JPH0649144A - Graft polymer-containing resin composition and thermoplastic resin composition - Google Patents

Abstract

(57) [Summary] [Structure] One of a styrene-based polymer, an alkyl (meth) acrylate-based polymer, and a vinyl chloride-based polymer obtained by copolymerizing a polyfunctional vinyl monomer in an amount of 0.001 to 5% by weight. To 100 parts by weight of the above polymer (e), 5 to 200 parts by weight of a monomer (d) consisting of a monomer containing an epoxy group, an aromatic vinyl compound and a monomer copolymerizable with them, is added. Graft polymer-containing resin composition (D) grafted on (e), and polymer-containing resin composition (D) 0.5
˜200 parts by weight of thermoplastic resin composition (A) other than olefin resin (A) 5 to 95% by weight, and olefin resin (B)
A thermoplastic resin composition prepared by mixing 100 parts by weight (C) of 5 to 95% by weight. [Effect] In addition to having excellent surface layer peeling resistance, it also has excellent heat resistance and fluidity.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a graft polymer-containing resin composition and a thermoplastic resin composition using the same. More specifically, it relates to a modifier composed of a resin composition containing a graft polymer and a thermoplastic resin composition using the same, which is excellent in surface layer peeling resistance.

[0002]

2. Description of the Related Art Recently, a method of alloying polymers having different properties to modify a resin has been actively studied. For example, regarding the alloying of a polyolefin with a styrene resin or a vinyl chloride resin, a method of alloying with an ethylene-vinyl acetate copolymer (Japanese Patent Publication No. 60-36178) or a polyethylene-EPDM modified product is used. Method (JP-A-63-30403)
No. 9, JP-A-1-165640), and a method of alloying with a block of polypropylene and styrene resin (JP-A-2-199127, JP-A-2-19927).
No. 199128, JP-A-2-199129)
Have been reported.

[0003]

However, in these conventional methods, there is a problem that the compatibility between the polymers is insufficient, and the surface layer peeling of the resin molded product occurs under high shear such as injection molding. is there.

[0004]

Means for Solving the Problems As a result of intensive studies for solving the above-mentioned problems, the present inventors have found that polyfunctional vinyls are used in comparison with those composed of olefin resins and thermoplastic resins other than olefin resins. Monomers and aromatic vinyl compounds having an epoxy group in one or more polymers selected from styrene polymers obtained by polymerizing a small amount of monomers, alkyl (meth) acrylate polymers, and vinyl chloride polymers. It was surprisingly found that when a graft polymer-containing resin composition obtained by grafting is blended as a compatibilizing agent, the surface layer peeling of an injection-molded article hardly occurs.

That is, the present invention provides one or more of a styrene-based polymer, an alkyl (meth) acrylate-based polymer, and a vinyl chloride-based polymer obtained by copolymerizing 0.001 to 5% by weight of a polyfunctional vinyl monomer. 0.05 to 50% by weight of an epoxy group-containing monomer, 50 to 99.95% by weight of an aromatic vinyl compound, and 0 to 49.5% by weight of a monomer copolymerizable therewith with respect to 100 parts by weight of the polymer (e). Monomer (d) 5
The present invention relates to a graft polymer-containing resin composition (D) obtained by graft polymerization of about 200 parts by weight.

The present invention also relates to a thermoplastic resin (A) other than an olefin resin (A) of 5 to 95% by weight and an olefin resin (B).
5 to 95% by weight (C) 100 parts by weight,
The present invention relates to a thermoplastic resin composition containing 0.5 to 200 parts by weight of the graft polymer (D).

[0007]

[Functions and Examples] The graft polymer-containing resin composition (D) used in the present invention is a styrene polymer obtained by copolymerizing a polyfunctional vinyl monomer, an alkyl (meth) acrylate polymer, or a vinyl chloride resin. Polymer (e) comprising at least one of the polymers is impregnated with a monomer (d) comprising an epoxy group-containing monomer, an aromatic vinyl compound and a monomer copolymerizable therewith, and polymerized. The thus obtained graft polymer-containing resin composition acts as a modifier that promotes the compatibility between the thermoplastic resin (A) other than the olefin resin and the olefin resin (B).

