JPH09176400A - Filler-containing ethylene/alpha-olefin copolymer composition and molding using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an olefin-based resin composition not causing thermal degradation during molding such as injection molding, extrusion molding and blow molding, preventing roll stain and fuming during the molding, excellent in mechanical strength, etc., while maintaining characteristics such as calorific value or ready incineration. SOLUTION: This composition is obtained by blending (A) 100 pts.wt. of an ethylene copolymer which is obtained by copolymerizing ethylene with a 3-20C α-olefin in the presence of a catalyst containing at least one of a transition metal compound of the group IV of the periodic table containing a ligand having (i) a cyclopentadienyl skeleton, has (ii) 0.86-0.96g/cm<3> density, (iii) 0.01-50g/10 minutes melt flow rate, (iv) 1.5-5.0 molecular weight distribution Mw/Mn and (v) 1.01-1.2 composition distribution parameter Cb with (B) 10-400 pts.wt. of a filler and (C) 0.01-2.0 pts.wt. of an antioxidant.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a filler-containing ethylene / α-olefin copolymer having excellent mechanical strength while maintaining rigidity, heat resistance, dimensional stability, printability, writing property, easy incineration property, and the like. The present invention relates to a polymer composition, a molded article formed by subjecting the composition to extrusion molding, injection molding, blow molding, etc., particularly a film or sheet, a tube, a dust bag, a squeeze container or a porous film. More specifically, it is a composition in which a filler is blended with an ethylene / α-olefin copolymer obtained by a specific catalyst or a resin component containing the copolymer, which has excellent mechanical strength and high filling of the filler. The sheet is semi-transparent, has printing characteristics, writability, and the like, has a low calorific value when incinerated, and is easily incinerated, and is therefore suitable for applications such as a shopping bag and a garbage bag. Further, since the tube also has a moderate flexibility and a low restoring property, it is useful as a squeezing container such as a toothpaste tube or an emulsion tube, a hose and the like. Further, a porous film obtained by stretching a film made of the above composition has excellent air permeability, strength, and texture, and is therefore useful as a sanitary material, clothing, filter material and the like.

[0002]

2. Description of the Related Art Conventionally, an inorganic filler is blended with polyethylene such as high-pressure radical method low-density polyethylene and linear low-density polyethylene to improve the mechanical strength, dimensional stability, rigidity and heat resistance of polyethylene. Have been proposed. The above-mentioned low-density polyethylene generally has a wide molecular weight distribution, and when a large amount of a filler is mixed, the strength is remarkably reduced, and it is difficult to reduce the thickness of a molded product. Further, linear low-density polyethylene using a Ziegler catalyst has a wide composition distribution, and low-molecular weight components are eluted, causing stains and smoke on rolls during molding, and improvements thereof are desired. Also, a film in which an inorganic filler is mixed with these polyethylenes, a paper-like film, a molded product such as a plastic bag or a garbage bag, a tube, a hose, a squeezing container or a porous film obtained by stretching a film containing an inorganic filler is also good. Are known. However, even in these films, sheets, etc., garbage bags, plastic bags, etc., and porous films, etc., while maintaining various functions such as the above-mentioned printability, writability, and reduction in the amount of heat generated during incineration, tear strength and elongation are further increased. It is required to improve the mechanical strength. In addition, low density polyethylene or ethylene-vinyl acetate copolymer was used for tubes, especially toothpaste tubes and tubes for squeezing out food, but after squeezing out the contents, air was lost due to the restoration of the container. There is a need for a squeezed container that does not have a restorability because the contents may be altered due to returning to the container, so-called air bag.

[0003]

DISCLOSURE OF THE INVENTION The present invention is intended to solve the above-mentioned problems, in which an ethylene / α-olefin copolymer having a narrow molecular weight distribution and a narrow composition distribution obtained with a specific catalyst is used as a filler. By mixing with a specific antioxidant, there is no heat deterioration during molding such as injection molding, extrusion molding, blow molding, etc., roll fouling and smoking are prevented during molding, and easy incineration with low heat generation It is an object of the present invention to provide a resin composition having excellent mechanical strength and the like while maintaining the characteristics. Another object of the present invention is to provide a resin composition in which the above performance is further improved by improving the compatibility and dispersibility of the ethylene / α-olefin copolymer or its composition with the filler. That is. Also,
Another object is to provide a sheet, a film or the like which is molded with the above composition and retains various functions such as printability, writability, texture, flexibility, and reduction of calorific value during incineration, and which has higher mechanical strength. Another object is to provide a squeeze container from the above composition which is less likely to be restored by hollow molding and has no air bag, and another object is to stretch a film comprising the above composition. It is intended to provide a porous film having excellent texture, flexibility, breathability, and high mechanical strength.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that ethylene / α- having a narrow molecular weight distribution and composition distribution polymerized by a specific catalyst.
In order to prevent heat deterioration and deterioration during melt molding of a resin composition containing a large amount of a filler in an olefin polymer, there is no roll stain or smoke during molding, and further to improve the dispersibility of the filler. By introducing a specific functional group into the composition, there is no deterioration during melt processing, texture, flexibility, a resin composition excellent in mechanical strength, etc., or a film, sheet or tube using these compositions. It has been found that a porous film or the like retains the above-mentioned various performances and that a particularly excellent mechanical property is obtained. That is, the present invention is, firstly,
(A) (a) Ethylene and α having 3 to 20 carbon atoms in the presence of a catalyst containing at least one transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton.
— Obtained by copolymerizing olefin (b)
Density 0.86 to 0.96 g / cm ³ , (c) Melt florate 0.01 to 50 g / 10 minutes, (d) Molecular weight distribution M
Ethylene copolymer 10 having w / Mn of 1.5 to 5.0 and (e) composition distribution parameter Cb of 1.01 to 1.2.
0 to 20% by weight, (A ') 100 parts by weight of a resin component consisting of 80% by weight or less of another ethylene polymer, (B) 10 to 400 parts by weight of a filler, and (C) 0.01 to 0.01% of an antioxidant.
It is an ethylene / α-olefin copolymer composition containing 2.0 parts by weight.

Secondly, the present invention relates to (A) (i) ethylene in the presence of a catalyst containing at least one transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton. (B) Density obtained by copolymerizing an α-olefin having 3 to 20 carbon atoms 0.86 to 0.96
g / cm ³ , (c) Melt florate 0.01 to 50 g
/ 10 minutes, (d) molecular weight distribution Mw / Mn 1.5-5.
0, (e) The composition distribution parameter Cb is 1.01 to 1.
100 to 20% by weight of an ethylene copolymer which is 2,
(A ') 100 parts by weight of a resin component consisting of 80% by weight or less of another ethylene polymer, (B) 10 to 400 parts by weight of a filler, and (C) 0.01 to 2.0 parts by weight of an antioxidant. The resin component of the resin composition is 10 ^-8 to 1 per 1 g of the resin component.
0 ^-3 mol of D1: carboxylic acid group, carboxylic acid ester group or acid anhydride group-containing monomer, D2: epoxy group-containing monomer, D3: hydroxyl group-containing monomer, D4:
An ethylene / α-olefin copolymer composition having units based on at least one functional group-containing monomer selected from an amino group-containing monomer, D5: an alkenyl cyclic iminoether derivative-containing monomer, and D6: a polyfunctional monomer.

Thirdly, the present invention provides a molded article such as a film, sheet or tube obtained by molding the composition of the first or second invention by a molding method such as extrusion, injection, hollow or rotation. The present invention is, fourthly, a porous film using the composition of the first or second invention.

