JPH0742367B2 - Injection-fusing property and good gloss thermoplastic elastomer composition - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to thermoplastic elastomer compositions, and more particularly to ethylene-α
-Injection fusion of propylene-1-butene low crystalline copolymer blended with partially crosslinked thermoplastic elastomer obtained by dynamically heat-treating an olefin-based amorphous copolymer and a radical-decomposable crystalline polyolefin And a thermoplastic elastomer composition having good gloss.

[0002]

BACKGROUND OF THE INVENTION Olefinic thermoplastic elastomers have the same elastomeric properties as vulcanized rubbers, but on the other hand, they have the same moldability as thermoplastic resins such as polyethylene and polypropylene. The molded products have begun to be used mainly as automobile bumpers, exterior moldings, windshield gaskets, emblems and interior skin materials, which are applications requiring elastomeric properties, and also as gaskets for building materials. Among the above applications, olefin-based thermoplastic elastomers that should be used in the fields of automobile windshield gaskets and various gaskets for building materials, which require properties similar to vulcanized rubber, are among the usual olefin-based thermoplastic elastomers. It can be obtained by increasing the content of the ethylene-α-olefin copolymer elastomer component.

[0003]

However, the flexible thermoplastic elastomer thus obtained has poor fluidity when melted and is used for windshield gaskets and building materials for automobiles that require complicated shapes. It is difficult to directly mold a molded product such as a gasket by injection molding.

On the other hand, since this soft thermoplastic elastomer has good deformability, it is possible to use the property to mold the above-mentioned article by extrusion molding, but in this case, it is deformed. It is necessary to join the ends of the molded product together. In order to perform this joining, two or more extrusion-molded products to be joined are placed in a split mold, and a thermoplastic elastomer having good fusion property is injected and injected between the ends of both molded products to melt them. It is preferable to wear. In this case, the split mold preferably has a structure to which an injection molding method can be applied.

In many cases, however, it is difficult to join the extruded articles of the thermoplastic elastomer by the above-mentioned method with sufficient strength for practical use. As a measure to solve this problem, the present applicant has already applied for a method for improving the joint strength by preheating the ends of the extruded products to be joined in a split mold (Japanese Patent Laid-Open No. 55-105670).
issue).

The inventors of the present invention have earnestly studied the method of injection-melting the ends of a thermoplastic elastomer extruded product without performing the above-mentioned preheating, and as a result, the following exemplified compositions were obtained. The present invention has been completed by finding that a molded product joined with the strength that can be practically used can be obtained by charging the ends of two or more thermoplastic elastomer extruded products in a split mold.

[0007]

According to the present invention, an ethylene-α-olefin-based amorphous copolymer (a) and a radical-decomposable crystalline polyolefin (b) are added in the presence of an organic peroxide. Partially crosslinked thermoplastic elastomer obtained by dynamic heat treatment and propylene unit content 55 to 85 mol%, melt flow rate [MFR (230
C)] is 1 to 10 g / 10 min, and the crystallinity measured by X-ray diffractometry is 10 to 30%, and the injection fusion property of the propylene-1-butene low crystalline copolymer (c) and Provided is a thermoplastic elastomer composition having good gloss.

[0008]

In the thermoplastic elastomer composition of the present invention, the ethylene-α-olefin-based amorphous copolymer (a) and the crystalline polyolefin (b) are combined and blended, and these are moved in the presence of an organic peroxide. Of the propylene-1-butene low crystallinity copolymer (c) is melt-kneaded with the partially heat-treated partially crosslinked elastomer, and the components (a) and (b) are dynamically heat treated. The partially crosslinked elastomer component is subjected to a dynamic heat treatment in the presence of an organic peroxide to form a crosslink bond in the molecular chain, resulting in an increase in the molecular weight and a decrease in the melt fluidity of amorphous ethylene. −
Contrary to the α-olefin-based copolymer component (a), a crystalline polyolefin whose molecular chain is cut by dynamic heat treatment to increase melt fluidity is melted, and crosslinking and decomposition are repeated during kneading, and as a result, A polymer composition having a molecular chain structure different from that obtained by simply kneading both polymers (a) and (b).