The polymer (e) used in the present invention is
Among styrene-based polymers, alkyl (meth) acrylate-based polymers, and vinyl chloride-based polymers obtained by copolymerizing 0.001 to 5% (weight%, the same applies below) of polyfunctional vinyl monomers, preferably 0.01 to 3% Of one or more polymers of (e) to facilitate the graft polymerization of the monomer (d) onto the polymer (e) by copolymerization with the polyfunctional vinyl monomer. ) Is a vinyl group introduced into.

Examples of the polyfunctional vinyl monomer include divinylbenzene, diallyl phthalate, allyl (meth) acrylate, vinyl (meth) acrylate,
Ethylene glycol di (meth) acrylate, 1,3-
Butylene glycol di (meth) acrylate, 1,4-
Butylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, pentaethylene glycol di (meth) acrylate, Nonaethylene glycol di (meth) acrylate, tetradecaethylene glycol di (meth) acrylate, eicosa ethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, pentapropylene glycol di (meth) acrylate, nonapropylene glycol Di (meth) acrylate, tetradecapropylene glycol di (meth) acrylate, eicosa propylene glycol di (meth) acrylate , 1,6-hexanediol di (meth) acrylate.

When the amount of the polyfunctional vinyl monomer in the polymer (e) is less than 0.001%, the effect of improving the surface layer peeling resistance is small, and when it exceeds 5%, the fluidity is remarkably reduced.

As the styrene-based polymer, polystyrene obtained by copolymerizing a polyfunctional vinyl monomer, styrene-butadiene block copolymer, styrene-methyl methacrylate copolymer, acrylonitrile-styrene copolymer, acrylonitrile-styrene is used. -Methyl methacrylate copolymer, acrylonitrile-α-methylstyrene-
Examples thereof include styrene copolymers, maleic anhydride-styrene copolymers, maleimide-styrene copolymers, maleimide-styrene-acrylonitrile copolymers and rubber-reinforced resins of these copolymers.

Of these styrenic polymers, those which are easily compatible with polymethylmethacrylate or polyvinyl chloride are preferred, but aromatic vinyl compounds are especially preferred.
~ 85%, vinyl cyanide compound 15-40%, and other vinyl compounds copolymerizable with these 20% or less copolymerized polymer such as acrylonitrile-styrene copolymer,
Acrylonitrile-α-methylstyrene-styrene copolymer obtained by copolymerizing 0.001 to 5% of a polyfunctional vinyl monomer is preferable from the viewpoint of improving the surface layer peeling resistance.

Examples of the alkyl (meth) acrylate polymer include polymethyl (meth) acrylate obtained by copolymerizing a polyfunctional vinyl monomer, polyethyl (meth) acrylate, polypropyl (meth) acrylate, polybutyl (meth). ) Homopolymers such as acrylate and methyl (meth) acrylate-butyl (meth)
Acrylate copolymer, methylmethacrylate-styrene copolymer, methylmethacrylate-α-methylstyrene-styrene copolymer, methylmethacrylate-styrene-acrylonitrile copolymer, and the like, but from the viewpoint of surface layer peeling resistance, methyl. Polymers having a methacrylate content of 60% or more are preferred.

Examples of the vinyl chloride polymer include polyvinyl chloride obtained by copolymerizing a polyfunctional vinyl monomer, and a vinyl chloride copolymer having a vinyl chloride content of 80% or more. Examples of the monomer to be copolymerized include monovinylidene compounds such as ethylene and vinyl acetate.

From the viewpoint of heat resistance, the polymer (e) has a Tg of
Is preferably 50 ° C. or higher, and an alkyl (meth) acrylate polymer having a Tg of 50 ° C. or higher is particularly preferable.

The polymer (e) can be obtained by a known method, and its operation is not particularly limited.

Since the polymer (e) itself does not have an affinity for olefins and thus does not act as a compatibilizer, the surface layer peeling resistance is not improved, but by grafting the monomer (d), a polyolefin is obtained. Since a graft branch portion such as aromatic vinyl having an affinity for is formed, it is easily compatible with polyolefin. Since the polymer (e) has a quick trunk that is compatible with the thermoplastic resin (A) other than the olefin resin, the thermoplastic resin (A) other than the olefin resin
The olefin resin (B) and the olefin resin (B) have a large compatibility through the graft polymer-containing resin composition obtained by grafting the monomer (d) on the polymer (e), and as a result, the heat of the present invention is improved. It is considered to improve the surface layer peeling resistance of the plastic resin composition.

