JPS6136344A - Polymeric composition - Google Patents

Abstract

PURPOSE:A composition, obtained by incorporating an olefinic thermoplastic elastomer with an ethylenic ionomer resin, and having both improved oil and scratch resistance and surface gloss. CONSTITUTION:A composition obtained by incorporating (A) 100pts.wt. thermoplastic elastomer consisting of a polyolefin resin and ethylene-alpha-olefinic copolymer rubber, and at least one thereof being partially crosslinked with (B) 10- 100pts.wt., preferably 15-99pts.wt. ethylenic ionomer resin. Propylene is used as the polyolefin resin of the component (A). An ethylenic ionomer resin obtained by neutralizing 5-80mol% carboxylic acid groups of an ethylenic copolymer, consisting of 75-99.5mol% ethylenic units and 0.5-15mol% alpha,beta-unsaturated carboxylic acid units with mono--trivalent metallic ions is used as the component (B).

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a polymer composition having excellent oil resistance, scratch resistance, and surface gloss, which is a mixture of an olefinic thermoplastic nidistomer and an ethylene ionomer resin.

(Prior art) Thermoplastic elastomer mainly composed of a partially crosslinked product of polyolefin resin and ethylene/α-olefin copolymer rubber 1
-1 So-called olefin thermoplastic elastomers have the characteristics of both resins and elastomers, and have excellent flexibility, heat resistance, weather resistance, and moldability.
Body panels, bumper parts, site shields, protectors, moldings, window frames, human automobile parts, home appliance parts,
It is widely used as sporting goods, civil engineering seats, building materials, etc., and is particularly attracting attention as a molding material suitable for automobile parts. However, although this thermoplastic nidistomer has the excellent properties mentioned above, it has poor oil resistance, scratch resistance (abrasion resistance), and does not have good surface gloss. When used,■
Easily attacked by solvents such as gasoline, ■Easy to be scratched,
0 Due to the lack of surface gloss, there are disadvantages such as low commercial value, and oil resistance, which is a disadvantage of these thermoplastic elastomers.
There was a need to improve scratch resistance and surface gloss.

(Problems to be Solved by the Invention) The present invention maintains the excellent flexibility, heat and cold resistance, and moldability that are the features of conventional olefin-based thermoplastic elastomers, while improving oil resistance, which is the drawback of thermoplastic elastomers. ,
This was done to provide a new polymer composition with improved scratch resistance (abrasion resistance) and surface gloss.

(Summary of the Invention) That is, the present invention provides: (A) A thermoplastic elastomer 1 containing a polyolefin resin and an ethylene/α-olefin copolymer rubber as essential components, at least one of which is partially crosslinked.
B) Ethylene ionomer resin l per 00 parts by weight
A polymer composition containing at least f parts by weight and less than 100 parts by weight of O.

(Means for solving the problem) In the present invention, oil resistance, stress resistance, and surface gloss are improved by mixing an olefinic thermoplastic elastomer (A) with an ethylene-based ionomer resin (B). However, the thermoplastic m used in the present invention
The elastomer contains (A) a polyolefin resin and (B) an ethylene/α-olefin copolymer rubber as essential components, at least one of which is usually ethylene/α-olefin.
Olefin copolymer rubber alone or both the rubber and polyolefin resin are partially crosslinked, typically (,) Ethylene/α-olefin copolymer rubber i
oθ~-0 parts by weight (b) polyolefin resin O~za0 parts by weight (here, (a) + (b) are selected to be 100 parts by weight) and (c) peroxide non-crosslinked hydrocarbon rubber-like (d) A partially crosslinked rubber composition (c100 to A composition containing 30 parts by weight of polyolefin resin (1) and 11 to 70 parts by weight of polyolefin resin (1) (however, the total amount of (b) in the final composition is 100 parts by weight of the final composition, and 5 to 70 parts by weight). Examples of the thermoplastic elastomers used in the present invention include the following compositions.

+tl (a) Ethylene/α-olefin copolymer rubber 100-20 overlapping parts, preferably to to 30
Mixture (1) of polyolefin resin o-go parts by weight, preferably -0 to 0 parts by weight, or (C) peroxide non-crosslinked hydrocarbon rubber to ioo parts by weight of this mixture 15 or (1) mineral oil softener o-io.

Thermoplastic elastomer compositions (partially crosslinked rubber compositions) that are dynamically heat treated in the presence of a crosslinking agent and partially crosslinked to form a thermoplastic elastomer composition, preferably a partially crosslinked rubber composition. Product (I)] (21 (To 100 parts by weight of the thermoplastic elastomer composition of 11, polyolefin resin (1) is further added in a proportion of up to 13 parts by weight (about 433 parts by weight).
A thermoplastic elastomer composition made by mixing.

