JPH0516303A - Thermoplastic resin laminated film - Google Patents

Abstract

(57) [Abstract] [Purpose] To provide a thermoplastic resin laminated film having excellent antistatic properties and printability. [Structure] A polyolefin resin having a weight average molecular weight of 1000 to 50,000, which is linearly and irregularly arranged and comprises 65 to 99 mol% of ethylene structural units, 0 to 15 mol% of acrylate structural units, and 1 to 35 mol% of acrylamide structural units. 0.3-50
It is characterized in that a resin layer containing wt% is provided.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a thermoplastic resin laminated film. More specifically, it relates to a thermoplastic resin laminated film having excellent antistatic properties and printability, which can be suitably used as, for example, a packaging material.

[0002]

2. Description of the Related Art Generally, a thermoplastic resin laminated film is
Since the hydrophobicity is large and the polarity of the resin is strong, the generation of static electricity is remarkable. Therefore, when such a film is used as a packaging material, for example,
Dust may adhere to the product, lower the commercial value of the contents, cause poor adhesion, poor printing, poor vapor deposition, uneven edges at the time of winding, or may give a shock to the human body due to electrostatic discharge. In an atmosphere using a flammable organic solvent, there are problems such as ignition.

Therefore, in order to impart antistatic properties to the foam, a method of adding or coating an anionic, cationic or amphoteric surfactant has been conventionally used.

However, in the above method, since the surfactant has a relatively small molecular weight of about 500 to 600, it volatilizes during the production of the film, or bleeds with time after being formed into a film. There is a problem in that the film is out of the film, contaminates the surface of the film, causes blocking, and deteriorates adhesiveness, printability, vapor deposition property, and the like. In addition to the thermoplastic resin film using the above-mentioned surfactant, as a polyolefin resin film having excellent antistatic properties, a resin having one or more specific functional groups in the thermoplastic resin or a special modified resin (JP Sho
62-121717, Japanese Patent Publication No. 1-29820),
Known as a film.

However, since none of the above-mentioned resins has an acrylate structure or an acrylamide structure, the compatibility with various thermoplastic resins is poor, and the transparency is deteriorated or voids are generated, resulting in poor surface properties. There's a problem.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and it is excellent not only in antistatic property but also in adhesive property and printability, and bleeding and blocking It is an object of the present invention to provide a thermoplastic resin laminated film which does not generate.

[0007]

The present invention has the formula:

[0008]

[Chemical 4]

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

[0010]

[Chemical 5]

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:

[0012]

[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
Thermoplastic resin laminated film formed by providing a resin layer containing a 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₎ Regarding

[0014]

FUNCTION AND EXAMPLE The thermoplastic resin laminated film of the present invention has the formula:

[0015]

[Chemical 7]

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

[0017]

[Chemical 8]

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

[0019]

[Chemical 9]

(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 number 6-12 alicyclic alkyl group having a carbon, X is a halogen atom, CH ₃ OSO ₃ or C ₂ H ₅
(Representing OSO ₃ ), a resin layer containing a polyolefin resin having a weight average molecular weight of 1000 to 50,000 linearly and irregularly composed of 1 to 35 mol% of an acrylamide structural unit is provided.

The formula in the polyolefin resin is:

[0022]

[Chemical 10]

The proportion of ethylene structural units 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 85 to 97 mol% from the viewpoint of the balance between the softening point and the antistatic property.

The general formula in the polyolefin resin is:

[0025]

[Chemical 11]

The ratio 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 or stickiness occurs. In the present invention, the presence of the acrylate structural unit is preferable because it imparts toughness and impact resistance.
In the present invention, the proportion of the acrylate structural unit is particularly preferably 1 to 15 mol%, especially 3 to 7 mol% from the viewpoint of the balance between the softening point and the toughness and impact resistance.

In the acrylate structural unit, R ¹
Is an alkyl group having 1 to 4 carbon atoms. Specific examples of 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, the methyl group and the ethyl group are preferable for maintaining the softening point of the polyolefin resin.

The general formula in the polyolefin resin is:

[0029]

[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, and a propylene group is particularly preferable, from the viewpoint of ease of production and economy.

