JPS5950172B2 - improved composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a polyolefin composite composition having a number of characteristics such as excellent heat sealing properties, impact strength properties, tensile strength properties, flexibility, transparency, heat resistance, and cold resistance. There is something to do.

Specifically, monomers copolymerizable with ethylene: vinyl esters, aliphatic unsaturated monocarboxylic acids, alkyl esters of the monocarboxylic acids: copolymers with ethylene or low density polyethylene selected from the group consisting of: Consisting of at least one polymer, preferably ethylene monovinyl acetate copolymer (4), a specific ethylene/α-olefin copolymer elastomer (B), crystalline polypropylene, high density polyethylene, crystalline Polybutene-1 or a mixed polymer thereof (crosslinked boiling xylene-insoluble gel consisting of a mixed composition with O; 0.1 to 60% by weight, melt index: 5 or less, composition for film molding) Although these are not particularly limited, they are useful as compositions constituting at least one layer of a single layer and a composite layer for film molding.

Conventionally, ethylene-propylene copolymer rubber (hereinafter abbreviated as EPR) has been used to improve various properties of crystalline polypropylene (hereinafter abbreviated as PP), particularly thermal stability, strength at low temperatures, impact resistance, etc. Japanese Patent Publication No. 35-7083, Japanese Patent Publication No. 36-15042, Japanese Patent Application Laid-open No. 78977-1987, etc. have proposed a method of mixing one part of

However, with these methods, the compatibility of PP and EPR is not necessarily good, and when processed into a thin film, it is uneven and fluffy, the surface is rough, the optical properties are greatly deteriorated, and the strength is insufficient. It was hot. In order to improve these even a little, there is a method of further mixing amorphous attack polypropylene: JP-A-49-112946
No. 48-96638, etc. have been proposed. All of these have been improved based on PP as a main ingredient, and they still have problems when made into thin films. The purpose and characteristics of the present invention are to provide a relatively soft composition with improved heat sealing properties, various strength properties, flexibility, transparency, heat resistance, cold resistance, stiffness (modulus of elasticity) of molded products, etc. Preferably, a composition for film is provided.

More specifically, (4) is a monomer copolymerizable with ethylene; a vinyl ester, an aliphatic unsaturated monocarboxylic acid, an alkyl ester of the carboxylic acid; a copolymer with ethylene selected from the group consisting of; Or, the polymer (B) containing at least one selected from low-density polyethylene is a random copolymer consisting of an ethylene-α-olefin copolymer and has a density of 0.919/d.
Hereinafter, the thermoplastic elastomer (C) having a melt index of 0.1 to 10 is at least one selected from crystalline polypropylene, high density polyethylene, and crystalline polybutene-1.
Ratio of each component in seed polymer: 0.90≧B/(A+
B) ≧0.05 and 2.0≧C/(A+B)≧0.0
Cross-linked boiling xylene-insoluble gel consisting of a mixed component mainly consisting of 0.5 and 03) and (C): 0.1~
An improved composition having a melt index of 5.0 or less at 60% by weight Herein, for each component, the polymer used in the present invention is a relatively low crystallinity polymer that is intermediate between hard and soft, A polymer containing at least one monomer copolymerizable with ethylene, a copolymer with ethylene selected from the group consisting of vinyl esters, aliphatic unsaturated monocarboxylic acids, and alkyl esters of the monocarboxylic acids, or low density polyethylene. These include ethylene-vinyl acetate common polymer, ethylene-ethyl acrylate copolymer (
(herein abbreviated as EEA), ethylene-methacrylic acid methyl ester copolymer (herein abbreviated as EMMA)
, ethylene-acrylic acid copolymer (herein abbreviated as EAA), ethylene-methacrylic acid copolymer, etc.
The amount of monomers other than ethylene in these copolymers is 3 to 3
0 weight (Wt)%, preferably 5 to 25 wt%, more preferably 7 to 25 wt%.

