JPH0649814B2 - Modified olefin polymer composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a modified olefin polymer composition having excellent adhesion between poly-1-butene and a polar material.

[Conventional technology]

Poly 1-butene is flexible and has excellent impact resistance, heat-resistant creep properties, stress crack resistance and wear resistance, and is used for general packaging films, water supply / hot water supply pipes, pipes for slurry transportation, etc. ing.

However, poly 1-butene, like other polyolefins such as polyethylene and polypropylene, remains
Since it does not adhere to polar materials such as metal, concrete, or saponified products of nylon, ethylene / vinyl acetate copolymer, some modification is required to improve the adhesiveness. As a method for improving the adhesion between the polyolefin and such a polar material, a method using a modified polyolefin in which a part or all of the polyolefin is modified with an unsaturated carboxylic acid or a derivative thereof (for example, JP-B-49-4822).
JP-B, JP-B-55-49989, JP-B-53-36872, etc.) have been proposed and are widely used for laminating polyolefins and polar materials. And this method is poly 1
It has been found that the use of modified poly-1-butene modified with unsaturated carboxylic acid anhydrides as an adhesive for poly-1-butene, also improves the adhesion between poly-1-butene and polar materials. . However, as described above, poly-1-butene is superior in durability to other polyolefins such as polyethylene and polypropylene. Therefore, when it is used for those purposes, the adhesive strength of the modified poly-1-butene is slightly insufficient. It was found that further improvement was necessary. On the other hand, it was also found that the modified polyethylene and modified polypropylene described in the above publications have excellent adhesiveness with polar materials but poor adhesiveness with poly 1-butene.

On the other hand, a method of using a composition of modified polyethylene and a butene-1 polymer (JP-A-59-196242) has been proposed as a method for improving the adhesion to a metal. The adhesiveness with the 1-butene layer is not improved,
In any case, it was insufficient as an adhesive between poly-1-butene and a polar material.

[Problems to be solved by the invention]

In view of such a situation, the present inventors have conducted various studies to develop a composition having excellent adhesion between poly-1-butene and a polar material, and as a result, 1-butene polymer, propylene polymer and specific propylene / α It has been found that a composition comprising an olefin random copolymer and at least a part of which is graft-modified with an unsaturated carboxylic acid or a derivative thereof has excellent adhesiveness to both poly-1-butene and polar materials. Has reached the present invention.

[Means for solving problems]

That is, the present invention relates to (a) 1-butene polymer (A) 14 to 80% by weight, (b) propylene homopolymer (B-1), propylene and 50 mol% or less of other α-olefin. 80 to 10% by weight of a block copolymer (B-2) or a propylene polymer (B) selected from a crystalline random copolymer (B-3) of propylene and 10 mol% or less of an α-olefin, And (c) a propylene content of 50 to 87 mol% and a heat of crystal fusion of 10 to 8 based on a thermal analysis of a differential scanning calorimeter (DSC).
0 Joule / g of propylene / α-olefin random copolymer (C) 76 to 6% by weight, and at least a part of which is graft-modified with unsaturated carboxylic acid or its derivative (D) The present invention provides a modified olefin polymer composition which is excellent in adhesiveness with both poly-1-butene and polar materials.

[Action]

The 1-butene polymer (A) used in the present invention is a homopolymer of 1-butene or 1-butene and other α of 40 mol% or less.
-Olefins such as ethylene, propylene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-
Ordinary carbon number of 2 to 20 such as decene and 1-tetradecene
Which is a copolymer of one or more kinds of α-olefin and is crystalline. The molecular weight of the 1-butene polymer (A) used in the present invention is such that the intrinsic viscosity [η] at 135 ° C. of a decalin solvent is usually 0.7 to 10 dl / g, preferably 1 to 5 dl / g. If [η] is outside the above range, the moldability tends to be poor in any case, and if [η] is less than 0.7 dl / g, the adhesive strength may be low.

