pentad fraction, see T.W. The method performed by Hayashi et al. [Pol
ymer, 29, 138 to 143 (1988)], the peak derived from the methyl group was assigned to 21.855 ppm for the spectrum derived from the methyl group, each peak was 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 w
t%) / 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 points : 32K Accumulation times: 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.
After drying at 30 ° C. for 6 hours, the weight W ′ (mg) is measured at room temperature 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) Coating Layer Thickness, Thickness of Metal Vapor Deposited Film and Metal Oxide Deposited Layer The cross-sectional structure of the film was observed using a transmission electron microscope (TEM), and the thickness of the coating layer, metal deposited layer and metal oxide deposited were observed. The thickness of the layer was measured.

(5) 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.

(6) Young's modulus of film The film wound into a roll is cut into a 10 mm-width strip, and the length of the measurement is set to 50 mm, and the film is mounted on a Tensilon (manufactured by Toyo Sokki). 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

(7) Film Surface Gloss (%) 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.

(8) Surface Gloss (%) of Metal Evaporated Film A polypropylene film for metal evaporation is loaded into a continuous vacuum evaporation apparatus, aluminum is evaporated from an electron beam heating type evaporation source, and the film is run continuously. 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 surface gloss of this metal-deposited polypropylene film was determined based on JIS Z8741.

(9) Adhesive Strength (N / cm) The adhesive strength between the coating layer and the base layer of the polypropylene film for metal vapor deposition was determined by bonding a biaxially oriented polypropylene film (Toray's S645) having a thickness of 20 μm to the coating layer surface. After bonding using an agent and leaving at 40 ° C for 48 hours,
Using Tensilon made by Toyo Baldwin with 15mm width,
It was measured by 180 ° peeling at a peeling speed of 10 cm / min.
The adhesion strength between the metal-deposited film and the metal oxide-deposited film and the metal oxide-deposited polypropylene film is the same as described above with a biaxially oriented polypropylene film (Toray S645) having a thickness of 20 μm on the metal-deposited film and the metal oxide-deposited film surface. The measurement was carried out in the same manner as described above, using a polyurethane adhesive.

(10) Oxygen permeability (ml / m ² · d · M)
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%.

(11) Water vapor transmission rate (g / m ² · d) 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 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.

[0060]

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, 100 parts by weight of “Hydran” AP-40F (manufactured by Dainippon Ink and Chemicals, Inc., solid content concentration: 20%) as a polyester urethane-based water-dispersible resin and N-— as a water-soluble organic solvent were used. Methylpyrrolidone
A melamine compound "Beckamine" APM (Dainippon Ink and Chemicals Co., Ltd.)
5 parts by weight) and 1.5 parts by weight of a water-soluble acidic compound "Catalyst" PTS (manufactured by Dainippon Ink and Chemicals, Inc.) as a crosslinking accelerator. Dilute to 10% solids.

Next, an isotactic polypropylene polymer having a mesopentad fraction of 92% (isotactic index: 96%, MFI:
2.5 g / 10 min), a resin composition in which 0.05 parts by weight of crosslinked polymethyl methacrylate particles (crosslinked PMMA particles) having an average particle size of 3 μm as an organic crosslinked organic particle lubricant was added, and a base layer for laminating a coating layer On the other side, an ethylene / propylene / butene copolymer (ethylene copolymerization amount: 1.5% by weight, butene copolymerization amount:
15% by weight) as an organic cross-linked particle lubricant with an average particle size of 3 μm
And 0.15% by weight of cross-linked silicone particles (cross-linked Si) were supplied to separate extruders.
After being melt-extruded at 0 ° C. and passed through a filtration filter, they were merged in a short tube so as to form a base layer / heat-sealing layer, extruded from a slit die, wound around a metal drum heated to 40 ° C., and formed into a sheet. 135 ° C
, Stretched 5 times in the longitudinal direction, cooled, and then subjected to corona discharge treatment on the base layer surface in air at 15 W. min / m ²
After applying the mixed coating agent for the coating layer on the base layer surface to form a coating layer, the coating is continued to a tenter type stretching machine, preheated at 170 ° C., and then continuously at 165 ° C. in the width direction. After stretching 9 times, the film was heat-treated at 160 ° C. while giving 10% relaxation in the width direction, and cooled. The thickness of the film is
Coating layer / base layer / heat seal layer: 0.1 μm / 15 μm
/ 2 μm was obtained. The coating composition of the coating layer at this time is shown in Table 1, the film composition is shown in Table 3, and the characteristics evaluation results of the film are shown in Table 4. The adhesive strength between the coating layer and the base layer of the film of the present invention was 2.0 N / cm, the center line average roughness Ra of the coating layer was 0.05 μm, and the glossiness was 142%.