If this amount is less than 3 wt%, sealing properties, flexibility, transparency, strength characteristics, etc. will be deteriorated. Moreover, if it exceeds 30 wtq6, extrusion processability and mixability with other components will be poor, and when processed into a film, the surfaces will tend to stick together, causing problems in handling. Further, the melt index is 0.2 to 10, preferably 0.3 to 5. 0.2
If it is less than 10, there will be problems in the mixability and extrudability of the raw materials, and if it is more than 10, the strength as a base material will be insufficient and it will be easy to tear during stretching, which is not preferable.

This tendency remains the same even when the degree of crosslinking treatment described below is increased. Among the above, the most preferred is ethylene-vinyl acetate copolymer (hereinafter abbreviated as EVA). Next, a thermoplastic elastomer made of ethylene and an α-olefin copolymer is a soft copolymer of ethylene and one or more α-olefins selected from α-olefins having 3 to 12 carbon atoms. In some cases, even smaller amounts of hydrocarbons having a polyene structure, such as synchropentadiene, 1,4-hexadiene, ethylidene, etc.
Norbornene or the like may be further copolymerized.

Examples of α-olefin include propylene, butene-1, hexene-1, heptene-1,4-methyl-1-benzene, and octene-1, with propylene and butene-1 being preferred. The ethylene content of the copolymer is 20 to 93 mol%, preferably 40 to 90 mol%, more preferably 6
It ranges from 5 to 83 mol%. The properties of these copolymers include a density of 0.91 g/l or less, and preferably a Vicat softening point [ASTM Dl525 (value at 1 kg load)] of 80°C.
Below, the temperature is more preferably 70°C or less, and generally includes rubber-like and substantially amorphous materials to low-degree partially crystalline materials with a degree of crystallinity (X-ray method) of approximately 30% or less. shall be held. Preferred is a copolymer of ethylene and propylene or butene-1, or a copolymer containing a small amount of a compound having a diene structure, such as a random copolymer polymerized with a vanadium compound and an organic aluminum compound catalyst. Copolymer with melt index of 0.1
-10, preferably 0.2-6, these thermoplastic elastomers are supplied in the form of pellets, which are not block-like like general non-vulcanized rubber and do not cause cold flow. Preferably, the material has sufficient thermoplasticity to allow extrusion processing. Next, polymer IC) is composed of relatively hard and relatively high crystallinity components, such as crystalline polypropylene, high density polyethylene, and high molecular weight crystalline polybutene-1 (hereinafter, respectively, I
(abbreviated as PP, HDPE, PB-1).

These preferably consist of relatively hard polymers with a Vicat softening point of 100°C or higher. Crystalline polypropylene, which is one of the polymers (O), refers to the crystalline polypropylene with high isotaxity that is usually commercially available, and is a homopolymer of propylene, or propylene and 7 mol% or less of ethylene, Those containing copolymers with butene etc. or other α-olefins are preferred. Alternatively, they may be mixed arbitrarily. Also, high-density polyethylene with a density of 0.935 (fl/C- Fit) above, it is low pressure polyethylene with a melt index of 0.
．． 1 to 10) It is preferably about 0.2 to about 7, preferably includes a copolymer, and the content of ethylene is 93 mol % or more, preferably about 95 mol %.

If the melt index is less than 0.1, there will be problems with mixing properties and optical properties during processing, and if it is more than 10, the strength of the base material will be impaired, which means that the processability during film formation will deteriorate. Undesirable. In addition, polybutene-1 is crystalline with a butene-1 content of 93 mol% or more and has a high molecular weight that also includes copolymers with other monomers. For the same reason, those with a melt index of 0.2 to 10 are preferred. Among the above, it is preferable to mainly use crystalline polypropylene. Moreover, it is more preferable to arrange the above-mentioned polybutene-1 on crystalline polypropylene, and a mixture of polypropylene and high-density polyethylene or a mixture of the three may also be used. Other hard polymers that have appropriate compatibility and dispersibility and meet the purpose of the present invention may also be used. The composition of the present invention is composed of a mixed composition of each of the above components (5), (B), and (C), and the range of these amounts is preferably 0.90≧B/(A+B)≧0 in terms of weight ratio. .05 and 2.0≧
C/(A+B)≧0.05, more preferably 0
．． 70≧B/(A+B)≧0.07 and 1.0≧C/
(A+B)≧0.10, more preferably 0.5
0≧B/(A+B)≧0.10 and 1.0≧C/(A
+B)≧0.10, more preferably 0.30
≧B/(A+B)≧0.10 and 0.7≧C/(A+
B) ≧0.10.

