JP2001009994A - High frequency fusible laminate and production thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a high frequency fusible laminate free from surface stickiness and excellent in high frequency fusibility and a method for producing the same. SOLUTION: A high frequency fusible laminate has (A) a layer comprising an ethylene/α-olefin copolymer with a density of 0.88-0.96 g/cm3, a melt flow rate of 0.01-50 g/10 min, a mol.wt. distribution (Mw/Mn) of 1.5-4.0 and a compsn. distribution parameter Cb of 2 or less and (B) a layer comprising high frequency exothermic polyolefin and is produced by water cooling inflation molding.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-frequency fusion laminate having excellent high-frequency fusion property, high heat sealing strength, good pinhole resistance, and excellent transparency and flexibility. The present invention relates to a molded product such as a bag formed by sealing a film or sheet of the laminate by high-frequency heating, and a method for producing a laminate that can be subjected to high-frequency fusion.

[0002]

2. Description of the Related Art Unlike a polyvinyl chloride resin, a polyolefin resin does not have a polar group in its molecule, so that it has been difficult to fuse it using high frequency or microwave. For this reason, there has been proposed a method of adding various polar compounds in order to impart high-frequency fusion to a nonpolar polyolefin resin.

Although homopolymers of ethylene and propylene and ethylene / α-olefin copolymers are not suitable for high-frequency heating, an ethylene / vinyl acetate copolymer having a polar group (EVA) has a certain frequency. It can be heated by electromagnetic waves. However, if the vinyl acetate (VA) concentration in the constituent monomers of EVA is not increased, there is a disadvantage that the fusion at a high frequency becomes insufficient. Therefore, in order to obtain practical fusion strength, EVA having a high VA concentration was required.

On the other hand, when the VA concentration is high, for example, when the VA concentration is 25%, the stickiness of the film and the sheet becomes severe, and there is a disadvantage that the blocking and the practical performance are lowered. To solve this, EVA
There has been proposed a method of forming a laminate in which inner and outer layers (surface layers) of low-density polyethylene (LDPE) or linear low-density polyethylene (LLDPE) are formed on both surfaces.

[0005]

SUMMARY OF THE INVENTION However, EVA
When crystalline polyethylene (PE) such as LDPE or LLDPE is used for both inner and outer layers, the intermediate layer EVA layer heated by high frequency is melted from the crystalline surface layer PE layer and fused together. For this purpose, long-time heating and sealing pressure were required. Therefore, the high-frequency fusion property is insufficient, and it has not been industrialized.

Accordingly, it is an object of the present invention to provide a non-sticky surface, excellent high-frequency fusion property, good heat sealability and pinhole resistance, heat resistance, mechanical properties, moldability and moldability. It is an object of the present invention to provide a high-frequency-fusible laminate excellent in properties such as blocking properties and a method for producing the same. Another object of the present invention is to provide a laminate which is excellent in transparency and flexibility and which can be subjected to high frequency fusion and a method for producing the same.

[0007]

The present inventors have conducted intensive studies to improve the above-mentioned drawbacks. As a result, the present inventors have solved these problems by using a specific ethylene / α-olefin copolymer for the surface layer. The present inventors have found that the problem can be solved, and have reached the present invention.

That is, the high-frequency-fusible laminate of the present invention comprises (A) a layer comprising an ethylene / α-olefin copolymer or a composition thereof satisfying the following requirements (a) to (d): (B) a layer containing a high-frequency heat-generating polyolefin. (A) a density of 0.88 to 0.96 g / cm ³ (b) a melt flow rate of 0.01 to 50 g / 10 min (c) a molecular weight distribution (Mw / Mn) of 1.5 to 4.0 (d ) Composition distribution parameter Cb is 2 or less

It is preferable that the high-frequency-fusible laminate of the present invention further comprises (C) a layer containing the ethylene / α-olefin copolymer or another polyolefin polymer. Further, it is desirable that the high-frequency-fusible laminate of the present invention further has (D) a barrier layer. The thickness of the layer (B) is desirably 50% or more of the total thickness of the laminate.

It is desirable that the haze value of the laminate composed of the (A) layer / (B) layer or the (A) layer / (B) layer / (C) layer is 5% or less. Further, the (A) layer / (B) layer or (A) layer / (B) layer / (C)
The rigidity (Young's modulus) of the laminate composed of layers is 1000 k
gf / cm ² or less is desirable. Further, it is desirable that the (d) composition distribution parameter of the ethylene / α-olefin copolymer is in the range of 1.10 to 2.00.

The electrical activation energy of the ethylene / α-olefin copolymer or its composition is as follows:
Desirably, it is 0.4 eV or less. In addition, 90% of the ethylene / α-olefin copolymer or the composition thereof
It is desirable that the volume specific resistance at 1 ° C. is 1 × 10 ¹⁶ Ω · cm or more. Further, it is desirable that the ethylene / α-olefin copolymer is an ethylene / α-olefin copolymer obtained by a single-site catalyst.

The high-frequency heat-generating polyolefin is preferably a polar group-containing olefin polymer. Further, the polar group-containing olefin polymer is preferably an ethylene / vinyl acetate copolymer or a composition containing the copolymer. The molded article of the present invention is characterized in that the high-frequency-fusible laminate is sealed by high-frequency heating. Further, the method for producing a high-frequency fusion-bondable laminate of the present invention comprises: (A) a layer comprising an ethylene / α-olefin copolymer or a composition thereof satisfying the requirements (a) to (d) above; B) a laminate having a layer containing a polyolefin capable of high frequency, or the (A) layer, the (B) layer, and (C) the ethylene α-
A laminate having a layer containing an olefin copolymer or a polyolefin polymer and / or a (D) barrier layer is formed by water-cooled inflation molding.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. <(A) Layer of ethylene / α-olefin copolymer or composition thereof> The ethylene / α-olefin copolymer according to the present invention is obtained by copolymerizing ethylene with an α-olefin having 3 to 20 carbon atoms. The resulting (a) has a density of 0.88 to 0.96 g / cm ³ , (b) a melt flow rate of 0.01 to 50 g / 10 minutes, and (c) a molecular weight distribution (Mw / Mn) of 1. 5 to 4.0, (d) ethylene satisfying the requirement that the composition distribution parameter Cb is 2 or less (co)
It is a polymer.

The ethylene / α-olefin copolymer according to the present invention is a copolymer of ethylene and at least one selected from α-olefins having 3 to 20 carbon atoms. Here, the α-olefin having 3 to 20 carbon atoms is preferably 3 to 1
2, specifically, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene and the like. In addition, the content of these α-olefins is desirably selected in a total of usually 30 mol% or less, preferably 3 to 20 mol%.