R ³ and R ⁴ are each 1 to 1 carbon atoms.
4 is an alkyl group. Specific examples of R ³ and R ⁴ include a methyl group, an ethyl group, a propyl group, and a butyl group, and these groups may be mixed 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, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, n-octyl group, n-lauryl group and other alkyl groups; benzyl group, 4-methylbenzyl group, etc. Arylalkyl group of cyclohexyl group,
Examples thereof include alicyclic alkyl groups such as a methylcyclohexyl group, and these groups may be mixed in one molecule. Note that R ⁵ is preferably a linear alkyl group or an arylalkyl group from the viewpoint of heat resistance, and is preferably a lower alkyl group 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, CH ₃ OSO are used from the viewpoint of antistatic property.
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 to volatilize when heated, and when it exceeds 50,000, the viscosity when melted becomes too large, resulting in poor workability. Become. The preferred weight average molecular weight is 3000 to 30,000.

The weight average molecular weight in the present invention refers to 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)).

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

[0039]

[Chemical 13]

An ethylene structural unit represented by the general formula:

[0041]

[Chemical 14]

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

[0043]

[Chemical 15]

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

First, the raw material for the olefin-based 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 the 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 of about 5 to 300, a low molecular weight is obtained by a degradation method in which hydrolysis is carried out simultaneously with hydrolysis under high temperature and high pressure in the presence of water. Preferably.

At this time, a general formula derived from acrylate:

[0049]

[Chemical 16]

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:

[0051]

[Chemical 17]

It becomes an acrylic acid structural unit represented by:

In order to reduce the molecular weight of the copolymer by pyrolyzing it to prepare a copolymer having a weight average molecular weight of 1,000 to 50,000, 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 its commercial value if 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 and cymene, and to this, the carboxyl group of the intermediate is dissolved. Add 100 to 150 mol% of dialkylamine-based monomer such as dialkylaminoalkylamine, and add 130 to 22
After reaction at 0 ° C to convert the carboxyl group contained in the acrylic acid structural unit into a dialkylaminoalkylamide group to give an intermediate, cation modification with a known quaternizing agent such as alkyl halide or dialkyl sulfate is carried out. By doing so, a polyolefin resin that is a linear random copolymer used in the present invention can be obtained.

The polyolefin resin thus obtained exhibits excellent antistatic properties. The reason why the antistatic property is exhibited is not clear, but the acrylamide structural unit contained in the polyolefin resin takes in the water contained in the air,

[0061]

[Chemical 18]

It is considered that this is due to the low electrical resistance exhibited by ionization and electrical conductivity.

Further, in the present invention, since the acrylamide structural unit does not exhibit volatility even at high temperature and is chemically incorporated into 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 resin layer used in the present invention contains the above polyolefin resin and 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 20% by weight, based on the total amount of the polyolefin resin and the thermoplastic resin.
Is. The amount of such polyolefin resin used is 0.3
When the amount is less than wt%, the molecular weight is larger than that of a known surfactant type antistatic agent, so that the ratio of the resin composition in the resin composition becomes small, which is good in terms of blocking property, but surface resistance and charge Half-life, that is, the antistatic property becomes inferior, and when it exceeds 50% by weight, since the molecular weight of the polyolefin resin is smaller than that of the thermoplastic resin to be mixed, it is preferable in terms of antistatic property. ,
The resulting laminated film has poor mechanical properties.

The thickness of the resin layer may be 0.1 to 50 μm in the final product. Such thickness is 0.1 μm
When it is less than 50 μm, cohesive failure occurs at the interface between the resin layer and the resin film, resulting in deterioration of adhesion and vapor deposition properties. Since the property becomes remarkable, blocking occurs.

The resin used in the thermoplastic resin film used as the substrate in the present invention is, for example, a polypropylene-based resin containing propylene as a main component, a low-pressure high-density polyethylene having a density of 0.925 g / cm ³ or more, and a linear chain resin. Examples include polyolefin resins such as low density polyethylene, polyester resins, polyamide resins, polystyrene resins, polycarbonate resins, ABS resins, etc. These resins may be used alone or in admixture of two or more as necessary. Used.

The method for producing the resin film 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, casting method, inflation method,
Tubular method, tenter method and the like can be mentioned.

The resin film may be unstretched, longitudinally uniaxially stretched or biaxially stretched.

