JP3375187B2 - Polyethylene composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to a polyethylene composition.
In particular, it has a wide molecular weight distribution,
Specific ethylene / α-olefin copolymer with excellent properties
Polyethylene Composition Consisting of Polyethylene and Inorganic Filler
Heat resistance, rigidity, dimensional stability,
Excellent leap characteristics, mechanical properties, flame retardancy, etc., and fill
It is semi-transparent, and has a low calorific value when incinerated.
The present invention relates to an incinerated polyethylene composition. Have such advantages
As a result, the polyethylene composition is extruded and hollow
Shape, can be suitably used for molding methods such as injection molding,
Various films, sheets, pipes, hollow containers, various coating materials
That can be used as a wide range of molded products such as
is there. [0002] 2. Description of the Related Art Conventionally, polyethylene resin
, Calcium carbonate, barium sulfate, mica, hydroxide
By blending inorganic fillers such as gnesium,
Improves thermal properties, rigidity, dimensional stability, creep characteristics, etc.
Improves transparency and flame retardancy, and generates less heat when incinerated
Polyethylene-based trees that provide easy incineration by
Fat improvements have been made. However, a large amount of inorganic filler
When incorporated, the improvement effect is sufficiently significant.
However, the tear strength and stretchability are not enough and the mechanical strength is reduced.
And the moldability was insufficient (see JP-A-50-275).
No. 3, JP-A-51-28846, JP-A-53-106746
Bulletin, JP-A-60-69145). [0003] That is, low density by high pressure radical polymerization method
Polyethylene has long chain branches and lengths comparable to the main chain.
And has a short-chain branch consisting of an alkyl group having 1 to 6 carbon atoms
Because of this structure, it has low crystallinity and is soft. This
Density polyethylene by high pressure radical polymerization
Has a tensile strength and
Inferior to mechanical properties such as heat impact value and tear strength
Having. On the other hand, linear low-density polyethylene is
Gas phase method, slurry method, solution method, high pressure ion polymerization method, etc.
Using various processes, various catalysts and polymerization conditions
The ethylene / α-olefin copolymer produced
Depends on the type of α-olefin used.
Mechanical properties are high pressure radio
It is superior to low-density polyethylene produced by the polymerization method.
However, linear low-density polyethylene generally has a molecular weight distribution.
Since it is very narrow, the melt elasticity such as melt tension and
Flow, including n-value, flow parameters, critical shear rate, etc.
Poor dynamic characteristics. The disadvantages of melt elasticity and flow properties are
Appears mainly in moldability, specifically, the pressing during molding.
Lower output, higher extrusion pressure, higher power consumption, high speed
Poor moldability, rough surface of molded product, fish eye
Problems such as heat deterioration due to heat generation in the extruder
The moldability is further deteriorated by adding inorganic filler
You. [0005] Improve the flow characteristics of linear low density polyethylene
Therefore, if the molecular weight is reduced, mechanical characteristics such as impact strength
Resistance and environmental stress cracking, especially mechanical properties at low temperatures and
The disadvantage that the melt elasticity is significantly reduced appears. Also machine
Even if the density is lowered to improve the mechanical properties, the melt elasticity
Little improvement. As mentioned above, linear low density poly
For ethylene, its mechanical properties, especially at low temperatures
Improve properties, flow properties and melt elasticity at the same time
Was extremely difficult. Conventionally, in order to improve the flow characteristics, the
To broaden the molecular weight distribution of the α-olefin copolymer
Have been reported (for example, Japanese Patent Application Laid-Open No. 57-21409,
Japanese Patent Publication No. 63-47741, etc.)
Only widen the melt elasticity and mechanical properties, especially at low temperatures
Mechanical properties of the time, rather than improve
descend. In addition, improvement of mechanical and flow characteristics
Of ethylene consisting of a high molecular weight component and a low molecular weight component
.Alpha.-olefin copolymer, high molecular weight component
Identify the degree of chain branching and increase short-chain branching in high molecular weight components
By introducing, not only mechanical properties and fluidity,
Attempts have also been made to improve environmental stress cracking resistance (ESCR)
(Japanese Patent Laid-Open No. 54-100444, Japanese Patent Publication No. 64-7096)
Information). However, the mechanical properties, especially at low temperatures,
Significant differences depending on the short-chain branch distribution of high molecular weight components
Therefore, although some improvement is seen in the above method,
As a means to improve mechanical and flow properties at low temperatures
It was not satisfactory. Applicant believes that such
Mechanical properties of linear low density polyethylene, especially at low temperatures
Technology to simultaneously improve mechanical properties, flow properties and melt elasticity
Technique has already been proposed (JP-A-4-249562).
Although the above object was achieved, heat resistance and rigidity
Higher performance in terms of properties, dimensional stability, creep characteristics, etc.
