JPH11140241A - Resin composition for extrusion lamination and antistatic laminate using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition capable of providing excellent preventing effects on generation of static electricity and useful as an antistatic laminate by compounding a specific ethylene-α-olefin copolymeric resin with a betaine type amphoteric surfactant. SOLUTION: This composition comprises (A) an ethylene-α-olefin copolymeric resin having 0.1-100 g/ 10 min melt flow rate(MFR) and 0.870-0.935 g/cm<3> density, preferably by using a metallocene catalyst with (B) 0.01-2 wt.% betaine type amphoteric surfactant. A compound represented by the formula (R<1> is a 6-22C hydrocarbon; R<2> to R<4> are each a 1-10C hydrocarbon; X is OH, COOH, CONH2 or the like) is preferably used in the component B.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for extrusion lamination having excellent antistatic properties and an antistatic laminate using the same.

[0002]

2. Description of the Related Art Conventionally, a polyolefin resin film is hydrophobic, so that static electricity is remarkably generated at the time of film production or molding processing, so that dust easily adheres to the film, and workability deteriorates. The value of the product as a packaging material has declined. Therefore, in order to prevent the generation of such static electricity, a polyglycol-based resin film is mixed with a monoglycol-based antistatic agent or an amine-based antistatic agent and used.

[0003]

On the other hand, in recent years, ethylene / α-olefin copolymer resins produced using a metallocene catalyst have appeared, and attention has been paid to their excellent physical properties. However, the ethylene / α-olefin copolymer-based resin produced using such a metallocene catalyst is blended with the above-mentioned monoglycol-based and amine-based antistatic agents used in conventional polyolefin-based resin films. However, the effect of preventing generation of static electricity is extremely small, and there is a problem in practicality.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in view of the above problems, and as a result of studying using various antistatic agents, have found that ethylene produced using a metallocene catalyst has been obtained. The present invention has been completed based on the finding that the addition of a betaine-type amphoteric surfactant to an α-olefin copolymer-based resin provides an excellent effect of preventing the generation of static electricity. That is, the resin composition for extrusion lamination of the present invention has an MFR of 0.1 to 1
00g / 10 min, density 0.870-0.935 g / c
m- ³ ethylene / α-olefin copolymer resin containing 0.01 to 2% by weight of a betaine-type amphoteric surfactant. The antistatic laminate according to another aspect of the present invention has a base material layer having an MFR of 0.1.
1-100 g / 10 min, density 0.870-0.935
g / cm ^{3 of} an ethylene / α-olefin copolymer-based resin layer by extrusion lamination, wherein the ethylene / α-olefin copolymer-based resin contains a betaine-type amphoteric surfactant. It is a feature.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS [I] Resin composition for extrusion lamination (1) Constituents (a) Ethylene / α-olefin copolymer resin Ethylene / α-olefin used in the resin composition for extrusion lamination of the present invention As copolymer resin,
Ethylene and α-olefin, preferably 3 to 20 carbon atoms
Α-olefin, particularly preferably α having 4 to 10 carbon atoms.
-A resin obtained by copolymerizing olefin with JIS-
MFR (melt flow rate: melt flow rate) by K7210 is 0.1 to 100 g / 10 minutes, preferably 1 to 50
g / 10 min, particularly preferably 3 to 30 g / 10 min, JI
Density (D) by S-K7112 is 0.870 to 0.9
35 g / cm ³ , preferably 0.875 to 0.920 g
/ Cm ³ , particularly preferably 0.875 to 0.915 g /
cm ³ . If the MFR is less than the above range, the extensibility of the resin is lost, and if the MFR exceeds the above range, the neck-in becomes large and a uniform molten thin film cannot be obtained in any case. If the density (D) is less than the above range, stickiness is severe and moldability is poor. On the other hand, if it exceeds the above range, the adhesiveness to the base material becomes small, and a laminate having high strength cannot be obtained.

[0006] The ethylene / α-olefin copolymer resin is JIS-71 in addition to the MFR and density (D).
Differential Scanning Calorimetry (DSC) measured according to 21
End of extrapolation melting, which is the temperature of the intersection of the line obtained by extending the high-temperature base line of the DSC curve of the melting peak due to the low-temperature side and the tangent drawn at the point where the gradient of the high-temperature curve of the melting peak becomes maximum. The relationship between temperature (Tem) and density (D) is
The one that satisfies the following relational expression is used. Tem ≦ 286D-137, preferably Tem ≦ 349D-197, particularly preferably Tem ≦ 429D-271, such an ethylene / α-olefin copolymer resin produced using a metallocene-based catalyst shown below, and , Manufactured using a conventional vanadium-based catalyst,
However, those produced using a metallocene catalyst are preferred.