If the amount of soft component (B) mixed is small, the mixture will not exhibit a synergistic effect, and the moldability, optical properties, and mechanical strength will decrease. The above range is preferable since it tends to cause the product to block and the sealing properties to deteriorate.

Hard component (0 improves the tensile/impact strength, heat resistance, extrusion moldability, elastic modulus, and heat sealing range of the mixed composition synergistically with other components, especially heat resistance, extrusion moldability, elastic modulus, and heat sealing range) The effect is large when the mixing amount is small, for example, the unevenness of thickness due to efflation processability and flow characteristics in the die becomes large, and the effect of improving the heat sealing range and strength is reduced. The expected value of heat resistance also decreases.

If the amount is too large, extrusion moldability, transparency, flexibility, impact strength, etc. will deteriorate, so it is preferably within the above range. The melt index of these mixtures is usually 0.2 to 10. Here, component (4) is preferably composed of a specific ethylene copolymer described in the description, and is the main component in the mixture of the three described components (A), (auto), and 0.

Mixing only component (4) and component (C) of the three components is usually
Mixability and compatibility are poor, and it is difficult to expect the above-mentioned synergistic effect, but when the component(s) is added, these drawbacks are significantly improved.

These reasons are due to the characteristics of ethylene contained in component (4), the structure related to polar functional groups, delicate interactions with other components, and complex interactions such as the crystal structure of the mixture and the dispersion state of the mixture. This seems to be due to the effect.

For example, when component (4) is the main component, when the above components are dry blended in the form of pellets and melt-kneaded and extruded using an extruder with excellent kneading ability to form a molded product, component (4)
Component B is inside or near component 0, which is dispersed in
It is possible to imagine a situation where the objects are distributed and interact in a complicated manner. Depending on the molding conditions, for example, when they are processed into films or other molded products and given fluidity and orientation, their shapes become different. For example, at a relatively high temperature of 230-260°C, the above mixture is passed through a small slit, for example 1.5 mw! When extruded from a die for films, sheets, etc. having a
In the case of mixing I-Pp, component (C) I-
PP is the main component (4) in which its dispersed particles are oriented in the flow direction in the form of fibers, creating a structure similar to that reinforced with glass fibers, and exhibiting greatly improved properties such as strength. It seems that there are cases. The mixed composition of the present invention, in addition to these, an electron beam (β ray) as a high energy beam,
Boiling xylene insoluble gel modified by γ-ray or U-ray treatment or peroxides to a degree of 0.1 to 6
At 0% by weight, the melt index is 5 or less, more preferably from 0.5 to 50% by weight, the melt index is 1.
．． 0 or less, more preferably 1 to 40% by weight of the gel, and a melt index of 0.5 or less, and still more preferably 1 to 30% by weight of the gel, and a melt index of 0.2 or less.

If the amount of insoluble gel is more than the above amount, the molded product will elongate, lose strength, and deteriorate, and especially when it is made into a film, the heat sealing properties will deteriorate, such as not being able to be sealed, not being able to be cut by hot wire, and becoming easy to tear. Start having problems.

Furthermore, if the melt index is larger than the above range, it is difficult to expect synergistic effects from crosslinking treatment, that is, effects on processability, heat resistance when made into a film, various strengths, heat sealability, etc., so the above range is preferable. In order to produce the composition of the present invention, the above-mentioned components are thoroughly kneaded using a kneader or an extruder, and then formed into a sheet or film shape using a high-energy beam such as an electron beam.
It is obtained by irradiating 20 Mrad, preferably 0.5 to 15 Mrad.