Has been required. [0007] SUMMARY OF THE INVENTION The present invention has been made in view of the above points.
Properties, such as heat resistance, ESCR, flexibility, etc.
Melt elasticity, flow characteristics, mechanical characteristics
Ethylene-α- with excellent properties, especially mechanical properties at low temperatures
An inorganic filler is added to the resin composition containing the olefin copolymer.
Heat resistance, rigidity and dimensional stability of molded products by mixing
Properties, creep properties, mechanical properties, flame retardancy, etc.
Film can be made translucent and generate heat when incinerated.
To provide a polyethylene composition having a low amount and exhibiting easy incineration.
The purpose is to do so. [0008] SUMMARY OF THE INVENTION The present inventors have achieved the above object.
As a result of intensive studies along the
Specific ethylene / α with extremely wide short-chain branch distribution
-Olefin copolymer and relatively low molecular weight ethylene
Melt elasticity and flow characteristics
Superb with excellent mechanical properties and mechanical properties, especially at low temperatures
High molecular weight polyethylene is obtained, and at the same time
When combined, it has sufficient mechanical strength and has good moldability
That an easily incinerated polyethylene composition is obtained
And arrived at the present invention. That is, the present invention provides (A)
Highly active Ziegler-type catalyst supported on a solid support
Polymerized withThe following conditions (a) and (b) and the following
Ethylene and satisfies conditions (e) and (f)
20 to 80 parts by weight of a copolymer with an α-olefin, (a) Intrinsic viscosity (η₁) 2.0-9.0 dl / g (b) Density (d₁) 0.88 ~ 0.94 g / cm^Three, And (B) ethylene single weight satisfying the following conditions (c) and (d):
Coalesced or ethylene and an α-olefin having 3 to 18 carbon atoms
80 to 20 parts by weight of a copolymer of (c) Intrinsic viscosity (η_Two) Less than 0.2-2.0 dl / g (d) Density (d_Two) 0.88 ~ 0.97 g / cm^Three And a limiting viscosity (η) of 2.0 to
5.2 dl / g, density (d) 0.88 ~ 0.94 g / cm^ThreeAnd n-value
Is ultra high molecular weight polyethylene which is 1.7 to 3.5, and (C) Polyethylene composition containing 10 to 50% by weight of inorganic filler
Is provided. Hereinafter, the contents of the present invention will be described in detail. Departure
Ethylene / α-olefin which is a light high molecular weight component (A)
The copolymer isHighly active chi supported on a solid carrier
Polymerized with a Glar type catalyst,Ethylene and α with 3-18 carbon atoms
-Consisting of a copolymer with olefins, especially 4 to 10 carbon atoms
Are preferred in terms of mechanical properties. Specifically, 1-
Butene, 1-pentene, 1-hexene, 4-methyl-1-pente
, 1-octene, 1-nonene, 1-decene and the like.
The α-olefin may be used in combination of two or more kinds.
No. The high molecular weight component (A) ethylene / α
-The olefin copolymer is (a) intrinsic viscosity (η₁) Is 2.0 ~
9.0 dl / g, preferably 2.3 to 8.5 dl / g, more preferably
Those having a range of 2.5 to 8.0 dl / g are used. (Η₁) Is 2.
Below 0 dl / g, the melt elasticity and mechanical
If the mechanical properties are inferior and it exceeds 9.0 dl / g,
Deterioration of molding processability such as generation of roughness and fish eyes
You. The density (d) (d) of component (A)₁) Is 0.88
~ 0.94 g / cm^ThreeRange, preferably 0.89 to 0.925 g / cm^ThreeBut
Used. (D₁) Is 0.88 g / cm^ThreeLess than
In addition to being difficult, it may cause stickiness of the resulting composition.
Therefore, it is not preferable. On the other hand (d₁) Is 0.94g / cm^ThreeExceeds
Is sometimes preferred due to reduced melt elasticity and mechanical properties.
Not good. The component (A) used in the present invention also includes, in particular,
ethylene-α-olefin satisfying the conditions of (e) and (f)
Resin significantly improves the mechanical strength at low temperatures.
Preferred for (e) In the elution temperature-elution amount curve by the continuous heating elution fractionation method
And the area Ia under the curve at an elution temperature of 90 ° C. or higher.
The ratio S (Ib / I) of the area Ib under the curve at an elution temperature of 25 to 90 ° C.
a) is calculated from the following equation:₁Less than, S₁= 20η₁ ^-1 exp [-50 (d₁-0.90)] (f) 25 ° C orthodichlorobenzene soluble matter W wt% is
W calculated from₁that's all W₁= 20 exp (-η₁). As described in (e) above, the branch distribution was measured from the dissolution temperature in the solvent.