The propylene polymer (B) used in the present invention is a propylene homopolymer (B-1), propylene and other α of 50 mol% or less.
-Olefins such as ethylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-
Ordinary carbon number of 2 to 20 such as decene and 1-tetradecene
Selected from block copolymers (B-2) with one or more α-olefins, or crystalline random copolymers (B-3) with propylene and 10 mol% or less α-olefins. It is a propylene polymer (B). The propylene polymer (B) used in the present invention usually has a melt flow rate (MF
R: ASTM D 1238, L) is in the range of 0.1 to 200 g / 10 min, preferably 0.3 to 100 g / 10 min. If the MFR is out of the above range, the moldability tends to be poor in any case. The propylene / α-olefin block copolymer is an individual polymer obtained by sequentially polymerizing olefins in the presence of a stereoregular catalyst in one polymerization reaction system while changing the monomer composition. It also includes a so-called non-polymer blend type copolymer which is not necessarily subjected to block copolymerization.

Among the propylene polymers, a block copolymer and a random copolymer are preferable because they have a larger adhesive strength with a polar material and an interlayer adhesiveness with a poly-1-butene layer than a homopolymer of propylene, and in particular, a packaging film. Random copolymers are suitable when optical properties such as transparency are required as in the field, and fields in which adhesion strength and impact strength are particularly required for lamination with metal such as inner or outer surface coating on steel pipe. A block copolymer is suitable for this.

Propylene / α-olefin copolymer used in the present invention
(C) has a propylene content of 50 to 87 mol%, preferably 60 to 80 mol%, and a calorific value of crystal fusion based on the thermal analysis of a differential scanning calorimeter (DSC) of 10 to 80 Joule / g, preferably 20 to 80 mol%. 70 Joule / g, preferably 0.5 melt flow rate (MFR: ASTM D 1238, L)
To 200g / 10min, more preferably 2 to 50g / 10mi
n, preferably having a melting point of 90 to 130 ° C., more preferably 10
It is in the range of 5 to 125 ° C.

Propylene content is 87 mol% or heat of crystal fusion is 80
All that exceed Joule / g are 1-butene polymers
Since the compatibility with (A) decreases, the adhesive strength tends to decrease, while the propylene content of 50 mol% or the heat of crystal fusion of less than 10 Joule / g results in a low melting point. It is not preferable because the heat resistance of the butene polymer (A) and the propylene polymer (B) may be impaired.

When the MFR is outside the above range, the moldability may be poor, and when the melting point is outside the above range, the adhesiveness tends to be poor.

In addition to the above-mentioned properties, the propylene / α-olefin random copolymer (C) used in the present invention has a microisotacticity (hereinafter referred to as MI
(Abbreviated as T) is 0.7 or more, further 0.8 or more, and boiling n-heptane insoluble matter is 5% by weight or less, further preferably 3% by weight or less. When MIT less than 0.7 is used, a low molecular weight substance may bleed out at the interface of the composition, which may lower the adhesive strength. The large amount of boiling n-heptane insoluble matter means that propylene is a block. This is because the amount of the chemically polymerized components is large, and when such a copolymer is used, the effect of improving the adhesiveness may be small.

In the random copolymer (C), the α-olefin copolymerized with propylene is usually an α-olefin having 2 to 20 carbon atoms excluding propylene, and specifically,
For example, ethylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-tetradecene, 1-octadecene and the like can be mentioned. Among these, those having 4 to 10 carbon atoms are particularly preferable.

The measurement of the heat of fusion of the propylene / α-olefin random copolymer (C) in the present invention is carried out by using a differential scanning calorimeter for the specific heat curve of the copolymer in a completely molten state (preferably,
It is a value calculated by using a straight line obtained by extrapolating the specific heat curve (160 ° C to 240 ° C) directly to the low temperature side as the baseline.