The monomer (d) used for grafting the polymer (e) is an epoxy group-containing monomer 0.05 to 50.
%, Preferably 0.1-30%, aromatic vinyl compound 50-9
9.95%, preferably 70 to 99.9%, and 49.5% or less, preferably 20% or less, of a monomer copolymerizable therewith.

As the above-mentioned monomer having an epoxy group,
Examples thereof include glycidyl (meth) acrylate, glycidyl (eth) acrylate, and allyl glycidyl ether.

If the amount of the epoxy-containing monomer is less than 0.05%, the resistance to peeling of the surface layer is remarkable, and if it exceeds 50%, the fluidity is greatly reduced.

Examples of the aromatic vinyl compound include styrene, methylstyrene, α-methylstyrene, chlorostyrene, β-isopropenylnaphthalene, and the like. From the viewpoint of resistance to peeling of the surface layer, 80% by weight of the aromatic vinyl compound is used. % Or more is one of styrene, methylstyrene, α-methylstyrene and β-isopropenylnaphthalene.
It is preferably one or more kinds.

Aromatic vinyl compound is less than 50% or 9
If it exceeds 9.5%, the releasability of the molded product becomes remarkable.

The above-mentioned epoxy group-containing monomer and monomer copolymerizable with an aromatic vinyl compound are not necessarily used, but when they are used, they are within the range of 49.5%, such as butyl acrylate and 2-ethylhexyl acrylate. , And long-chain alkyl (meth) acrylates such as stearyl methacrylate. If the amount of the copolymerizable monomer exceeds 49.5%, the surface layer peeling resistance is deteriorated.

A known polymerization method can be used for grafting the monomer (d) onto the polymer (e).
There are no particular restrictions on the operation. After completion of the polymerization, the target powder is obtained by a known method.

As the thermoplastic resin (A) other than the olefin resin used in the thermoplastic resin composition of the present invention,
Examples thereof include styrene resin, vinyl chloride resin, polyester resin, polycarbonate resin, polyamide resin and polyphenylene oxide resin. Of these, styrene-based resins and vinyl chloride-based resins are preferable from the viewpoint of surface layer peeling resistance of the thermoplastic resin composition of the present invention.

Preferred styrene resins as (A) are AS resin, ABS resin, AES resin and AAS.
Resin, ACS resin, acrylonitrile-α-methylstyrene copolymer, acrylonitrile-maleimide-styrene copolymer, acrylonitrile-maleimide-α-methylstyrene-styrene copolymer, polystyrene, high-impact polystyrene, etc. Among them, aromatic vinyl compounds 10-85%, vinyl cyanide compounds 15
-40%, 50% or less of N-substituted maleimide compound and 20% or less of other vinyl compound copolymerizable with them are used as the styrene resin in view of the peeling resistance of the thermoplastic resin composition of the present invention. Especially preferred.

Examples of the aromatic vinyl compound used for the copolymerization of the above particularly preferable styrene resin include styrene, α-methylstyrene, methylstyrene, chlorostyrene and β-isopropenylnaphthalene.

Examples of the vinyl cyanide compound used in the copolymerization include acrylonitrile and methacrylonitrile.

Examples of the N-substituted maleimide compound used in the copolymerization include N-phenylmaleimide,
N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, N-
Butyl maleimide, N-isobutyl maleimide, Nt
-Butyl maleimide, N-cyclohexyl maleimide and the like can be mentioned.

Other copolymerizable vinyl compounds used in the above copolymerization include methyl acrylate, ethyl acrylate, butyl acrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate, 2-ethylhexyl methacrylate and methacrylic acid.

The preferred vinyl chloride resin as (A) is polyvinyl chloride, a vinyl chloride copolymer having a vinyl chloride content of 80% or more, and a post-chlorinated vinyl chloride resin obtained by chlorinating the vinyl chloride resin. Examples include resins. Examples of the monomer to be copolymerized include monopyridene compounds such as ethylene and vinyl acetate.