L. Wild et al.'S continuous heating elution fractionation method (Temperature Ri
sing Elution Fractionation (TREF); Journalof Polymer
 Science: Polymer Physics Edition, Vol.20,441-455 (19
82)), the elution temperature-9
Area Ia under the curve above 0 ° C and the curve of the elution temperature 25-90 ° C
A specific relationship needs to be established with the lower area Ib
It is. That is, the area ratio S = I shown in the schematic diagram of FIG.
The value of b / Ia is determined by the following equation.₁It is as follows. S₁= 20η₁ ^-1 exp [-50 (d₁-0.90)] The value of S is S₁Above, the distribution of branches approaches almost uniform
The resulting melt elasticity and mechanical properties, especially at low temperatures
Highly branched components that are extremely effective for the characteristics are relatively reduced
This is unfavorable because it is small. [0013] The component (A) used in the present invention (f)
The elution temperature of sodichlorobenzene solubles was too low
To the extent that it cannot be quantified by continuous heating elution fractionation
Means the amount of the component having a large amount of branching.
Must be greater than or equal to That is, the soluble component
The amount W is calculated by the following formula.₁That is all. W₁= 20 exp (-η₁) W value is W₁Below, the melt elasticity and mechanical properties, especially
High degree of branching that is extremely effective for mechanical properties at low temperatures
As a result of the reduced components, the same is not preferred. (B) which is a low-molecular-weight component of the present invention
Homopolymer or ethylene / α-olefin copolymer
It is. As the α-olefin, the same as in the case of the component (A)
3 to 18 carbon atoms are used, especially 4 to 10 carbon atoms.
Are preferred in terms of mechanical properties. Specifically, 1-
Ten, 1-pentene, 1-hexene, 4-methyl-1-pente
, 1-octene, 1-nonene, 1-decene and the like.
The α-olefin may be used in combination of two or more kinds.
No. The above component (B)
(c) Intrinsic viscosity (η_Two) Is used in the range of 0.2 to less than 2.0 dl / g
And preferably from 0.3 to 1.8 dl / g, more preferably from 0.4 to
It is in the range of 1.6 dl / g. (Η_Two) Is less than 0.2 dl / g,
Mechanical properties of the resulting composition, especially at low temperatures
Is poor, while above 2.0 dl / g, its flow properties deteriorate
Are not preferred. The component (B)
(d) Density (d_Two) Is 0.88 ~ 0.97 g / cm^ThreeRange, preferred
0.91 to 0.96 g / cm^ThreeIs used. (D₁) Is 0.88 g /
cm^ThreeLess than is difficult to manufacture and the resulting composition
It is not preferable because it causes stickiness of the object. on the other hand,
(D₁) Is 0.97g / cm^ThreeIf it exceeds, the melt elasticity and machine
It is not preferable because mechanical properties are deteriorated. In the present invention, the distribution of component (A) and component (B)
The mixing ratio is 20 to 80 parts by weight of the component (A) and 80 to 20 parts by weight of the component (B).
Parts, preferably 30 to 70 parts by weight and 70 to 70 parts by weight, respectively.
30 parts by weight (however, (A) + (B) = 100 parts by weight). Success
If the amount of component (A) is less than 20 parts by weight, melt elasticity and mechanical characteristics
Performance, especially at low temperatures, while 80 parts by weight
If it exceeds, the flow characteristics will be reduced.
I can't. The mixture of the components (A) and (B) of the present invention
As described above, it can be obtained by blending both components.
The properties of the compound must be in a specific range. Ie
The intrinsic viscosity (η) of the mixture is 2.0 to 5.2 dl / g.
Preferably, it is 2.5 to 4.0 dl / g. (Η) is less than 2.0 dl / g
At full melt viscosity and mechanical properties, especially at low temperatures
Poor properties, poor flow properties above 5.2 dl / g
Are not preferred. Also the density of the mixture
(D) is 0.88 to 0.94 g / cm^ThreeAnd preferably 0.89-0.
93 g / cm^ThreeIt is. (D) is 0.88 g / cm^ThreeLess than is difficult to manufacture
Difficult and causes stickiness of the mixture and 0.94
 g / cm^ThreeIf it exceeds, mechanical properties such as tensile impact value are low.
Down. Further, the n-value of the mixture is 1.7 to 3.5.
Is required, and is preferably 2.0 to 3.0. n-value is
If it is less than 1.7, the high-speed moldability is poor, and if it exceeds 3.5, it is low.
Due to the increase in molecular weight components, white powder and smoke are generated during molding.
It will be cool. About the method for producing the mixture of the present invention
Is such that each component of the composition satisfies specific conditions.
IfThere is no particular limitation. For example, component (A) and component (B)
Are each independently produced by one-stage polymerization, and
Both may be mixed, or two or more stages
It may be produced by a known polymerization method by multi-stage polymerization. Previous
When manufacturing by mixing
Kneading with a dispenser or Banbury mixer, etc.