The heat of fusion and the melting point are measured under the following measurement conditions. That is, the sample is left at 200 ° C. for 5 minutes, cooled to −40 ° C. at a rate of 10 ° C./min, and left at −40 ° C. for 5 minutes. afterwards
Measure from -40 ℃ to 200 ℃ at a heating rate of 20 ℃ / min.

Microisotacticity refers to the part of three propylene chains in the ¹³ C nuclear magnetic resonance spectrum and
This is a value obtained by quantifying the fraction of individual propylene arranged isotactically.

The boiling n-heptane insoluble matter is quantified by the following method. That is, a strip sample of about 1 mm x 1 mm x 1 mm and glass beads are placed in a cylindrical glass filter (G3) and extracted with a Soxhlet extractor for 14 hours. In this case, the frequency of reflux is set to about once / 5 minutes. The weight% of the insoluble matter is determined by measuring the melted portion or the insoluble matter.

Propylene content of 50 to 50 having the above-mentioned properties
87 mol% of propylene / α-olefin random copolymer (C) is, for example, (a) a complex containing at least magnesium, titanium and halogen, (b) an organic group 1 to 3 metal of the periodic table. It is obtained by random copolymerization of propylene and α-olefin with a catalyst formed from a metal compound and (c) an electron donor. Part or all of the electron donor (c) may be fixed to part or all of the composite (a), and may be pre-contacted with the organometallic compound (b) prior to use. Good.
It is particularly preferable that a part of the electron donor (c) is the complex (a).
In this embodiment, the rest is added to the polymerization system as it is, or is pre-contacted with the organometallic compound (b) before use. In this case, the electron donor fixed to the complex (a) may be the same as or different from the electron donor used by adding it to the polymerization system as it is or by making a preliminary contact with (b). May be.

Unsaturated carboxylic acid or its derivative used in the present invention (D)
As, acrylic acid, maleic acid, fumaric acid, tet
Lahydrophthalic acid, itaconic acid, citraconic acid, croto
Acid, isocrotonic acid, nadic acid (Endosis
Cyclo [2,2,1] hept-5-ene-2,3-dicarboxylic
Acid) and other unsaturated carboxylic acids or their derivatives, eg
Acid halides, amides, imides, anhydrides, esters, etc.
And specifically, maleenyl chloride, maleimide,
Maleic anhydride, citraconic anhydride, maleic acid monomer
Chill, dimethyl maleate, glycidyl maleate, etc.
Is exemplified. Among these, unsaturated dicarboxylic acids or
Or its acid anhydride is preferred, and maleic acid, sodium
Dickic acid Alternatively, these acid anhydrides are suitable.

The modified olefin polymer composition of the present invention, the 1-butene polymer (A) 14 to 80 wt%, preferably 20 to 60
% By weight, 80 to 10% by weight of the propylene polymer (B),
Preferably 60 to 20% by weight and said propylene.α-
Olefin random copolymer (C) is composed of 76 to 6% by weight, preferably 60 to 20% by weight, and at least a part thereof is unsaturated carboxylic acid or its derivative (D)
Is a modified olefin polymer composition which is graft-modified, preferably 0.001 to 5% by weight, more preferably 0.01 to 4% by weight.

When the amount of the 1-butene polymer (A) is less than 14% by weight, poly 1-
Poor adhesion to butene. The amount of propylene polymer (B) is 1
If it is less than 0% by weight, the adhesive strength with polar materials is low, while 8
When it exceeds 0% by weight, the adhesive strength between the polar material and the polybutene layer is lowered. Similarly, when the amount of propylene / α-olefin random copolymer (C) is less than 6% by weight, the adhesive strength between the polar material and the polybutene layer is low, while when it exceeds 76% by weight, the heat resistance of the modified olefin polymer composition is high. In addition to the decrease in the adhesiveness, the adhesion strength with the polar material also decreases. When the amount of the unsaturated carboxylic acid or its derivative (D) grafted is less than 0.001% by weight, the adhesiveness to polar materials may be poor, while 5
On the other hand, if the content is more than 10% by weight, the adhesive strength tends to be low, and further the appearance tends to be low in molding.