The thickness of the resin film is not particularly limited and may be appropriately selected depending on the intended use of the obtained laminated film, but the thickness of such a film is usually 10 to 50.
It is assumed to be 0 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, coloring agents, polyfunctional monomers, etc. The various auxiliaries and the like may be included in the resin layer and the resin film.

In the present invention, a known low molecular weight surfactant may be used in the resin layer within a range not exceeding 30% by weight based on the polyolefin resin.
Thus, when the surfactant is used within the range not exceeding 30% by weight, bleeding from the obtained resin layer is not recognized.

As a method for integrating the resin layer and the resin film, for example, a reverse roll coating method, a gravure coating method, or a bar coating method in a state where the resin for the resin layer is heated and melted or in an emulsion state. A method of coating on a resin film by, for example, a method of composite-integrating a resin for resin film and a resin for resin layer by a short pipe inner composite method, a die inner composite method, a melt extrusion laminating method, etc. when manufacturing the resin film. However, the present invention is not limited to such a method.

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

Next, the thermoplastic resin laminated film 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:

[0078]

[Chemical 19]

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

[0080]

[Chemical 20]

5 mol% of acrylate structural unit represented by
And expression:

[0082]

[Chemical 21]

A weight-average molecular weight of 10 mol% of an acrylamide structural unit represented by
Linear polyolefin low density polyethylene resin (density: 0.930 g / cm ³ , melt index: 3.
7 g / 10 min) 20 parts were added to 100 parts (parts by weight, the same applies hereinafter) and dry blended to obtain a resin composition for a resin layer.

The resin composition for a resin layer is put into a sub-extruder,
Linear low density polyethylene (density: 0.930 g / cm ³ ,
Melt index: 3.7 g / 10 min) was introduced into the main extruder, and then introduced into a coextrusion film forming device equipped with a short pipe compounding device and coextruded, and a thickness of 100 μm was passed through a cooling roll set at 20 ° C. An unstretched film having a width of 1200 mm was obtained. The thickness of the obtained unstretched film is 20 μm for the resin layer.
m 2 and the resin film layer was 80 μm. At this time, the temperature of the extruder, the compound device in the short pipe, and the die were all 180
It was ~ 220 ° C.

When the surface resistivity of the obtained laminated film was examined according to the method described below, it was found to be extremely small at 3.2 × 10 ¹¹ Ω and excellent in antistatic property.

Next, two obtained laminated films were superposed and left in an atmosphere of 40 ° C. and 80% RH (relative humidity) for 7 days, and then the laminated film was peeled off and the surface condition was observed. There was no stickiness due to the above, and printing was performed on the surface of the obtained laminated film using a printing ink for polypropylene, but there was no printing failure due to bleeding out.

Next, one surface of the obtained laminated film was subjected to corona discharge treatment so that the surface wetting tension was 37 dyne / cm or more, and the adhesion with various coating agents could be improved.

Further, it was possible to provide a coating agent layer, bond it to another film or sheet, and apply a heat sealant layer to use it as various packaging materials or packaging materials. In addition, a metal film was vapor-deposited on at least one surface of the obtained laminated film, and a heat sealant layer was further applied, which could be used as various packaging materials and packaging materials.

(Surface specific resistance) A laminated film of 10 cm × 10 cm
Cut out and leave for 48 hours in a thermostatic chamber controlled at 20 ° C and 60% RH for aging.

After completion of aging, the surface resistivity is measured in the atmosphere.

Measuring instrument: Ultra-insulator (VE-40 type) manufactured by Kawaguchi Electric Co., Ltd. and room temperature measuring box (RC-02 type) connected Measuring conditions: Applied voltage 100V adopt.

The surface resistivity is 1 × 10 ¹³ Ω
Hereinafter, the one having a charge half-life of 3 minutes or less is assumed to have antistatic properties.

Example 2 Polypropylene (melt index: 2.8 g / 10 minutes) was used as the resin for the resin film.

As the resin for the resin layer, the formula:

[0095]

[Chemical formula 22]

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

[0097]

[Chemical formula 23]

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

[0099]

[Chemical formula 24]

A weight-average molecular weight of 10 mol% of the acrylamide structural unit represented by
500 polyolefin resins were used.