Alternatively, a known method such as a solution mixing method can be used.
You. The latter method using multi-stage polymerization involves the use of multiple reactors.
Used, for example, the first stage reactor corresponds to component (A)
Polymerization of high molecular weight ethylene / α-olefin copolymer
And the second stage reactor was subjected to low molecular weight polymerization of component (B).
While maintaining the polymerization conditions of the polymer, the polymer
Is a method for producing a mixture by continuously circulating the mixture in the second stage.
You. However, each component of (A) and (B) should be
The order and number of stages are particularly limited
It is not done.In addition, two-stage polymerization or more
The composition produced by the multistage polymerization method of
The composition obtained by blending after separate polymerization is
Have the same properties. In any of the above cases, the reaction format
There is no particular limitation on the slurry method, gas phase method, solution method, high pressure
Various methods such as an ON method can be used. these
All the compositions obtained in the method have comparable properties.
Is what you do. The reaction temperature in these methods
Well-known operating conditions such as degree and pressure are, for example, chemical engineering,
47, [5] (1983) Fujita, Ushida, p329 and
Convertec (1990.1) Doi, p77
Have been. Also polymerizationThe catalyst is, Eg Ziegler typeCatalyst
Can be used.Particularly a catalyst for producing the component (A)
IsZiegler-type contact with high activity supported on solid support
In mediumNeed to beYes, and the details are described below. The highly active Ziegler catalyst is an inorganic solid support.
Body such as metallic magnesium, magnesium hydroxide, carbonic acid
Magnesium, magnesium oxide, various alumina, silicon
Mosquito, silica alumina, magnesium chloride, etc., or mug
Choose from nesium, silicon, aluminum and calcium
Salt, double oxide, hydrated carbonate, hydrated silica containing
Acid salt, etc., furthermore, these inorganic solid carriers are oxygenated compounds,
Treated with sulfur-containing compounds, hydrocarbons, and halogen-containing substances
Is transition metallization on an inorganic solid support such as a reacted one.
Compounds, such as titanium, vanadium, zirconium,
Halides of metals such as metals, alkoxy halides,
Solids supporting oxides, halogenated oxides, etc.
Used as an ingredient, which contains organic compounds of Group I-IV metals
Organometallic compounds, preferably zinc or aluminum
Or a combination of these
And those pretreated by contact with a refin. As the inorganic filler which is the component (C) of the present invention,
Examples include powders, plates, needles, spheres, fibers, etc.
Specifically, calcium carbonate, magnesium carbonate
, Calcium sulfate, calcium silicate, aluminum hydroxide
Um, magnesium hydroxide, clay, diatomaceous earth, talc,
Alumina, silica sand, iron oxide, metal powder, antimony trioxide,
Silicon carbide, silicon nitride, silica, boron nitride, aluminum nitride
Particulate fillers such as
Mosquito, sericite, pyrophyllite, aluminum flake
Any foil-like filler, flat shape such as carbon graphite
Or flaky filler, glass fiber, carbon fiber, grapha
Fiber, whisker, metal fiber, silicone carbide
Mineral fiber such as fiber, asbestos, wollastonite
And the like. These inorganic fillers
When adding properties such as easy incineration and heat resistance,
Calcium carbonate is most preferred. As the calcium carbonate, limestone is used.
So-called heavy calcium carbonate mechanically ground may be used,
So-called sedimentary carbon dioxide obtained by the carbon dioxide compounding method
It may be sium. However, it is measured by the specific surface area measuring instrument
The average particle size obtained needs to be 4 μm or less. 4μm or more
Excellent impact resistance when using calcium carbonate of particle size
No composition is obtained. Average particle size is preferably 3 μm or less
It is. In the present invention, the inorganic filler is used as it is.
May improve the dispersibility of the inorganic filler in the composition.
(Thus improving the impact resistance, etc.)
To improve the surface, stearic acid, oleic acid, etc.
Fatty acids or derivatives thereof, or paraffin or wax
Box, organic silane, organic titanate, epoxy resin, etc.
It is preferable to perform a surface treatment such as coating. The above compound
When surface treatment is performed with a material, the amount of surface treatment is
About 0.2 to 2% by weight is preferable. Less than 0.2% by weight
2% by weight
Even if a surface treatment agent that exceeds
Is not economical and can not be hoped for. Distribution of (C) inorganic filler in the resin composition
The total amount is 10 to 50% by weight, preferably 20 to 40% by weight.
If less than 10% by weight, the effect of easy incineration cannot be obtained, and 50 weight
If the amount exceeds%, tensile strength, tear strength, dart impact strength, etc.
Since the mechanical strength of
Good. An inorganic filler is compounded in the resin composition of the present invention.
Is generally used as a conventional resin composition compounding method.
