JP2555820B2 - Thermoplastic resin film having vapor deposition layer - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a thermoplastic resin film having a vapor deposited layer. More specifically, it relates to a thermoplastic resin film having a vapor-deposition layer excellent in antistatic property, which can be suitably used as a packaging material, for example.

[0002]

2. Description of the Related Art Generally, a thermoplastic resin film is inferior in adhesiveness because it is non-polar or has a polarity that does not participate in adhesion. Therefore, metal vapor deposition is performed only after a special surface treatment is performed in advance. There was a problem that I could not.

Therefore, as means for solving the above problems, a copolymer of ethylene and (meth) acrylic acid, a copolymer of ethylene and (meth) acrylic acid ester, and a copolymer of ethylene and a vinyl compound containing a glycidyl group are used. Films made by adding polar group-containing resin such as coalesce, corona discharge treatment in air, corona discharge treatment in inert gas or plasma treatment, or metal vapor deposition after applying adhesive Although it has been carried out, the means for adding the polar group-containing resin needs to be added in a large amount in order to improve the adhesiveness, which is economically disadvantageous. Also,
Since the melting point of an ethylene-containing copolymer decreases as the ethylene content increases, there are problems such as shrinkage and melting due to heat received during vapor deposition. Further, in various physical surface treatments, the effect of treatment changes with time, which causes a problem in the durability of the effect. Further, there is a problem in that a large amount of investment is required for applying the adhesive in terms of equipment.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above prior art, and an object of the present invention is to provide a thermoplastic resin film having a vapor-deposited layer having excellent adhesion to a metal vapor-deposited layer. It is a thing.

[0005]

The present invention provides a compound of the formula:

[0006]

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An ethylene structural unit represented by the formula: 65 to 99 mol%, a general formula:

[0008]

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An acrylate structural unit represented by the formula (wherein R ¹ represents an alkyl group having 1 to 4 carbon atoms) and 0 to 15 mol% and a general formula:

[0010]

[Chemical 6]

(In the formula, R ² is an alkylene group having 2 to 8 carbon atoms, R ³ and R ⁴ are each an alkyl group having 1 to 4 carbon atoms, R ⁵ is an alkyl group having 1 to 12 carbon atoms, and 6 carbon atoms. 12 arylalkyl group or an alicyclic alkyl group having 6 to 12 carbon atoms, X is a halogen atom, CH ₃ OSO ₃ or C ₂ H ₅
0.3 The polyolefin resin having a weight average molecular weight from 1,000 to 50,000 were irregularly arranged linearly consisting of acrylamide structural units 1 to 35 mol% represented by showing a OSO ₃₎ to 50
The present invention relates to a thermoplastic resin film having a vapor deposition layer, which is characterized in that a vapor deposition layer is provided on a thermoplastic resin film containing wt%.

[0012]

FUNCTION AND EXAMPLE The thermoplastic resin film used in the present invention has the formula:

[0013]

[Chemical 7]

An ethylene structural unit represented by the formula: 65 to 99 mol%, a general formula:

[0015]

Embedded image

An acrylate structural unit represented by the formula (wherein R ¹ represents an alkyl group having 1 to 4 carbon atoms) and 0 to 15 mol% and a general formula:

[0017]

[Chemical 9]

(Wherein R ² is an alkylene group having 2 to 8 carbon atoms, R ³ and R ⁴ are each an alkyl group having 1 to 4 carbon atoms, R ⁵ is an alkyl group having 1 to 12 carbon atoms, and 6 carbon atoms. 12 arylalkyl group or number 6-12 alicyclic alkyl group having a carbon, X is a halogen atom, CH ₃ OSO ₃ or C ₂ H ₅
0.3 The polyolefin resin having a weight average molecular weight from 1,000 to 50,000 were irregularly arranged linearly consisting of acrylamide structural units 1 to 35 mol% represented by showing a OSO ₃₎ to 50
It is the one containing the weight%.

The formula in the polyolefin resin is:

[0020]

[Chemical 10]

The ratio of the ethylene structural unit represented by is 65
~ 99 mol%. When the proportion of the ethylene structural unit is less than 65 mol%, the softening point of the polyolefin-based resin becomes low to cause tack and stickiness, and when it exceeds 99 mol%, the polyolefin-based resin is The antistatic property of becomes too small. In the present invention, the proportion of the ethylene structural unit is particularly preferably from 85 to 97 mol% from the viewpoint of the balance between the softening point and the antistatic property.