Resins produced using metallocene catalysts Resins produced using metallocene catalysts include those described in JP-A-58-19309, JP-A-59-95292, JP-A-60-35005, and JP-A-60-35005. Showa 60-35006,
JP-A-60-35007, JP-A-60-35008
JP-A-60-35009, JP-A-61-13033
No. 14, JP-A-3-163088, EP-A-420,436, U.S. Pat. No. 5,055,438, and WO-A-WO
No. 91/04257, that is, a metallocene catalyst, a metallocene / alumoxane catalyst, or, for example, WO92 / 07123.
And the like, using a catalyst composed of a metallocene compound and a compound that reacts with a metallocene catalyst to form a stable ion as disclosed in
-It is produced by copolymerizing an olefin.

Resins prepared using vanadium-based catalysts Resins prepared using vanadium-based catalysts include those described in JP-A-52-39741, ie, vanadium compounds and organic aluminum compounds.
In some cases, it is further produced by using a catalyst to which a third component is added and copolymerizing ethylene as a main component and α-olefin as a subcomponent.

(B) Betaine-type amphoteric surfactant As the betaine-type amphoteric surfactant used in the resin composition for extrusion lamination of the present invention, a compound represented by the following general formula is used. General formula

[0010]

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[Wherein R ¹ represents a hydrocarbon group having 6 to 22 carbon atoms, preferably 8 to 22 carbon atoms, and R ² , R ³ and R ⁴
Represents the same or different hydrocarbon groups having 1 to 10, preferably 1 to 6, carbon atoms, and X represents -OH, -COOH, -CO
NH ₂ represents —COONa, preferably —COONa. ] In particular,

[0012]

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[0013]

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[0014]

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[0015]

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[0016]

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[0017]

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[0018]

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[0019]

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[0020]

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Compounds of the formula Among these, it is preferable to use the compound of the above [10].

(C) Other components (optional components) In the resin composition for extrusion lamination of the present invention, optional components other than the essential components of the ethylene / α-olefin copolymer resin and the betaine-type amphoteric surfactant are used. Other components (arbitrary components) can be blended as components as long as the effects of the present invention are not significantly impaired. Examples of the other components include additives such as slip agents, antistatic agents, antifogging agents, ultraviolet absorbers, antioxidants, and inorganic fillers such as calcium carbonate, silica, titanium oxide, and talc, and pigments. And the like.

(2) Blending ratio In the resin composition for extrusion lamination of the present invention, a betaine-type amphoteric surfactant is added to the ethylene / α-olefin copolymer-based resin in an amount of 0.01 to 2% by weight, preferably 0.1 to 2% by weight.
0.5 to 1% by weight, particularly preferably 0.1 to 0.5% by weight
Is used in the mixing ratio. Further, as optional components added as necessary, it is generally preferable to mix them in a mixing ratio of 0.01 to 2% by weight, particularly 0.05 to 1% by weight.

[II] Antistatic Laminate (1) Layer Structure (a) Base Layer The base layer used in the antistatic laminate of the present invention may be a high-pressure polyethylene or a low-pressure low-density polyethylene. Polyethylene resin such as polyethylene, polypropylene, etc., ethylene-vinyl acetate copolymer, saponified ethylene-vinyl acetate copolymer, polystyrene resin, polyester resin such as polyethylene terephthalate (PET), polyamide resin such as nylon, polyvinyl alcohol Resin, polyvinyl chloride resin, unstretched or stretched film or sheet of various resins such as polyvinylidene chloride resin, or metal foil or metal plate of aluminum, iron, copper, etc., woven or nonwoven fabric, paper, cellophane, etc. be able to. Among these, polyethylene terephthalate (PE
T) and other stretched polyester and nylon films (ON
It is preferable to use a polyamide resin such as Y), a stretched polypropylene film (OPP), or a metal foil. These can be corona treated, flame treated,
Ozone treatment or the like can be performed.