Alternatively, extrusion molding may be carried out after kneading and irradiating the pelletized pellets, and there is no particular limitation. Alternatively, peroxides may be mixed and kneaded to generate radicals to cause a reaction, and then molded. can get. An example of a particularly preferable range: IA) + Q3) + (C). Usually, crystalline polypropylene [polymer component (O
] is hardly crosslinked even when treated with high-energy radiation, and its mixing and compatibility with the base material ethylene-vinyl acetate copolymer (hereinafter abbreviated as EVA) (A) is not very good. However, EVA is more susceptible to crosslinking reactions than ordinary high-pressure polyethylene due to high-energy radiation, etc., and on the other hand, α-olefin copolymer elastomer 03
) is a component that has relatively good mixing compatibility with both EVA (A) and is as easily crosslinked as EVA. In addition to this effect, a synergistic effect from high-energy rays appears to form a sterically non-uniform cross-linked matrix in terms of specific molecules, resulting in radical-induced graft reactions, cross-linking reactions, and collapse from a microscopic perspective. There may be cases where a reaction or the like is occurring.

In addition to the above components, reactive components may be added to utilize the original characteristics. When treated as above, compared to the case without the same treatment, it has more stable secondary processability, heat resistance, heat sealing range when made into a film, heat sealing strength, tensile/impact strength, optical properties (transparency) is demonstrated. The composition of the present invention can be freely used as a molded product, a film, or for other adhesive purposes, and is not particularly limited, but it is preferable to use it as a film. , an inflation method using a water cooling method, a method of forming a film using a T-die casting method, or a method of biaxially stretching these materials. In addition, when molded as a multilayer composite as at least one of its constituent layers,
It is preferred as a film with processing stability, strength, sealing properties, and optical properties, and as an adhesive for inner and outer layers. Furthermore, it has very good processability and is convenient for processing into molded objects, such as films, which have been given a high degree of cold orientation. or,
As a preferred example, a small amount of 0.3 to 5% by weight, preferably 0.5 to 3% by weight of a nonionic surfactant, which is a normal liquid and has a boiling point of 200°C or higher, is mixed into the composition of the present invention as an additive. In this case, more desirable properties can be imparted synergistically. These nonionic surfactants include polyhydric alcohols such as glycerin, sorbitol, pentaerythritol, and polyglycerin, linear saturated fatty acids with an alkyl group of 5 to 13 carbon atoms, or alkyl groups with 17 to 2 carbon atoms.
1, such as esters with linear unsaturated fatty acids, such as diglycerin monooleate, and polyoxyethylene alkyl phenyl ethers, such as polyoxyethylene nonyl phenyl ether or polyoxyethylene octyl phenyl ether. Yes, and ethylene oxide 3 to 10 as polyoxyethylene fatty acid esters
Esters with the above-mentioned fatty acids to which polyoxyethylene units have been added are preferred, and these may be used alone or in combination.

These exhibit anti-blocking, anti-static and anti-fogging effects when made into films, and are suitable as packaging films.

In addition, these additives are easily dissolved in any of the components in the mixed resin component, and have the effect of gradually penetrating and bleeding out from the inner layer to the surface layer. The low-molecular components that tend to be present are immediately removed, and the surface does not become sticky or other negative effects, and even if the surface is washed away, it remains effective for a long time. It also has favorable properties such as a plasticizing effect. In addition, other additives (1 to 5% by weight, preferably 1 to 5% by weight, preferably 1 to 5% by weight of mineral oils that are liquid at room temperature, such as paraffinic, isoparaffinic, and naphthenic oils) may be added to the mixed composition of the present invention.
When ~3% by weight is included, a mixture matrix is formed that is enriched with lipophilic components (e.g. can be plasticized.

In addition, when appropriate amounts of the above additives (self) and (D) are mixed and used, the characteristics become even more distinctive. It can be made to appear by containing each additive due to the difference in affinity in the mixed matrix composition.

In particular, with highly crystalline HDPE, PP, etc., even a small amount of additives will mostly come out on the surface and cannot be mixed uniformly, but the composition of the present invention is different in this respect.

In addition, films made with these compositions or additives added thereto can have an appropriate film stiffness and have a plasticized effect. If you roll it up with your hands, it will be compressed into a small size, and even if you loosen your hands, it will remain the same shape.On the other hand, a film made of EVA alone cannot be rolled up into a small size, and when you loosen it, it will instantly return to its original shape. It can be made into a film with properties similar to that of plasticized PVC, and can be used for, but not limited to, shrink wrapping films, stretch wrapping films, other packaging films, agricultural films,
As a multilayer film, a barrier film by adding a via layer or a shrink packaging film thereof, or a multilayer film with other types of resins can be used.