The general formula in the above polyolefin resin:

[0023]

[Chemical 11]

The proportion of the acrylate structural unit represented by the formula (wherein R ¹ is the same as above) is 0 to 15 mol%. When the proportion of the acrylate structural unit exceeds 15 mol%, the softening point of the polyolefin resin becomes low, and tack and stickiness occur. In the present invention, when the acrylate structural unit is contained, toughness and impact resistance are imparted, which is preferable.
In the present invention, the proportion of the acrylate structural unit is particularly preferably 1 to 15 mol%, particularly preferably 3 to 7 mol%, from the viewpoint of the balance between the softening point and toughness and impact resistance.

In the acrylate structural unit, R ¹
Is an alkyl group having 1 to 4 carbon atoms. Specific examples of such R ¹ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and an i-butyl group, and these groups may be mixed in one molecule. Good. Among these groups, a methyl group and an ethyl group are preferable for maintaining the softening point of the polyolefin resin.

The general formula in the polyolefin resin is:

[0027]

[Chemical 12]

The proportion of the acrylamide structural unit represented by the formula (wherein R ² , R ³ , R ⁴ and R ⁵ are the same as above) is 1 to 35 mol%. When the proportion of the acrylamide structural unit is less than 1 mol%, the antistatic property becomes too small, and when it exceeds 35 mol%, the polyolefin resin becomes hygroscopic. In the present invention, the proportion of the acrylamide structural unit, from the viewpoint of the balance between antistatic property and hygroscopicity,
It is particularly preferably 3 to 15 mol%.

In the acrylamide structural unit, R
² is an alkylene group having 2 to 8 carbon atoms. Specific examples of R ² include, for example, ethylene group, propylene group,
Hexamethylene group, neopentylene group and the like,
These groups may be mixed in one molecule. Among these groups, an ethylene group and a propylene group are preferable from the viewpoint of easiness of production and economy, and a propylene group is particularly preferable.

R ³ and R ⁴ each have 1 to 1 carbon atoms.
4 alkyl group. Specific examples of such R ³ and R ⁴ include a methyl group, an ethyl group, a propyl group, and a butyl group, and these groups may be present in one molecule. Among these groups, a methyl group and an ethyl group are preferable from the viewpoint of antistatic property.

R ⁵ is an alkyl group having 1 to 12 carbon atoms, an arylalkyl group having 6 to 12 carbon atoms or an alicyclic alkyl group having 6 to 12 carbon atoms. Specific examples of such R ⁵ include:
For example, alkyl groups such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, n-octyl group, n-lauryl group; benzyl group, 4-methylbenzyl group, etc. An arylalkyl group; a cyclohexyl group,
An alicyclic alkyl group such as a methylcyclohexyl group may be mentioned, and these groups may be present in one molecule. R ⁵ is preferably a linear alkyl group or an arylalkyl group from the viewpoint of heat resistance, and a lower alkyl group is preferable from the viewpoint of antistatic properties. Particularly preferred R ⁵ includes a methyl group and an ethyl group.

The X is, for example, a halogen atom such as Cl, Br or I, CH ₃ OSO ₃ or C ₂ H ₅ OSO ₃ , and these may be mixed in one molecule. Among these, Cl and CH ₃ OSO are preferred from the viewpoint of antistatic properties.
₃ and C ₂ H ₅ OSO ₃ are preferred.

The weight average molecular weight of the polyolefin resin is 1,000 to 50,000. When the weight average molecular weight is less than 1000, the molecular weight becomes too small and volatilizes when heated, and when it exceeds 50,000, the viscosity when melted becomes too large and workability becomes poor. Become. The preferred weight average molecular weight is 1,000 to 50,000.

The weight average molecular weight in the present invention means a monodisperse polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC).

Since the polyolefin resin used in the present invention is hardly soluble in a normal gel permeation eluent such as tetrahydrofuran (THF) or xylene, its weight average molecular weight cannot be easily measured.
It can be measured in accordance with GPC (Kinukawa, Kobunshi Kobun, Vol. 44, No. 2, pp. 139-141 (1987)).