(B) Extrusion Lamination Layer The extrusion lamination layer to be laminated on the base material layer is the resin composition for extrusion lamination.

(C) Other Layers (Arbitrary Layers) In addition to the essential layers of the base layer and the extruded laminate layer in the antistatic laminate of the present invention, arbitrary layers can be formed. The optional layer may be an intermediate layer provided between the two layers. These optional layers may be stretched uniaxial or biaxially stretched resins. As a material used for the optional layer, for example, a high pressure method polyethylene resin (high pressure method L
DPE), a polyethylene resin such as an ethylene-vinyl acetate copolymer resin, an ethylene-vinyl alcohol copolymer resin, and a polyolefin resin such as a polypropylene resin.

(2) Thickness The thickness of the base material layer is generally 7 to 200 μm, preferably 7 to 50 μm. The thickness of the extruded laminate layer is generally 10 to 100 μm, preferably 15 to 50 μm, and particularly preferably 3 to 35 μm. The thickness of the optional layer is generally 1
Thicknesses of from 100 to 100 μm, especially from 10 to 50 μm, are preferred.

(3) Extrusion lamination As the extrusion lamination method for forming the above-mentioned antistatic laminate, generally, the surface of the base material layer is subjected to a primer coating treatment or not, and the extruded laminate layer is further formed. The extrusion resin temperature of the resin composition for extrusion lamination comprising an ethylene / α-olefin copolymer-based resin and 0.01 to 2% by weight of a betaine-type amphoteric surfactant is generally set to 150.
It is manufactured by extruding to form a molten film at a high temperature of ~ 320 ° C, preferably 200-300 ° C, and then subjecting the molten film to ozone treatment, followed by pressure lamination to the substrate layer with the treated surface as an adhesive surface. be able to.

(4) Thickness The thickness of the coat layer used for extrusion lamination should be
When forming the α-olefin copolymer resin in a single layer,
Generally 10 to 40 μm, 3 to 3 when co-extrusion molding
5 μm molten film. The air gap of the laminator is generally performed at 100 to 150 mm. The laminating speed is generally preferably from 80 to 150 m / min from the viewpoint of productivity.

[III] Heat treatment of laminate The antistatic laminate of the present invention is preferably prepared by laminating a film-like base layer and an extrusion laminate layer comprising a resin composition for extrusion lamination, preferably at 30 ° C or higher. Is desirably heat-treated at a temperature of 35 to 50C. The heat treatment may be in contact with a heated roll, passing through an oven,
For example, treatment in a heated atmosphere such as is employed. If the temperature of the heat treatment is lower than 30 ° C., the treatment effect is not sufficient, and the initial antistatic property is not improved.

[IV] Physical Properties The laminate obtained as described above has a surface resistivity (M
Ω) is 10 ¹⁰ to 10 ¹³ MΩ, preferably 10 ¹⁰ to 10 ¹² MΩ.
In MΩ, the half-life of the charge is 60 to 1 second, preferably 20 to
The heat sealing temperature is 90 to 110 ° C, preferably 90 to 100 ° C in one second.

[0032]

The present invention will be described more specifically with reference to the following examples and comparative examples. [I] Evaluation Method Measurement of physical properties and evaluation of film physical properties in Examples and Comparative Examples were performed by the following methods. (1) Evaluation method of physical properties of laminated film (A) Antistatic property (a-1) Surface specific resistance Connect an electrode box for measuring ultra-high resistance to a vibration-type micro-current / electrometer manufactured by ADVANTEST, and set it at 23 ° C. , 50% RH
Measure in a constant temperature / humidity room controlled by. The surface resistivity (MΩ) is calculated by the following equation. [Ps: surface specific resistance (MΩ) D: inner diameter of the surface annular electrode d: outer shape of the inner circle of the surface main electrode Rs: surface resistance (MΩ) π: pi = 3.14]

(A-2) Half-life of electric charge In a constant temperature and humidity chamber controlled at 23 ° C. and 50% RH, a static honest meter (TAPE manufactured by Shishido Shosha Co., Ltd.)
Using S-4104), a voltage of 10 kV is applied to the sample, and the time until the applied charge attenuates to 1/2 is determined as a half-life.