The ethylene / α-olefin copolymer according to the present invention has a (a) density of 0.88 to 0.96 g / cm.
³ , preferably 0.89 to 0.94 g / cm ³ , more preferably 0.89 to 0.935 g / cm ³ . If the density is less than 0.88 g / cm ³ , the rigidity and heat resistance are inferior, and the blocking property of the film is deteriorated. Also, when it exceeds 0.96 g / cm ³ ,
It is too hard, resulting in low tear strength and impact strength.

The ethylene / α-olefin copolymer according to the present invention has a melt flow rate (b) (hereinafter referred to as MFR) of 0.01 to 50 g / 10 min, preferably 0.1 to 50 g / 10 min.
-40 g / 10 min, more preferably 0.1-30 g /
The range is 10 minutes. If the MFR is less than 0.01 g / 10 min, the moldability is poor, and if it exceeds 50 g / 10 min,
The mechanical strength decreases.

The (c) molecular weight distribution (Mw / Mn) of the ethylene / α-olefin copolymer according to the present invention is 1.5 to 1.5.
The range is 4.0, preferably 1.6 to 4.0, and more preferably 1.7 to 3.5. If Mw / Mn is less than 1.5, the moldability is poor, and if it exceeds 4.0, impact resistance, pinhole resistance and the like may be poor. Here, the molecular weight distribution of the ethylene / α-olefin copolymer (Mw / M
n) is gel permeation chromatography (G
PC), the weight average molecular weight (Mw) and the number average molecular weight (Mn) are determined, and the ratio (Mw / Mn) is calculated.

The (d) composition distribution parameter Cb of the ethylene / α-olefin copolymer according to the present invention is 2 or less. If the composition distribution parameter Cb is more than 2, blocking is likely to occur, heat sealability is poor, and a low molecular weight or high branching component often oozes out onto the resin surface, resulting in a hygienic problem. The composition distribution parameter Cb is preferably 1.08 to 2.00, more preferably 1.10 to 1.70, and still more preferably 1.10 to 1.70.
The range is 10 to 1.60, and more preferably 1.10 to 1.60.
It is desirable to be in the range of 50. If the composition distribution parameter Cb is less than 1.08, the moldability tends to be poor.

The composition distribution parameter (Cb) is measured as follows. A sample was dissolved in orthodichlorobenzene (ODCB) to which an antioxidant had been added by heating at 135 ° C. to a concentration of 0.2% by weight, and then diatomaceous earth (Celite 5)
45) to a packed column. Then 0.1 ° C
Cool at 25 ° C./min to deposit the copolymer sample on the Celite surface. Next, the column temperature is increased stepwise to 120 ° C. in steps of 5 ° C. while flowing ODCB at a constant flow rate through the column on which the sample is deposited. Then, a solution containing an eluted component corresponding to each temperature is collected. After cooling the solution, methanol is added, and the sample is precipitated, filtered and dried to obtain an eluted sample at each temperature. The weight fraction and the degree of branching (the number of branches per 1000 carbon atoms) of each of the separated samples are measured. Branching degree is ¹³ C
-Measured by NMR.

According to such a method, 30 ° C. to 90 ° C.
The following branching correction is performed on the fractions collected between the steps. That is, the degree of branching measured with respect to the elution temperature is plotted, and the correlation is approximated to a straight line by the least squares method to create a calibration curve. The correlation coefficient of this approximation is large enough. The value obtained from this calibration curve is defined as the degree of branching of each fraction. Note that, for a fraction collected at an elution temperature of 95 ° C. or higher, this correction is not performed because a linear relationship is not always established between the elution temperature and the degree of branching.

[0021] Then, the weight fraction w _i of each fraction to obtain the relative concentration c _i divided by the amount of change in the degree of branching b _i per the elution temperature _{5 ℃ (b i -b i-} 1), the degree of branching Is plotted against the relative concentration to obtain a composition distribution curve.
This composition distribution curve is divided by a certain width, and the composition distribution parameter Cb is calculated from the following equation. Cb = (Σc _j・ b _j ² / Σc _j・ b _j ) / (Σc _j・ b _j /
Σc _j ) where c _j and b _j are the relative density and branching degree of the j-th section, respectively. The composition distribution parameter Cb is 1.0 when the composition of the sample is uniform, and the value increases as the composition distribution spreads.

The ethylene / α-olefin copolymer according to the present invention is not particularly limited to a catalyst or a production method as long as the above parameters are satisfied. Preferably, the ethylene / α-olefin copolymer is used in the presence of a single-site catalyst. And an α-olefin obtained by copolymerizing the α-olefin with an ethylene-α-olefin copolymer. Such ethylene
The α-olefin copolymer has a narrow molecular weight distribution and a narrow composition distribution, and thus has excellent mechanical properties, and is excellent in heat sealing properties, blocking properties, and the like.

A typical example of the single-site catalyst is a catalyst comprising a transition metal compound belonging to Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton and an organoaluminum oxy compound. The cyclopentadienyl skeleton includes a cyclopentadienyl group, a substituted cyclopentadienyl group, and the like. Examples of the substituted cyclopentadienyl group include a hydrocarbon group having 1 to 10 carbon atoms, a silyl group, a silyl-substituted alkyl group, a silyl-substituted aryl group, a cyano group, a cyanoalkyl group, a cyanoaryl group, a halogen group, a haloalkyl group, and a halosilyl group. And a substituted cyclopentadienyl group having at least one substituent selected from groups and the like. The substituted cyclopentadienyl group may have two or more substituents, and the substituents may combine with each other to form a ring.

The hydrocarbon group having 1 to 10 carbon atoms includes an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and the like.
n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group,
Examples include an alkyl group such as a decyl group; a cycloalkyl group such as a cyclopentyl group and a cycloalkyl group; an aryl group such as a phenyl group and a tolyl group; and an aralkyl group such as a benzyl group and a neoyl group. Among these, an alkyl group is preferable.

Preferred examples of the substituted cyclopentadienyl group include a methylcyclopentadienyl group, an ethylcyclopentadienyl group, an n-hexylcyclopentadienyl group, a 1,3-dimethylcyclopentadienyl group, 1,
3-n-butylmethylcyclopentadienyl group, 1,3
Specific examples include -n-propylmethylethylcyclopentadienyl group. As the substituted cyclopentadienyl group according to the present invention, among these, a cyclopentadienyl group substituted by an alkyl group having 3 or more carbon atoms, particularly a 1,3-substituted cyclopentadienyl group, is preferred.