The formula which is an intermediate of the above polyolefin resin:

[0037]

[Chemical 13]

An ethylene structural unit represented by the general formula:

[0039]

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(Wherein R ¹ is the same as the above) and a general formula:

[0041]

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(In the formula, R ² , R ³ and R ⁴ are the same as described above) The olefinic copolymer having a weight average molecular weight of 1000 to 50000, which is linearly and irregularly arranged and has an acrylamide structural unit, is For example, it can be obtained by the following method.

First, the raw material of the olefin copolymer is not particularly limited, but more advantageously ethylene (C ₂ H ₄ ) and the general formula: CH ₂ CHCOOR ¹ (wherein
A (partial) hydrolyzate of a copolymer comprising an acrylate represented by R ¹ is the same as the above). Such a copolymer can be easily obtained by copolymerizing ethylene and the acrylate by a high-pressure polymerization method.

The ratio of the ethylene structural unit derived from ethylene to the acrylate structural unit derived from the acrylate is determined by determining the ratio of the ethylene structural unit, the acrylate structural unit and the acrylamide structural unit of the obtained olefinic copolymer. become.

Since the above-mentioned copolymer usually has a high molecular weight with a melt index of about 5 to 300, it has a low molecular weight by a degradation method in which hydrolysis is carried out at the same time as hydrolysis under high temperature and high pressure in the presence of water. Preferably.

At this time, the general formula derived from acrylate:

[0047]

Embedded image

All or part of the acrylate structural unit represented by the formula (wherein R ¹ is the same as above) is hydrolyzed to form the formula:

[0049]

[Chemical 17]

It becomes an acrylic acid structural unit represented by:

In order to prepare a copolymer having a weight average molecular weight of 1,000 to 50,000 by lowering the molecular weight by pyrolyzing the copolymer, the copolymer is reacted in the presence of water at a reaction temperature of 150 to 500. Molecules may be cut by heating at a temperature of 3 to 500 kg / cm ² .

In the present invention, the proportion of the acrylic acid structural unit can be appropriately adjusted by adjusting the charged amount of water, the reaction temperature, the pressure and the reaction time.

Specific examples of the degradation method include, for example, JP-A-53-57295, JP-A-53-65389, JP-A-60-79008, and JP-A-60-79015. The method described in 1.

Since the polyolefin resin used in the present invention may impair the commercial value when it is colored, the raw material used in the present invention is disclosed in, for example, JP-A-60-79008. Preference is given to using the products of the processes exemplified.

The polyolefin resin used in the present invention can be obtained by using the thus obtained intermediate of the polyolefin resin.

The method for producing the polyolefin resin used in the present invention from the above intermediate is not particularly limited. An example thereof will be described below.

The above-mentioned intermediate is dissolved in an inert solvent such as aromatic or aliphatic hydrocarbon such as benzene, toluene, xylene, cyclohexanone, decane, cumene, cymene and the like, and to the carboxyl group of the intermediate. Add 100 to 150 mol% of dialkylamine-based monomer such as dialkylaminoalkylamine, and add 130 to 22
At 0 ° C., the carboxyl group contained in the acrylic acid structural unit is converted into a dialkylaminoalkylamide group to form an intermediate, which is then cationically modified with a known quaternizing agent such as an alkyl halide or dialkyl sulfate. By doing so, a polyolefin resin which is a linear random copolymer used in the present invention is obtained.

The polyolefin resin thus obtained exhibits excellent antistatic properties. Although the reason for exhibiting such antistatic properties is not clear, the acrylamide structural unit contained in the polyolefin resin takes in moisture contained in the air,

[0059]

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It is considered that this is due to the low electric resistance due to ionization and electric conductivity.

Further, in the present invention, since the acrylamide structural unit does not exhibit volatility even at high temperature and is chemically incorporated in the polyolefin resin used in the present invention, it is volatilized during processing. Therefore, it is considered that blocking does not occur after processing.

The thermoplastic resin film used in the present invention contains the above-mentioned polyolefin resin,
It is used as a mixture with a thermoplastic resin.