Furthermore, the mixture of the present invention may be mixed with other plastic materials. A specific example will be described below using a film as an example, but the present invention is not limited thereto.

Example 1 EVA (vinyl acetate group content: 10% by weight, melt index: 1.0): (a1): 65 parts by weight and ethylene-α-olefin copolymer elastomer (α-olefin is 15 mol% of propylene, ethylidene・Random copolymerization of 2% by weight of norbornene, melt index 0.45,
Vigatuto softening point 40℃ or less, density: 0.889/Cfl
): (b1): 15 parts by weight, crystalline polypropylene (melt index: 11.0, density: 0.889/d1
Copolymerized with 4% ethylene, Vigatto softening point: 143°C
): (c1): Mix 20 parts by weight and make L/L with a diameter of 6511.
Using a D=37 mixing head type screw, the composition was plasticized and kneaded at a maximum cylinder temperature of 240°C.
The film was extruded through an annular tie having a diameter of 0.0011 mm and a slit of 1.0 m1, and was inflated by introducing air into the inside, followed by rapid cooling to obtain a uniform film with a diameter of 350 m1 and a thickness of 50 μm.

This film was continuously irradiated with an electron beam of 5 Mrad (megarad) with an energy of 500 KV at room temperature using an electron beam accelerator (Juan de Graff type), and was treated with a boiling xylene insoluble gel of 2% by weight and MI: 0.09. It was wound up to form a roll of film. (Run Waterfall 1) The Vicat softening point of this mixed composition was 72°C. The film formation processability was good and the film could be formed stably. Also, the thickness deviation in the width direction is ±2.
4 (F6) and the fold width variation was uniform (R=3m7!L).The characteristics of this film were as follows.H
aze-1.1%, tensile strength (vertical/horizontal) = 4.5/
3.7 (Kg/Md), elastic modulus: 18/12 (Kg/d
), Falling impact strength (abbreviated as Dart strength): 39kg
・The heat sealing range was wide at 90 to 280°C, and the strength was 3.71<9/15 mm width, and the heat resistance during sealing was good and there were no holes.

Haze here: ASTM DlOO3-52, tensile strength is ASTM D882-67, Dart strength is ASTM D
17O9-67, and the elastic modulus is a value obtained by converting the stress at 2% elongation to 100%.

Heat seal is part type sealer (seal width: 5m7
1! ) shows the range in which a seal can be preferably achieved by changing the temperature of This value indicates heat resistance that cannot be achieved. The pressure when sealing is 1kg/CTi.
The time was adjusted accordingly. Haze if no processing:
1.701), tensile strength (vertical/horizontal): 3.7/2.
8 (K9/Md), Dart strength: 291 < 9, sealing range is 110 to 260 degrees, sealing strength is 2
．． The weight was 91<g/15. Example 2 A film was prepared in the same manner as in Example 1 with the composition and conditions shown in Table 1, and the properties of the obtained film are shown in Table 2.
The block-shaped (B3) was cut with a cutter and kneaded with other ingredients in a kneader to form pellets and used as pellets.

In both cases, the processing stability of the film formation is good, there is little uneven thickness of the film (due to the structure of the die, etc.), the strength is greatly improved, and each has excellent sealing properties. There was no occurrence of seal failure. Also, in cold resistance (-30°C), the film did not become hard or easily tear. Run. /462 composition and die slit 2.0m7! A 100 micron film with a diameter of 100 microliters was formed at an extrusion temperature of 260°C with a large draw ratio, and the tensile modulus (vertical/horizontal) of this film was obtained by performing the treatment of 7 Mrad. When measured, it is 42/
21 (Kg/1). When this film was observed using a phase contrast microscope, it was observed that the polypropylene components were finely grained and oriented in the flow direction (vertical). RunA62-1) had a strong Dart impact strength of 45 kg・3.
7 kg・I, and in the case of EVA alone and untreated, the elastic modulus was 5/5 (K9/1). Matamoto Ru
The film of No. 2-1 had stiffness in the vertical direction and was soft in the horizontal direction. Example 3 The composition of Rnn 1 was used as the inner layer and outer layer, and the middle layer was made of polyvinylidene chloride (a copolymer modified with vinyl chloride), extruded through a three-layer die, subjected to inflation, and rapidly cooled.Outer layer: 20μ, middle layer. Layer: 10μ,
Inner layer: A film of 30μ was obtained.