Next, a laminated film was obtained in the same manner as in Example 1 using the resin for resin film and the resin for resin layer. This laminated film had an overall thickness of 40 μm, a width of 1200 mm, and a resin layer thickness of 5 μm.

Next, as the physical properties of the obtained laminated film, the surface resistivity was examined in the same manner as in Example 1, and the half-life of charge, bleed-out, blocking shear force and printability were examined by the following methods. The results are shown in Table 1.

(Half-life of charge) A static Honest meter (manufactured by Shishido Shokai Co., Ltd.) was used to apply a voltage of 10 KV to the sample in the same atmosphere as when the surface resistivity was measured. Determine the decay rate as the half-life.

(Bleed out) An additive-free biaxially oriented polypropylene film was laid on the surface of the laminated film,
After putting it in an atmosphere of 80% RH for 7 days, it is taken out, the film is peeled from the foam, and the presence or absence of deposits on the surface of the film is examined.

(Blocking Shearing Force) Two laminated films were superposed on each other over a width of 3 cm and a length of 4 cm, and the laminated films were placed on the laminated film.
After placing a weight of 550 g and putting it in an atmosphere of 40 ° C. and 80% RH for 7 days, the shear peeling force of the two films is determined by a Shopper-type tensile tester.

A shear peeling force of 1000 g or less is regarded as acceptable. The amount is preferably 500 g or less.

(Printability) Printing ink PP for polypropylene
ST (manufactured by Toyo Ink Mfg. Co., Ltd.) was applied using a # 50 bar coater and dried with a hot air dryer at 80 ° C, and then a cellotape (manufactured by Nichiban Co., Ltd., 24 mm width) was lengthened on the printed part. Cut it out to 20 cm and attach 15 cm of it to the print section.
Rub it firmly on the cellophane tape several times to firmly attach it. Quickly peel the tape with the remaining tape portion in hand and check the remaining amount of the peeled ink portion on the film to determine printability.

The printability is judged according to the following evaluation criteria.

(Evaluation criteria) Less than 50% Index 1 50% or more but less than 75% Index 2 75% or more but less than 90% Index 3 90% or more but less than 100% Index 4 100% index 5 It should be noted that the pass is an index of 4 or more.

Example 3 Low density polyethylene (density:
0.921 g / cm ³ , melt index: 3.2 g / 10 min) was used.

The resin for the resin layer has the formula:

[0112]

[Chemical 25]

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

[0114]

[Chemical formula 26]

The weight average molecular weight of the acrylamide structural unit represented by
30 parts of 000 polyolefin resin and low density polyethylene (density: 0.921 g / cm ³ , melt index: 3.2 g / 10
Min) 70 parts were used.

A laminated film was obtained in the same manner as in Example 1 using the resin for resin film and the resin for resin layer thus obtained. This laminated film has an overall thickness of 40 μm,
The width was 1200 mm and the thickness of the resin layer was 5 μm.

The physical properties of the obtained laminated film were examined in the same manner as in Example 2. The results are shown in Table 1.

Example 4 Linear low density polyethylene (density: 0.935 g / cm ³ , melt index: 8.3 g / 10 as a resin for resin film)
Min) and low density polyethylene (density: 0.923 g / cm ³ , melt index: 3.7 g / 10 min) were mixed at a weight ratio of 30/70.

The resin for the resin layer has the formula:

[0120]

[Chemical 27]

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

[0122]

[Chemical 28]

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

[0124]

[Chemical 29]

A weight average molecular weight of 19 mol% of the acrylamide structural unit represented by
20 parts of 000 polyolefin resin and 80 parts of the same low density polyethylene as used in Example 3 were used.

A laminated film was obtained in the same manner as in Example 1 by using the resin for resin film and the resin for resin layer thus obtained. This laminated film had a total thickness of 27 μm, a total width of 1200 mm, and a resin layer thickness of 2 μm.

The physical properties of the obtained laminated film were examined in the same manner as in Example 2. The results are shown in Table 1.

Example 5 As a resin for resin film, ethylene-propylene copolymer (ethylene content: 8% by weight, melt index: 2.
3 g / 10 min) was used.

As the resin for the resin layer, the formula:

[0130]

[Chemical 30]

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

[0132]

[Chemical 31]

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

[0134]

[Chemical 32]

A weight average molecular weight 33 of 9 mol% of acrylamide structural units linearly and irregularly arranged.
60 parts of 000 polyolefin resin was added to 40 parts of polypropylene (melt index: 2.5 g / 10 minutes).