The modified olefin polymer composition of the present invention is composed of 1-butene polymer (A), propylene polymer (B) and propylene / α-olefin random polymer (C) and unsaturated carboxylic acid or a derivative thereof. (D) is mixed with the entire mixture by graft modification, or 1-butene polymer
(A), a propylene polymer (B) and a propylene / α-olefin random copolymer (C) are partially or preliminarily grafted with an unsaturated carboxylic acid or a derivative thereof (D) partially or wholly. It is obtained by a method of melt-mixing after modification. Whichever method is adopted, the amount of the unsaturated carboxylic acid or its derivative (D) to be grafted is preferably in the range of 0.001 to 5% by weight in the entire composition after grafting.

A graft monomer selected from the unsaturated carboxylic acid or its derivative (D) is added to the 1-butene polymer (A) and / or the propylene polymer (B) and / or the propylene / α-olefin random copolymer (C). In order to produce the modified polymer by graft copolymerization, various conventionally known methods can be adopted. For example, a method or solvent in which 1-butene polymer (A) and / or propylene polymer (B) and / or propylene / α-olefin random copolymer (C) is melted and a graft monomer is added to carry out graft copolymerization. There is a method in which a graft monomer dissolved in is added to perform graft copolymerization. In any case, it is preferable to carry out the reaction in the presence of a radical initiator in order to efficiently graft-copolymerize the graft monomer. The grafting reaction is usually performed at a temperature of 60 to 350 ° C. The proportion of the radical initiator used is usually in the range of 0.001 to 1 part by weight based on 100 parts by weight of the polymer. Radical initiators include organic peroxides, organic peresters such as benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-
Butyl peroxide, 2,5-dimethyl-2,5-di (peroxide benzoate) hexyne-3,1,4-bis (tert
-Butylperoxyisopropyl) benzene, lauroyl peroxide, tert-butyl peracetate, 2,5-
Dimethyl-2,5-di (tert-butylperoxy) hexyne-3,2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, tert-butylperbenzoate, tert
-Butyl perphenyl acetate, tert-butyl perisobutyrate, tert-butyl per-sec-octoate, tert-butyl perpivalate, cumyl perpivalate and tert-butyl perdiethyl acetate, other azo compounds such as azobis There are isobutyronitrile and dimethylazoisobutyrate. Among these, dicumyl peroxide, di-tert-butyl peroxide, 2,
5-Dimethyl-2,5-di (tert-butylperoxy) hexyne-3,2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 1,4-bis (tert-butylperoxyisopropyl) Dialkyl peroxides such as benzene are preferred.

The modified olefin polymer composition of the present invention includes the 1-butene polymer (A), the propylene polymer (B) and propylene.
In addition to α-olefin random copolymer (C), low crystalline or amorphous α-olefin random copolymer,
For example, ethylene / propylene random copolymer, ethylene-1-butene random copolymer, or elastomer such as ethylene / propylene / diene monomer copolymer,
Polybutadiene, or crystalline polyolefin such as polyethylene, poly-4-methyl-1-pentene or ethylene / vinyl acetate copolymer is used in a range that does not impair the object of the present invention, and usually relative to 100 parts by weight of the modified olefin polymer composition. An amount of 40 parts by weight or less may be added.

In the modified olefin polymer composition of the present invention, heat stabilizers, weather stabilizers, antistatic agents, lubricants, slip agents, nucleating agents, pigments or dyes, natural oils, synthetic oils, etc. You may mix | blend the compounding agent of this with the range which does not impair the objective of this invention.

Poly 1-butene, which is one of the adherends of the modified olefin polymer composition of the present invention, is a homopolymer of 1-butene and 1-butene in the same category as the 1-butene polymer (A) and a small amount of 1-butene. It is a copolymer with other α-olefins.