Hereinafter, the present invention will be described in detail. The ethylene / α-olefin copolymer (A) in the present invention is (i) a transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton, and if necessary, a promoter, an organoaluminum compound, It is obtained by copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of a catalyst containing a carrier. Also,
A product obtained by preliminarily polymerizing ethylene and / or the α-olefin with the above catalyst may be used as the catalyst. The α-olefin has 3 to 20 carbon atoms, preferably 3 to 12 carbon atoms, and specifically, propylene, butene-1, 4-methylpentene-1, hexene-1, octene-1, decene. -1, dodecene-1 and the like. The content of these α-olefins is usually 3
It is desirably selected at 0 mol% or less, preferably within the range of 3 to 20 mol%.

Cyclopentadiene, a transition metal compound of Group IV of the Periodic Table, containing (a) a ligand having a cyclopentadienyl skeleton, which is a catalyst for producing the ethylene / α-olefin copolymer (A). The enyl skeleton is a cyclopentadienyl group, a substituted cyclopentadienyl group or 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 be bonded to each other to form a ring.

Examples of the hydrocarbon group having 3 to 10 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group and the like. Specific examples include a methyl group, an ethyl group, an n-propyl group and isopropyl. Group, n-butyl group,
Alkyl groups such as isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group and decyl group; cycloalkyl groups such as cyclopentyl group and cycloalkyl group; phenyl group and tolyl And an aralkyl group such as a benzyl group and a neofuyl 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,
3-n-butylmethylcyclopentadienyl group, 1,3
Specific examples thereof include -n-propylmethylethylcyclopentadienyl group. Among these, the substituted cyclopentadienyl group of the present invention is preferably a cyclopentadienyl group substituted with an alkyl group having 3 or more carbon atoms,
A 1,3-substituted cyclopentadienyl group is particularly preferable.
The substituted cyclopentadienyl groups in the case where the substituted hydrocarbons, that is, the hydrocarbons are bonded to each other to form one or more rings, include an indenyl group, a hydrocarbon group having 1 to 8 carbon atoms (such as an alkyl group), Substituted naphthyl group substituted by a substituent such as a substituted indenyl group substituted by a substituent, naphthyl group, hydrocarbon group having 1 to 8 carbon atoms (alkyl group, etc.), hydrocarbon group having 1 to 8 carbon atoms (alkyl group) Substituents such as a substituted fluorenyl group substituted with a substituent such as a group) are preferable.

Examples of the transition metal of the transition metal compound of group IV of the periodic table containing the ligand (a) having a cyclopentadienyl skeleton include zirconium, titanium and hafnium, and zirconium is particularly preferable. The transition metal compound usually has 1 to 3 ligands having a cyclopentadienyl skeleton, and when they have 2 or more ligands, they may be bonded to each other by a bridging group. Examples of the cross-linking group include an alkylene group having 1 to 4 carbon atoms, an alkylsilanediyl group, and a silanediyl group.

As a ligand other than the ligand having a cyclopentadienyl skeleton in the transition metal compound of Group IV of the periodic table, hydrogen and C1 to C2 are typical.
And a hydrocarbon group of 0 (alkyl group, alkenyl group, aryl group, alkylaryl group, aralkyl group, polyenyl group, etc.), halogen, metaalkyl group, metaaryl group and the like.

Specific examples of these are as follows. As dialkyl metallocenes, bis (cyclopentadienyl) titanium dimethyl, bis (cyclopentadienyl) titanium diphenyl, bis (cyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl) zirconium diphenyl, bis (cyclopentadienyl) ) Hafnium dimethyl, bis (cyclopentadienyl) hafnium diphenyl and the like. Monoalkyl metallocenes include bis (cyclopentadienyl)
Examples include titanium methyl chloride, bis (cyclopentadienyl) titanium phenyl chloride, bis (cyclopentadienyl) zirconium methyl chloride, and bis (cyclopentadienyl) zirconium phenyl chloride. Moreover, pentamethylcyclopentadienyl titanium trichloride, which is monocyclopentadienyl titanocene, pentaethylcyclopentadienyl titanium trichloride, bis (pentamethylcyclopentadienyl) titanium diphenyl, and the like can be mentioned.

Examples of the substituted bis (cyclopentadienyl) titanium compound include bis (indenyl) titanium diphenyl or dichloride, bis (methylcyclopentadienyl) titanium diphenyl or dichloride, dialkyl, trialkyl, tetraalkyl or pentaalkylcyclopenta. Examples of the dienyl titanium compound include bis (1,2-dimethylcyclopentadienyl) titanium diphenyl or dichloride, bis (1,2-diethylcyclopentadienyl) titanium diphenyl or dichloride or other dihalide complex, silicon, amine or Carbon-bonded cyclopentadiene complexes include dimethylsilyldicyclopentadienyl titanium diphenyl or dichloride, methylenedicyclopentadienyl Data iodonium diphenyl or dichloride, and other dihalide complexes.

As the zirconocene compound, pentamethylcyclopentadienyl zirconium trichloride,
Pentaethylcyclopentadienyl zirconium trichloride, bis (pentamethylcyclopentadienyl)
Examples of zirconium diphenyl and alkyl-substituted cyclopentadiene include bis (ethylcyclopentadienyl) zirconium dimethyl, bis (methylcyclopentadienyl) zirconium dimethyl, bis (n-butylcyclopentadienyl) zirconium dimethyl, and haloalkyl or dihalide thereof. Examples of the complex, dialkyl, trialkyl, tetraalkyl or pentaalkylcyclopentadiene include 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.

Still other metallocenes include bis (cyclopentadienyl) hafnium dichloride, bis (cyclopentadienyl) hafnium dimethyl and bis (cyclopentadienyl) vanadium dichloride.

As another example of the transition metal compound of Group IV of the periodic table of the present invention, a ligand having a cyclopentadienyl skeleton represented by the following general formula and other ligands and transition metal atoms are The thing which forms a ring is also mentioned.

[0017]

Embedded image

In the formula, Cp is a ligand having the cyclopentadienyl skeleton, X is hydrogen, halogen, and having 1 to 2 carbon atoms.
0 represents an alkyl group, an arylsilyl group, an aryloxy group, an alkoxy group, an amido group, a silyloxy group, etc., and Z is —O—, —S—, —NR—, —PR— or O.
A divalent neutral ligand selected from the group consisting of R, SR, NR ₂ and PR ₂ , Y is SiR ₂ , CR ₂ , SiR ₂ SiR
₂ , CR ₂ CR ₂ , CR = CR, SiR ₂ CR ₂ , BR
₂ represents a divalent group selected from the group consisting of BR. However, R is hydrogen or an alkyl group having 1 to 20 carbon atoms, an aryl group, a silyl group, a halogenated alkyl group, a halogenated aryl group, or Y, Z or 2 from both Y and Z.
One or more R groups form a fused ring system. M represents a transition metal atom of Group IV of the periodic table.

As an example of the compound represented by the formula 1, (t
-Butylamide) (tetramethylcyclopentadienyl) -1,2-ethanediylzirconium dichloride, (t-butylamide) (tetramethylcyclopentadienyl) -1,2-ethanediyltitanium dichloride, (methylamide) (tetramethyl Cyclopentadienyl) -1,2-ethanediylzirconium dichloride, (methylamide) (tetramethylcyclopentadienyl) -1,2-ethanediyltitanium dichloride,
(Ethylamide) (tetramethylcyclopentadienyl) methylenetan dichloride, (t-butylamide)
Dimethyl (tetramethylcyclopentadienyl) silane titanium dichloride, (t-butylamido) dimethyl (tetramethylcyclopentadienyl) silanezirconium dibenzyl, (benzylamido) dimethyl (tetramethylcyclopentadienyl) silane titanium dichloride, Phenylphosphido) dimethyl (tetramethylcyclopentadienyl) silanetitanium dichloride.