When the substituents, that is, the hydrocarbons are bonded to each other to form one or more rings, the substituted cyclopentadienyl group may be an indenyl group,
-Substituted indenyl group, naphthyl group having 1 to 8 carbon atoms, which is substituted by a substituent such as
Preferred are a substituted naphthyl group substituted by a substituent such as a hydrocarbon group (such as an alkyl group), and a substituted fluorenyl group substituted by a substituent such as a hydrocarbon group having 1 to 8 carbon atoms (such as an alkyl group). Are listed.

The transition metal of the transition metal compound belonging to Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton includes zirconium, titanium, hafnium and the like, with zirconium being particularly preferred. The transition metal compound usually has a ligand having a cyclopentadienyl skeleton of 1
In the case of having 3 or more, or having 2 or more, these ligands may be bonded to each other by a crosslinking group. In addition, examples of such a crosslinking group include an alkylene group having 1 to 4 carbon atoms, an alkylsilanediyl group, and a silanediyl group.

In the transition metal compounds belonging to Group IV of the periodic table, typical ligands other than those having a cyclopentadienyl skeleton include hydrogen and C 1 to C 1.
20 hydrocarbon groups (such as an alkyl group, an alkenyl group, an aryl group, an alkylaryl group, an aralkyl group, and a polyenyl group), a halogen, a methalkyl group, and a metaaryl group.

Specific examples of transition metal compounds of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton include the following. Examples of the monoalkyl metallocene include bis (cyclopentadienyl) titanium methyl chloride, bis (cyclopentadienyl) titanium phenyl chloride, bis (cyclopentadienyl) zirconium methyl chloride, and bis (cyclopentadienyl) zirconium phenyl chloride. There is. Examples of the dialkyl metallocene include bis (cyclopentadienyl) titanium dimethyl, bis (cyclopentadienyl) titanium diphenyl, bis (cyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl) zirconium diphenyl, bis (cyclopentadienyl) Enyl) hafnium dimethyl and bis (cyclopentadienyl) hafnium diphenyl. Examples of the trialkyl metallocene include cyclopentadienyl titanium trimethyl, cyclopentadienyl zirconium trimethyl, cyclopentadienyl zirconium triphenyl,
Cyclopentadienyl zirconium trineopentyl,
Examples include cyclopentadienyl hafconium trimethyl and cyclopentadienyl hafnium triphenyl.

Examples of the monocyclopentadienyl titanocene include pentamethylcyclopentadienyl titanium trichloride, pentaethylcyclopentadienyl titanium trichloride, bis (pentamethylcyclopentadienyl) titanium diphenyl and the like.

Examples of the substituted bis (cyclopentadienyl) titanium compound include bis (indenyl) titanium diphenyl or dichloride, bis (methylcyclopentadienyl) titanium diphenyl or dihalide; dialkyl, trialkyl, tetraalkyl or pentaalkylcyclopentane. Dienyl titanium compounds include bis (1,2-dimethylcyclopentadienyl) titanium diphenyl or dichloride, bis (1,2-diethylcyclopentadienyl) titanium diphenyl or dichloride or other dihalide complexes; silicon, amine or Examples of the carbon-linked cyclopentadiene complex include dimethylsilyldicyclopentadienyltitanium diphenyl or dichloride, methylenedicyclopentadienyl Data iodonium diphenyl or dichloride, and other dihalide complexes.

Examples of the zirconocene compound include pentamethylcyclopentadienyl zirconium trichloride,
Pentaethylcyclopentadienyl zirconium trichloride, bis (pentamethylcyclopentadienyl)
Zirconium diphenyl; alkyl-substituted cyclopentadiene includes bis (ethylcyclopentadienyl) zirconium dimethyl, bis (methylcyclopentadienyl) zirconium dimethyl, bis (n-butylcyclopentadienyl) zirconium dimethyl, haloalkyl or dihalide thereof Complexes: dialkyl, trialkyl, tetraalkyl or pentaalkylcyclopentadiene such as bis (pentamethylcyclopentadienyl) zirconium dimethyl, bis (1,2-dimethylcyclopentadienyl) zirconium dimethyl, and dihalide complexes thereof; silicon And carbon-linked cyclopentadiene complexes such as dimethylsilyldicyclopentadienylzirconium dimethyl or dihalide, methylenedicyclopentene Dienyl zirconium dimethyl or dihalide, such as methylene dicyclopentadienyl zirconium dimethyl or dihalide, and the like.

Examples of other transition metal compounds belonging to Group IV of the periodic table include (t-butylamide) (tetramethyl-
η5-cyclopentadienyl) -1,2-ethanediylzirconium dichloride, (t-butylamido) (tetramethylcyclopentadienyl) -1,2-ethanediyltitanium dichloride, (methylamido) (tetramethylcyclopentadienyl ) -1,2-ethanediylzirconium dichloride, (methylamide) (tetramethylcyclopentadienyl) -1,2-ethanediyltitanium dichloride, (ethylamide) (tetramethylcyclopentadienyl) -methylenetan dichloride,
(T-butylamido) dimethyl (tetramethylcyclopentadienyl) silanetitanium dichloride, (t-butylamido) dimethyl (tetramethylcyclopentadienyl) silanezirconium dichloride, (t-butylamido) dimethyl (tetramethylcyclopentadienyl)
Silane zirconium dibenzyl, (benzylamido) dimethyl- (tetramethylcyclopentadienyl) silane titanium dichloride, (phenylphosphido) dimethyl- (tetramethylcyclopentadienyl) silane titanium dichloride, and the like.

As the co-catalyst according to the present invention, the above-mentioned transition metal compound of Group IV of the periodic table can be effectively used as a polymerization catalyst, or it can balance ionic charges in a catalytically activated state. The specific co-catalyst is
Examples of the organic aluminum oxy compound include benzene-soluble aluminoxanes, benzene-insoluble organic aluminum oxy compounds, boron compounds, lanthanoid salts such as lanthanum oxide, and tin oxide. Of these, aluminoxanes are most preferred.

The above catalyst may be used by being supported on a carrier of an inorganic compound or an organic compound. As the carrier, a porous oxide of an inorganic compound or an organic compound is preferable,
Specifically, SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , Ti
O ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO _{2 and the} like or a mixture thereof, and SiO ₂ —Al ₂ O ₃ , S
_{iO 2 -V 2 O 5, SiO} 2 -TiO 2, SiO 2 -V 2 O 5,
SiO ₂ —MgO, SiO ₂ —Cr ₂ O _{3 and the} like can be mentioned.
Among these, those containing at least one component selected from the group consisting of SiO ₂ and Al ₂ O ₃ as a main component are preferable. Further, as the organic compound, a thermoplastic resin,
Any of thermosetting resins can be used, and specific examples thereof include particulate polyolefin, polyester, polyamide, polyvinyl chloride, polymethyl (meth) acrylate, polystyrene, polynorbornene, various natural polymers, and mixtures thereof. Is mentioned.