The above-mentioned (A) is styrene resin 5 to 95
%, And a mixture of 95% to 5% vinyl chloride resin is also preferably used. In particular, styrene resin is aromatic vinyl compound 10-85%, vinyl cyanide compound 15-40%, N-
From the viewpoint of resistance to peeling of the surface layer, a copolymer of a substituted maleimide compound of 50% or less and another vinyl compound of 20% or less copolymerizable therewith is preferable.

For the above-mentioned polymerization of (A), a known method can be used, and the kind and operation thereof are not particularly limited. After completion of the polymerization, it can be made into powder by a known method.

Examples of the olefin resin (B) used in the present invention include polypropylene, a copolymer of propylene and α-olefin, high density polyethylene, medium density polyethylene, low density polyethylene, ethylene and α-olefin. Copolymer with, polybutene, poly-
Polyolefins such as 4-methylpentene-1 or oligomers thereof, ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-vinyl acetate copolymer, butyl rubber, butadiene rubber, propylene-butene copolymer, ethylene-acrylic acid Examples thereof include polyolefinic elastomers such as ester copolymers, and mixtures of two or more thereof. Among them, polypropylene and a copolymer of 50% or more propylene are preferable from the viewpoint of heat resistance.

The olefin resin (B) can be obtained by a known method, and there is no particular limitation on its operation. After completion of the polymerization, it can be made into powder by a known method.

The thermoplastic resin composition of the present invention may be prepared by blending powdery thermoplastic resin (A) and olefin resin (B), graft polymer-containing resin composition (D), compounding agents and the like together. However, the operation is not particularly limited.

The ratio of the resins (A) and (B) in the thermoplastic resin composition of the present invention is preferably in the range of 5/95 to 95/5 by weight, of which 15/85 to 85/15 is particularly preferred. If the amount of (A) is less than the above range, the heat resistance will decrease, and if it exceeds the above range, the fluidity will decrease significantly.

The graft polymer-containing resin composition (D)
Is 0.5 to 200 parts, preferably 1 to 10 parts per 100 parts of the total amount of the thermoplastic resin (A) and the olefin resin (B).
Used 0 copies. If the amount of (D) is less than 0.5 part, it is difficult to improve the surface layer peeling resistance of the molded product, and if it exceeds 200 parts, the fluidity is markedly reduced.

The thermoplastic resin of the present invention also includes, in addition to well-known antioxidants, heat stabilizers, and lubricants, UV absorbers, pigments, antistatic agents and flame retardants, and flame retardants as needed. Agents can also be used in combination. In particular, phenolic antioxidants used for styrene resins and olefin resins, phosphite stabilizers, tin stabilizers mixed with vinyl chloride resins, lead stabilizers, and various fatty acid esters, metal soaps, waxes. An internal / external lubricant such as a class can be used to improve the performance of the thermoplastic resin of the present invention as a molding resin.

The thermoplastic resin of the present invention is excellent in surface layer peeling resistance, and also excellent in heat resistance and fluidity. Molded products are housings and parts of home electric appliances and OA equipment,
It is preferably used for interior and exterior parts of automobiles.

The present invention will be shown below with reference to specific examples.
Examples such as these do not limit the invention.

Reference Example 1 (Production of Graft Polymer-Containing Resin Composition (D)) Using a 8 liter polymerization machine equipped with a stirrer under a nitrogen atmosphere, water 200
Parts, sodium alkylbenzene sulfonate 2 parts, ethylenediamine tetraacetate Na salt 0.01 parts, sulfuric acid first
Add 0.0025 parts of iron, 99 parts of methyl methacrylate at 60 ℃,
A mixture of 1 part of diallyl methacrylate, 0.1 part of cumene hydroperoxide and 0.5 part of t-dodecyl mercaptan was continuously added dropwise over 6 hours. After that, stirring was continued for 1 hour to complete the polymerization of the polymer (e-1).