It is easily blended by a known method. One of the formulations
As the method, the above components (A), (B) and (C), and further,
Various additives, tumbler, ribbon blender as desired
Or using a mixer such as a Henschel type mixer
After dry blending for about 1 to 30 minutes, screw L / D
Single screw extruder with twin screw with a ratio of 20 or more, twin screw extrusion
Extrusion temperature of 150 to 250 ° C by continuous melt kneader such as
Melt, mix and extrude to prepare pellets
A fat composition can be obtained. As another compounding method, the following (D₁) ~
(D_Three)) And a total of component (C)
And the mixture is melt-kneaded.
Of resin composition (hereinafter referred to as “masterbatch”)
And then the masterbatch and (A) and / or
(B) and, if desired, further mixing various additives.
The resin composition can be obtained by the master batch method.
You. (D₁) Density 0.86-0.94 g / cm^ThreeEthylene-α-olef
In copolymer (D_Two) Ethylene (co) polymer by high pressure radical polymerization (D_Three) Ethylene / α-olefin copolymer rubber The mixing ratio of the master batch is determined by the component (D₁)-(D_Three)
10-50% by weight of at least one polymer and calcium carbonate
It is preferable that the content be 50% to 90% by weight of calcium. The above (D1) density is 0.86 to 0.94 g / cm^ThreeEtch
As the len-α-olefin copolymer, the component (A)
And the ethylene / α-olefin copolymer of (B)
High-medium-low pressure method using a Ziegler catalyst, etc.
And ethylene having 3 to 12 carbon atoms by another known method.
A copolymer with an olefin, having a density of 0.86-0.91
g / cm^ThreeUltra-low-density polyethylene (hereinafter "VLDP")
E "), with a density of 0.91 to 0.94 g / cm^ThreeLinear low-density
It may be ethylene (hereinafter referred to as “LLDPE”) or the like.
Specific α-olefins include propylene and 1-butene.
4-methyl-1-pentene, 1-hexene, 1-octene, 1
And dedecene. Of these,
Preferred is 1-butene, 4-methyl-1-pentene, 1-hex
1-octene, with 1-butene being especially preferred.
is there. Α-olefin content in the ethylene copolymer is 5
Preferably, it is 4040 mol%. The above VLDPE has a density of 0.86 to 0.91 g.
/cm^Three And according to differential scanning calorimetry (DSC).
The melting point is 100 ° C or higher, preferably 110 ° C or higher, more preferably
Or at least 116 ° C and boiling n-hexane insoluble matter 10 weight
%, Preferably at least 20% by weight
Low density polyethylene and ethylene / α-olefin copolymerization
Polyethylene showing intermediate properties with body rubber. Further
In detail, ethylene and α-olefin having 3 to 12 carbon atoms
Highly crystalline portion of LLDPE
And amorphous part of ethylene / α-olefin copolymer rubber
It is a resin that has both
Strength, heat resistance, etc.
Elasticity and low-temperature impact resistance
It is extremely useful when used in the present invention. VLDP
E is a solid containing at least magnesium and titanium
Catalyst combining organoaluminum compound with catalyst component
System using a vanadium catalyst
Ethylene-α-olefin with a melting point of less than 100 ° C.
It is distinctly different from copolymers. The above (D)_Two) Ethyl by high pressure radical polymerization
As a len (co) polymer, high pressure radical polymerization
Density 0.91-0.94 g / cm^ThreeEthylene homopolymer, ethylene
-Vinyl ester copolymer, and ethylene and α, β-
Copolymers with unsaturated carboxylic acid alkyl ester derivatives
Is mentioned. Density 0.91 by the high pressure radical polymerization method
~ 0.94 g / cm^ThreeEthylene homopolymer is a known high pressure method
Is a low-density polyethylene. The above ethylene-vinyl ester copolymer
Is based on ethylene produced by high-pressure radical polymerization
Vinyl propionate, vinyl acetate,
Nil, vinyl caprylate, vinyl laurate, stearyl
Vinyl esters such as vinyl acetate and vinyl trifluoroacetate
It is a copolymer with a ter monomer and another unsaturated monomer.
You. Of these, particularly preferred are ethyl
And vinyl acetate copolymer. Sand
C., 50 to 99.5% by weight of ethylene, 0.5 to 50% by weight of vinyl acetate
% By weight and other unsaturated monomers from 0 to 25% by weight
The body is preferred. The above ethylene and α, β-unsaturated carboxylic acid
Examples of copolymers with alkyl ester derivatives include ethylene
And α, β-unsaturated carboxylic acid alkyl esters and
Copolymers with other unsaturated monomers and their metals
Salts, amides, imides, etc.
Ethylene-acrylates produced by radical polymerization
Copolymers and the like. That is, Echire
50 to 99.5% by weight, acrylic acid ethyl ester 0.5 to 50
% By weight and 0 to 25% by weight of other unsaturated monomers.