Examples of the organoaluminum compound according to the present invention include trialkylaluminums such as triethylaluminum and triisopropylaluminum; dialkylaluminum halides; alkylaluminum sesquihalides; alkylaluminum dihalides; alkylaluminum hydrides; Can be

The method for producing an ethylene / α-olefin copolymer according to the present invention is carried out by a gas phase polymerization method, a slurry polymerization method, a solution polymerization method, etc., in the presence of the catalyst, in which substantially no solvent is present, In a state where oxygen, water, etc. are substantially turned off, aliphatic hydrocarbons such as butane, pentane, hexane, and heptane; aromatic hydrocarbons such as benzene, toluene, and xylene; and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane It is produced in the presence or absence of an inert hydrocarbon solvent exemplified as above. The polymerization conditions are not particularly limited, but the polymerization temperature is usually 15 to 350 ° C, preferably 20 to
To 200 ° C, more preferably 50 to 110 ° C,
The polymerization pressure is usually from normal pressure to 70 kg / cm ^{2 in} the case of the low and medium pressure method.
G, preferably normal pressure to 20 kg / cm ² G, the case of high pressure process typically 1500 kg / cm ² G or less.
The polymerization time is usually from 3 minutes to 10 hours, preferably from 5 minutes to 5 hours in the case of the low and medium pressure method. In the case of the high-pressure method, it is usually 1 minute to 30 minutes, preferably about 2 minutes to 20 minutes. In addition, the polymerization is not particularly limited to a single-stage polymerization method, as well as a multi-stage polymerization method of two or more stages in which polymerization conditions such as hydrogen concentration, monomer concentration, polymerization pressure, polymerization temperature, and catalyst are different from each other. A particularly preferred method is disclosed in
And a method described in JP-A-132518.

<Composition of ethylene / α-olefin copolymer> The composition of the ethylene / α-olefin copolymer according to the present invention is different from the above-mentioned ethylene / α-olefin copolymer. Compositions containing other polyolefin polymers such as high-density polyethylene, linear medium / low-density polyethylene, ethylene polymers obtained by radical polymerization (hereinafter referred to as ethylene polymers), propylene polymers, etc. It is.

The ethylene polymer according to the present invention includes:
Different from (but not overlapping with) the ethylene / α-olefin copolymer, a conventionally known Ziegler-based catalyst or Phillips catalyst (hereinafter, referred to as a Ziegler-type catalyst including both), or a high-density polymerized using a metallocene catalyst Polyethylene, linear medium / low density polyethylene polymer,
It is an ethylene polymer obtained by a radical polymerization method. These generally have a wider molecular weight distribution or composition distribution than the ethylene / α-olefin copolymer according to the present invention. As the ethylene polymer, the density is 0.86 ~
0.96 g / cm ³ and MFR in the range of 0.1 to 50 g / 10 min are preferable. So-called very low density polyethylene (VLDPE), linear low density polyethylene (LLD)
PE), medium density polyethylene (MDPE), and high density polyethylene (HDPE).

High-density polyethylene (HDPE) and medium-density polyethylene (MDP) using the above Ziegler-type catalyst
E), linear low density polyethylene (LLDPE)
The density is from 0.91 to 0.97 g / cm ³ , preferably from 0.1 to 0.97 g / cm ³ .
91 to 0.96 g / cm ³ , more preferably 0.91 to 0.96 g / cm ³
It is in the range of 0.94 g / cm ³ and has an MFR of 0.
01-50 g / 10 min, preferably 0.05-40 g /
It is selected in the range of 10 minutes, more preferably 0.1 to 30 g / 10 minutes.

The ultra low density polyethylene (VLDPE) using the Ziegler type catalyst has a density of 0.86 to 0.9.
Less than 1 g / cm ³ , preferably 0.88 to 0.905 g
/ Cm ³ and MFR are selected in the range of 0.01 to 50 g / 10 min, preferably 0.1 to 30 g / 10 min. The very low density polyethylene (VLDPE) is composed of linear low density polyethylene (LLDPE) and ethylene α-
It has properties intermediate to those of olefin copolymer rubbers (EPR, EPDM) and has a maximum peak temperature (Tm) by differential scanning calorimetry (DSC) of 60 ° C. or higher, preferably 100 ° C. or higher, and a boiling point of n. -Hexane insoluble content 10% by weight
A specific ethylene / α-olefin copolymer having the above properties, which is polymerized using a solid catalyst component containing at least titanium and / or vanadium and an organoaluminum compound, or a metallocene-based catalyst to obtain a linear low-density polymer. A resin having both a high crystalline portion represented by polyethylene (LLDPE) and an amorphous portion represented by ethylene / α-olefin copolymer rubber. The former is characterized by mechanical strength and heat resistance, and the latter is characterized by: Rubber-like elasticity and low-temperature impact resistance coexist in a well-balanced manner.

The α-olefin of the ethylene polymer has 3 to 12 carbon atoms, preferably 3 to 10 carbon atoms, and specifically includes propylene, 1-butene and 4-methyl-1-pentene. , 1-hexene, 1-octene, 1
-Decene, 1-dodecene and the like. Further, the content of these α-olefins is preferably selected in a range of usually 3 to 40 mol% in total.

Examples of the ethylene polymer obtained by the radical polymerization method include low-density polyethylene (LDPE) obtained by a high-pressure radical polymerization method, an ethylene / vinyl ester copolymer, ethylene and an α, β-unsaturated carboxylic acid or a mixture thereof. Copolymers with derivatives are mentioned.

M of the above low density polyethylene (LDPE)
FR is in the range of 0.05 to 20 g / 10 min, more preferably 0.1 to 10 g / 10 min. Within this range, the melt tension is in an appropriate range, and the moldability is improved. The density is 0.91 to 0.94 g / cm.
³ , more preferably 0.912 to 0.935 g / cm ³
Range. Within this range, the melt tension is in an appropriate range, and the moldability is improved. The melt tension is 1.5 to 25 g, preferably 3 to 20 g, more preferably 3 to 15 g. In addition, the molecular weight distribution M
w / Mn is 3.0 to 12, preferably 4.0 to 8.0.
It is. Melt tension is an elasticity item of the resin, and the moldability is good in the above range.