Examples of polar materials that are other adherends of the present invention include metals such as aluminum, iron, brass, zinc or alloys, inorganic polar materials such as glass and cement, such as nylon 6, nylon 6-6, nylon 6-10. , Nylon 11, nylon
Polyamides such as 12 and the like, polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyvinyl chloride, polyvinylidene chloride, polymethyl methacrylate,
Examples thereof include polyvinyl compounds such as polymethyl acrylate, polycarbonate, polyphenylene oxide, saponified ethylene / vinyl acetate copolymer, and organic polar materials such as epoxy resin.

Using the modified olefin polymer composition of the present invention, poly 1-
As a method for obtaining a laminate of butene and a polar material, each film and sheet are manufactured in advance, and the two are thermocompression bonded, and a modified olefin polymer composition of poly1-butene and the polar material is used. Laminating by extrusion laminating, if the polar material is a thermoplastic resin, the poly-1-butene, the modified olefin polymer composition and the polar material are melted in separate extruders respectively, A method of extruding can be adopted. In either method, at least the modified olefin polymer composition needs to be heated above its melting point to be laminated on the polar material.

In addition, the modified olefin polymer composition of the present invention does not necessarily need to be laminated with poly 1-butene, and a powdered composition is used to dip a preheated polar material in the fluidized bed to form the polar material. It may be used for powder coating by a fluidized dipping method of coating the composition or a thermal spray coating method of spraying the composition with a gas burner.

Specific examples of the laminated structure using the modified olefin polymer composition of the present invention include composition / polar material, poly 1
-Butene / composition / polar material, composition / polar material / composition, poly 1-butene / composition / polar material / composition / poly 1-butene, etc.

〔The invention's effect〕

Since the modified olefin polymer composition of the present invention has excellent adhesiveness to both poly 1-butene and polar materials, poly 1 is used as an adhesive layer on the inner surface and / or the outer surface of a metal tube.
-By coating with butene, making full use of the original characteristics of poly 1-butene, such as wear resistance, stress rack resistance, heat resistant creep characteristics, and chemical resistance, slurry transportation pipes, water pipes, hot water supply pipes, It can be used as a chemical transport pipe. Alternatively, by laminating it with an adherend having gas barrier resistance such as polyamide, saponified ethylene / vinyl acetate copolymer, or aluminum foil, the heat and creep resistance, impact resistance and chemical resistance of poly 1-butene can be improved. It can be suitably used as a film for food packaging, a hollow molded container for foods and medicines, a pipe for transporting medicines and slurries, a tube, etc. by taking advantage of hygiene and the like.

Further, since the modified olefin polymer composition of the present invention contains a large amount of 1-butene polymer having excellent durability in its components, it is coated with a metal or the like for powder coating, and a slurry transport pipe or the like as described above. It can also be suitably used for the intended purpose.

〔Example〕

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples as long as the gist thereof is not exceeded.

Examples 1 to 3 Poly 1-butene (PB-I; MFR: 0.4 g / 10 min,
[Η]: 2.6 dl / g, density 0.92 g / cm ³ ), propylene
Ethylene block copolymer (PEB; ethylene content:
20 mol%, MFR: 0.5 g / 10 min), propylene / 1-
Butene random copolymer (PBR; propylene content:
71.0 mol%, heat of fusion of crystal: 50 Joule / g, melting point: 110
C, MFR: 7.0 g / 10 min, boiling n-heptane insoluble matter:
0.5 wt%, boiling methyl acetate solubles: 0.5 wt% and MI
T: 0.94) and a maleic anhydride graft-modified propylene polymer (MAH-PP; maleic anhydride graft amount: 3% by weight, intrinsic viscosity in decalin solvent at 135 ° C [η] = 0.4).
dl / g) in the proportions shown in Table 1, respectively, in a tumbler blender, and then melt-kneaded in a 40 mmφ extruder (set temperature: 200 ° C. full flight type screw) to obtain the modified olefin polymer compositions-I to III. Obtained.