The cocatalyst referred to in the present invention can effectively use the transition metal compound of Group IV of the periodic table as a polymerization catalyst, or can balance the ionic charge in a catalytically activated state. Say. Examples of the co-catalyst used in the present invention include benzene-soluble aluminoxane, benzene-insoluble organic aluminum oxy compound, boron compound, lanthanide salts such as lanthanum oxide, and tin oxide of the organic aluminum oxy compound. Of these, aluminoxane is most preferable.

The catalyst is a carrier of an inorganic or organic compound.
May be used. The carrier may be inorganic or
Is preferably a porous oxide of an organic compound.
iO _Two, Al_TwoO_Three, MgO, ZrO_Two, TiO_Two, B
_TwoO_Three, CaO, ZnO, BaO, ThO_TwoEtc. or this
These mixtures include SiO 2_Two-Al_TwoO_Three, Si
O_Two-V_TwoO_Five, SiO_Two-TiO_Two, SiO_Two-Mg
O, SiO_Two−Cr_TwoO_ThreeAnd the like.

Examples of the organic aluminum compound include trialkyl aluminum such as triethyl aluminum and triisopropyl aluminum; dialkyl aluminum halide; alkyl aluminum sesquihalide; alkyl aluminum dihalide; dialkyl aluminum hydride and organic aluminum alkoxide.

The ethylene / α-olefin copolymer (A) of the present invention is produced by a gas phase polymerization method, a slurry polymerization method, a solution polymerization method or the like in the presence of the above-mentioned catalyst, which is substantially free of a solvent. And with oxygen and water turned off,
In the presence of an inert hydrocarbon solvent exemplified by aliphatic hydrocarbons such as butane, pentane, hexane and heptane, aromatic hydrocarbons such as benzene, toluene and xylene, cyclohexane and alicyclic hydrocarbons such as methylcyclohexane. Or manufactured in the absence. 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 normal pressure to 70 kg / cm ^{2 in} the case of low and medium pressure method.
G, preferably normal pressure to 20 kg / cm ² G, and usually 1500 kg / cm ² G or less in the high pressure method.
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 2 minutes to 20 minutes. Further, the polymerization is not limited to the one-step polymerization method, and is not particularly limited to a two-step or more multi-step polymerization method in which the polymerization conditions such as hydrogen concentration, monomer concentration, polymerization pressure, polymerization temperature and catalyst are different from each other.

The specific (A) of the present invention obtained with the above catalyst
Ethylene / α-olefin copolymers have different properties from those of ethylene / α-olefin copolymers obtained by conventional Ziegler type catalysts and Phillips type catalysts (hereinafter collectively referred to as Ziegler type catalysts). . In other words, the specific (A) ethylene / α-olefin copolymer of the present invention obtained with the above catalyst has a narrow molecular weight distribution and a narrow composition distribution because the active sites of the catalyst are uniform. . Ethylene / α-olefin copolymers with a narrow molecular weight distribution have higher mechanical strength than resins with a wide molecular weight distribution obtained by Ziegler type catalysts. Can be thinned. In an ethylene / α-olefin copolymer having a narrow composition distribution, short-chain branching efficiently lowers the melting point, so that the melting point is low relative to the density and the moldability is excellent. Moreover, since the flexibility is excellent for the density, a molded product having a good texture can be obtained. The acceptability of the filler when blending the filler with the ethylene / α-olefin copolymer has a correlation with the flexibility of the resin, and the softer the resin, the less the deterioration of the physical properties even if the filler is blended in a large amount. Have. Further, since the amount of short chain branching components and the amount of low molecular weight components are small, bleeding to the resin surface is small.

The ethylene / α-olefin copolymer (A) has a (b) melt florate of 0.01 to 50 g.
/ 10 minutes, preferably 0.1 to 20 g / 10 minutes, more preferably 0.5 to 10 g / 10 minutes. Further, the density is 0.86 to 0.96 g / cm ³ , preferably 0.89 to 0.95 g / cm ³ , and more preferably 0.
In the range of 89 to 0.94 g / cm ³ , (c) breadth Mw / Mn of molecular weight distribution is 1.5 to 5.0, preferably 1.8.
In the range of -4.5, (d) the composition distribution parameter (Cb), which is a measure of the breadth of the composition distribution, must be 1.01 to 1.2. If this value exceeds 1.2, the flexibility, the acceptability of the filler, and the strength may deteriorate.

The method for measuring the composition distribution parameter (Cb) of the ethylene / α-olefin copolymer of the present invention is as follows. That is, the sample was heated and dissolved at 135 ° C. in an ODCB solvent containing an antioxidant so as to have a concentration of 0.2% by weight, transferred to a column packed with diatomaceous earth (Celite 545), and 2 at a cooling rate of 1 ° C / min
Cool to 5 ° C. and deposit copolymer sample on Celite surface. Next, ODCB was applied to the column on which this sample was deposited.
Column temperature at 5 ℃ increments
The temperature is gradually raised to 20 ° C. Then, a solution containing an eluted component corresponding to each temperature is collected. Methanol is added to this solution, 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 sample are measured.
The degree of branching (measured value) is determined by ¹³ C-NMR.

With respect to each fraction collected at 30 ° C. to 90 ° C. by such a method, the branching degree is corrected as follows. That is, the degree of branching measured against the elution temperature is plotted, and the correlation is approximated to a straight line by the least square method,
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.

Next, the weight separation w of each fraction
i is the change amount (bi-
Bi-1) is divided to obtain the relative concentration ci, and the relative concentration is plotted against the branching degree 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.

[0029]

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Here, cj and bj are the relative density and branching degree of the j-th section, respectively. Composition distribution parameter Cb
Becomes 1.0 when the composition of the sample is uniform, and the composition distribution spreads, and therefore the value increases.

Many methods have been proposed for describing the composition distribution of ethylene / α-olefin copolymers. For example, in Japanese Patent Application Laid-Open No. 60-88016, numerical processing is performed on the assumption that the cumulative weight fraction has a specific distribution (log normal distribution) with respect to the number of branches of each separated sample obtained by solvent separation of the sample. The ratio between the weight average branching degree (Cw) and the number average branching degree (Cn) is determined. The accuracy of this approximation calculation decreases when the number of branches and the cumulative weight fraction of the sample deviate from the lognormal distribution, and when a commercially available LLDPE is measured, the correlation coefficient R2 is considerably low, and the accuracy of the value is not sufficient. Further, this Cw / Cn measurement method and numerical processing method are the same as those of the Cb of the present invention.
Although it is different from that of Cw /
The value of Cn is considerably larger than Cb.

The first (A'1) of the other ethylene-based polymer (A ') of the present invention is a Ziegler type catalyst or a Phillips catalyst ionic polymerization method (hereinafter collectively referred to as Ziegler type catalyst) by a conventional ionic polymerization method. ), The density obtained by
86 to 0.96 g / cm ³ of ethylene / α-olefin copolymer, specifically, medium density polyethylene (M
DPE), linear low density polyethylene (LLDPE), ultra low density polyethylene (VLDPE) and the like.

The medium-low density polyethylene (MDPE, LLDPE) using the Ziegler type catalyst of the present invention has a density of 0.91 to 0.96 g / cm ³ , preferably 0.91 to 0.96 g / cm ³ .
MF in the range of 0.94 g / cm ³ (LLDPE)
R is 0.1 to 20 g / 10 minutes, preferably 0.5 to 15
g / 10 minutes, more preferably 0.7 to 10 g / 10 minutes. The melt tension is 0.3 to 5.0 g, preferably 0.4 to 4.0 g, and more preferably 0.5 to
It is 3.5 g. Mw / Mn is 2.5 to 5.0, preferably 3.0 to 4.5.