The above-mentioned ethylene / vinyl ester copolymer means ethylene-based vinyl propionate, vinyl acetate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl stearate produced by a high-pressure radical polymerization method. And a copolymer with a vinyl ester monomer such as vinyl trifluoroacetate. Among them, particularly preferred is vinyl acetate. Also, 50 to 99.5% by weight of ethylene, 0.5 to 50% by weight of vinyl ester, and 0
A copolymer consisting of 49.5% by weight is preferred. In particular,
The content of vinyl ester is in the range of 3 to 30% by weight, preferably 5 to 25% by weight. The MFR of the ethylene / vinyl ester copolymer is in the range of 0.1 to 50 g / 10 minutes, more preferably 0.3 to 30 g / 10 minutes.

Examples of the copolymer of ethylene and an α, β-unsaturated carboxylic acid or a derivative thereof include an ethylene / (meth) acrylic acid or an alkyl ester copolymer thereof. ,
Methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, cyclohexyl acrylate And cyclohexyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, glycidyl acrylate, glycidyl methacrylate and the like. Of these, particularly preferred are alkyl esters of (meth) acrylic acid such as methyl and ethyl. In particular, the content of the (meth) acrylate is 3 to
It is in the range of 30% by weight, preferably 5 to 25% by weight.
The MFR of a copolymer of ethylene and an α, β-unsaturated carboxylic acid or a derivative thereof is 0.1 to 50 g / 10 min, and more preferably 0.3 to 30 g / 10 min.

Examples of the propylene-based polymer include a propylene homopolymer, a random copolymer of propylene and another α-olefin such as ethylene, a block copolymer and the like.

<Blending ratio of composition of ethylene / α-olefin copolymer> The blending ratio of the ethylene / α-olefin copolymer according to the present invention and the above-mentioned ethylene polymer or propylene polymer is not particularly limited. Is 90% by weight of the ethylene polymer or the propylene polymer.
Is preferably less than 60% by weight, more preferably 50% by weight or less.

<Electrical Properties> Ethylene / α according to the present invention
-The electrical activation energy of the olefin copolymer and its composition is desirably 0.4 V or less. Further, the volume resistivity at 90 ° C. is 1 × 10 ¹⁶ Ω · cm.
Or more, preferably 1 × 10 ¹⁷ Ω ·
cm or more, more preferably 5 × 10 ¹⁷ Ω · cm or more. When the electrical property satisfies the above conditions, the layer containing the high-frequency exothermic polyolefin (B) generates heat during high-frequency fusion, and the (A) ethylene-α-olefin copolymer and its composition Even if the temperature of the layer increases, the layer (A) has excellent electrical insulation at high temperatures,
The (A) layer efficiently promotes heat generation at a high frequency without sparking. As a result, the temperature can be easily increased, and the heat fusion can be obtained only at a high frequency. Also, the sealing strength is high.

The electric activation energy can be obtained by the Arrhenius equation showing the temperature dependence of the current.
The small activation energy indicates that the temperature dependence of the current is small. I∝ (−U / kT) (where I: current, U: activation energy, k: Boltzmann constant, T: absolute temperature)

<(B) Layer containing high-frequency heat-generating polyolefin> Examples of the high-frequency heat-generating polyolefin according to the present invention include a polar group-containing polyolefin polymer and a filler-containing polymer. Among them, a polar group-containing polyolefin polymer is preferably used in terms of excellent transparency and flexibility. Specific examples of the polar group-containing polyolefin polymer include an ethylene / vinyl ester copolymer, an ethylene copolymer such as a copolymer of ethylene and an α, β-unsaturated carboxylic acid or a derivative thereof, and a modified polyolefin. Can be

The above-mentioned ethylene / vinyl ester copolymer is a vinyl propionate, vinyl acetate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl stearate containing ethylene as a main component produced by a high-pressure radical polymerization method. And a copolymer with a vinyl ester monomer such as vinyl trifluoroacetate. Above all, vinyl acetate is preferably used because it is generally easily available and has a heating effect. Further, a copolymer comprising 50 to 99.5% by weight of ethylene, 0.5 to 50% by weight of a vinyl ester, and 0 to 49.5% by weight of another copolymerizable unsaturated monomer is preferable. In particular, the content of the vinyl ester is 3 to 50% by weight,
Preferably, it is in the range of 5 to 40% by weight, more preferably 7 to 30% by weight.

Examples of the copolymer of ethylene and an α, β-unsaturated carboxylic acid or a derivative thereof include an ethylene / (meth) acrylic acid or an alkyl ester copolymer thereof. ,
Methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, cyclohexyl acrylate And cyclohexyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, glycidyl acrylate, glycidyl methacrylate, maleic anhydride, citraconic acid, itaconic acid, and the like. These include binary copolymers, terpolymers, and the like. Specific examples include an ethylene / (meth) acrylic copolymer, an ethylene / maleic anhydride / (meth) acrylic ester copolymer, and an ethylene / maleic anhydride / vinyl acetate copolymer. In particular, the content of α, β-unsaturated carboxylic acid is 3-4.
0% by weight, preferably 5 to 30% by weight, more preferably 7 to 2%
Desirably, it is in the range of 5 weight.

Also, as the modified polyolefin, HD
It is a modified polyolefin obtained by grafting a polar group such as the above α, β-unsaturated carboxylic acid onto a base resin of a polyolefin such as PE, LLDPE, VLDPE or polypropylene. Of the α, β-unsaturated carboxylic acids, maleic anhydride is particularly preferred.

The filler-containing polyolefin polymer composition may be prepared by adding Mg, Al, C
a, a composition containing an inorganic compound having Si, specifically, metal oxides such as magnesium oxide, aluminum oxide, calcium oxide, and silicon oxide, carbonates, metal hydroxides, magnesium silicate, calcium silicate, and silicate Aluminum and the like can be mentioned.

<(C) Layer Containing Ethylene / α-Olefin Copolymer or Other Polyolefin Polymer> The high-frequency-fusible laminate of the present invention comprises the above-mentioned layer (A), (B)
In addition to the layer, it is desirable to further have (C) a layer containing the ethylene / α-olefin copolymer or another polyolefin polymer. By having the (C) layer, new functionality (slip property, antistatic property, etc.) can be exhibited. Examples of the layer (C) according to the present invention include the ethylene / α-olefin copolymer or the other polyolefin polymer used in the layer (A). These can be used alone or as a mixture depending on the use and purpose.