Examples of the thermoplastic resin include polypropylene and ethylene having an ethylene content of 2 to 30% by weight.
Propylene copolymer, terpolymer obtained by further copolymerizing butene-1 with the ethylene-propylene copolymer, high-pressure low-density polyethylene, linear low-density polyethylene, linear ultra-low-density polyethylene, high density Polyethylene, ethylene-vinyl acetate copolymer, saponified ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, ethylene- (meth) Acrylic acid-maleic anhydride terpolymer, ethylene- (meth) acrylic acid ester-maleic anhydride terpolymer such as polyolefin resin, polyester resin, polyamide resin, polystyrene resin, polycarbonate resin , ABS resins and the like, and these resins may be used alone or in combination of two or more kinds.

The amount of the polyolefin resin used is 0.3 to 50% by weight, preferably 0.5 to 30% by weight, based on the total amount of the polyolefin resin and the thermoplastic resin.
Is. The amount of the polyolefin resin used is 0.3
When it is less than 50% by weight, the high molecular weight of the polyolefin-based resin is damaged and the amount present in the surface layer portion decreases, so the adhesiveness decreases, and when it exceeds 50% by weight, The low melting point of the polyolefin resin becomes remarkable, and as a result, problems such as shrinkage and melting occur.

The method for producing the thermoplastic resin film used in the present invention is not particularly limited, and various known film forming methods can be adopted. Specific examples of the method for producing such a thermoplastic resin film include, for example, a casting method, an inflation method, a tubular method, and a tenter method.

The thermoplastic resin film used in the present invention may be unstretched, longitudinally uniaxially stretched or biaxially stretched.

The thickness of the thermoplastic resin film is not particularly limited and may be appropriately selected depending on the application of the thermoplastic resin film to be obtained, but the thickness of such a film is usually 2 to 200 μm. .

In the present invention, as long as the object of the present invention is not impaired, for example, inorganic fillers such as calcium carbonate, talc, glass single fiber, antioxidants, flame retardants, colorants, polyfunctional monomers, etc. Various auxiliaries, etc. may be included in the thermoplastic resin film.

In the present invention, a known low molecular weight surfactant may be used in the polyolefin resin within a range not exceeding 30% by weight based on the polyolefin resin. When the surfactant is used within a range not exceeding 30% by weight, no bleeding from the obtained film is observed.

There is no particular limitation on the kind of metal of the vapor deposition layer used in the present invention. Specific examples of such a metal include aluminum, gold, silver, copper, zinc, tin, palladium, cobalt, nickel, a composite metal or an alloy of these, and the like.

The thickness of the vapor-deposited layer may be appropriately adjusted depending on the application of the thermoplastic resin film having the vapor-deposited layer of the present invention, but is usually 10 to 50 nm, especially 20 to 30 nm.

The thermoplastic resin film having a vapor-deposited layer of the present invention has remarkably excellent adhesiveness between the film and the vapor-deposited layer, so that the oxygen permeability of the film is remarkably reduced. Therefore, the film of the present invention,
It is suitable for use as various packaging materials that require low gas permeability, such as packaging bag materials such as oil confectionery, whose contents are easily altered by oxygen.

Further, the film of the present invention can be further subjected to corona discharge treatment on at least one side to increase the surface wetting tension and improve the adhesiveness with various water-soluble coating agents. Further, a coating agent layer is provided, and various films, sheets, heat sealant layers and the like are laminated to form a composite, which can be used as various packaging materials and packaging materials. In addition, a metal film can be deposited on at least one surface of the film of the present invention, and further provided with a heat sealant layer, and used as various packaging materials and packaging materials.

Next, the thermoplastic resin film having a vapor deposition layer of the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

Example 1 Formula:

[0076]

[Chemical 19]

85 mol% of ethylene structural unit represented by:
formula:

[0078]

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5 mol% of acrylate structural unit represented by
And the formula:

[0080]

[Chemical 21]

A weight-average molecular weight of 10 mol% of an acrylamide structural unit represented by
300 parts of polyolefin resin was added to 20 parts of 100 parts of polyethylene-polypropylene copolymer (melt index 4.3 g / 10 min) containing 2.3% by weight of ethylene (melt index 4.3 g / 10 min) and dry blended to form a film. A resin composition for use.