Then, using the obtained resin for resin film and resin for resin layer, a laminated film was obtained in the same manner as in Example 2. The resulting laminated film has an overall thickness of 14
The thickness was 1200 μm, the total width was 1200 mm, and the thickness of the resin layer was 2 μm.

The physical properties of the obtained laminated film were examined in the same manner as in Example 2. The results are shown in Table 1.

Example 6 Nylon-6 (CM1021T, manufactured by Toray Industries, Inc.) was used as the resin for the resin film.

The resin for the resin layer has the formula:

[0140]

[Chemical 33]

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

[0142]

[Chemical 34]

The weight average molecular weight of the acrylamide structural unit represented by
30 parts of 000 polyolefin resin and low density polyethylene (density: 0.921 g / cm ³ , melt index: 3.2 g / 10
Min) 70 parts were used.

The resin film for resin and the resin for resin layer thus obtained were laminated in the same manner as in Example 1 except that the temperature of the extruder, the single tube composite device and the die were each 220 to 250 ° C. I got a film. This laminated film had an overall thickness of 40 μm, an overall width of 1200 mm, and a resin layer thickness of 5 μm.

The physical properties of the obtained laminated film were examined in the same manner as in Example 2. The results are shown in Table 1.

Example 7 70 parts of polyethylene terephthalate (intrinsic viscosity: 0.598) was added to 15 parts of a thermoplastic elastomer (Hytrel 4074, manufactured by Toray DuPont Co., Ltd.) as a resin for resin film.

As the resin for the resin layer, the formula:

[0148]

[Chemical 35]

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

[0150]

[Chemical 36]

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

[0152]

[Chemical 37]

A weight average molecular weight of 19 mol% of the acrylamide structural unit represented by
20 parts of 000 polyolefin resin and 80 parts of the same low density polyethylene as used in Example 3 were used.

A laminated film was prepared in the same manner as in Example 1 except that the resin for resin film and the resin for resin layer thus obtained were used, the cylinder temperature was set to 240 to 280 ° C, and the die temperature was set to 260 to 280 ° C. I got it. This laminated film is
The total thickness is 27 μm, the total width is 1200 mm, and the thickness of the resin layer is 2
It was of μm.

The physical properties of the obtained laminated film were examined in the same manner as in Example 2. The results are shown in Table 1.

[0156]

[Table 1]

Comparative Example 1 Polypropylene (melt index: 2.8 g / 10 minutes) was used as a resin for resin film.

Ethylene-propylene copolymer (ethylene content: 8% by weight, melt index: 2.3 g / 10 minutes) 99
Parts and stearic acid monoglyceride as antistatic agent 1
The parts were mixed to obtain a resin for resin layer.

Next, a laminated film was obtained in the same manner as in Example 2 using the resin for resin film and the resin for resin layer.

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

Comparative Example 2 99.2 parts of low-density polyethylene (density: 0.921 g / cm ³ , melt index: 3.2 g / 10 min) and the formula as an antistatic agent:

[0162]

[Chemical 38]

Betaine-type amphoteric surfactant represented by
The resin for the resin layer was obtained by mixing 8 parts.

The same low density polyethylene as used above was used as the resin for the resin film.

Then, using the obtained resin for resin film and resin for resin layer, a laminated film was obtained in the same manner as in Example 2.

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

Comparative Example 3 98.5 parts of low-density polyethylene (density: 0.921 g / cm ³ , melt index: 3.2 g / 10 min) and stearic acid monoglyceride as an antistatic agent and a formula:

[0168]

[Chemical Formula 39]

The betaine-type amphoteric surfactant represented by the formula (3) was mixed in a weight ratio of 3: 7, and 1.5 parts was mixed to obtain a resin for resin layer.

In addition, linear low-density polyethylene (density:
0.930 g / cm ³ , melt index: 5.2 g / 10 min) and low density polyethylene (density: 0.920 g / cm ³ , melt index: 2.1 g / 10 min) were mixed to obtain a resin for resin.

A laminated film was obtained in the same manner as in Example 4 using the resin for resin film and the resin for resin layer thus obtained.