<(D) Barrier Layer> It is desirable that the high-frequency-fusible laminate of the present invention further has (D) a barrier layer. By having the (D) layer, it can be used in various fields as a packaging material in the food field, the pharmaceutical field, and the like. (D) As the barrier material used for the barrier layer, a polyamide resin, a polyester resin, Barrier thermoplastic resin such as saponified ethylene / vinyl acetate copolymer, polycarbonate and / or metal-deposited film of such thermoplastic resin, biaxially oriented polypropylene, biaxially oriented polyamide, uniaxial or biaxial such as biaxially oriented polyester Stretched films, metal foils such as aluminum foils and the like are included. These barrier materials are appropriately selected according to the purpose of blocking gas, blocking water vapor, blocking odor and odor, and the like.

<Structure of Laminated Body> The laminated body capable of being subjected to high frequency fusion (hereinafter referred to as a laminated body) of the present invention comprises: (A) a layer comprising the above-mentioned ethylene / α-olefin copolymer or a composition thereof; B) A laminate having at least a two-layer structure [(A) layer / (B) layer] with a layer containing a high-frequency heat-generating polyolefin.

As a specific combination, (sLL / EV
A), (sLL / EEA), ｛sLL / filler (magnesium oxide, etc.) + PO (EVA, EPR, VL)
Etc.)｝, (sLL + LD / EVA), (sLL + LL /
EVA), (sLL + VL / EVA), (sLL / EV
A + LL), (sLL / EVA + sLL), (sLL /
EVA + LD), (sLL + LD / EVA + LD),
(SLL + VL / EVA + VL). (However, sLL: ethylene / α-olefin copolymer according to the present invention, EVA: ethylene / vinyl acetate copolymer, E
EA: ethylene / ethyl acrylate copolymer, PO:
Polyolefin, EPR: Ethylene / propylene copolymer rubber, LL: Linear low density polyethylene, VL: Ultra low density polyethylene, LD: Radical polymerization low density polyethylene, sLL + LD: Blend of sLL and LD, sLL / EVA : Represents the layer configuration of the sLL layer and the EVA layer. )

As the high-frequency heat-generating polyolefin used in the layer (B), EVA is particularly preferable because it is generally easily available and has a good heat-generating effect, and the content of VA in the monomer constituting EVA is preferable. Is 10% by weight or more, preferably 15% to 30% by weight, more preferably 18% by weight.
It is desirably in the range of 30 to 30% by weight.

Further, another embodiment of the laminate of the present invention comprises:
(A) layer, (B) layer and (C) a three-layer structure of a layer containing an ethylene / α-olefin copolymer or another polyolefin polymer (for example, [(A) layer / (B) layer /
(A) layer], [(A) layer / (B) layer / (C) layer]).

As a specific combination of the above laminates, (s
LL / EVA / sLL), (sLL / EEA / sL)
L), (sLL / PO / sLL containing filler (such as magnesium oxide)), (sLL + LD / EVA / sLL),
(SLL + LL / EVA / sLL), (sLL + VL /
EVA / sLL), (sLL / EVA + LL / sL
L), (sLL / EVA + sLL / sLL), (sLL
/ EVA + LD / sLL), (sLL + LD / EVA)
+ LD / sLL), (sLL + VL / EVA + VL / s
LL) and the like.

These laminates, for example, (A)
(B) for ethylene / α-olefin copolymer layer and intermediate layer
The laminate provided with the EVA layer becomes a laminate having an appropriate slip property and excellent surface properties without blocking and non-stickiness even in molding by rapid cooling such as a water-cooled inflation method. Furthermore, as described in the above section on electrical properties, by sandwiching the surface of the EVA layer with an ethylene / α-olefin copolymer having excellent electrical properties, unlike conventional LDPE and LLDPE, intermediate heating is achieved by high-frequency heating. Even if the EVA of the layer generates heat and the temperature of this surface layer rises, the electrical insulation at high temperatures is excellent, so that the temperature rise can be easily obtained, and the thermal fusion between the surface layers can be efficiently obtained only by high frequency. .

Further, in another embodiment of the laminate of the present invention, a laminate having a multilayer structure further including (D) a barrier layer (for example, [(A) layer / (B) layer / (D) layer]); (A) layer /
(B) layer / (D) layer / (B) layer / (A) layer], [(A)
Layer / (B) layer / ad / (D) layer / ad / (A) layer],
[(A) layer / (B) layer / (C) layer / (D) layer],
[(A) layer / (B) layer / (C) layer / ad / (D) layer],
[(A) layer / (B) layer / (C) layer / ad / (D) layer / ad /
(A) layer] etc.). (Here, ad is an adhesive resin.) By providing a gas barrier layer such as the (D) layer, a water vapor barrier layer, and the like, it can be used in various fields as a packaging material in a food field, a pharmaceutical field, and the like. It becomes possible. An adhesive, an adhesive resin (hereinafter abbreviated as ad) such as an ethylene / unsaturated carboxylic acid copolymer, a modified polyolefin resin, or the like may be used for these laminates as necessary.

As a specific combination of the above laminates,
(SLL / EVA / OPP), (sLL / ET / OPE)
T / ET / sLL), (sLL / EMA / PA), (s
LL / PO / Man containing filler (magnesium oxide)
LL / PA / ManLL / sLL), (sLL + LD /
EVA / ManLL / ONY / ManLL / sLL),
(SLL + LL / EVA / ManLL / ONY / Man
LL / EVA / sLL + LL), (sLL / EVA + L)
L / ManLL / AL / ManLL / sLL). (Here, OPP: biaxially oriented polypropylene,
EMA: ethylene / methyl acrylate copolymer, P
A: Polyamide, ET: Ethylene / maleic anhydride / acrylate copolymer, OPET: Oriented polyethylene terephthalate, ManLL: Maleic anhydride-grafted linear polyethylene, ONY: Oriented polyamide. )

Although it depends on the use and purpose, etc., the above-mentioned (A) layer / (B) layer or (A) layer / (B) layer / (C)
In a laminate having a two-layer or three-layer structure, for example, the layer (A) may be replaced with an ethylene / α-olefin copolymer,
When the layer (B) is made of EVA, it has excellent flexibility and transparency,
A laminate having a suitable high-frequency sealing property, that is, a haze value of 5% or less and a rigidity (Young's modulus) of 1000 kgf / c
In order to obtain a laminate of m ² or less, the density of the ethylene / α-olefin copolymer layer should be 0.90 g / cm ³ or more, preferably 0, if the thickness of the laminate is in the range of 0.05 to 1 mm. The purpose can be easily achieved by selecting from the range of from .905 g / cm ^{3 to} 0.930 g / cm ³ .