Such an elastomer component has excellent rubber elasticity, mechanical properties, and appropriate flexibility, but the elastomer component has a low crystalline propylene-1-butene copolymer (c). The melt-blended thermoplastic elastomer composition of the present invention has, in addition to the above-mentioned properties, excellent melt adhesion with an olefin-based thermoplastic elastomer, and is molded after molding the composition. The surface gloss of the body is also excellent. Furthermore, the flow characteristics of the melting degree are also improved, and for example, injection injection into the split mold becomes possible as described above.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Ethylene which is the component (a) of the present invention
The α-olefin-based amorphous copolymer is a binary copolymer of ethylene and α-olefin or a non-conjugated diene as a third component thereof, for example, an aliphatic diene such as 1,4-hexadiene, or a diene. It is a terpolymer containing an alicyclic diene such as cyclopentadiene, 5-ethylidene norbornene, 5-methylene norbornene, and 5-vinyl norbornene, and has a crystallinity of usually 35 as measured by X-ray diffractometry.
% Or less, preferably 20% or less.

The ethylene unit content of the binary copolymer is usually 30 to 95 mol%, preferably 50 to 85 mol%, the balance is α-olefin, and the melt flow rate (190
C) is usually 0.1 to 120 g / 10 mm, preferably 0.1 to 20 g / 10 mm, melt flow rate (23
(0 ° C.) is usually 0.1 to 200 g / 10 mm, preferably 0.1 to 50 g / 10 mm, and the iodine value is usually 1 or less. The ethylene unit content of the terpolymer is usually 30 to 9
5 mol%, preferably 50 to 85 mol%, the α-olefin unit content is usually 5 to 70 mol%, preferably 15 to
50 mole% non-conjugated diene unit content is usually 1 to 10 mol%, preferably 3-6 mol%, a Mooney viscosity [ML _{1 + 4} (100 ℃)] is usually 5 to 200, preferably 40 to 120, the iodine value is usually 1 to 50, preferably 5 to 30.

Preferred binary copolymers are ethylene-propylene copolymers (EPM) or ethylene-1-butene copolymers (EBM) with an ethylene unit content of 50-9.
5 mol%, crystallinity 20% or less, melt flow rate (190 ° C) 0.1 to 20 g / 10 mm, (230 ° C)
0.1 to 50 g / mm. Preferred terpolymers are ethylene-propylene-dicyclopentadiene copolymers or ethylene-propylene-2-ethylidene-5-norbornene copolymers or ethylene-1-butene-dicyclopentadiene copolymers or ethylene-1.
A butene-2-ethylidene-5-norbornene copolymer having an ethylene unit content of 50 to 95 mol%, a propylene unit or 1-butene unit content of 5 to 50 mol%,
The rest is non-conjugated diene, crystallinity is 20% or less, Mooney viscosity ML _{1 + 4} (100 ° C.) 40 to 120, iodine value 5 to
30's.

The radical-decomposable crystalline polyolefin (b) used together with the component (a) of the composition of the present invention is usually a homopolymer, a copolymer or a mixture of α-olefins having 3 or more carbon atoms. Therefore, the crystallinity measured by X-ray diffraction is usually 40% or more, preferably 50% or more. The copolymerized unit may contain ethylene, but its amount is usually 40 mol% or less, preferably 20 mol% or less.

The copolymer can be produced by either a block polymerization method or a random polymerization method. However, in the random copolymerization method, the smaller number of copolymerized units is required because it is necessary to achieve the above crystallinity lower limit or more. The content of the copolymer is set to 15 mol% or less, preferably 10 mol% or less, and in the block copolymerization method, the content of the lesser copolymerized unit in the copolymer is usually 40 mol%. Less than,
It is preferably set to 20 mol% or less. Among them, polypropylene having a crystallinity of 50% or more is preferable.

The propylene-1-butene low crystalline copolymer which is the component (c) of the composition of the present invention is obtained by copolymerization of propylene and 1-butene, and has a propylene unit content of 55 to 85. Mol%, the crystallinity measured by X-ray diffractometry is 10 to 30%, and the melt flow rate [MFR (230 ° C.)] is 1 to 10 g / min. Such a copolymer is, for example, Japanese Patent Publication No. 57-
11322 and 57-36859.

[0016]

The organic peroxide, which is a radical generator used for producing the composition of the present invention, is one that decomposes in a temperature range above the softening point of the polymer component which is the most difficult to soften among the components. Sufficient for the purposes of the present invention.