Then, after introducing into a T-die method extruder set to a cylinder temperature of 220 to 250 ° C. and a die temperature of 240 to 250 ° C., the mixture was melted, kneaded, extruded and passed through a cooling roll set to 20 ° C. An unstretched film having a size of 900 μm and a width of 660 mm was formed.

The film is then heated to a temperature of 135 ° C.
After stretching 5.0 times in the length direction, at a temperature of 170 ° C in the perpendicular direction 9.
The film was stretched 0 times and then relaxed at 140 ° C. and wound up. The film had a thickness of 20 μm. This film was attached to a vacuum vapor deposition machine equipped with an unwinder, a vapor deposition device, a cooling device and a winder, a predetermined amount of aluminum was put into a crucible of the vapor deposition device, the vapor deposition device was sealed, and a vacuum pump was operated. 10 ^-5 to 10 ^-4 Torr in the evaporation system
I made a vacuum. While the film is running at a specified speed, the crucible is heated to 700 to 800 ° C to evaporate aluminum, and while cooling with a cooling device, aluminum is evaporated to a thickness of 25 nm on the film surface and wound up. It was

Next, a coating agent layer is provided on the surface of the obtained film where the vapor deposition layer is not provided, and various skin materials,
Films, sheets, other foams, metal foils, papers, nonwoven fabrics made of natural fibers or synthetic fibers or synthetic leathers were laminated to form a composite, which could be formed into a desired shape by various methods.

Example 2 85 parts of high-pressure low-density polyethylene (density: 0.923 g / cm ³ , melt index: 5.6 g / 10 minutes, particle size: 32 mesh pass) and the formula:

[0086]

[Chemical formula 22]

85 mol% of an ethylene structural unit represented by:
formula:

[0088]

[Chemical formula 23]

5 mol% of an acrylate structural unit represented by the formula:

[0090]

[Chemical formula 24]

A weight-average molecular weight of 10 mol% of an arylamide structural unit represented by
Dry blend 15 parts of 000 polyolefin resin,
After being introduced into a T-die method extruder having a cylinder temperature of 200 to 220 ° C and a die temperature of 230 ° C, the mixture is melted and kneaded.
After extrusion, an unstretched film was obtained by passing through a cooling roll set at 20 ° C. This film has a thickness of 32 μm
It was.

Next, the film was vapor-deposited in the same manner as in Example 1 so that the thickness of the vapor-deposited aluminum layer was 30 nm.

The physical properties of the film having the vapor deposition layer thus obtained were examined by the following methods. Table 1 shows the results.

(Surface Resistance) The film is cut out into 10 cm × 10 cm and left in a constant temperature and constant temperature room controlled at 20 ° C. and 60% RH (relative humidity) for 48 hours for aging.

After aging, the surface resistance is measured in the same atmosphere as above.

Measuring instrument: Takeda Riken Co., Ltd. digital multimeter, type TR-6843 was used, and an electrode 1 having a shape shown in FIG. 1 (a circular electrode 1a having a diameter of 34 mm, an outer diameter of 80 mm, an annular electrode 1b having an inner diameter of 66 mm, Insulation layer 2 (thickness 9mm)
mm), a load 3 having a weight of 1 kg is applied, and the electric resistance (Ω) of the vapor deposition surface of the vapor deposition film 4 when the potential difference from the circular electrode 1b is set to 500 V is represented by Ω / □.

(Blocking Shearing Force) Two vapor-deposited films were superposed on each other over a width of 3 cm and a length of 4 cm, and they were placed on this.
After placing a weight of 500 g and putting it in an atmosphere of 40 ° C. and 80% RH for 24 hours, the shear peeling force of the two films is determined by a Shopper type tensile tester.

A product having a shear peeling force of 1000 g or less and having no vapor-deposited layer falling off is regarded as acceptable. In addition, it is preferably 500 g or less.

(Vapor Deposition Strength) A vacuum vapor deposition machine equipped with an unwinder, a vapor deposition apparatus, a cooling device and a winding machine was installed. The inside of the vapor deposition system was closed by operating the pump, and the inside of the vapor deposition system was brought to a vacuum state of 10 ⁻⁵ to 10 ⁻⁴ Torr by operating the vacuum pump. The film was run at a predetermined speed, and while being cooled by a cooling device, the crucible was heated to 700 to 800 ° C. to vapor-deposit aluminum to a thickness of 25 nm and wound.