Next, 200 parts of water, 50 parts of the above-mentioned polymer (e-1), 0.01 part of ethylenediaminetetraacetate Na salt, and 0.0025 part of ferrous sulfate were charged into the same apparatus as above, and 60 parts
A mixture of 45 parts of styrene, 5 parts of glycidyl methacrylate and 0.1 part of cumene hydroperoxide was continuously added dropwise at 5 ° C over 5 hours. After that, stirring was continued for 1 hour to complete the graft polymerization.

After completion of the polymerization, salting out, granulation, dehydration and drying were carried out to obtain a graft polymer-containing resin composition (D-1).

Similarly, a polymer (e-
2 to e-4), graft polymer-containing resin compositions (D-2 to D-4) were obtained from the monomers having the compositions shown in Table 2.

The abbreviations used in Tables 1 to 3 represent the following.

MMA: Methyl Methacrylate AN: Acrylonitrile St: Styrene AMA: Allyl Methacrylate GMA: Glycidyl Methacrylate PMI: N-Phenylmaleimide αS: α-Methylstyrene PBD: Polybutadiene

[0048]

[Table 1]

[0049]

[Table 2]

Example 1 40 parts of resin (A-1) shown in Table 3, polypropylene (B)
(Polypropylene manufactured by Mitsui Petrochemical Co., Ltd., trade name Polypro Hypol J-600 (melt flow index 7.0
g / 10 min, impact strength 3.0 kg · cm / cm)) 60 parts, resin composition containing graft polymer obtained in Reference Example 1 (D-1)
10 parts were blended with a super mixer and pellets were produced with a 44 m / m twin-screw extruder.

From the pellets on a 5 ounce injection molding machine,
A test piece was molded under the conditions of a screw rotation speed of 80 rpm and a nozzle set temperature of 230 ° C.

[0052]

[Table 3]

Examples 2 to 4, Comparative Examples 1 and 2 (A-1) having the composition shown in Table 3 in the same manner as in Example 1
(A-2), polypropylene (B) used in Example 1 and graft polymer-containing resin composition (D-1 to D-3)
To obtain a thermoplastic resin composition having the composition shown in Table 5,
The test piece was molded.

Example 5 40 parts of vinyl chloride resin (A-3) shown in Table 4, 60 parts of polypropylene (B) used in Example 1, 10 parts of graft polymer-containing resin composition (D-1), stable 2 parts of dibutyl tin malate as an agent and 1 part of polyethylene wax as a lubricant were blended with a super mixer, and pellets were produced with a 44 m / m twin-screw extruder.

From the pellets on a 5 ounce injection molding machine,
A test piece was molded under the conditions of a screw rotation speed of 80 rpm and a nozzle set temperature of 170 ° C.

[0056]

[Table 4]

Examples 6 and 7, Comparative Examples 3 to 5 In the same manner as in Example 5, compositions (A) shown in Tables 3 and 4 were used.
-1, A-4), the polypropylene (B) used in Example 1 and the graft polymer-containing resin composition (D-1,
D-4) was used to obtain a thermoplastic resin composition having the composition shown in Table 5, and the test piece was molded.

The obtained molded product was examined for its surface layer peeling resistance, heat distortion temperature and fluidity.

The results are shown in Table 5.

The surface layer peeling resistance of the molded product was evaluated by using the above-mentioned molding machine and evaluating the peeling property from the gate portion of a flat plate molded product having a thickness of 2.5 mm. Evaluation is a 5-point visual inspection method,
The highest was 5 points and the lowest was 1 point. That is, the evaluation shows that the larger the number, the better the resistance to peeling of the surface layer.

The heat resistance was evaluated based on the ASTM D-256 standard at a deformation temperature of a thermoplastic resin composition under a load of 18.6 kg / cm ² .

The fluidity was measured by using the above-mentioned molding machine and the thickness was 3
Evaluation was made by the flow distance in a mosquito coiled mold with a size of mm × width 10 mm. The unit is mm.

[0063]

[Table 5]

From the results shown in Table 5, it can be seen that the thermoplastic resin compositions of the present invention represented by Examples are particularly excellent in surface layer peeling resistance and fluidity, and also have good heat resistance.

[0065]

INDUSTRIAL APPLICABILITY The thermoplastic resin composition of the present invention has excellent surface layer peeling resistance, fluidity and heat resistance, and its molded products are used for housings and parts of home electric appliances and office automation equipment, and for automobiles. It can be used for interior and exterior parts.