Examples of organic peroxides include the following. As aromatic compounds, dibenzoyl peroxide, dicumyl peroxide, 1,3-
Bis (t-butylperoxyisopropyl) benzene (trade name Percadox 14), and aliphatic compounds include di-t-butyl peroxide, dilauroyl peroxide, 2,5-dimethyl-2,5-bis (t-butyl). Peroxy) hexane (trade name Perhexa 25B),
2,5-Dimethyl-2,5-bis (t-butylperoxy) hexene-3,2,5-dimethyl-2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-
3 (trade name Perhexin), di (t-butylperoxy) perbenzoate as a compound belonging to both aromatic and aliphatic, and p-menthane peroxide as an alicyclic compound.

Of these, preferred are bisperoxide compounds. Examples of the radically polymerizable monomer (d) having two or more polymerizable groups which may be used together with the radical generator in the method of the present invention include the following. (D-1) Aromatic compound: divinylbenzene (DV
B), isopropenylstyrene, diisopropenylbenzene, (d-2) aliphatic compound: ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, allyl methacrylate, (d-3) heterocyclic ring Family compounds: triarylyl isocyanurate. Among these, preferred are p-divinylbenzene and p-diisopropenylbenzene.

A crosslinking aid may be used in the partial crosslinking treatment. Examples thereof include p-quinone dioxime, p, p'-dibenzoylquinone dioxime, N-methyl-N, 4-dinitrosoaniline, nitrobenzene,
Diphenylguanidine, trimethylolpropane-N,
Examples thereof include N'-m-phenylene dimaleimide.

The amount of each component constituting the composition of the present invention is as follows. Radical-decomposable crystalline polyolefin (b) usually 0 to 90 parts by weight, preferably 10 to 6
0 parts by weight, ethylene-α-olefin-based amorphous copolymer (a) usually 10 to 95 parts by weight, preferably 40 to 90
By weight, the propylene-1-butene low crystalline copolymer (c) is usually 5 to 90 parts by weight, preferably 10 to 60 parts by weight, and it is convenient to select such that the sum is 100 parts by weight.

Organic peroxides which are radical initiators and 2
The addition amount of the radically polymerizable monomer having a polymerizable group is 100, which is the total amount of the components (a), (b) and (c).
Each is usually 0.05 to 3 parts by weight, preferably 0.1 to 1 part by weight.

In the present invention, the dynamic heat treatment is as follows.
Processing. The polymer component to be treated, i.e.
-Α-olefin-based amorphous copolymer (a) and radical
A combination of degradable crystalline polyolefin (b),
Has an organic peroxide or two or more polymerizable groups
A system in which the radical polymerizable monomer
And kneading under the decomposition condition of (b). Kneading is open type
It is preferable to carry out in an apparatus, such as nitrogen or carbon dioxide gas.
It is preferable to carry out under an inert gas atmosphere. Its temperature
Is the temperature at which the half-life of the organic peroxide used is less than 1 minute,
Usually 150 to 280 ° C, preferably 170 to 240 ° C,
The kneading time is usually 1 to 20 minutes, preferably 3 to 10 minutes
Is. The shearing force applied is usually 10 at a shearing rate.
-10^Foursec^- 1, Preferably 10²-10 ³sec
 ^- 1Choose to.

As a kneading device, a mixing roll, an intensive mixer such as a Banbury mixer, a kneader, a single-screw or twin-screw extruder, etc. can be used, but a non-open type is preferable.

The composition of the present invention further comprises a softening agent (also known as extender oil or plasticizer), carbon black, white carbon, other physical property-improving agents, fillers and anti-aging agents, oxidation, weather resistance or light resistance stabilizer, Processing aids, antistatic agents, pigments and the like may be added depending on the application.

[0026]