Cellophane tape (manufactured by Nichiban Co., Ltd., width 24 mm) was adhered to the vapor deposition surface of this vapor deposition film, and the following 5 steps were taken based on the deposition area of the vapor deposition metal after peeling at 180 ° C. at a speed of 50 mm / min. An evaluation was performed.

Vapor deposition area after peeling Vapor deposition index 100% 5 90% or more and less than 100% 4 70% or more and less than 90% 3 50% or more and less than 70% 2 50% or less 1 To pass.

(Oxygen permeability) General hood (GENAL F
OOD) method. The measurement conditions are as follows.

Measurement temperature: 25 ° C. Gas: 99.99% dry oxygen The above measurement value is expressed in cc (NPT) / 24 hr · m ² /0.1 mm / atm. The values obtained for the film before vapor deposition are shown in Table 1 with parentheses.

From the above measured values, 1/2 or less before vapor deposition is regarded as acceptable.

Example 3 80 parts of low-pressure high-density polyethylene (density: 0.955 g / cm ³ , melt index: 7.3 g / 10 minutes) and the formula:

[0106]

[Chemical 25]

80 mol% of the ethylene structural unit represented by the formula:

[0108]

[Chemical formula 26]

A weight-average molecular weight of 20 mol% of an acrylamide structural unit represented by
20 parts of 000 polyolefin resin was dry-blended and introduced into a T-die extruder having a cylinder temperature of 220 to 230 ° C. and a die temperature of 250 ° C., melted and kneaded, and then set to 20 ° C. An unstretched film having a thickness of 150 μm was obtained through a cooling roll. Then this film 13
The film was heated to a temperature of 5 ° C. and stretched 5 times in the machine direction to obtain a uniaxially stretched film.

The film had a total thickness of 30 μm.

The film thus obtained was vapor-deposited in the same manner as in Example 1 so that the aluminum vapor deposition layer had a thickness of 26 nm.

The physical properties of the obtained film having a vapor deposition layer were examined in the same manner as in Example 2. Table 1 shows the results.

Example 4 88 parts of linear low-density polyethylene (density: 0.935 g / cm ³ , melt index: 8.5 g / 10 minutes) and the formula:

[0114]

[Chemical 27]

80 mol% of an ethylene structural unit represented by:
formula:

[0116]

Embedded image

1 mol% of an acrylate structural unit represented by the formula:

[0118]

[Chemical 29]

Weight average molecular weight of linearly irregularly arranged molecular weight of 27% consisting of 19 mol% of the acrylamide structural unit
A uniaxially stretched film was obtained in the same manner as in Example 3 except that 12 parts of 000 polyolefin resin was used. The film had a thickness of 25 μm.

The film thus obtained was vapor-deposited in the same manner as in Example 1 so that the aluminum vapor deposition layer had a thickness of 30 nm.

The physical properties of the obtained film having a vapor deposition layer were examined in the same manner as in Example 2. Table 1 shows the results.

Example 5 Polypropylene (melt index: 2.5 g / 10 minutes) 98
Part and expression:

[0123]

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88 mol% of an ethylene structural unit represented by:
formula:

[0125]

[Chemical 31]

3 mol% of the acrylate structural unit represented by the formula:

[0127]

Embedded image

A weight average molecular weight 33 of 9 mol% of an acrylamide structural unit represented by
2 parts of 000 polyolefin resin were dry blended, introduced into a T-die extruder set to a cylinder temperature of 230 to 250 ° C and a die temperature of 250 ° C, and then melted, kneaded, extruded, and then 20 ° C. An unstretched film having a thickness of 450 μm was obtained through the cooling roll set to. Next, this film was heated to a temperature of 155 ° C. and subjected to a tenter method simultaneous biaxial stretching device to stretch it 6 times in the longitudinal and transverse directions to obtain a simultaneous biaxially stretched film. The obtained film had a thickness of 12.5 μm.

Next, vapor deposition was performed in the same manner as in Example 1 except that tin was used instead of aluminum in the obtained film so that the thickness of the tin vapor deposition layer was 28 nm.

The physical properties of the film laminate having the vapor deposition layer thus obtained were examined in the same manner as in Example 2. Table 1 shows the results.