Next, aluminum metal is heated and melted and evaporated in the vacuum evaporation apparatus so that the light transmittance of the polypropylene film for metal evaporation becomes 85%, 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. Gas barrier performance of metal oxide-deposited polypropylene film, oxygen permeability is 70m
1 / m ² · dMPa, water vapor transmission rate 0.8 g / m ² · d
Met. The adhesive strength between the coating layer and the metal oxide deposited layer was 1.5 N / cm.

Example 2 Example 2 was repeated except that 0.2 parts by weight of water-dispersed silica particles having an average particle diameter of 0.1 μm were mixed with the mixed coating material of Example 1 and applied to the base layer surface to form a coating layer. 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 3 shows the film composition, and Table 4 shows the results of evaluating the properties of the film. The adhesive strength between the coating layer and the base layer is 1.
The coating layer had a center line average roughness Ra of 0.10 μm and a glossiness of 140%. Regarding the gas barrier performance of the metal oxide-deposited polypropylene film, the oxygen permeability was 80 ml / m ² · d · MPa, and the water vapor permeability was 1.2 g / m ² · d. The adhesive strength between the coating layer and the metal oxide deposited layer was 1.0 N / cm.

Example 3 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 1, the coating composition of the coating layer at this time is shown in Table 1, the film composition is shown in Table 3, and the property evaluation results of the film are shown in Table 4. The gas barrier performance of metal-deposited polypropylene film is as follows.
ml / m ² · d · MPa, water vapor transmission rate 0.3 g / m ² ·
d. The glossiness of the vapor deposition layer surface is 700%, and the adhesive strength between the coating layer and the metal oxide vapor deposition layer is 0.8N.
/ Cm.

Example 4 The amount of the active ingredient of the polyester urethane resin of Example 1 was 10
5 parts by weight of hexamethylene diisocyanate of an isocyanate compound is added as a crosslinking agent per 0 parts by weight, and 1.5 parts by weight of "Catalyst" PTS (manufactured by Dainippon Ink and Chemicals, Inc.) as a crosslinking catalyst. And 10 parts by weight of ethyl cellosolve acetate for improving the adhesion to the base layer and the metal deposition layer, and 0.1 parts by weight of water-dispersed silica particles having an average particle diameter of 0.05 μm for improving the slipperiness.
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 1 part by weight was mixed and applied to the base layer surface to form a coating layer. The coating composition of the coating layer at this time is shown in Table 1, the film composition is shown in Table 3, and the characteristics evaluation results of the film are shown in Table 4. The adhesive strength between the coating layer and the base layer is 2.1 N / cm, and the center line average roughness Ra of the coating layer is 0.07 μm.
And the glossiness was 138%. The gas barrier performance of a metal oxide-deposited polypropylene film is
4 ml / m ² · d · MPa, water vapor permeability 0.4 g / m ²
-It was d. The adhesive strength between the coating layer and the metal oxide vapor-deposited layer was 1.7 N / cm.

Example 5 The amount of the active ingredient of the polyester urethane resin of Example 1 was 10
5 parts by weight of epoxy compound isophthalic acid diglycidyl ether as a cross-linking agent is added per 0 parts by weight, and 1.5 parts by weight of "Catalyst" PTS (manufactured by Dainippon Ink and Chemicals, Inc.) as a cross-linking catalyst. And 10 parts by weight of N-methylpyrrolidone for improving the adhesion to the base layer and the metal deposition layer, and 0.1 part by weight of water-dispersed silica particles having an average particle diameter of 0.05 μm for improving the slipperiness. 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 mixture was partially mixed and applied to the base layer surface to form a coating layer. Table 1 shows the coating composition of the coating layer and Table 3 shows the film composition.
Table 4 shows the results of evaluating the properties of the film. The adhesive strength between the coating layer and the base layer was 2.2 N / cm, the center line average roughness Ra of the coating layer was 0.04 μm, and the glossiness was 139%. The gas barrier performance of the metal oxide-deposited polypropylene film was as follows: the oxygen transmission rate was 66 ml /
m ² · d · MPa and water vapor transmission rate were 0.5 g / m ² · d. In addition, the adhesive strength between the coating layer and the metal oxide deposited layer was 1.8 N / cm.