This film was treated with the electron beam at 5 Mrad. This film has excellent heat sealability (90~
C) of 280 and heat seal strength of 3.7kg/15
mm width and strong enough, tensile strength: 4.7/4.1 (Kg/
Md), elastic modulus: 23/18 (Kg/Md), has a waist, is flexible, and has a Dar. t Impact strength: 45k9
・I found that the film had a haze of 2.7% and was excellent in cold resistance. Also, the oxygen permeability is 20 (CC/24hr-
Atm-i) (Run./F6l6). Example 4 The composition of Run/F6l was melt-plasticized using the same extruder as in Example 1, and then a liquid additive (D1
) as 1.5% by weight of diglycerin monooleate (
Run/F6l7), or liquid additive (E,) on top of it
Add 1.5% by weight of mineral oil (specific gravity: 0.885 Saybolt viscosity: 350 cps) and hydrogenated rosin.
Dissolve the glycerin ester and adjust the final amount to 0.7% by weight (Run Waterfall 18), press-fit both mixed solutions, and extrude the kneaded composition in the same way. Butcher 1.7%) quenched raw fabric was obtained.

This raw fabric tube was exposed to 6 Mrad using the electron beam irradiation equipment.
Treated gel: 3.0, 2.0%, MI: 0.10, . 0
．． 13, reheated at 150° C. between two pairs of nip rolls, and biaxially stretched 3.5 times vertically and 4.7 times horizontally to obtain a uniform film of 12 μm. This film is Run
Waterfalls 17 and 18 Tensile strength (vertical/horizontal): 7.5
Elongation at 7/7.1, 6.9/6.1 (K9/111):
460/420, 480/450 (%), Dart impact strength: 37, 35 (Kg・(177!) and strong 200%
The stress during elongation is 26012409 in the horizontal direction, the elastic modulus is 14/12, 12/9 (Kg/Md), and Haze
:1.1, 0.9%, it has sufficient elongation, flexibility, strength, and adhesiveness as a stretch packaging film, has excellent fitting properties for irregularly shaped objects, and has moderate film stiffness during packaging, and is heat resistant. As a comparative example, the film was found to have particularly excellent sealing properties with plates and heat resistance.As a result of conducting the same test using EVA alone, the tensile strength was 3.2/3.1 (1
<9/Md), Dart strength: 16 (1<g・CTn)
It is easy to tear when packaged, has no stiffness, and has an elastic modulus of 3/2.
kg/Md, so it could not be used at 12μ, and the additives added quickly bled excessively onto the surface, resulting in a sticky mess.When sealing the folded part with a hot plate during sealing, holes appeared. I was easily irritated. Moreover, when the same process was made using untreated EVA alone, each of the properties was at an even lower level and did not cause any problems. In particular, the tearing during packaging and the tearing during sealing are of a low level. In addition, when the same composition was used without irradiation and without treatment, tensile strength: 4.6/4.3, 3.8/3.7
(1<g/Md), Dart strength: 30, 29 (K9・
CT! L), and the processed film was superior in practical tests and overall. This means that commercially available plasticized P
It was comparable to VC stretch film (18-20μ) and had superior properties and cost advantages. These films are flexible and pliable, and can be wrapped under excellent stretch packaging conditions.In particular, even when multiple layers of the same film are stacked, they are tightly fixed, and films that are untreated with only EVA will quickly return to their original state due to their rubber elasticity. The film showed the same dynamic behavior as plasticized PVC.
Example 5 0.5% by weight of peroxide (benzoyl peroxide) was mixed with the composition of Run7f61, and the mixture was heated at 180°C to 1% by weight.
Kneaded in a kneader for 0 minutes, gel: 28% by weight, melt index: 0.05 or less, compressed into a sheet, stretched at 150°C (vertical x horizontal =
4×4 times) to form a 30μ film.