The ultra-low density polyethylene (VLDPE) using the Ziegler type catalyst of the present invention has a density of 0.86 to
Less than 0.91 g / cm ³ , preferably 0.88 to 0.9
05 g / cm ³ and MFR are selected in the range of 0.1 to 20 g / 10 minutes, preferably 0.5 to 10 g / 10 minutes.
The ultra low density polyethylene (VLDPE) has a polyethylene having an intermediate property between linear low density polyethylene (LLDPE) and ethylene / α-olefin copolymer rubber (EPR, EPDM), and preferably Density 0.
86 to 0.91 g / cm ³ , differential scanning calorimetry (DS
C) is a specific ethylene / α-olefin copolymer having a maximum peak temperature (Tm) of 60 ° C. or higher, and preferably having a boiling n-hexane insoluble content of 10% by weight or higher, at least titanium and / or Polymerized using a catalyst consisting of a vanadium-containing solid catalyst component and an organoaluminum compound, and the high crystalline portion of linear low-density polyethylene and the amorphous portion of ethylene / α-olefin copolymer rubber are combined. It is a resin that has the characteristics of the former, such as mechanical strength and heat resistance, and the characteristics of the latter, such as rubber elasticity and low-temperature impact resistance, coexist in a well-balanced manner.

Ethylene / α by the above Ziegler type catalyst
-The α-olefin of the olefin copolymer has a carbon number of 3 to 12, preferably 3 to 10, specifically, propylene, butene-1,4-methylpentene-
1, hexene-1, octene-1, decene-1, dodecene-1 and the like. The content of these α-olefins is preferably selected in the range of 3 to 40 mol%.

Second ethylene-based polymer of the present invention
(A'2) is low-density polyethylene, ethylene / vinyl ester copolymer, ethylene /
It is a copolymer with an α, β-unsaturated carboxylic acid or its derivative.

The above low density polyethylene (LDPE) is
MFR is 0.1 to 20 g / 10 minutes, preferably 0.5 to
15 g / 10 minutes, more preferably 1.0 to 10 g / 1
0 minutes. Within this range, the melt tension of the composition is in an appropriate range, and film formation is easy. The density is 0.
91 to 0.94 g / cm ³ , preferably 0.912 to
0.935 g / cm ³ , more preferably 0.912 to
0.930 g / cm ³ , and the melt tension is 1.5 to 25
g, preferably 3 to 20 g, more preferably 3 to 15
g. Melt tension is an item of elasticity of the resin, and if it is in the above range, the film can be easily formed. Further, Mw / Mn is 3.0 to 10, preferably 4.0 to 8.0. In addition, Mw / Mn here is a weight average amount / number average molecular weight by GPC analysis.

The ethylene / vinyl ester copolymer of the present invention means vinyl propionate, vinyl acetate, vinyl caproate, vinyl caprylate, vinyl laurate, stearin produced by a high pressure radical polymerization method and containing ethylene as a main component. It is a copolymer with vinyl ester monomers such as vinyl acrylate and vinyl trifluoroacetate. Among them, particularly preferred is vinyl acetate (EVA). That is, 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. Particularly, the vinyl ester content is in the range of 3 to 30% by weight, preferably 5 to 20% by weight. The MFR of these copolymers is 0.1 to 20 g / 10 min, preferably 0.3 to 10 g / 10 min, and the melt tension is 2.0
２５25 g, preferably 3-20 g.

Representative copolymers of the ethylene / α, β-unsaturated carboxylic acid or its derivative of the present invention include ethylene / (meth) acrylic acid or its alkyl ester copolymer. Examples of these comonomers include acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, acrylic acid-n. -Butyl, n-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate,
Glycidyl acrylate, glycidyl methacrylate and the like can be mentioned. Among them, particularly preferred are alkyl esters of (meth) acrylic acid such as methyl and ethyl (EEA). In particular, the (meth) acrylic acid ester content is in the range of 3 to 30% by weight, preferably 5 to 25% by weight. MFR of these copolymers
Is 0.1 to 20 g / 10 min, preferably 0.3 to 10 g
g / 10 minutes, and the melt tension is 2.0 to 25 g, preferably 3 to 20 g.

The blending ratio of the component (A) and the component (A ') is such that the component (A) is blended in an amount of 20% by weight or more and the component (A') is blended up to 80% by weight. In this case, it is desirable to use the component (A) as the main component, but if strength, low temperature heat sealing properties are retained to some extent, and processability, flexibility, and texture are taken into consideration, (A ')
It is desirable to properly mix the components. When molding a film by inflation film molding,
Since the melt tension of the component (A) is small, bubbles tend to be unstable, and in T-die molding, uneven thickness of the both edge portions of the film due to neck-in and draw resonance phenomenon occur. 10 to 5 components (A'2)
It is desirable to add 0% by weight.

As the filler (B) of the present invention, both an inorganic filler and an organic filler are used. Inorganic fillers include calcium carbonate, talc, silica, clay,
Kaolin, alumina, magnesia, calcium sulfate, calcium sulfite, barium sulfate, aluminum silicate, calcium silicate, sodium silicate, magnesium carbonate, calcium oxide, titanium oxide, mica, glass flakes,
Zeolite, diatomaceous earth, perlite, permiculite,
Examples thereof include glass balloons and shirasu balloons. Examples of the organic filler include wood powder, pulp powder, phenol resin, acrylic resin and other synthetic resin powders. Preferred among these fillers are calcium carbonate, talc, barium sulfate, calcium sulfite and the like. The most preferable of these is calcium carbonate. The average particle size of the inorganic filler is 20 μm or less, preferably 10 μm or less.
It is less than or equal to μm, more preferably less than or equal to 5 μm. If the particle size is large, it may cause film breakage during film formation or stretching, and in the case of a porous film, the obtained film has a large pore size, resulting in a poor function as a porous film. In the present invention, in order to improve the compatibility between the filler and the ethylene / α-olefin copolymer, surface treatment of the filler with a fatty acid, a metal soap, a silane coupling agent, a titanate coupling agent, or the like. However, preferable results may be obtained in the present invention in some cases.

The above-mentioned various fillers may be used alone or in combination. The amount of the filler compounded is 10 to 400 parts by weight, preferably 20 to 200 parts by weight, and more preferably 2 to 100 parts by weight of the resin.
0 to 100 parts by weight. 10 for applications such as garbage bags
˜150 parts by weight is preferably used, and in the film, 30
-100 parts by weight is preferably blended. If the amount is less than 10 parts by weight, not only the translucency and air permeability of the resin will be insufficient, but also the combustion energy will be too large at the time of incineration, which will cause damage to the incinerator. If the blending amount exceeds 400 parts by weight, the molding process deteriorates and the strength becomes extremely weak.

As the antioxidant which is the component (C) of the present invention, known antioxidants are used. Among them, hindered phenol compounds, organic phosphite compounds and organic phosphonite compounds are preferably used. . Specific examples of the hindered phenol compound include:
2,6-di-t-butyl-4-methylphenol, 2-
t-butyl-4-methoxyphenol, n-octadecyl-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate, 2,2'ethylden-
Bis (2,4-t-butylphenol), 1,3,5-
Trimethyl-2,4,6-tris (3,5-di-butyl-4-hydroxybenzyl) benzene, 4,4'-thiobis (3-methyl-6-t-butylphenol), tris (3,5-di) -Butyl-4-hydroxybenzyl) isocyanurate, tris (4-t-butyl-2,6-di-methyl-3-hydroxybenzyl) isocyanurate, tetrakis- [methylene-3- (3 ', 5'-di −
t-butyl) -4'-hydroxy-phenyl) propionate] methane, 3,9-bis [1,1-di-methyl-
2- {β- (3-t-butyl-4-hydroxy-5-methylphenyl) propynyloxy} ethyl] -2,4
There are 8,10-tetraoxaspiro [5,5] undecane and the like. In particular 1,3,5-trimethyl-2,4,6-tris (3,5-di-butyl-4-hydroxybenzyl)
Benzene, tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 3,9-bis [1,1-di-methyl-2- {β- (3-t-butyl-
4-Hydroxy-5-methylphenyl) propynyloxy} ethyl] -2,4,8,10-tetraoxazaspiro [5,5] undecane does not adsorb to the filler and has an antioxidant performance at high temperature. Since it is excellent, it is preferably used. These are ethylene / α-olefin copolymers (A)
Or 0.01 to 1.0 parts by weight, preferably 0.03 to 0.5 parts by weight, relative to 100 parts by weight of the composition (A + A ′).
Parts by weight are added and used. If it is less than 0.01 parts by weight, the antioxidant effect is extremely low, and the resin is likely to deteriorate. Further, even if the amount exceeds 1 part by weight, the effect reaches the ceiling, which is uneconomical or causes deterioration of hue.