Polymers are preferred. Alkyl group of the above alkyl ester
From 1 to 12, preferably from 1 to 8 carbon atoms
Good to choose. The other unsaturated monomers include propylene,
1-butene, 1-hexene, 4-methyl-1-pentene, 1-octane
C3-10 olefins such as ten, 1-decene, C
_Two~ C_ThreeAlkanecarboxylic acid vinyl esters, acrylic
Methyl acrylate or methacrylate, acrylic acid or meth
Ethyl acrylate, acrylic acid or methacrylic acid
Glycidyl acrylate or glycidyl methacrylate
Acrylic acid or methacrylic acid esters such as acrylates,
Acrylic acid, methacrylic acid, maleic acid, fumaric acid and
And ethylenically unsaturated carboxylic acids such as maleic anhydride
Is at least one member selected from the group of anhydrides, etc.
is there. The above (D)_Three) Ethylene / α-olefin copolymer
As a united rubber, ethylene and propylene are the main components
Random copolymer rubber (EPM), ethylene-1-
Butene copolymer rubber, and dienemono as the third component
Mer (dicyclopentadiene, ethylidene norbornene
Random copolymer rubber containing as a main component
(EPDM). In the present invention, components (A) to (C) are contained.
When the components are melt-mixed and molded,
Antistatic agent, antifogging agent, organic filler, oxidation as required
Inhibitors, lubricants, organic or inorganic pigments, UV protection
Addition of well-known agents such as agents, dispersants, nucleating agents, foaming agents, crosslinking agents, etc.
Agent to the extent that the properties of the present invention are not substantially impaired.
can do. [0036] The present invention will be described in more detail with reference to the following examples.
However, the present invention is not limited by these.
No. First, (C) used in Examples and Comparative Examples
Filling material, (D) resin for master batch, and (H) comparison
The resin components used in the examples are shown below. (C) Inorganic filler: Calcium carbonate [Average particle size = 1.7 μm; trade name: BSK-
5, Dowa Calfine Co., Ltd.] (D) Masterbatch resin: (D₁) Very low density polyethylene (VLDPE) [Density = 0.900 g / cm^Three , MFR = 1.0 g / 10min; product
Name: Nisseki Softlex D9010, Nippon Petrochemical
Co., Ltd.] (D_Two) Linear low density polyethylene (LLDPE) [Density = 0.922 g / cm^Three , MFR = 2.0 g / 10min; product
Name: Nisseki Linirex AF3310, Nippon Petrochemical Co., Ltd.
Made (D_Three) Ethylene-vinyl acetate copolymer (EVA) [VA content = 3% by weight, MFR = 0.3 g / 10min;
Name: Nisseki Lexlon V152, manufactured by Nippon Petrochemical Co., Ltd.] (D_Four) Ethylene-propylene copolymer rubber (EPM) [Propylene = 27 wt%, MFR = 0.7 g / 10min;
Name: EP07P, manufactured by Nippon Synthetic Rubber Co., Ltd.] (H) Comparative resin H_Four: Linear low density polyethylene (LLDPE) [Density = 0.922 g / cm^Three , MFR = 0.35 g / 10min; product
Name: Nisseki Linirex BF0310, Nippon Petrochemical
Co., Ltd.] H_Five: High density polyethylene (HDPE) [Density = 0.949 g / cm^Three , MFR = 0.05 g / 10min;
Name: Nisseki Staphlen E905F (A), Nippon Petrochemical
Co., Ltd.] H₆: Linear low density polyethylene (LLDPE) [Density = 0.921 g / cm^Three , MFR = 0.95 g / 10min; Product
Name: # 10, manufactured by Phil-lips] Next, the test method used in the present invention will be described. (1) Intrinsic viscosity The intrinsic viscosity [η] measured with a decalin solution at 135 ° C. is shown. (2) Density Measured by density gradient tube method (23 ℃) according to JIS K6760
Indicates the density. (3) Continuous heating elution fractionation method L. Wild et al. (J. Polymer Sci, P.P.E 20, 44 198
The method of 2) was followed. (Measurement method) 8.5 liter stainless steel filled with Celite 545
Adjust the sample concentration in the ram to 0.05% by weight,
Heat and dissolve at 5 ° C, and add 5 ml of orthodichlorobenzene solution.
After injecting, cool to 25 ° C at a cooling rate of 4 ° C / min.
Deposits on the celite surface. Next, add
Run sodichlorobenzene at a constant rate of 1 ml / min.
Temperature at a constant rate of 50 ° C / hr to elute the sample sequentially.
You. At this time, the sample eluted in the solvent
Asymmetric stretching vibration wave number 2925cm^-1Absorption for infrared
Elution temperature and elution volume by detecting and recording with detector
, That is, the relationship of the composition distribution. (4) Area ratio S by continuous heating elution fractionation method Relationship between elution temperature and elution volume by continuous heating elution fractionation method?