This film has tensile strength: 7.8/7.7 (Kg/Md
), Dart strength: 37kg・Tensile modulus: 17/
17 (K9/M7l), heat seal range: 100-2
The seal strength was 2.0 (Kg/15 mm width) at 60°C. Comparative Example 1 A film having the composition shown in Table 3 below was obtained in the same manner as in Example 1.

The results are shown in Table 4. The processing stability was not very good for the ratio Runs 7f6l to 10, and the thickness deviation of the film was also not very good.In particular, both the ratio Runs 7f65 and 6 were not good. %F Hibiki? ? Ll ratios of 3 and 8 were non-uniform when viewed through the film due to poor kneading.

Hitaki 6 and 10 appeared optically white and cloudy. Dart strength is often low because it is difficult to knead, and ratios of 5, 6, 8
, No. 9, and No. 10 were all hard-feeling films, and all had poor optical properties.

Claims (1)

[Scope of Claims] 1 (A) is a monomer copolymerizable with ethylene; a copolymer with ethylene selected from the group consisting of a vinyl ester, an aliphatic unsaturated monocarboxylic acid, and an alkyl ester of the carboxylic acid; or low-density polyethylene, the polymer (B) is a random copolymer consisting of an ethylene-α olefin copolymer and has a density of 0.91 g.
/cm^3 or less, the thermoplastic elastomer (C) with a melt index of 0.1 to 10 is at least one polymer selected from crystalline polypropylene, high density polyethylene, and crystalline polybutene-1, and the proportion of each component is :0.90≧
B/(A+B)≧0.05 and 2.0≧C/(A+B
)≧0.05, boiling xylene-insoluble gel that is cross-linked and consists of a mixed component mainly consisting of (A), (B), and (C): 0.1 to 60% by weight, melt index: 5.0
An improved composition that is: 2 Composition (A) is ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer, ethylene-acrylic acid copolymer, ethylene-methyl methacrylic acid ester copolymer, ethylene-methacrylic acid copolymer The composition according to claim 1, comprising one or more polymers selected from the group consisting of: 3. The composition according to claim 1, wherein composition (A) is an ethylene-vinyl acetate copolymer. 4 Ethylene-vinyl acetate copolymer has 3 to 3 vinyl acetate groups
A composition according to claim 3 containing 30% by weight. 5 Component (B) is ethylene 95 mol% or less, 20 mol%
The composition according to claim 1, which is a copolymer of the above. 6 Component (B) is ethylene 93 mol% or less, 40 mol%
The composition according to claim 1 or 5, which is a copolymer as described above. 7 Component (B) is a soft copolymer consisting of one or more α-olefins selected from α-olefins having 3 to 12 carbon atoms, with a Vicat softening point of 80°C or less and a crystallinity of 3
The composition according to claim 1, wherein the composition has a content of 0% or less. 8. The composition according to claim 1 or 7, wherein the α-olefin is a random copolymer selected from propylene or butene-1. 9. The composition according to claim 1 or 7, wherein the ethylene/α-olefin copolymer of component (B) is a copolymer of polyenes in addition to ethylene and α-olefin. 10 Polyene is a non-conjugated diene selected from the group consisting of pentadiene, hexadiene, and norbornene derivatives 5
10. The composition according to claim 9, wherein the composition contains mol % or less. 11 Component (C) has a Vicat softening point of 100
The composition according to claim 1, which is a hard copolymer having a temperature of at least .degree. 12. The composition according to claim 1 or 11, wherein component (C) is composed of crystalline polypropylene or a copolymer thereof containing 10 mol% or less of ethylene. 13 The weight ratio of the mixed composition components is 0.90≧B/(A+B
)≧0.05 and 2.0≧C/(A+B)≧0.0
5. The composition according to claim 1, which is 14 The mixed composition components are 0.70≧B/(A+B)≧0.
07 and 1.0≧C/(A+B)≧0.10. 15 The mixed composition components are 0.50≧B/(A+B)≧0.
10 and 1.0≧C/(A+B)≧0.10. 16 Melt index of mixed composition components is 0.2 to 1
0. The composition according to claim 1, wherein