【Example】

Reference Example 1 ethylene content of 78 mol%, iodine value 15, Mooney viscosity _{ML 1 + 4 (100 ℃)} 70 ethylene - propylene -
75 parts of 2-ethylidene, 5-norbornene copolymer rubber (hereinafter abbreviated as EPDM), melt flow rate (M
FR) (230 ° C, 2.16kg) 11, density 0.91
15 parts of crystalline polypropylene (hereinafter abbreviated as PP), isobutene-isoprene copolymer rubber (hereinafter abbreviated as IIR)
10 parts, tetrakis [methylene (3,5-di-t-butyl-4-hydroxyphenyl) as an antioxidant
Propionate] 0.3 part of methane was kneaded with a Banbury mixer in a nitrogen atmosphere at 180 ° C. for 5 minutes, and then
Pellets were produced with a sheet cutter through the roll. Next, the pellets and a solution of 0.3 parts by weight of 1,3-bis (tert-butylperoxyisopropyl) benzene dissolved and dispersed in 0.5 parts by weight of divinylbenzene are mixed by a Henschel mixer, and the solution is uniformly distributed on the pellet surface. Attached to. Next, the pellets were extruded in an extruder under a nitrogen atmosphere at 210 ° C. for a residence time of 5 minutes and dynamically heat-treated to obtain a thermoplastic elastomer.

This thermoplastic elastomer was molded using an injection molding machine to obtain a sheet of 120 × 100 × 2 mm.
Then, a test piece having a width of 25 mm was cut out from this sheet, and the stress at break was measured in the lengthwise direction.
It was cm ² . In addition, its gloss was 8%.

Example 1 80 parts by weight of the thermoplastic elastomer obtained in Reference Example 1 and propylene-1-butene low crystalline copolymer pellets [propylene unit content 70 mol%, MFR (230 ° C.) 7
g / 10 mm] 20 parts by weight was mixed by a Henschel mixer, and then the pellets were extruded by an extruder under a nitrogen atmosphere at 210 ° C. for a residence time of 5 minutes to obtain a target composition. The injection-molded sheet obtained in Reference Example 1 was cut into halves, and the sheet was loaded into a molded mold, and then the thermoplastic elastomer composition of Example 2 was injection-welded to measure the bonding strength. The gloss of the welded part was measured based on JIS Z8741. The results are shown in Table 1.

Comparative Example 1 In place of 20 parts of PBR in the example, MFR (19
The thermoplastic elastomer was obtained using 20 parts of an ethylene-vinyl acetate copolymer resin (hereinafter abbreviated as EVA) having a density of 0.93 and a vinyl acetate content of 14 wt% at 0 ° C and 2.16 kg. The injection-molded sheet obtained in Reference Example 1 was cut in half, and the sheet was loaded into a molded mold,
The thermoplastic elastomer composition of Comparative Example 1 was injection welded and the joint strength was measured. The results are shown in Table 1.

[0030]

[Table 1]

It can be seen from Table 1 that the composition of the present invention can be firmly injection-welded to a molded article made of a thermoplastic elastomer. That is, the bonding strength in Example 1 was 32 kg / cm ^{2 as} evaluated by the strength at break of the sheet, and not only reached about twice the stress at break of 15 kg / cm ² in Comparative Example 1, but also Since the fractured state is also a partial material destruction, it can be seen that the joining is not merely adhesion, but the fusion of both materials at the joining portion. Since the reference example is the breaking strength of the veneer, it is surprising that the breaking strength of the example reaches 80% of the value of the veneer that surprisingly strong fusion bonding was formed between different materials. This is the evidence to show.

Claims (4)

[Claims] 1. A partial product obtained by dynamically heat-treating an ethylene-α-olefin-based amorphous copolymer (a) and a radical-decomposable crystalline polyolefin (b) in the presence of an organic peroxide. A crosslinked thermoplastic elastomer and a propylene unit content of 55 to 85 mol%, a melt flow rate [MFR (230 ° C.)] of 1 to 10 g / 10 min,
The crystallinity measured by X-ray diffractometry is 10 to 30.
% Of propylene-1-butene low crystalline copolymer (c), which is a thermoplastic elastomer composition having good injection fusion properties and good gloss. 2. The -α-ethylene olefin-based amorphous copolymer (a) is an ethylene-propylene-copolymer rubber, an ethylene-1-butene copolymer rubber or an ethylene-propylene-diene copolymer. The thermoplastic elastomer composition according to claim 1, which is a rubber. 3. The radically decomposable crystalline polyolefin (b) has a crystallinity of 5 as measured by an X-ray diffraction method.
The thermoplastic elastomer composition according to claim 1, which is 0% or more of crystalline polypropylene. 4. The partially crosslinked thermoplastic elastomer is obtained by further mixing the components (a) and (b) with a radically polymerizable monomer having two or more polymerizable functional groups to obtain an organic peroxide. The thermoplastic elastomer composition according to claim 1, which is obtained by dynamically heat-treating in the presence of a substance.