Examples of the organic phosphite compound include organic phosphite compounds represented by the following general formula (3) or (4).

[0045]

Embedded image

(R ¹ , R ² and R ³ represent the same or different hydrogen or an alkyl group, an aryl group, an alkaryl group, an aralkyl group or an alkylthio group)

[0047]

Embedded image

(R ⁴ and R ⁵ represent the same or different aryl groups or alkaryl groups) Examples of the phosphite represented by the general formula (3) include tristridecyl phosphite, triphenyl phosphite, Tris (2,4-di-t-butylphenyl) phosphite, trisnonylphenylphosphite, tris (mixed mono, dinonylphenyl) phosphite,
Examples thereof include trisbiphenylphosphite, tricyclohexylphosphite, diphenylisodecylphosphite, trilauryltrithiophosphite, tris (octylthiopropyl) phosphite, and dilaurylhydrogenphosphite.

Examples of the phosphite represented by the general formula (4) include bistridecyl pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, and di (2,4). -Di-t-butylphenyl) pentaerythritol diphosphite, di (2,6
-Di-t-butyl-4-methyl) pentaerythritol diphosphite and the like.

As the phosphite other than the general formulas (3) and (4), 4,4'-isopropylidene-di-phenolalkylphosphite, tetratridecyl 4,4'-
Butylidene bis (3-methyl-6-butylphenol)
Diphosphite, hexatridecyl 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane triphosphite and the like can be mentioned.

Examples of the organic phosphonite compound include phosphonite compounds represented by the following general formula (5) or (6).

[0052]

Embedded image

(In the formula, R ⁶ and R ⁷ are the same or different hydrocarbons having 1 to 4 carbon atoms.)

[0054]

[Chemical 6]

(In the formula, R ⁸ , R ⁹ , and R ¹⁰ are the same or different hydrocarbons having 1 to 4 carbon atoms.) Tetrakis () is a typical compound represented by the general formula (5). 2,4-di-butylphenyl) -4,4'-
Biphenylene phosphonite is mentioned. Typical compounds represented by the above general formula (6) include tetrakis (2,4-di-butyl-5-methyl-phenyl) -4,
4'-biphenylene phosphonite is mentioned.

The mixing ratio of the above-mentioned component (C) used in the present invention is 0.01 to 2 parts by weight, preferably 0.02 to 100 parts by weight of the ethylene copolymer or its composition.
1.0 part by weight. If the amount is less than 0.01 parts by weight, the antioxidant effect is insufficient and the resin is easily deteriorated by heat. Even if the amount is more than 2 parts by weight, the effect is not reached and it is uneconomical and causes deterioration of hue.

The above-mentioned organic phosphite compound and organic phosphonite compound may be used alone, but when they are used in combination with a phenolic antioxidant, the composition has a synergistic effect on the stability of the composition against heat, particularly heat resistance during high temperature molding. Is significantly improved. Further, the phenolic antioxidant may yellow due to aging when used in combination with the filler, but by using these organic phosphite compounds and organic phosphonite compounds in combination, there is an effect that the color stability is improved, Considering these effects, it is desirable to add them in combination.

The second aspect of the present invention is to provide a composition in which a specific functional group monomer is bound and contained in an ethylene / α-olefin copolymer and a filler composition. As the specific functional group monomer, D1: carboxylic acid group, carboxylic acid ester group or acid anhydride group-containing monomer, D2: epoxy group-containing monomer, D3: hydroxyl group-containing monomer, D4: amino group-containing monomer, D5: alkenyl Cyclic iminoether derivative-containing monomer, D6: A monomer having at least one functional group selected from polyfunctional monomers. The functional group monomer may be included in the form of a random copolymer, a graft copolymer or the like of an olefin and the functional group monomer. The functional group is ethylene
Since the resin component such as the α-olefin copolymer has an affinity with the filler, it has an effect of increasing the affinity at the interface between the two and thus preventing the strength of the composition from decreasing.

The copolymer of the above olefin and the functional group-containing monomer includes olefins such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene, and the functional group-containing monomer. Any of the above random copolymers, olefin polymers or polymers of the above-mentioned component (A), component (A'1) and component (A'2) graft-modified with the functional group-containing monomer may be used. Further, among the above-mentioned component (A'2), ethylene-vinyl ester copolymer, ethylene and α, β unsaturated carboxylic acid or its alkyl ester copolymer are also random copolymers of the olefin of the present invention and a functional group-containing monomer. Included in the polymer.

Examples of the D1: carboxylic acid group, carboxylic acid derivative or acid anhydride group-containing monomer of the possible group-containing monomer include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, itaconic acid and citracone. Examples thereof include unsaturated monobasic acids such as acids, dibasic acids and their anhydrides, with maleic acid or maleic anhydride being particularly preferred. Examples of unsaturated carboxylic acid derivatives include metal salts, amides, imides and esters of the above carboxylic acids.

D2: As the epoxy group-containing monomer,
Examples thereof include glycidyl (meth) acrylate, allyl glycidyl ether, vinyl glycidyl ether and the like.

D3: 1-hydroxypropyl (meth) acrylate as the hydroxyl group-containing monomer, 2
-Hydroxypropyl (meth) acrylate, hydroxyethyl (meth) acrylate and the like can be mentioned.

D4: Examples of the amino group-containing monomer include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and dibutylaminoethyl (meth) acrylate.

D5: The alkenyl cyclic imino ether derivative monomer is represented by the following structural formula (7).

[0065]

Embedded image

Where n is 1, 2 and 3, preferably
Is 2 and 3, more preferably 2. Also R¹¹, R
¹², R¹³And R¹⁴Is C₁~ C₁₂The inactive
Alkyl group and / or hydrogen, the alkyl group is
Each may have an inert substituent. Inactivity here
The property has a negative effect on the graft reaction and the function of the product.
Means not. Also, all R must be the same
There is no. Preferably R ¹= R^Two= H or Me, R =
H or 2-vinyl and / or 2-isopropenyl
Le-2-oxazoline, 2-vinyl and / or 2-a
Sopropenyl-5,6-dihydro-4H-1,3-oxy
It is Sajin. These may be used alone or as a mixture.

D6: As the polyfunctional monomer, polyfunctional methacrylate monomers represented by trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, etc., divinylbenzene, triallyl isocyanurate,
Polyfunctional vinyl monomers typified by diallyl phthalate and vinyl butyrate, bismaleimides typified by N, N′-m-phenylene bismaleimide, N, N′-ethylene bismaleimide, p-quinone dioxime And other dioximes.