Example 6 Nylon-6 (manufactured by Toray Industries, Inc., CM1021T, particle size: 32 mesh pass) (85 parts) and formula:

[0132]

[Chemical 33]

85 mol% of an ethylene structural unit represented by:
formula:

[0134]

Embedded image

5 mol% of an acrylate structural unit represented by the formula:

[0136]

Embedded image

The weight average molecular weight of the acrylamide structural unit represented by
15 parts of 000 polyolefin resin was dry blended to obtain a resin composition for film. Next cylinder temperature 23
Melt, knead, and extrude in the same manner as in Example 1 except that the temperature was set to 0 to 250 ° C and the die temperature to 250 to 260 ° C.
An unstretched film was obtained through a cooling roll set at 0 ° C. The film had a thickness of 24 μm.

Then, the film was vapor-deposited in the same manner as in Example 1 so that the thickness of the vapor-deposited aluminum layer was 30 nm.

The physical properties of the obtained film having a vapor deposition layer were examined in the same manner as in Example 2. Table 1 shows the results.

Example 7 Polyethylene terephthalate (intrinsic viscosity 0.598, particle size
32 mesh pass) 80 parts and formula:

[0141]

Embedded image

80 mol% of the ethylene structural unit represented by the formula:

[0143]

Embedded image

The weight average molecular weight of the acrylamide structural unit represented by
Dry blend with 20 parts of 000 polyolefin resin and introduce into a T-die extruder with cylinder temperature of 260-280 ℃ and die temperature of 280 ℃, melt, knead, and cool to 20 ℃ An unstretched film having a thickness of 150 μm was obtained through the roll. Next, apply this film to 95 ℃
The film was heated to the temperature of 3.5 times and stretched in the longitudinal direction by 3.5 times, further introduced into a tenter, heated to 135 ° C., stretched in the transverse direction to 3.2 times, and then heat set at 230 ° C. to obtain a biaxially stretched film. .

The film had an overall thickness of 12 μm.

The film thus obtained was vapor-deposited in the same manner as in Example 1 so that the aluminum vapor-deposited layer had a thickness of 26 nm.

The physical properties of the film having the vapor deposition layer thus obtained were examined in the same manner as in Example 2. Table 1 shows the results.

[0148]

[Table 1]

Comparative Example 1 A resin composition for a film was prepared by mixing 85 parts of high-pressure low density polyethylene (density 0.923 g / cm ³ , melt index: 5.6 g / 10 minutes) and 15 parts of stearic acid monoglyceride as an antistatic agent. I got it. A 32 μm thick film was obtained in the same manner as in Example 2 using the obtained resin composition for a film.

The film thus obtained was vapor-deposited in the same manner as in Example 1 so that the aluminum vapor deposition layer had a thickness of 25 nm. The physical properties of the obtained film having a vapor deposition layer were examined in the same manner as in Example 2. The results are shown in Table 2.

Comparative Example 2 80 parts of low-pressure high-density polyethylene (density 0.955 g / cm ³ , melt index: 7.3 g / 10 min) and the formula as an antistatic agent:

[0152]

[Chemical 38]

Betaine-type amphoteric surfactant 20 represented by
The parts were mixed to obtain a resin composition for film. Using the obtained resin composition for a film, the same thickness as in Example 3 was obtained.
A 28 μm film was obtained.

The resulting film was vapor-deposited in the same manner as in Example 1 so that the aluminum vapor deposition layer had a thickness of 20 nm. The physical properties of the film having the vapor deposition layer are shown in Example 2.
I examined it in the same way. The results are shown in Table 2.

Comparative Example 3 88 parts of linear low-density polyethylene (density: 0.935 g / cm ³ , melt index: 8.5 g / 10 min) and stearic acid monoglyceride as an antistatic agent and the formula:

[0156]

[Chemical Formula 39]

A betaine-type amphoteric surfactant represented by
12 parts of a mixture of 15:85 by weight was mixed to obtain a resin composition for film. A film having a thickness of 18 μm was obtained in the same manner as in Example 5 by using the obtained resin composition for a film.

Vapor deposition was performed in the same manner as in Example 3 except that tin was used instead of aluminum in the obtained film so that the tin vapor deposition layer had a thickness of 30 nm.