(B) Heat sealing temperature 3 kg load Heat sealing temperature: Two laminated films cut to a width of 15 mm were put together with the sealant surfaces together, and were placed at intervals of 80 ° C. to 5 ° C. with a hot plate heat sealer manufactured by Toyo Seiki. Heat sealing is performed at a sealing pressure of 2 kg / cm ² and a sealing time of 1 second, and the strength of the heat sealed portion is measured by a tensile tester at a pulling speed of 500 mm / min. The temperature at which the strength of the heat seal portion is obtained at 3 kg / 15 mm is defined as a heat seal temperature under a load of 3 kg.

[II] Experimental Examples Example 1 Production of Ethylene / 1-hexene Copolymer A catalyst was prepared by the method described in JP-A-61-130314. That is, to 2.0 mmol of the complex ethylenebis (4,5,6,7-tetrahydroindenyl) zirconium chloride, methylalumoxane (manufactured by Toyo Stouffer Co., Ltd.) was added 1,000 times as much as the above complex, and the mixture was diluted to 10 liters with toluene. After dilution, a catalyst solution was prepared and polymerized by the following method. Inner volume 1.5
A mixture of ethylene and 1-hexene was supplied to a 1-liter stirred autoclave type continuous reactor so that the composition of 1-hexene was 83% by weight, and the pressure in the reactor was 1,
The reaction was performed at a temperature of 145 ° C. while maintaining the pressure at 300 kg / cm ² . After the reaction was completed, the MFR was 16.5 g / 10 min, the density was 0.895 g / cm ³ , and the differential scanning calorimetry (DS
An ethylene / 1-hexene copolymer having one melting peak due to C) and having an extrapolated melting end temperature (Tem) of 95 ° C was obtained.

Preparation of resin composition for extrusion lamination 80% by weight of the obtained ethylene / 1-hexene copolymer
Low density polyethylene LC600A (manufactured by Nippon Polychem: MFR 7 g / 10 min, density 0.919 g / cm ³ )
20% by weight, Irganox 1076 as antioxidant
(Ciba-Geigy) and P-EPQ (Sand),
An appropriate amount of dicalite white filler (manufactured by Rasa Shoji) as an anti-blocking agent and an appropriate amount of oleic amide (manufactured by Nippon Kasei Co., Ltd.) as a slip agent were prepared to prepare a copolymer composition. Next, 0.2% by weight of a betaine-type amphoteric surfactant (“Chemistat 4700” manufactured by Sanyo Chemical Co., Ltd.) was added as an antistatic agent to 99.8% by weight of the composition.
The resin composition for extrusion lamination was obtained by melt-kneading at a temperature of 160 ° C. with a twin-screw extruder.

Production of Laminated Body Antistatic Polypropylene Biaxially Stretched Film (OPP)
(Toyobo's P2241 25 μm) and ethylene
Saponified vinyl acetate copolymer (ethylene / vinyl alcohol copolymer: EVOH) film (Kuraray Co., Ltd.)
F-Xl) is subjected to an anchor coat treatment on the surface of the substrate laminated by a dry lamination method, and a high-pressure low-density polyethylene (high-pressure LDPE:
Nippon Polychem Co., Ltd. Novatec LC600A) 32
It was extruded at a temperature of 0 ° C. and laminated so that the resin layer became 25 μm. Then, a melt-kneaded product of the resin composition for extrusion lamination is added to this laminate by an extrusion laminator for 280.
Extruded at a temperature of 100 ° C., laminated at a laminating speed of 100 m / min, and laminated so that the resin layer became 25 μm.
Antistatic OPP / EVOH / High-pressure LDPE / Ethylene / α-olefin copolymer resin = 25 μm / 12 μm /
A laminate having a thickness of 25 μm / 25 μm was obtained.

Evaluation The surface resistivity of the laminate and the half-life of the charge and the heat-sealing temperature after 1 day and 1 month were measured. The results are shown in Table 1.

Example 2 In Example 1, the copolymer resin of the resin composition for extrusion lamination was an ethylene / butene-1 copolymer resin (Mitsui Petrochemical's “A20090” vanadium-based material: MFR
A laminate was obtained in exactly the same manner as in Example 1 except that the density was changed to 18 g / 10 minutes, the density was 0.89 g / cm ³ , and the butene content was 20% by weight.

Comparative Example 1 A laminate was prepared in the same manner as in Example 1 except that no antistatic agent was added to the ethylene / butene-1 copolymer resin, and the surface resistivity of the laminate and one day later The half-life of the charge after 1 month and the heat sealing temperature were measured. The results are shown in Table 1.