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

Comparative Example 4 95 parts by weight of ethylene-propylene copolymer having an ethylene content of 5% by weight (melt index: 1.2 g / 10 min) and sodium dodecylbenzenesulfonate as an antistatic agent and polyethylene glycol at a ratio of 15:85. The resin for resin layer was obtained by mixing 5 parts of the mixture obtained in step 1.

The same ethylene-propylene copolymer as used in Comparative Example 1 was used as the resin for the resin film.

Next, a laminated film was obtained in the same manner as in Example 1 using the resin for resin film and the resin for resin layer.

The physical properties of the obtained laminated film 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) 9
A resin for a resin layer was obtained by mixing 9.5 parts and 20 parts of stearyldiethanolamine as an antistatic agent and 80 parts of the same betaine-type amphoteric surfactant used in Comparative Example 2.

Further, the same ethylene as used in Comparative Example 4 was used.
-Propylene copolymer was used as resin for resin film.

Next, using the obtained resin for resin film and resin for resin layer, a laminated film was obtained in the same manner as in Example 2.

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

[0181]

[Table 2]

From the results shown in Table 1, the laminated film of the present invention has a surface resistivity of 1 × 10 ¹³ which is an index of antistatic property.
Ω or less and half-life of charge is 180 seconds or less, and there is no bleed-out from the resin layer of the laminated film of the antistatic component, therefore it is a laminated film with excellent antistatic properties without blocking. .

On the other hand, the laminated films 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, the antistatic It can be seen that if the properties are to be satisfied, the antistatic agent bleeds out from the resin layer, resulting in blocking.

Example 8 The same polyolefin resin as that used in Example 1 was prepared, and the polyolefin resin was poured into ion-converted pure water heated to 60 ° C., and the resin was dispersed by stirring at high speed with a homogenizer. This was made into an emulsion, and this was further cooled to room temperature to obtain an emulsion containing 24% by weight of the resin.

Next, an unstretched film of 900 μm in thickness made of polypropylene obtained by melting, kneading and extruding with a T-die method extruder and passing through a cooling roll set at 20 ° C. was formed at a temperature of 130 ° C. After stretching 5 times in the direction, roll-coat the emulsion to a thickness of 18 μm
Was coated so that In addition, 16
The film was supplied to a tenter set at 0 ° C., stretched 9 times in the width direction, subjected to a relaxation treatment, and then wound as a film. The resin layer had a thickness of 2 μm and the resin film had a thickness of 20 μm.

When the surface resistivity of the obtained laminated film was examined in the same manner as in Example 1, it was found to be extremely small, 3.2 × 10 ⁸ Ω, and that it had excellent antistatic properties.

Next, two obtained laminated films were prepared, and the coated surface and the coated surface were overlapped,
After putting it in an atmosphere of 40 ° C. and 80% RH for 7 days, it was peeled off and the surface of the laminated film was observed, but no stickiness due to bleeding out occurred and no blocking occurred. Printing was performed on the resin layer surface of the obtained laminated film using a printing ink for polypropylene and a printing ink for cellophane, but the printability was good and there were no printing defects due to bleed-out.

Next, aluminum was vapor-deposited on the resin layer surface of the obtained laminated film so as to have a thickness of about 28 nm. The vapor-deposited film showed extremely good adhesiveness, and whitening of the vapor-deposited film by bleeding out occurred. No phenomenon, peeling or dropping was observed.

Further, at least one surface of the obtained laminated film was subjected to corona discharge treatment so that the surface wetting tension was 37 dyne /
By making it cm or more, the adhesiveness with various coating agents could be improved.

Further, a coating agent layer was provided on the resin layer and laminated with another film or sheet, or a heat sealant layer was provided, and it could be used as various packaging materials and packaging materials.

Example 9 Polypropylene (melt index: 2.8 g / 10 minutes) was used as a resin for resin film.

The same polyolefin resin as used in Example 2 and an ethylene-vinyl acetate copolymer (vinyl acetate content: 45% by weight) emulsion (resin solid content: 35% by weight) were weighed at 10:90. A mixture prepared in a ratio was prepared.

Next, a film was formed in the same manner as in Example 8 using the resin for resin film obtained above, and then the emulsion was coated to a thickness of 20.3 μm.
The laminated film of

The thickness of the resin layer of the obtained laminated film is 0.
It was 3 μm.