In particular, the thickness of the layer (B) of the laminate is desirably 50% or more, preferably 70% or more, more preferably 80% or more of the total thickness of the laminate.
With such a thickness ratio of the layer (B), effective high-frequency fusion can be performed. Films and sheets made of such a laminate are made of conventional soft vinyl chloride resin (PV
It can be handled in the same way as in C).

The molded article of the present invention is obtained by sealing the laminate of the present invention by high-frequency heating. Examples of such a molded body include a bag formed by sealing the periphery or the like of the film or sheet of the laminate by high-frequency heating. In addition, a molded product made of a laminate having excellent flexibility and transparency is a substitute for a conventional bag in the field of PVC in which transparency, flexibility and high-frequency heating are required.
Specific examples of such a molded article include an amulet bag, a bag such as a case, a flexible container, a water barrier material, an agricultural film, and the like.

The method for producing the high-frequency-fusible laminate of the present invention is not particularly limited, and the laminate may be formed by a known molding method,
And a molding machine. For example,
Examples include a multilayer coextrusion inflation method, a multilayer coextrusion water-cooled inflation method, a multilayer coextrusion T-die method, and an extrusion lamination method. Among these, a multilayer coextrusion water-cooled inflation method is particularly desirable.

The laminate of the present invention can be prepared by a multi-layer coextrusion water-cooled inflation method using layers (A) and (B), or layers (A), (B), (C) and / or (D) gas. It is preferably a multilayer water-cooled blown film formed by laminating barrier layers.

The production of a multilayer water-cooled blown film can be performed by a water-cooled blown film manufacturing apparatus, extruded through a circular die from an extruder at a temperature of 120 to 280 ° C., quenched by contact with a water-cooled air ring, It is performed by solidifying and taking out with a pinch roll, and then winding it around a frame. By this method, blocking of the film at the time of molding, elimination of stickiness of EVA having a high concentration VA content, transparency, strength and heat sealability can be simultaneously solved.

The ethylene / α-olefin copolymer and its composition, other polyolefin polymers and the like according to the present invention may contain, if necessary, stabilizers, antistatic agents, coloring agents such as pigments, and other additives. Agents can be added within a range that does not impair the purpose of the present invention.

[0073]

The present invention will be described below in more detail with reference to examples. Note that the present invention is not limited to this embodiment. Hereinafter, the measurement method in this example will be described.

Density (g / cm ³ ): JIS K676
0. -MFR (g / 10 min): Based on JIS K6760. -Mw / Mn: GPC (Waters 150C type)
And 135 ° C. ODCB was used as a solvent. The column used was GMH _HR- H (S) from Tosoh. Electric activation energy (eV): The electric activation energy (U) was determined by the above-mentioned Arrhenius equation based on the current value obtained at the time of measuring the volume resistance. -Volume resistivity (Ω · cm): based on ASTM D257.

Adhesive strength (kg / 15 mm width): Using a tensile tester, peeling between the inner layer and the inner layer of the test piece (15 mm width) after high-frequency sealing was performed at a tensile speed of 300 mm / min. The 180 degree peel strength at that time was determined. Transparency (haze value%): The laminate before high-frequency sealing was measured in accordance with ASTM D1003. Elastic modulus (kg / cm ² ): Measured according to ASTM D882 for the laminate before high frequency sealing. Appearance: The appearance of the laminate before the high-frequency sealing was visually observed in the following three stages. ：: No stickiness and no blocking occurred. Δ: There is no stickiness, and the surface is slightly blocking but excellent. ×: Strongly sticky, blocked, and not easily peeled.

The physical properties of the resin used in this example are as follows. <Ethylene / α-olefin copolymer with single-site catalyst>

[0077]

[Table 1]

<Existing resin>

[0079]

[Table 2]

LLD1: LLDPE, JALEX A
C404, manufactured by Nippon Polyolefin Co., Ltd. mLLD: LLDPE with metallocene catalyst, Evolu, Mitsui Chemicals, Inc. LDPE: High pressure radical method LDPE, J-LEX J
H606H, manufactured by Japan Polyolefin Co., Ltd.

<(B) Layer: Ethylene / vinyl acetate copolymer>

[0082]

[Table 3]

[Example 1] EVA was applied to the intermediate layer ((B) layer).
5 and sLL3 for the inner and outer layers ((A) layer), a water-cooled inflation molding machine (45 m
Using two φ extruders, one 55 mφ extruder, 100 mφ three-layer die, three types of three-layer water-cooled inflation films (intermediate layer thickness 180 μm, inner and outer layer thickness 10 μm)
m) was molded. Table 4 shows the evaluation results of the film. Two sheets of the obtained film were prepared, these inner layers were overlapped, and a high-frequency welder (manufactured by Seidensha Electronics Co., Ltd.)
KV3000TA type, frequency 40.68Mhz, output 1
(kW) under a pressure of 1 kg / cm ² for 5 seconds to perform high frequency sealing. Table 4 shows the results of the adhesive strength.

[Examples 2 to 14] A water-cooled inflation film was obtained in the same manner as in Example 1 except that the materials and thicknesses of the intermediate layer and the inner and outer layers were changed as shown in Table 4. Table 4 shows the results. In Table 4, BL1 is sLLD1
(90% by weight) + LDPE (10% by weight), BL2 is sLLD1 (90% by weight) + EVA1
(10% by weight) of BL3, EVA2 (8
0% by weight) + ET (20% by weight) BL4
Is a blend of EVA4 (80% by weight) + VL (20% by weight). ET and VL are as follows. ET: ethylene / maleic anhydride / acrylate copolymer, Lexpearl ET184M, manufactured by Nippon Polyolefin Co., Ltd. VL: VLDPE, JELEX ULD0410, manufactured by Nippon Polyolefin Co., Ltd.

[0085]

[Table 4]

[Comparative Examples 1 to 5] Materials of the intermediate layer and the inner and outer layers
A water-cooled inflation film was obtained in the same manner as in Example 1 except that the thickness was changed as shown in Table 4. Table 5 shows the results.

[0087]

[Table 5]

[0088]

As described above, the high frequency fusion-bondable laminate of the present invention comprises (A) an ethylene / α-olefin copolymer or a copolymer thereof satisfying the requirements (a) to (d) described above. Since it has a layer made of the composition and a layer containing (B) a high-frequency heat-generating polyolefin, it has no stickiness on the surface, is excellent in high-frequency fusion property, has good heat sealability and pinhole resistance, and Excellent properties such as heat resistance, mechanical properties, moldability, blocking resistance, optical properties, etc.