Example 6 An isotactic polypropylene polymer having a mesopentad fraction of 98% (isotactic index: 99%, MFI: 2.3 g / 10) was used as the base layer resin of the present invention.
90% by weight) and 10% by weight of hydrogenated dicyclopentadiene resin as a petroleum resin substantially free of polar groups.
The same procedure as in Example 1 was followed, except that 0.05 parts by weight of zeolite having an average particle diameter of 4 μm was added as inorganic particles to form a base resin composition, and the coating resin was changed to the composition of 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 1, the film composition is shown in Table 3, and the characteristics evaluation results of the film are shown in Table 4. The adhesive strength between the coating layer and the base layer was 2.7 N / cm, the center line average roughness Ra of the coating layer was 0.08 μm, and the glossiness was 137%. The gas barrier performance of the metal oxide-deposited polypropylene film was such that the oxygen permeability was 54 ml / m ^2.
D · MPa and water vapor transmission rate were 0.3 g / m ² · d. The adhesive strength between the coating layer and the metal oxide vapor-deposited layer was 2.0 N / cm.

COMPARATIVE EXAMPLE 1 A metal-deposited polypropylene film was prepared in the same manner as in Example 4 except that a polypropylene film having only a base film was obtained without providing a coating layer in Example 1, and aluminum was deposited on the base layer. Obtained. The coating composition of the coating layer at this time is shown in Table 2, the film composition is shown in Table 3, and the characteristics evaluation results of the film are shown in Table 4. The adhesive strength between the base layer and the metal deposition layer is as low as 0.2 N / cm. The gas barrier performance is as follows: oxygen permeability is 520 ml / m ² · d · MPa, water vapor permeability is 5.4 g / m ² · d, and gas barrier performance Was inferior.

Comparative Example 2 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 a water-soluble organic solvent N-methylpyrrolidone and 10 parts by weight of hexamethylene diisocyanate of an isocyanate compound as a cross-linking agent were added per 100 parts by weight of the active ingredient of the polyester resin, and further cross-linking was performed. "Catalyst" PTS as catalyst (Dai Nippon Ink & Chemicals, Inc.)
Was added, and 0.1 part by weight of water-dispersed silica particles having an average particle diameter of 0.05 μm was further mixed for improving slipperiness.

Next, as the resin of the base layer of the present invention, an isotactic polypropylene polymer having a mesopentad fraction of 96% (isotactic index: 98%, M
FI: 2.3 g / 10 min) and 0.05% by weight of crosslinked polymethyl methacrylate particles (crosslinked PMMA particles) having an average particle size of 4 μm as an organic crosslinked particle lubricant were added to the extruder, and the mixture was supplied to an extruder at 270 ° C. , And after passing through a filter, extruded from a slit-shaped die and wound around a metal drum heated to 30 ° C. to form a sheet. This sheet was heated to a temperature of 137 ° C., stretched 5 times in the longitudinal direction, cooled, and then subjected to a corona discharge treatment on the base layer surface in the air for 1 hour.
5W. The treatment was carried out at a processing strength of min / m ² , and the coating agent of the polyester resin was applied to the base layer surface to form a coating layer. Thereafter, the coating material was guided to a tenter type stretching machine, preheated at 170 ° C., and subsequently heated at 165 ° C. After stretching 9 times in the width direction, 160 ° C
At 10 ° C. while giving a 10% relaxation in the width direction. The thickness of the film is: coating layer / base layer: 0.5 μm
A polypropylene film for metal deposition having a thickness of / 15 μm was obtained. The coating composition of the coating layer at this time is shown in Table 2, the film composition is shown in Table 3, and the characteristics evaluation results of the film are shown in Table 4.
Shown in The adhesive strength between the coating layer and the base layer is 0.2 N / cm
And the center line average roughness Ra of the coating layer is 0.12 μm.
m and 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 4 shows the results of evaluating the properties of the film. The oxygen permeability of the metal oxide-deposited polypropylene film is 490
(Ml / m ² · d · MPa), water vapor transmission rate 4.2 (g
/ M ² · d), which is inferior to the guy barrier performance. In addition, the adhesive strength between the coating layer and the metal oxide deposition layer,
The measurement was not possible due to low adhesive strength between the coating layer and the base layer.