When the olefin polymer is graft-modified with at least one of the above-mentioned monomers, it is preferably carried out in the presence of a crosslinking agent. Examples of the cross-linking agent used include at least one selected from hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, organic peroxides such as ketone peroxides, dihydroaromatic compounds, and vulcanizing agents such as sulfur. . The graft reaction with the ethylene / α-olefin copolymer or the composition thereof, the functional group-containing monomer, the cross-linking agent and the like is performed while the resin is melted by an extruder or the like, or in a heated organic solvent. When the reaction is carried out in the extruder, it is preferably carried out because there is no solvent removal step.

The grafting amount of the graft copolymer is 0.01 to 30% by weight, preferably 0.1% to 20% by weight, and more preferably 0.2 to the olefin polymer.
１５15% by weight. If the graft amount is less than 0.01% by weight, the affinity is insufficient and the strength, flexibility and air permeability are not sufficiently improved, and if the amount is more than 30% by weight, gel may be generated during denaturation or the resin may be discolored. .

It is important that the amount of the functional group-containing monomer in the resin component of the present invention is adjusted to 10 ^-8 to 10 ^-3 mol per 1 g of the resin component. When the amount of the functional group-containing monomer is less than 10 ^-8 mol, the affinity is not sufficiently exhibited, and even when the amount exceeds 10 ^-3 mol, the effect of improving mechanical strength and the like cannot be expected any more.

A third aspect of the present invention is to use the above-mentioned composition by a molding method such as extrusion molding, injection molding, blow molding, rotational molding or the like to form a film / sheet, tube, bottle, profile extrusion molding,
Molded products such as lids and ducts. In particular, since the films and sheets are composed of a composition of a specific ethylene / α-olefin copolymer and a filler, the printability, the writing property, the incineration property, the heat resistance and the rigidity are maintained and the mechanical properties are maintained. Will be excellent.

These films or sheets can be molded by all the conventionally known methods, but are used for shopping bags, standard bags, packaging bags and the like, and are particularly suitable for dust bags. It is also preferably used for low-calorie film, matte film, wallpaper and the like. These films and sheets are low in calories, have a thickness of about 5 to 200 μm, and are formed by an air-cooled or water-cooled inflation molding method. Further, since only the component A has a narrow molecular weight distribution and a large torque is applied during molding, it is desirable to use an extruder dedicated to linear low-density polyethylene and widen the die lip gap to 2-3 mm for molding. Since the molding temperature is as high as about 200 ° C., it is desirable to attach and mold an air ring that can sufficiently cool. Particularly, it is in the range of 20 to 100 μm for a general dust bag and 50 to 200 μm for a large dust bag. The tensile strength is measured according to the method of JIS K-6781 and is 250 kg / cm ² or more in the longitudinal direction (MD) and 150 kg / cm ² in the lateral direction (CD).
In the case of film or sheet molding of about μm, T-
A cast film molding method using a die is preferably used.

The tubes are molded by extrusion molding or hollow molding and used for hoses, squeeze containers and the like. Particularly, the squeeze container is generally formed by blow molding. In order to make the wall thickness uniform, it is desirable to mold with a molding machine equipped with a parison controller that controls the gap between the die and the mandrel according to the wall thickness distribution of the molded product. The container is generally used in a single-layer container using the resin or composition of the present invention, but if the filler is considered to affect the contents, low-density polyethylene, wire A multilayer container provided with a layer of low density polyethylene is also preferably used.

The fourth aspect of the present invention relates to a porous film. Conventionally, a porous film can be obtained by blending a filler into linear low-density polyethylene and stretching the melt-formed film. As properties of these porous films, films excellent in balance between mechanical strength such as tensile strength and moisture permeability are required, and in recent years, it has been desired to make these porous films thinner.

In view of the above, the present invention provides a porous film having an excellent balance of mechanical strength and moisture permeability, which comprises the specific ethylene / α-olefin copolymerization weight of the first invention or the second invention. A filler is blended with a resin component including coalescence, and a formed film or sheet is stretched at a draw ratio of 1.2 to
It is a uniaxially and / or biaxially stretched porous film in the range of 10 times. In particular, when the mechanical strength of the porous film is maintained and the processability and melt tension are taken into consideration, the resin composition of the resin component is 90 to 50% by weight of the component (A),
The component (A ') is preferably 10 to 50% by weight, preferably the component (A) is 80 to 60% by weight, and the component (A') is 20 to 40% by weight. Also the flexibility of the film,
When considering the texture, etc., within the range of the above mixing ratio,
As component (A '), ultra-low density polyethylene, ethylene-vinyl ester copolymer such as ethylene-vinyl acetate copolymer, α, β unsaturated carboxylic acid such as ethylene- (meth) acrylic acid alkyl ester copolymer Alternatively, its derivative is preferably used. Further, by introducing the above-mentioned functional group into the resin component, the dispersibility with the filler is further improved, and the properties such as mechanical strength are improved.

As the filler, calcium carbonate,
Talc, clay, kaolin, silica, diatomaceous earth, magnesium carbonate, barium carbonate, magnesium sulfate, barium sulfate, zinc oxide, calcium oxide, titanium oxide, alumina, mica and the like are used. Of these, calcium carbonate, talc, clay, kaolin, silica, diatomaceous earth, barium sulfate and the like are particularly preferable. The average particle size of the filler is selected to be 30 μm or less, preferably 10 μm or less, and more preferably 0.8 to 5 μm.
If the particle size is too large, the denseness of the pores of the stretched film will be poor, and if the particle size is too small, the dispersibility in resin and the moldability will be poor. The surface treatment of the filler with a fatty acid or a metal salt thereof, or liquid polybutene, liquid polybutadiene, blending a hydrocarbon polymer such as wax,
It is desirable in terms of dispersibility in a resin and stretchability of a film.

The blending amount of the filler of the present invention is the resin component 10
10 to 400 parts by weight relative to 0 parts by weight, preferably 30
To 300 parts by weight, more preferably 50 to 200 parts by weight. If the amount is less than the above range, the pores of the obtained porous film are not sufficiently formed, and if the amount exceeds the range, the strength and processability of the film may deteriorate.

The stretching treatment temperature of the present invention is in the range of 100 ° C. lower than the melting point of the resin composition to 10 ° C. lower than the melting point, and particularly 90 ° C. to 30 ° C. lower than the melting point of the resin composition. It is preferable to carry out in the range. If the temperature is lower than this range, uneven stretching is likely to occur, and if the temperature exceeds this range, the porosity of the film may decrease.

Stretching ratio of the film / sheet of the present invention is 1.
The porous film is uniaxially and / or biaxially stretched in the range of 2 to 10 times, preferably 1.5 to 8 times, and more preferably 2.0 to 7 times. If the stretching ratio is less than 1.2 times, the effect of stretching is insufficient and the porosity of the film,
Mechanical strength such as tensile strength is not sufficient. If the stretching ratio exceeds 10 times, the molecular orientation of the film is oriented in one direction, and the film strength is reduced, which is not preferable. The stretching method of the present invention may be a conventional method such as a roll stretching method, an inflation method or a tenter method. Further, the film may be subjected to known surface treatments such as corona discharge treatment, plasma treatment and ultraviolet treatment.

The moisture permeability of the porous film of the present invention is 100.
0 g / m ² · 24 hr or more, preferably 1200 g / m
² · 24 hr or more, more preferably 1500 g / m ²
・ It is 24 hours or more, and the average pore size is 0.05 μm to 5 μm.
m is desirable.

The thickness of the porous film of the present invention varies depending on the purpose, use, etc., and is generally used for medical treatment, clothing, leak preventive materials,
The filter medium is in the range of 5 to 200 μm, preferably 1
It is used in the range of 0 to 100 μm or less, and in the range of 100 to 400 μm for construction and civil engineering such as roofing materials and underground burying materials.