In the graph (FIG. 1) showing the composition distribution obtained from FIG.
The area where the discharge temperature is 90 ° C or higher is defined as Ia, and the elution temperature is 90 ° C or lower 25
The area ratio S is given by S = I
b / Ia. (5) Orthodichlorobenzene soluble matter W at 25 ° C 0.5 g of sample is placed in 135 ml of 20 ml of orthodichlorobenzene at 135 ° C.
After heating for 2 hours to completely dissolve the sample, 2 hours to 25 ° C
Cool with. The solution was left overnight at room temperature 25 ° C,
The filtrate is collected by filtration through a CFC filter, and then infrared spectroscopy is performed.
Wave number of asymmetric stretching vibration of methylene at 2950 cm by photometer^-1To
Was measured in advance and the results were
The sample concentration in the filtrate is quantified by a calibration curve. (6) n-value Use Shimadzu's high-grade flow tester to measure resin temperature.
Extruded from a 2 mm φ × 40 mm die at 170 ° C, low test pressure 2
0kg / cm^TwoAnd higher test pressure 150kg / cm^TwoApparent in
Determine the cutting speed and the following formulaNumber 2It is calculated from: (Equation 2) (7) Melt flow rate (MFR) Indicates MFR according to JIS K6760. (Measurement temperature 190
° C, load 2.16 kg) (8) Tensile breaking strength (UTS) According to the provisions of JIS K6760. (Pulling speed 50 mm / min, test piece
2 mm thick) (9) Izod impact value (IIS) Measured at 23 ° C and -40 ° C according to the following method in accordance with JIS K7110.
Set. A 4 mm thick sheet is formed from the sample by pressing.
To make. The shape of the test piece shall be No. 2 A. Sample adjustment 23
Perform for 88 hours at 50 ° C and 50% humidity, then measure. At -40 ° C
When measuring, adjust the temperature to -40 ° C in advance.
Hold in a closed air tank for about 3 hours and measure in a cold room.
Five test pieces were prepared, and the average value of five measurements was used.
You. (10) Dart impact strength According to the provisions of ASTM D1709. <Example 1> As described in JP-A-4-249562,
Extreme as component (A) by a compliant two-stage polymerization process
Viscosity (η₁) 4.3 dl / g, density (d₁) 0.916 g / cm^ThreeEtch
47 parts by weight of a len-1-butene copolymer and component (B)
Limit viscosity (η_Two) 0.83 dl / g, density (d_Two) 0.917 g / c
m^ThreeFrom 53 parts by weight of ethylene / α-olefin copolymer
Mixture (J₁) Was prepared. J₁The composition and physical properties of
1 is shown. Component (C) was added to 70% by weight of this mixture.
Carbon dioxide with an average particle size of 1.7 μm
30% by weight of calcium (surface treatment with saturated fatty acids)
After mixing with a tumbler mixer, screw diameter 65mm
Extrusion temperature 20 using a co-axial twin screw extruder with φ, L / D = 30
Melting and mixing at 0 ° C (cylinder temperature 200 ° C, die temperature 200 ° C)
The pellets were combined and pelletized through a pelletizer. this
Using the composition obtained in this way as a raw material, the screw diameter
Inflation with 50mmφ, L / D = 30 single screw extruder
Extrusion temperature of 200 ° C (cylinder)
(Temperature 200 ° C, die temperature 210 ° C) and blow-up ratio 2.5
A film having a thickness of 30 μm was produced under the molding conditions, and the obtained
The physical properties of the film were measured. Table 3 shows the results. <Examples 2 to 5> The resin composition was changed to
Added masterbatch resin when compounding lucium
Same as Example 1 except that the masterbatch method was adopted.
Method. Resin component (J_Two~ J_Five) Composition and physical properties
Are shown in Table 1 and their physical properties are shown in Table 3. <Comparative Example 8> W value of component (A) is W₁Than
Small resin component (J₆), Except that) was used.
The method was used. J₆The composition and physical properties of2N
The film properties4Shown in Comparative Example 1 The amount of calcium carbonate was 60
The procedure was performed in the same manner as in Example 1 except that the weight% was used.