The surface resistivity of the obtained laminated film was the same as in Example 1, the charge half-life, bleed-out, blocking shear force and printability were the same as in Example 2, and the vapor deposition property was It measured according to the following method. The results are shown in Table 3.

(Vapor deposition property) The vacuum vapor deposition machine was equipped with a winder, a vapor deposition apparatus, a cooling device and a winder, and a predetermined amount of aluminum was put into the crucible of the vapor deposition apparatus. Was operated to close the inside of the vapor deposition system, and the vacuum pump was operated to bring the interior of the vapor deposition system to a vacuum state of 10 ⁻⁵ to 10 ⁻⁴ Torr. 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.

A cellophane adhesive tape (manufactured by Nichiban Co., Ltd., width: 24 mm) was attached to the vapor deposition surface of this vapor deposition film, and then peeled at 180 ° C. at a speed of 50 mm / min. It was judged according to the evaluation criteria.

(Evaluation criteria) Deposition area after peeling 100% index 5 90% or more but less than 100% Index 4 70% or more and less than 90% Index 3 50% or more but less than 70% Index 2 Less than 90% Index 1 It should be noted that the pass is an index of 4 or more.

Example 10 Low density polyethylene (density: 0.921 g / cm ³ , melt index: 3.2 g / 10 min) was used as a resin for a resin film.

Next, the same polyolefin resin as that used in Example 3 and the same ethylene as that used in Example 7 were used.
-Vinyl acetate copolymer emulsion was mixed at a weight ratio of 30:70 to prepare a resin layer emulsion.

Next, a film was formed in the same manner as in Example 8 using the resin for resin film obtained above, and then the emulsion was coated to a thickness of 40.1 μm.
The laminated film of The thickness of the resin layer of the obtained laminated film was 1 μm.

The physical properties of the laminated film thus obtained were examined in the same manner as in Example 7. The results are shown in Table 3.

Example 11 Linear low density polyethylene (density: 0.930 g / cm ³ , melt index: 5.2 g / 10 min) and low density polyethylene (density: 0.920 g / cm ³ , melt index: 2.1 g / 10
Min) was mixed at a weight ratio of 30:70 and used as a resin for resin film.

The same polyolefin resin as used in Example 4 and an ethylene-acrylic acid copolymer (acrylic acid content: 25% by weight) toluene solution (resin solid content: 30% by weight) were mixed at 20:80. A mixture prepared in a weight ratio was prepared.

Next, a film was formed in the same manner as in Example 8 using the resin for resin film obtained above, and then the toluene solution was coated to obtain a laminated film having a thickness of 62 μm.

The thickness of the resin layer of the obtained laminated film is 2
It was μm.

The physical properties of the laminated film thus obtained were examined in the same manner as in Example 9. The results are shown in Table 3.

Example 12 An ethylene-propylene copolymer (ethylene content: 8% by weight, melt index: 2.3 g / 10 minutes) was used as a resin for a resin film.

Expression:

[0210]

[Chemical 40]

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

[0212]

[Chemical 41]

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

[0214]

[Chemical 42]

A weight average molecular weight 33 of 9 mol% of an acrylamide structural unit represented by
A mixture of 000 polyolefin resin pulverized to a 32 mesh pass and ethylene-acrylic acid copolymer emulsion (resin solid content: 15% by weight) in a weight ratio of 30:70 was prepared. .

Next, a film was formed in the same manner as in Example 8 using the resin for resin film obtained above, and then the emulsion was coated to obtain a laminated film having a thickness of 27 μm.

The thickness of the resin layer of the obtained laminated film is
It was 2 μm.

The physical properties of the laminated film thus obtained were examined in the same manner as in Example 9. The results are shown in Table 3.

[0219]

[Table 3]

Comparative Example 6 A resin film was obtained in the same manner as in Example 9 except that polypropylene having a melt index of 2.8 g / 10 min was used. The thickness of the obtained resin film was 20 μm.

A 25% toluene solution was prepared by mixing an ethylene-vinyl acetate copolymer (vinyl acetate content 45% by weight) and chlorinated polyethylene (chlorination degree 34% by weight) in a weight ratio of 70:30.