Further, if the laminate capable of high frequency fusion of the present invention further comprises (C) a layer containing the ethylene / α-olefin copolymer or another polyolefin polymer, the additive may be modified. And functions such as slipperiness and antistatic property. Further, if the laminate capable of high-frequency fusion of the present invention further has a barrier layer (D), it can be used in various fields as a packaging material in the food field, the pharmaceutical field, and the like. If the thickness of the layer is 50% or more of the total thickness of the laminate, effective high-frequency fusion can be achieved. Further, the (A) layer / (B) layer or (A) layer /
The haze value of the laminate composed of the layer (B) / the layer (C) is 5%
If it is the following, a laminate excellent in transparency can be obtained. Further, the (A) layer / (B) layer or (A) layer /
When the rigidity (Young's modulus) of the laminate composed of the (B) layer / (C) layer is 1,000 kgf / cm ² or less, a laminate having excellent flexibility can be obtained.

The electrical activation energy of the ethylene / α-olefin copolymer or its composition is as follows:
If it is 0.4 eV or less, the high-frequency fusion property is further improved and the sealing strength is also increased. In addition, the ethylene
If the volume resistivity of the α-olefin copolymer or the composition at 90 ° C. is 1 × 10 ¹⁶ Ωcm or more,
Further, the high-frequency fusion property is improved, and the sealing strength is also increased. Further, the ethylene-α-olefin copolymer,
Ethylene α- obtained by single-site catalyst
If it is an olefin copolymer, the resulting laminate will be excellent in mechanical properties, heat sealing properties, blocking properties, and the like.

When the high-frequency heat-generating polyolefin is a polar group-containing olefin polymer, it exhibits excellent transparency, flexibility and high-frequency fusion. Further, if the polar group-containing olefin polymer is an ethylene-vinyl acetate copolymer or a composition containing the copolymer, excellent transparency,
Shows flexibility and high frequency welding. Further, the molded article of the present invention,
Since the laminated body capable of high-frequency fusion is sealed by high-frequency heating, the laminate has excellent appearance of the sealing surface and high adhesive strength.

Further, the method of forming a laminate which can be subjected to high-frequency fusion according to the present invention is characterized in that:
(A) Ethylene that satisfies the requirements (a) to (d) above.
a laminate having a layer composed of an α-olefin copolymer or a composition thereof and (B) a layer containing a polyolefin capable of high frequency, or the layer (A) or the layer (B)
(C) a layer containing the ethylene / α-olefin copolymer or polyolefin polymer and / or (D) a laminate having a barrier layer. High concentration VA
It is possible to simultaneously eliminate the stickiness and the like of the EVA having the content, and simultaneously solve the transparency, strength and heat sealability of the obtained laminate.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Seiji Matsuoka 2F, 1958 Yashima Nishi-machi, Takamatsu City, Kagawa Prefecture F-term in Kyowa Sangyo Co., Ltd. 4F100 AK03B AK03C AK62A AK62B AK62C AK66B AK66C AK68B AL05A AL05B AR00D BA02 BA03 BA04 BA07 BA10A BA10C BA10D BA15 EH202 EJ502 GB16 GB17 GB23 JA07A JA13A JA20B JD01D JG03 JG04A JG04C JG10A JG10C JJ03 JJ06B JK01 JK06 JK13 JK16 JK17 JL01 JL12 JL12B JN01 YY00Y

Claims (14)

[Claims] 1. A layer comprising an ethylene / α-olefin copolymer or a composition thereof which satisfies the following requirements (a) to (d); and (B) a layer containing a high-frequency heat-generating polyolefin. A laminate capable of high-frequency fusion, comprising: (A) a density of 0.88 to 0.96 g / cm ³ (b) a melt flow rate of 0.01 to 50 g / 10 min (c) a molecular weight distribution (Mw / Mn) of 1.5 to 4.0 (d ) Composition distribution parameter Cb is 2 or less 2. The high-frequency fusing laminate according to claim 1, further comprising (C) a layer containing the ethylene / α-olefin copolymer or another polyolefin polymer. 3. The high-frequency fusing laminate according to claim 1, further comprising (D) a barrier layer. 4. The high-frequency fusing laminate according to claim 1, wherein the thickness of the layer (B) is 50% or more of the total thickness of the laminate. 5. The laminate comprising the layer (A) / layer (B) or the layer (A) / layer (B) / layer (C) has a haze value of 5
% Or less, and the high-frequency fusing laminate according to any one of claims 1 to 4. 6. The rigidity (Young's modulus) of the laminate composed of the (A) layer / (B) layer or the (A) layer / (B) layer / (C) layer is 1000 kgf / cm ² or less. The high frequency fusion-bondable laminate according to any one of claims 1 to 5, characterized in that: 7. The ethylene / α-olefin copolymer according to claim 1, wherein the (d) composition distribution parameter is in the range of 1.10 to 2.00. High frequency fusion laminate. 8. The electric activation energy of the ethylene / α-olefin copolymer or the composition thereof is 0.4.
The high frequency fusion-bondable laminate according to any one of claims 1 to 7, wherein the laminate is not more than eV. 9. The volume resistivity of the ethylene / α-olefin copolymer or its composition at 90 ° C. of 1
2. The method according to claim 1, wherein the resistance is not less than × 10 ¹⁶ Ω · cm.
9. The laminate capable of high-frequency fusion according to any one of claims 8 to 8. 10. The ethylene / α-olefin copolymer according to claim 1, wherein the ethylene / α-olefin copolymer is an ethylene / α-olefin copolymer obtained by a single-site catalyst. High frequency fusion laminate. 11. The high-frequency heat-generating polyolefin is:
The high frequency fusion-bondable laminate according to any one of claims 1 to 10, wherein the laminate is a polar group-containing olefin polymer. 12. The polar group-containing olefin polymer,
The high-frequency fusing laminate according to claim 11, which is an ethylene / vinyl acetate copolymer or a composition containing the copolymer. 13. A molded product obtained by sealing the high-frequency-fusible laminate according to any one of claims 1 to 12 by high-frequency heating. (A) a layer comprising an ethylene / α-olefin copolymer or a composition thereof satisfying the following requirements (a) to (d); and (B) a layer containing a polyolefin capable of high-frequency waves. A laminate, or (A)
Forming a laminate having a layer, the layer (B), the layer (C) containing the ethylene / α-olefin copolymer or the polyolefin polymer, and / or the (D) barrier layer by water cooling inflation molding. A method for producing a laminate capable of high-frequency fusion. (A) a density of 0.88 to 0.96 g / cm ³ (b) a melt flow rate of 0.01 to 50 g / 10 min (c) a molecular weight distribution (Mw / Mn) of 1.5 to 4.0 (d ) Composition distribution parameter Cb is 2 or less