Was. Table 4 shows the physical properties of the film. As you can see from the table,
Poor formability, tensile strength, tensile elongation, Izod impact
Value and dart impact strength are inferior. <Comparative Example 2> The value of W of the component (A) was W₁Than
Small and the intrinsic viscosity of the mixture of components (A) and (B)
1.45 dl / g resin component (H₁Example) except for using)
This was performed using the same method as in Example 1. H₁The composition and physical properties of
2 and Table 4 show the physical properties of the film. As shown in the table
In addition, moldability is slightly poor, tensile strength, tensile elongation,
And dart impact strength are inferior. Comparative Example 3 16% by weight of component (A) and component
(B) The intrinsic viscosity of the mixture consisting of 84% by weight is 1.33 dl / g,
0.951 g / cm^ThreeAnd a resin component having an n-value of 1.6 (H
_Two) Was performed using the same method as in Example 1 except that
Was. H_TwoTable 2 shows the composition and physical properties of
It is shown in FIG. Poor moldability, tensile strength, tensile elongation,
The impact strength and the dart impact strength are inferior. <Comparative Example 4> 85% by weight of the component (A) and the component
(B) The intrinsic viscosity of the mixture consisting of 15% by weight is 1.81 dl / g.
Resin component (H_Three), Except for using)
Method. H_ThreeTable 2 shows the composition and physical properties of
Table 4 shows the physical properties of the film. Tensile strength, tensile elongation, Izo
The impact strength and the dart impact strength are inferior. Comparative Example 5 A resin component having a density of 0.922 g /
cm^Three, MFR 0.35 g / 10min linear low density polyethylene
(H_Four) Except that the same method as in Example 1 was used.
went. Table 4 shows the physical properties of the film. Moldability is slightly poor
, Tensile strength, tensile elongation, Izod impact value, dirt impact
Poor impact strength is not preferred. Comparative Example 6 High-density polyether as a resin component
Tylene (H_Five) Was used, except that) was used.
It was performed using. Table 4 shows the physical properties of the film. Moldability is slightly
Poor, tensile strength, tensile elongation, Izod impact value,
And the impact strength is inferior. Comparative Example 7 The resin component had a density of 0.921 g /
cm^Three, MFR 0.95 g / 10min linear low density polyethylene
(H₆) Except that the same method as in Example 1 was used.
went. Table 4 shows the physical properties of the film. Moldability is slightly poor
, Tensile strength, tensile elongation, Izod impact value, dirt impact
Poor impact strength is not preferred. [0048] [Table 1][0049] [Table 2][0050] [Table 3][0051] [Table 4][0052] The polyethylene composition of the present invention is particularly useful
Wide particle size distribution, excellent fluidity and excellent mechanical properties at low temperatures
Specific ethylene / α-olefin copolymer and inorganic filler
And heat resistance, rigidity, dimensional stability,
Adds leap characteristics, mechanical properties, flame retardancy, etc.
Lum can be made translucent and generate heat when incinerated
The amount is low, indicating easy incineration. Has these advantages
As a result, the polyethylene composition is extruded and hollow
Suitable for all molding methods such as molding and injection molding
And various films, sheets, pipes, hollow containers,
Can be used as a wide range of molded products such as various coating materials and foam materials
It can be.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic diagram of an area ratio S in an elution temperature-elution amount curve obtained by a continuous heating elution fractionation method.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-58-8713 (JP, A) JP-A-58-8712 (JP, A) JP-A-57-21409 (JP, A) JP-A-4- 249562 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 23/00-23/36 C08K 3/00-13/08 C08F 4/64-4/69

Claims (1)

(57) [Claims 1] (A) Having high activity supported on a solid carrier
Polymerized with a Ziegler-type catalyst, the following conditions (a), (b),
ethylene and α having 3 to 18 carbon atoms satisfying (e) and (f)
20 to 80 parts by weight of a copolymer with olefin, (a) intrinsic viscosity (η ₁ ) 2.0 to 9.0 dl / g (b) density (d ₁ ) 0.88 to 0.94 g / cm ³ (e) continuous heating and elution In the elution temperature-elution amount curve by the fractionation method, the ratio S (Ib / I) of the area Ib under the elution temperature of 25 to 90 ° C. to the area Ia under the elution temperature of 90 ° C. or more.
a) is less than or equal to S ₁ calculated from the following equation: S ₁ = 20η ₁ ⁻¹ exp [−50 (d ₁ −0.90)] (f) Soluble content of orthodichlorobenzene at 25 ° C., W weight% is calculated from the following equation W ₁ or more W ₁ = 20 exp (−η ₁ ), and (B) an ethylene homopolymer or ethylene and an α-olefin having 3 to 18 carbon atoms satisfying the following conditions (c) and (d): A mixture comprising 80 to 20 parts by weight of a copolymer, (c) intrinsic viscosity (η ₂ ) of 0.2 to less than 2.0 dl / g, (d) density (d ₂ ) of 0.88 to 0.97 g / cm ³ , (Η) is 2.0 ~
Ultra high molecular weight polyethylene having 5.2 dl / g, density (d) of 0.88 to 0.94 g / cm ^3, and an n-value of 1.7 to 3.5 calculated from the following equation 1, and (C) inorganic filler 10 to 50 A polyethylene composition comprising% by weight. (Equation 1)