By further adding a thioether type antioxidant to the composition of the present invention, fish eye formation, coloring, etc. due to thermal deterioration during molding can be prevented. The weather resistance can be improved by adding a light stabilizer such as an ultraviolet absorber or a hindered amine compound. Further, if necessary, an antistatic agent, a lubricant, an antifogging agent, a heavy metal deactivator, a metal soap, a pigment, a plasticizer, an epoxy compound, a foaming agent, a flame retardant, a processing aid and the like can be included. As a special additive for garbage bags, cats,
Repellents for animals such as birds, deodorants / deodorants, and fragrances may be added.

[0083]

Next, the present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto.

(Resin Component) (Polymerization of Ethylene / α-Olefin Copolymer) (A) Polymerization of Ethylene / Butene-1 Copolymer A stainless steel autoclave equipped with a stirrer was replaced with nitrogen, and purified toluene was added. Then, butene-1 was added, and bis (n-butylcyclopentadienyl) zirconium dichloride (0.02 mmol as Zr) methylalumoxane [MAO] (MAO / Zr = 500).
After the mixed solution of [molar ratio]) was added, the temperature was raised to 80 ° C. Next, ethylene was added to initiate polymerization. Polymerization was carried out for 1 hour while continuously polymerizing ethylene and maintaining the total pressure. In addition, these polymerizations were repeatedly produced in an amount necessary for Examples described later. The physical properties of the obtained ethylene / butene-1 copolymer (A1, A2) were as follows. Sample A1 Sample A2 MFR (g / 10 minutes): 1.0 3.0 Density (g / cm ³ ): 0.920 0.897 Melting point (° C.): 110 90 Molecular weight distribution (Mw / Mn): 2.3 2.1 Composition distribution Cb: 1.03 1.02

The samples and additives used in Examples and Comparative Examples are shown below. Component (A): A1, A2 Component (A ′) A′1: Ethylene-α-olefin copolymer (VLDPE) with Ziegler catalyst (Density = 0.900 g / cm
³ , MFR = 1.0g / 10min, product name: J-lex D9
010, manufactured by Nippon Polyolefin Co., Ltd. A′2: ethylene vinyl acetate copolymer (vinyl acetate content = 15% by weight, MFR = 1.5 g / 10 minutes, trade name:
J-Rex V270, manufactured by Nippon Polyolefin Co., Ltd. A'3: Ethylene-α-olefin copolymer (LLDPE) with Ziegler catalyst (density = 0.923 g / cm 2)
³ , MFR = 0.90g / 10 minutes, product name: J-lex B
F2382, manufactured by Nippon Polyolefin Co., Ltd.

Component (B) B1: Calcium carbonate average particle size 1.7 μm, surface-treated with saturated fatty acid, trade name: BKS-5, manufactured by Dowa Calfine Co., Ltd. B2: Talc average particle size 4 μm , Trade name Micro White 5000S, manufactured by Hayashi Kasei Co., Ltd. B3: Titanium oxide average particle size 0.4 μm, trade name Taipaque R-550, manufactured by Ishihara Sangyo Co., Ltd.

Component (C) C1: 1,3,5-trimethyl-2,4,6-tris (3,5-di-butyl-4-hydroxybenzyl) benzene (trade name Irganox 1330, Ciba Geigy Corporation) C2: tetrakis (2,4-di-butyl-5-methyl-)
Phenyl) -4,4'-biphenylene phosphonite,
Product name GSY-101, manufactured by Yoshitomi Pharmaceutical Co., Ltd.

Component (D) D1: Ziegler catalyzed ethylene-α by extruder
-Olefin copolymer (MFR = 1.0, density = 0.9
20 g / cm ³ modified with maleic acid (maleic acid content = 0.5 wt%, 0.005 mol%) D2: Sample A1 modified with maleic acid by an extruder method (maleic acid content = 0.50%). 5% by weight)

Examples 1 to 12 and Comparative Examples 1 to 7 The components shown in Tables 1 and 2 and 0.3 parts by weight of hydrotalcite (manufactured by Kyowa Chemical Industry Co., Ltd.) as an acid absorbent were added and pelletized. Inflation molding was performed under the conditions to obtain a film. The obtained film was evaluated. The results are shown in Tables 1 and 2. (All the following compounding amounts are parts by weight.) (Film molding) (Inflation film molding conditions) Equipment: Modern Machinery Co., Ltd. Extruder screw diameter: 50 mmφ Die: Diameter 100 mmφ Blow-up ratio: 3.0 Die lip gap : 3 mm Molding resin temperature: 200 ° C. Film thickness: 30 μm Screen mesh: 80 mesh / 120 mesh / 80 mesh

(Evaluation Results) In Examples 1 to 3, the filler (component B1) and the antioxidant (components C1, C2 and C1, C) were used.
2 is used together, it can be seen that all have high mechanical strength and good continuous operation. Comparative Example 1 shows an example in which the component (C) is not used, and in comparison with Examples 1 to 3, not only continuous operation cannot be performed due to generation of eye grease due to deterioration, but also strength is lowered. Comparative Examples 2 to 4 are examples in which the conventional A component was used, and the dirt strength is lower than that of the Examples. Example 4 shows an example in which another filler (component B2) was used, and like Example 1, continuous operation is possible and an excellent strength is obtained. Examples 5 to 6 are components (A)
And (A′1, A′2) are used in combination and the components (B) and (C) are blended. Comparative Examples 5 to 6 show the component (A′1), the component (A′3) and the component (A′3). An example was shown in which the same formulation as in Examples 5 and 6 was used except that A'2) and the component (A'3) were used.
All of the comparative examples are inferior in strength. Examples 7 to 9 are further modified to Examples 1, 5 and 6 (functional group-containing).
An example in which the resin component (D) is blended is shown, and it can be seen that the compositions in which the component (D) is blended have both improved strength and tensile modulus. In Examples 10 to 11, the filler (component B1) was added to 100 parts by weight of the resin component (A1).
It shows an example in which the compounding amount of 100 parts by weight, 300 parts by weight, and a functional group are mixed, and mechanical strength such as tensile strength, tensile elastic modulus and dart strength is obtained even if a relatively large amount of filler is added. It can be seen that the strength is retained. On the other hand, Comparative Example 7
Is a filler (component B1) in 100 parts by weight of the resin component (A1)
This is an example in which 500 parts by weight of the above was mixed with a functional group, and a good film could not be obtained. Example 1
No. 2 was evaluated in the same manner except that the resin component (A1) of Example 1 was replaced with (A2), and the results are shown below.
The result almost equal to that of Example 1 was obtained. The test method used is shown below. (Physical property test method) Density: Based on JIS K6760. Melt flow rate: Based on JIS K6760. Tensile strength: Based on JIS K6781. Dirt strength: In accordance with JIS K7124 Antioxidant performance: Evaluated by continuous operation time until film formation becomes impossible due to grease due to heat-deteriorated resin during film formation.

[0091]

[Table 1]

[0092]

[Table 2]

Examples 13 to 21 and Comparative Examples 8 to 9 The components shown in Table 3 and 0.3 part by weight of hydrotalcite (manufactured by Kyowa Chemical Industry Co., Ltd.) as an acid absorbent were added and pelletized under the following conditions. Hollow molding was performed to prepare a squeezed tube, and the air bag resistance, color and the like were evaluated, and the results are shown in Table 3.

(Blow molding conditions) Device: Japan Steel Works 50 mm extruder JB105 Temperature setting: C1 C2 C3 H D1 D2 (° C.) 220 210 210 200 195 195 195 Parison control: PC-1 5-point mold cooling water temperature : 15 ℃

(Evaluation of squeezed container) Air pack resistance: Evaluated by the time required for the air to return to its original shape after being crushed by hand by a distance of 1/3 of the entire length from the bottom of the container. (The longer the better)

(Evaluation Results) In Examples 13 to 16, the filler (component B1) and the antioxidant (components C1, C2 and C) were used.
1, C2 are used together), and Examples 17 to 1 are shown.
8 shows an example in which A1 and A'1 or A'2 are used in combination, and Examples 19 to 21 show those obtained by further adding a modified (functional group-containing) resin component (D) to the above-mentioned examples. It can be seen that it has excellent air pack resistance and good continuous operation.
Comparative Example 8 shows an example in which the component (C) is not used, and Example 1
Compared with No. 3, the continuous operation property was poor, and in Comparative Example 9, no filler was blended and the air pack resistance was poor.