The physical properties of the obtained film were examined in the same manner as in Example 2. The results are shown in Table 2.

Comparative Example 4 93 parts by weight of ethylene-propylene copolymer having an ethylene content of 3% by weight (melt index: 4.3 g / 10 min) and sodium dodecylbenzenesulfonate as an antistatic agent and polyethylene glycol in a weight ratio of 30:70. The resin composition for film was obtained by mixing 7 parts of the mixture prepared in step 1.

The resin composition for a film thus obtained was treated in the same manner as in Example 1 to obtain a biaxially stretched film having a thickness of 18 μm.

Vapor deposition was carried out in the same manner as in Example 1 except that gold was used instead of aluminum in the obtained film, so that the thickness of the gold vapor deposition layer was 18 nm.

The physical properties of the film having the vapor deposition layer thus obtained were examined in the same manner as in Example 2. The results are shown in Table 2.

Comparative Example 5 Polypropylene (melt index: 2.5 g / 10 minutes) 98
Parts and 2 parts of stearyldiethanolamine as an antistatic agent were mixed to obtain a resin composition for film. A film was obtained in the same manner as in Example 5 using the obtained resin composition for a film.

The film thus obtained was vapor-deposited in the same manner as in Example 1 so that the aluminum vapor-deposited layer had a thickness of 23 nm.

The physical properties of the obtained film having a vapor deposition layer were examined in the same manner as in Example 2. The results are shown in Table 2.

[0167]

[Table 2]

From the results shown in Table 1, since the thermoplastic resin film used in the present invention has excellent metal vapor deposition property, the film and the metal vapor deposition layer are extremely firmly adhered to each other, and the metal vapor deposition is performed. It can be seen that the layer does not crack or fall off.

On the other hand, the films having the vapor-deposited layers obtained in Comparative Examples 1 to 5 were those in which the conventional comparatively low molecular weight surfactant type antistatic agent was used, and from the results shown in Table 2, It can be seen that, even if vapor deposition can be performed, the adhesive strength is low, the vapor deposition layer falls off due to some friction, and the vapor deposition layer has cracks, so that the oxygen gas permeability is high.

From the above, the thermoplastic resin film having a vapor-deposited layer of the present invention has not only excellent metal vapor deposition property and vapor deposition film adhesiveness, but also has a strongly adhered vapor deposition layer, whereby the oxygen permeability is improved. Is small, so
For example, it can be seen that it can be suitably used in a wide range of fields as a packaging material and the like.

[0171]

EFFECT OF THE INVENTION The thermoplastic resin film having a vapor deposition layer of the present invention is a vapor deposition film having extremely excellent vapor deposition strength of a metal film and having no cracks or falling off in the metal vapor deposition film, and the weak point of the thermoplastic resin film. Since the oxygen transmission rate is remarkably reduced, it can be suitably used as, for example, a packaging material.

[Brief description of drawings]

FIG. 1 is a schematic explanatory view of an apparatus used in a method for measuring a surface resistance of a film having a vapor deposition layer in Examples and Comparative Examples of the present invention.

[Explanation of symbols]

 1 electrode 2 insulating layer 3 load 4 vapor deposition film

Claims (1)

(57) [Claims] 1. The formula: 65 to 99 mol% of an ethylene structural unit represented by the following general formula: (Wherein R ¹ represents an alkyl group having 1 to 4 carbon atoms), the acrylate structural unit is represented by 0 to 15 mol% and the general formula: (In the formula, R ² is an alkylene group having 2 to 8 carbon atoms, R ³ and R ⁴ are respectively alkyl groups having 1 to 4 carbon atoms, R ⁵ is an alkyl group having 1 to 12 carbon atoms, and 6 to 12 carbon atoms. An arylalkyl group or an alicyclic alkyl group having 6 to 12 carbon atoms, X represents a halogen atom, CH ₃ OSO ₃ or C ₂ H ₅ OSO ₃ ) and an acrylamide structural unit represented by 1 to 35 mol%
Weight average molecular weight 1000 ~
A thermoplastic resin film having a vapor-deposition layer, characterized in that a vapor-deposition layer is provided on a thermoplastic resin film containing 0.3 to 50% by weight of 50,000 polyolefin resin.