Then, using the compositions-I to III, the adhesion strength between poly-1-butene and a metal, a polyamide, and a saponified ethylene / vinyl acetate copolymer was measured by the following method.

(I) Method for evaluating adhesion strength with metal The above Compositions-I to III were separately heat compression molded to prepare sheets of 200 × 200 × 0.3 mm thickness, which were separately prepared.
A sheet of BI-200 × 200 × 2 mm thick and a sheet of 50 × 150 × 2 mm degreased steel sheet were laminated with the sheets of Compositions-I to III as an intermediate layer and then set to 200 ° C. After heating for 5 minutes under no pressure using a press molding machine, pressure was applied for 20 minutes under a pressure of 20 kg / cm ² G to produce a laminated sheet. After cutting a test piece having a width of 10 mm from each laminated sheet and peeling one end,
Instron tensile tester (made by Instron (USA))
The adhesive strength (peeling strength) F _Fe (kg / cm) was measured by using a 90 ° peeling method at a peeling speed of 50 mm / min.

(II) Method for evaluating adhesive strength between polyamide and saponified ethylene / vinyl acetate copolymer As nylon, nylon 6 (trade name Amilan CM 1021
XF, manufactured by Toray Industries, Inc., saponified ethylene-vinyl acetate copolymer (EVOH; trade name Eval EP-F, manufactured by Kuraray Co., Ltd., MFR: 1.3 g / 10 min (ASTM D 1238, E), density 1.19
g / cm ³ , ethylene content: 32 mol%, saponification degree: 100
%), The above compositions-I to III and the above PB-I were used to mold six types of three-layer water-cooled inflation films under the following conditions.

Film layer structure: Nylon 6 or EVOH (outer layer) / Compositions I to III (middle layer) / PB-I (inner layer) = 20/10 / 20μ Molding machine: 40mmφ extruder (for outer layer) Set temperature nylon (250 ° C ) EVOH (210 ℃) 30mmφ extruder (for middle layer) Set temperature 210 ℃ 40mm Extruder (for inner layer) Set temperature 210 ℃ Molding speed: 20m / min Test with width of 15mm from each of 6 kinds of three-layer film obtained After cutting off one piece and peeling off one end, the adhesive strength (peel strength) F _NY between the nylon layer and the composition I to III layers was measured by the T-type peeling method at a peeling speed of 300 mm / min using an Instron tensile tester.
(g / 15 mm) and the adhesive strength (peel strength) F _EVOH (g / 15 mm) between the EVOH layer and the composition-I to III layers were measured.

The results are shown in Table 1. All peeling occurred between the polar material and the compositions-I to III, and no peeling occurred between the compositions-I to III and the PB-I layer.

Examples 4 to 6 Instead of the composition-I used in Example 1, the components of Example 1 were added, and further 1-butene / ethylene random copolymer (B
EC; ethylene content: 6 mol%, MFR: 0.2 g / 10 m
in, [η]: 3.1 dl / g) was performed in the same manner as in Example 1 except that the compositions IV to VI were added in the proportions shown in Table 1.
The results are shown in Table 1.

Example 7 Instead of the composition-I used in Example 1, the components of Example 1 were added, and further an ethylene / propylene random copolymer (EP
C; ethylene content: 80 mol%, MFR: 0.4 g / 10 min,
Density: 0.88g / cm ³ , X-ray crystallinity: 6%)
Example 1 was repeated except that the composition-VII added in the ratio shown in the table was used. The results are shown in Table 1.

Example 8 Instead of the EPC used in Example 7, a propylene / ethylene random copolymer (PEC; propylene content: 60)
Mol%, crystallinity 0%, boiling n-heptane insoluble matter: 0.1
Wt%, boiling methyl acetate solubles: 0.8 wt%, MIT:
0.96, [η]: 4.5 dl / g) was used in the same manner as in Example 7. The results are shown in Table 1.