Then, in the same manner as in Example 9, the surface of the resin film was coated with a toluene solution to give a thickness of 22.5 μm.
A laminated film of m 3 was obtained.

The thickness of the resin layer of the obtained laminated film is 2.
It was 5 μm.

The physical properties of the laminated film thus obtained were examined in the same manner as in Example 9. The results are shown in Table 4.

Comparative Example 7 Using the same low density polyethylene as used in Example 10, a resin film having a thickness of 40 μm was obtained in the same manner as in Example 10.

Then, the same ethylene-vinyl acetate emulsion as used in Example 10 was used, and a laminated film was obtained in the same manner as in Example 10.

The thickness of the resin layer of the obtained laminated film is 4
It was μm.

The physical properties of the obtained laminated film were examined in the same manner as in Example 9. The results are shown in Table 4.

Comparative Example 8 A resin film having a thickness of 60 μm was obtained in the same manner as in Example 11 except that the same mixture of linear low density polyethylene and low density polyethylene as used in Example 11 was used.

An ethylene-acrylic acid copolymer (acrylic acid content: 25% by weight) neutralized with caustic soda was used as an emulsion (resin solid content: 20% by weight). A laminated film was obtained by coating in the same manner as 11.

The thickness of the resin layer of the obtained laminated film is 5.
It was 2 μm.

The physical properties of the laminated film thus obtained were examined in the same manner as in Example 9. The results are shown in Table 4.

Comparative Example 9 A resin film having a thickness of 30 μm was obtained in the same manner as in Example 12, except that the same ethylene-propylene copolymer as used in Example 12 was used.

Next, a 18% toluene solution of ethylene-acrylic acid copolymer (acrylic acid content 25% by weight) was used to coat the above-obtained film in the same manner as in Example 11 to obtain a laminated film. .

The thickness of the resin layer of the obtained laminated film is 5.
It was 2 μm.

The physical properties of the laminated film thus obtained were examined in the same manner as in Example 9. The results are shown in Table 4.

Comparative Example 10 Using the same ethylene-propylene copolymer as used in Example 12, a resin film having a thickness of 25 μm was obtained in the same manner as in Example 12.

An emulsion of a mixture of ethylene-acrylic acid copolymer (acrylic acid content: 25% by weight) and sodium dodecylbenzene sulfonate at a weight ratio of 90:10 (resin solid content: 20% by weight) was used. The resin film obtained above was coated in the same manner as in Example 12 to obtain a laminated film product.

The thickness of the resin layer of the obtained laminated film is 3
It was μm.

The physical properties of the laminated film thus obtained were examined in the same manner as in Example 9. The results are shown in Table 4.

[0241]

[Table 4]

As is clear from the results shown in Table 3, the laminated film of the present invention has an excellent surface resistivity of 1 × 10 ¹² or less and a charge half-life of 180 seconds or less, and the bleeding of the antistatic component. It can be seen that there is no out, no blocking occurs, and the printability and metal vapor deposition are excellent.

On the other hand, as is clear from the results shown in Table 4, the conventional laminated film is inferior in adhesiveness and vapor deposition property even if the antistatic property is satisfied by the surfactant added as the antistatic agent. I know there is.

From the above, the thermoplastic resin laminated film of the present invention has excellent antistatic properties, and since there is no bleed-out of the antistatic agent and no blocking occurs, for example, it is necessary to prevent damage due to static electricity. It can be seen that it can be suitably used in the fields where it must be printed, in the fields of packaging and packaging that require printing, vapor deposition, and the like.

[0245]

The thermoplastic resin laminated film of the present invention is
It has excellent antistatic properties without bleed-out, so it does not have dust adhesion and does not give a shock to the human body due to static electricity discharge.
It is a laminated film excellent in vapor deposition property and handling property.

Claims (3)

[Claims] 1. The formula: An ethylene structural unit represented by the formula: 65 to 99 mol%, a 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 of 1000 irregularly arranged in a line
A thermoplastic resin laminated film provided with a resin layer containing 50,000 polyolefin resins. 2. The thermoplastic resin laminated film according to claim 1, wherein the resin layer has a thickness of 0.1 to 50 μm. 3. A resin layer containing the polyolefin resin in an amount of 0.
The thermoplastic resin laminated film according to claim 1, which contains 3 to 50% by weight.