Comparative Example 2 An ethylene / butene-1 copolymer resin ("EXACT5008" manufactured by EXXON USA) metallocene material: MFR 10 g / 10 min, density 0.865 g / cm
³ , except that the butene content was changed to 30% by weight).
However, surging due to bridging of the pellets due to stickiness occurred, and the laminate could not be obtained due to poor roll separation from the cooling roll.

Comparative Example 3 An ethylene / butene-1 copolymer resin (Novatec LL “UC970” Ziegler-based material manufactured by Nippon Polychem Co., Ltd .: MFR 10 g / 10 min, density 0.936 g /
cm ³ , butene content: 4% by weight) to obtain a laminate in exactly the same manner as in Example 1.

Comparative Example 4 An antistatic agent was developed except that a monoglycol masterbatch ("AS04K" manufactured by Nippon Polychem Co., Ltd., antistatic 4% by weight) was developed at 2% by weight (final antistatic agent 0.2% by weight). Was obtained in the same manner as in Example 1.

[0044]

[Table 1]

[0045]

As described above, the resin composition for extrusion lamination of the present invention and the antistatic laminate using the same have a small surface resistivity and a half-life of electric charge, a low heat-sealing temperature of 3 kg load, and a low static pressure. It is excellent in antistatic and heat sealing properties, and is most suitable as a resin composition for extrusion lamination and an antistatic laminate using the same.

Claims (8)

[Claims] 1. An ethylene α-form having an MFR of 0.1 to 100 g / 10 min and a density of 0.870 to 0.935 g / cm ^3.
A resin composition for extrusion lamination, characterized in that the olefin copolymer resin contains 0.01 to 2% by weight of a betaine-type amphoteric surfactant. 2. The resin composition for extrusion lamination according to claim 1, wherein the ethylene / α-olefin copolymer resin is produced by using a metallocene catalyst. 3. A betaine-type amphoteric surfactant having the general formula: [Wherein R ¹ represents a hydrocarbon group having 6 to 22 carbon atoms;
R ² , R ³ and R ⁴ represent the same or different hydrocarbon groups having 1 to 10 carbon atoms, and X represents —OH, —COOH, —CO
NH ₂ represents —COONa. The resin composition for extrusion lamination according to claim 1, which is a compound represented by the following formula: 4. The ethylene / α-olefin copolymer-based resin extends a high-temperature base line of a DSC curve of a melting peak by a differential scanning calorimetry (DSC) measured according to JIS-7121 to a low-temperature side. The relationship between the extrapolated melting end temperature (Tem), which is the temperature at the intersection of the line and the tangent drawn at the point where the gradient of the curve on the high temperature side of the melting peak is the maximum, and the density (D) is represented by the following equation: The resin composition for extrusion lamination according to claim 1, which satisfies the following. Tem ≦ 286D-137 5. The base material layer has an MFR of 0.1 to 100 g / 10.
And an extrusion-laminated ethylene / α-olefin copolymer resin layer having a density of 0.870 to 0.935 g / cm ³ , wherein the ethylene / α-olefin copolymer resin is betaine. An antistatic laminate comprising an amphoteric surfactant. 6. The resin composition for extrusion lamination according to claim 5, wherein the ethylene / α-olefin copolymer resin is an ethylene / α-olefin copolymer resin produced by a metallocene catalyst. 7. A betaine-type amphoteric surfactant having the general formula: [Wherein R ¹ represents a hydrocarbon group having 6 to 22 carbon atoms;
R ² , R ³ and R ⁴ represent the same or different hydrocarbon groups having 1 to 10 carbon atoms, and X represents —OH, —COOH, —CO
NH ₂ represents —COONa. The antistatic laminate according to claim 5, which is a compound represented by the following formula: 8. The ethylene / α-olefin copolymer-based resin extends a high-temperature base line of a DSC curve of a melting peak by a differential scanning calorimetry (DSC) measured according to JIS-7121 to a low-temperature side. The relationship between the extrapolated melting end temperature (Tem), which is the temperature at the intersection of the line and the tangent drawn at the point where the gradient of the curve on the high temperature side of the melting peak is the maximum, and the density (D) is represented by the following equation: The resin composition for extrusion lamination according to claim 5, which satisfies the following.