Comparative Example 1 Instead of the composition-I used in Example 1, 90% by weight of BEC described in Example 4 and propylene homopolymer (PP; M).
FR: 0.5 g / 10 min) 10% by weight and BEC + PP = 100 parts by weight to 100 parts by weight of maleic anhydride (MAH): 0.2 parts by weight and 2,5-dimethyl-2,5-di (tert-butylperoxy)
Hexin-3 (trade name Perhexin 2.5B, manufactured by NOF Corporation): 0.05 parts by weight was mixed with a Henschel mixer, and then melt-kneaded with a 65 mmφ single-screw extruder (set temperature: 190 ° C., full flight type screw). Example 1 was repeated except that MAH was graft-reacted with the modified polymer composition-IX. The amount of MAH grafted on the composition-IX was measured by an infrared absorption spectrum analysis and found to be 0.15% by weight. The results are shown in Table 2.

Comparative Example 2 Instead of the composition-I used in Example 1, a modified polymer composition-X prepared by kneading PB-I, PEB and MAH-PP described in Example 1 in the proportions shown in Table 2 was used. The same procedure as in Example 1 was carried out except that it was used. The results are shown in Table 1.

Comparative Example 3 The BE described in Example 4 was used instead of the PB-I used in Comparative Example 2.
The procedure of Comparative Example 2 was repeated except that the modified polymer composition-XI was used instead of C. The results are shown in Table 2.

Comparative Example 4 The procedure of Example 1 was repeated except that the composition-XII obtained by kneading the components of Example 1 in the proportions shown in Table 2 was used instead of the composition-I used in Example 1. Ivy. The results are shown in Table 2. The peeling occurred between the composition-XII and the PB-I layer.

Comparative Examples 5 and 6 Instead of the composition-VIII used in Comparative Example 1, B of Comparative Example 1
Instead of a mixture of EC and PP, poly 1-butene (PB-I
I; Composition using MFR: 0.03 g / 10 min, density 0.92 g / cm ³ ) alone or BEC described in Comparative Example 1 alone-
The procedure of Comparative Example 1 was repeated except that XIII and XIV were used.
The results are shown in Table 2.

Comparative Example 7 Comparative Example 2 was carried out in the same manner as in Comparative Example 2 except that the composition -XV obtained by kneading PB-I and MAH-PP used in Comparative Example 2 in the proportions shown in Table 2 was used. The results are shown in Table 2.

Comparative Example 8 Composition used in Comparative Example 2 —Composition obtained by kneading components used in Comparative Example 2 in the ratio shown in Table 2 instead of X—
The procedure of Comparative Example 2 was repeated except that XVI was used. The results are shown in Table 2. In addition, peeling was done by composition-XVI and PB-I
Occurred between layers.

Comparative Example 9 Composition-XVII was used instead of the composition-X used in Comparative Example 2 except that the component used in Comparative Example 2 was further added with the BEC used in Example 4 in the ratio shown in Table 2. The same procedure as in Comparative Example 2 was performed. The results are shown in Table 2. The peeling occurred between the composition-XVII and PB-I layers in all three cases.

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Claims (1)

[Claims] (A) 1-butene polymer (A) 14 to 80% by weight, (b) propylene homopolymer (B-1), propylene and 50% by mole or less of other α-olefin 80 to 10% by weight of a block copolymer (B-2) or a propylene polymer (B) selected from a crystalline random copolymer (B-3) of propylene and 10 mol% or less of an α-olefin, And (c) a propylene content of 50 to 87 mol% and a heat of crystal fusion of 10 based on a thermal analysis of a differential scanning calorimeter (DSC).
To 80 Joule / g of propylene / α-olefin random copolymer (C) 76 to 6% by weight, and at least a part of which is graft-modified with unsaturated carboxylic acid or its derivative (D). A characteristic modified olefin polymer composition.