[0097]

[Table 3]

Examples 22 to 30 and Comparative Examples 10 to 15 The components shown in Tables 4 and 5 and 0.3 part by weight of hydrotalcite (manufactured by Kyowa Chemical Industry Co., Ltd.) as an acid absorbent were added and pelletized. A porous film was produced under the conditions, and the evaluation results are shown in Tables 4 and 5.

(Conditions for forming porous film) Using the above-mentioned inflation molding machine, except that the blow ratio was 1.7 and the wall thickness was 60 μm, a raw material for stretching was obtained. This film is drawn at a drawing temperature of 80 ° C. and a draw ratio of 3 using a proximity uniaxial drawing device.
Was uniaxially stretched to obtain a porous film. (Film Evaluation Method) Tensile Strength: According to ASTM D882 Tensile Elastic Modulus: Same as above Moisture Permeability: Pure water 50 in glass cup with diameter 85 mm
Put cm ^3, completely sealed and the temperature 23 ° C. around put the test film, the room was prepared in a relative humidity of 50% 1
Let stand for 0 days and measure the weight loss to obtain the moisture vapor transmission rate. The results are shown in terms of water vapor transmission rate per 1 m ² per day.

(Evaluation Results) In Examples 22 to 24, component B was used.
And an example in which the components C1, C2 and C1, C2 are used in combination, Example 25 shows an example in which the filler (B2) is used,
Examples 26 to 27 show examples in which the components (A) and (A′1, A′2) are used in combination and the components (B) and (C) are blended, and all of them are continuous operability and stretch unevenness. It was a porous film with a soft feel. Comparative Example 10 shows an example in which the component (C) is not used, uneven drawing occurs due to deterioration, continuous operation is not possible, and the obtained film is not uniform and does not have uniform pores during drawing, which is practical. No porous film was obtained. Comparative Examples 11 to 13 are conventional ethylene polymers (component A'1, component A'2, component A'3).
Comparative Examples 14 and 15 are examples of these mixtures, but the stretchability was poor as compared with Examples 26 and 27, and a porous film could not be obtained. Example 28
-30 is a maleic acid-modified (functional group-containing) resin component (D)
In the example of Examples 20, 24,
Compared with No. 25, a more uniform porous film was obtained and the film had a soft touch.

[0101]

[Table 4]

[0102]

[Table 5]

[0103]

INDUSTRIAL APPLICABILITY According to the present invention, by mixing a filler and an antioxidant with an ethylene / α-olefin copolymer having a narrow molecular weight distribution and a narrow composition distribution polymerized with a specific catalyst, heat deterioration during molding is achieved. No deterioration, stains on the molding roll,
It is possible to obtain a composition which is less likely to emit smoke and has high mechanical strength. Further, using the composition, a film which is translucent, has strength and generates little combustion heat, and a porous film having excellent flexibility can be obtained by further stretching after forming the film. By further incorporating the modified polyolefin, a composition and a molded product having further improved mechanical strength can be obtained.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08K 5/13 KER C08K 5/13 KER 5/524 KFM 5/524 KFM 5/5393 KFN 5/5393 KFN C08L 23/16 LCY C08L 23/16 LCY (72) Inventor Tokutake ▼ Atsu ▲ husband 1-3-1, Uchisaiwaicho, Chiyoda-ku, Tokyo Nihon Petrochemical Co., Ltd.

Claims (11)

[Claims] 1. Ethylene and a carbon number of 3 to 20 in the presence of a catalyst containing at least one transition metal compound of Group IV of the periodic table containing (A) (a) a ligand having a cyclopentadienyl skeleton. (B) Density obtained by copolymerizing the α-olefin of 0.86 to 0.96 g / cm ³ ,
(C) Melt florate 0.01 to 50 g / 10 minutes,
(D) 100 parts by weight of an ethylene copolymer having a molecular weight distribution Mw / Mn of 1.5 to 5.0, (e) a composition distribution parameter Cb of 1.01 to 1.2, and (B) a filler of 10 to 400 parts by weight. (C) A filler-containing ethylene / α-olefin copolymer composition containing 0.01 to 2.0 parts by weight of an antioxidant. 2. Ethylene and C3-20 in the presence of a catalyst containing at least one transition metal compound of Group IV of the periodic table containing (A) (a) a ligand having a cyclopentadienyl skeleton. (B) Density obtained by copolymerizing the α-olefin of 0.86 to 0.96 g / cm ³ ,
(C) Melt florate 0.01 to 50 g / 10 minutes,
(D) Molecular weight distribution Mw / Mn 1.5 to 5.0, (e) 20% by weight or more of an ethylene copolymer having a composition distribution parameter Cb of 1.01 to 1.2, and (A ') another ethylene-based polymer. A filler-containing ethylene / α-olefin copolymer containing 100 parts by weight of a resin component composed of 80% by weight or less of the combined product, (B) 10 to 400 parts by weight of the filler, and (C) 0.01 to 2.0 parts by weight of the antioxidant. Polymer composition. 3. The (A ′) other ethylene-based polymer is
The filler-containing ethylene / α-olefin copolymer composition according to claim 2, wherein the ethylene / α-olefin copolymer composition is at least one selected from the following ethylene polymers. [Ethylene Polymer] (A′1) Ethylene / α-olefin copolymer having a density of 0.86 to 0.96 g / cm ³ (A′2) Low density polyethylene and ethylene / vinyl ester copolymer by high pressure radical polymerization Polymer, ethylene
Copolymer with α, β-unsaturated carboxylic acid or its derivative 4. A unit based on at least one functional group-containing monomer selected from the following D1 to D6 in the resin component in a monomer amount of 10 ⁻⁸ to 10 ⁻³ mo per 1 g of the resin component.
The filler-containing ethylene / α-olefin copolymer composition according to any one of claims 1 to 3, wherein the filler / ethylene-α-olefin copolymer composition is contained. [Functional group-containing monomer] D1: Carboxylic acid group, carboxylic acid ester group or acid anhydride group-containing monomer D2: Epoxy group-containing monomer D3: Hydroxyl group-containing monomer D4: Amino group-containing monomer D5: Alkenyl cyclic imino ether derivative monomer D6: Polyfunctional monomer 5. The (C) antioxidant is one or more selected from the group consisting of a hindered phenol compound, an organic phosphite compound and an organic phosphonite compound, according to any one of claims 1 to 4. The filler-containing ethylene / α-olefin copolymer composition described. 6. The filler-containing ethylene / α-olefin copolymer composition according to any one of claims 1 to 5 is molded by extrusion molding, injection molding, blow molding or rotational molding. Molding. 7. The molding according to claim 6, which is a film or sheet obtained by extrusion molding the filler-containing ethylene / α-olefin copolymer composition according to any one of claims 1 to 5. Goods. 8. A molded article according to claim 6, which is a tube made of the filler-containing ethylene / α-olefin copolymer composition according to any one of claims 1 to 5. 9. A bag formed by bag-making the film or sheet according to claim 7. 10. A squeezing container comprising the tube according to claim 8. 11. A stretch ratio of 1.2 after forming the filler-containing ethylene / α-olefin copolymer composition according to any one of claims 1 to 5 into a film or sheet.
A porous film which is stretched to 10 times.