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Claims (13)

[Claims] 1. One or more polymers selected from the group consisting of styrene-based polymers, alkyl (meth) acrylate-based polymers and vinyl chloride-based polymers obtained by copolymerizing 0.001 to 5% by weight of a polyfunctional vinyl monomer. (E) 0.05 to 50% by weight of a monomer containing an epoxy group and 50 to 50% of an aromatic vinyl compound with respect to 100 parts by weight.
99.95% by weight and monomers copolymerizable with these 0 to
A graft polymer-containing resin composition (D) obtained by graft-polymerizing 5 to 200 parts by weight of a monomer (d) consisting of 49.5% by weight. 2. The graft polymer-containing resin composition according to claim 1, wherein the polymer (e) is a polymer having a glass transition temperature of 50 ° C. or higher. 3. The graft polymer-containing resin composition according to claim 1, wherein the polymer (e) is an alkyl (meth) acrylate polymer having a glass transition temperature of 50 ° C. or higher. 4. The polymer (e) is methyl methacrylate.
The graft polymer-containing resin composition according to claim 1, which is an alkyl (meth) acrylate polymer composed of 60% by weight or more. 5. The polymer (e) is an aromatic vinyl compound 50.
~ 85% by weight, vinyl cyanide compound 15-40% by weight, and other copolymerizable vinyl compounds 0-20% by weight
The graft polymer-containing resin composition according to claim 1, which is a styrene-based polymer obtained by copolymerizing 6. The monomer (d) is an aromatic vinyl compound.
80% by weight or more is one of styrene, methylstyrene, α-methylstyrene and β-isopropenylnaphthalene.
The resin composition containing a graft polymer according to claim 1, which is one or more kinds. 7. The monomer (d) comprises 0.1 to 30% by weight of a monomer containing an epoxy group, 70 to 99.9% by weight of an aromatic vinyl compound, and 0 to 20% by weight of a monomer copolymerizable therewith.
The graft polymer-containing resin composition according to claim 1, comprising: 8. A polyfunctional vinyl based on 100 parts by weight of a thermoplastic resin (A) other than an olefin resin (A) 5 to 95% by weight and an olefin resin (B) 5 to 95% by weight (C) 100 parts by weight. At least one polymer (e) 100 selected from styrene-based polymers, alkyl (meth) acrylate-based polymers, and vinyl chloride-based polymers obtained by copolymerizing monomers in an amount of 0.001 to 5% by weight.
Monomer (d) 5 consisting of 0.05 to 50% by weight of an epoxy group-containing monomer, 50 to 99.95% by weight of an aromatic vinyl compound, and 0 to 49.5% by weight of a monomer copolymerizable with these, based on parts by weight. A thermoplastic resin composition comprising 0.5 to 200 parts by weight of a graft polymer-containing resin composition (D) obtained by graft polymerization of up to 200 parts by weight. 9. The thermoplastic resin composition according to claim 8, wherein the thermoplastic resin (A) other than the olefin resin is a styrene resin and / or a vinyl chloride resin. 10. A thermoplastic resin (A) other than an olefin resin comprises 10 to 85% by weight of an aromatic vinyl compound, 15 to 40% by weight of a vinyl cyanide compound, 0 to 50% by weight of an N-substituted maleimide compound, and these. 10. The thermoplastic resin composition according to claim 8 or 9, which is a styrene-based resin copolymerized with 0 to 20% by weight of another vinyl compound copolymerizable with. 11. A thermoplastic resin (A) other than an olefin resin is a vinyl chloride resin comprising 80% by weight or more of vinyl chloride and / or a chlorinated vinyl chloride resin, a post-chlorinated vinyl chloride resin. A resin as claimed in claim 8 or 9.
The thermoplastic resin composition described. 12. The thermoplastic resin (A) other than the olefin resin is composed of 5 to 95% by weight of the styrene resin of claim 10 and 95 to 5% by weight of the vinyl chloride resin of claim 11. Or the thermoplastic resin composition according to item 9. 13. The thermoplastic resin composition according to claim 8, wherein the olefin resin (B) is obtained by polymerizing 50% by weight or more of propylene.