Comparative Example 3 The resin composition of the coating layer was only "Hydran" (a polyester urethane-based water-dispersible resin) HW-350 (manufactured by Dainippon Ink and Chemicals, Inc.), except that 3 μm was laminated on the base layer. A metal oxide-deposited polypropylene film was obtained in the same manner as in Example 1. The coating composition of the coating layer at this time is shown in Table 2, the film composition is shown in Table 3, and the characteristics evaluation results of the film are shown in Table 4. In this film, the coating composition of the coating layer is only a polyester urethane-based resin, a water-soluble organic solvent and a crosslinking agent and a crosslinking catalyst are not added and mixed, and the curing of the coating layer becomes insufficient because the lamination thickness is large, The adhesive strength with the base layer is as low as 0.1 N / cm, and the gas barrier performance is
The oxygen permeability was 350 (ml / m ² · d · MPa) and the water vapor permeability was 4.4 (g / m ² · d), which was inferior in gas barrier performance. Further, the adhesive strength between the coating layer and the metal oxide vapor-deposited layer could not be measured because the adhesive strength between the coating layer and the base layer was low.

Comparative Example 4 As a resin for the base layer, an isotactic polypropylene polymer having a mesopentad fraction of 80% (isotactic index: 84%, MFI: 2.1 g / 10 minutes)
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 2, the film composition is shown in Table 3, and the characteristics evaluation results of the film are shown in Table 4. 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 1.0 GPa, the film is stretched by the winding tension during metal deposition processing, and the gas barrier performance is reduced by oxygen permeation. Rate 450 (ml / m ²・ d ・
MPa) and water vapor transmission rate 4.8 (g / m ² · d). The adhesive strength between the coating layer and the metal oxide vapor-deposited layer was 1.0 N / cm.

Comparative Example 5 The procedure of Example 2 was repeated except that the thickness of the coating layer was changed to 0.02 μm.
In the same manner as in Example 2, 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 2, the film composition is shown in Table 3, and the characteristics evaluation results of the film are shown in Table 4. Adhesive strength with base layer of 0.2 due to thin coating layer thickness
N / cm and the gas barrier performance is reduced to an oxygen permeability of 43
0 (ml / m ² · d · MPa), water vapor transmission rate 5.0
(G / m ² · d). Further, the adhesive strength between the coating layer and the metal oxide vapor-deposited layer could not be measured because the adhesive strength between the coating layer and the base layer was low.

[0077]

[Table 1]

[0078]

[Table 2]

[0079]

[Table 3]

[0080]

[Table 4]

[0081]

The polypropylene film for metal deposition and the metallized polypropylene film of the present invention have a specific isotactic polypropylene resin as a base layer, and a specific water-soluble and / or water-dispersible polyester urethane resin on at least one surface thereof. By applying and drying a mixed coating of a water-soluble organic solvent, applying a coating layer, and depositing a metal on the coating layer surface, the adhesive strength between the coating layer and the base layer polypropylene layer, which could not be achieved by the prior art, is reduced. It is high and can have excellent gas barrier performance after metal deposition.

Claims (6)

[Claims] 1. A film comprising a coating layer of a mixture of a polyester urethane resin and a water-soluble organic solvent having a thickness of 0.05 μm to 2 μm provided on at least one surface of a base layer of a polypropylene resin. A polypropylene film for metal deposition having an adhesive strength to a coating layer of 0.3 N / cm or more. 2. The polypropylene film for metal deposition according to claim 1, wherein the polypropylene of the base layer has a mesopentad fraction of 88% or more. 3. The polypropylene film for metal deposition according to claim 1, wherein the water-soluble organic solvent is at least one of N-methylpyrrolidone, ethyl cellosolve acetate, and dimethylformamide. 4. At least one kind of a cross-linking agent selected from isocyanate compounds, epoxy compounds and amine compounds is used in an amount of 3 to 15 parts by weight per 100 parts by weight of a mixture of a polyester urethane resin and a water-soluble organic solvent. The polypropylene film for metal vapor deposition according to claim 1, further comprising a coating layer formed by adding a part. 5. A metal-deposited polypropylene film comprising a metal-deposited film provided on the coating layer surface of the metal-deposited polypropylene film according to claim 1. 6. The metallized polypropylene film according to claim 5, wherein the metallized film is aluminum and / or aluminum oxide.