In the present invention, as a thermoplastic elastomer, +31 (a) ethylene/α-olefin copolymer rubber or a peroxide non-crosslinked rubbery substance (c) and 15 is obtained by partially crosslinking a mixture containing a mineral oil softener (d) at a ratio of 100 parts by weight in the presence of a crosslinking agent by subjecting it to static K, for example, by pressing and heat-treating a rubber mixture. Partially crosslinked ethylene/α-olefin copolymer rubber tO~
- A thermoplastic elastomer composition formed by mixing the heavy background part and the olefin resin (1) - 10 parts by weight can also be used, but in the present invention, the thermoplastic elastomers (1) and (21) are particularly used. preferable.

In the present invention, it is not preferable to use an uncrosslinked nystomer composition instead of a partially crosslinked thermoplastic elastomer because the resulting polymer composition will have lower tensile properties, heat resistance, and oil resistance.

In the present invention, ethylene/α-olefin copolymer rubber (IL), which is a raw material for thermoplastic elastomers, includes, for example, ethylene-propylene copolymer rubber, ethylene-propylene-nonconjugated diene ternary or multicomponent copolymer rubber, ethylene -butadiene copolymer rubber, ethylene-/-butene copolymer rubber, ethylene-7-butene-nonconjugated diene multipolymer rubber, etc. with ethylene and α-carbon atoms of 3 to 47
A substantially amorphous elastomer containing olequin as a main component or a mixture thereof. Among them, Monoke ethylene-propylene copolymer rubber and ethylene-propylene-nonconjugated diene terpolymer rubber are preferred.

Here, non-conjugated dienes include dicyclopentadiene, heguhexadiene, cyclooctadiene, methylenenorbornene, and more! -Ethyritene-Norpornene etc.＼
Among these, a copolymer containing dicyclopentadiene and S-ethylidene-norbornene as the third component is preferred.

Mooney viscosity of these binary or multicomponent polymers [ML I+
4 (/00)] is usually 10 to /10°, preferably 1IO-/llO, and its iodine value (unsaturation degree)
is preferably #'i76 or less.

The amount of each structural unit contained in these elastomers is /
-In the olefin part, ethylene units/α-olefin units! θ/jθ ~ ri θ//θ, preferably ri θ/
The ratio of 3θ~8j~tS (molar ratio J), /-olefin (ethylene + α-olefin) units / non-conjugated diene units (in the case of ternary or multi-component copolymers) is usually q
t/a ~ t o/l o, preferably 97''/3 ~
It is the ratio of t'lt/l (molar ratio).

In the present invention, the polyolefin resin (b) to be mixed with the ethylene/α-olefin copolymer rubber during dynamic heat treatment includes ethylene, propylene, butene-11
Homopolymers of /-olefins such as hexene-/, l-methyl-/-hentene, copolymers of one or more thereof, or copolymers of α-olefins with other polymerizable monomers of /j mole or less Copolymer, such as ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate Examples include copolymers and resin-like polymer substances. In the present invention, the melt index (person STM-D-/ko3t-bsr) is o, i or roll/lom=, especially S or co01/10t.
A polyolefin resin in which the crystallinity is 1IO% or more and the degree of crystallinity determined by the xffpff standard method is preferably used.

In the present invention, particularly preferred polyolefin resin (b
), the melt index is 0. / or 101/
10mln, peroxide-decomposed polyolefin resin with a crystallinity of Jθ% or more (a polyolefin resin that is thermally decomposed by mixing with peroxide and cross-wired under heating to reduce the molecular weight and increase the fluidity of the resin), specifically is isotactic polypropylene, or propylene and l! A copolymer with other α-olefins of r mol or less,
For example, propylene-ethylene copolymer, propylene-1
Examples include -butene copolymer, propylene-1-hexene copolymer, and zorobylene-dermethyl-1-pentene copolymer.

In addition, in the present invention, the peroxide decomposition type polyolefin resin and the peroxide crosslinked polyolefin resin (
Polyolefin resin (polyolefin resin whose fluidity decreases due to crosslinking by mixing with peroxide and kneading under heat),
For example, a mixture with low or medium density polyethylene having a density of 0, delO to 06 deda θ is also preferably used as the polyolefin resin (b).

Next, when preparing a thermoplastic elastomer, (c) peroxide non-crosslinked hydrocarbon-based rubbery substance, which is blended as necessary, includes, for example, polyimbutylene, butyl rubber,
When mixed with peroxides such as propylene-ethylene copolymer rubber containing 70 moles or more of propylene, propylene-l-butene copolymer rubber, atactic polypropylene, etc., they do not crosslink and do not reduce fluidity even when kneaded under heat. A hydrocarbon-based rubbery substance. Among these, polyimbutylene and propylene-/-butene copolymer rubbers are most preferred.

(d) A mineral oil softener is a softening agent that weakens the intermolecular force of rubber during roll processing, making processing easier, and helping disperse carbon black, white carbon, etc. High boiling point petroleum fractions are used to reduce the hardness of sulfur rubber and increase flexibility and elasticity, and are classified into paraffinic, naphthenic, and aromatic fractions.

In the present invention, when preparing a thermoplastic elastomer,
These peroxide non-crosslinked hydrocarbon rubbery substances (
Although it is not necessary to incorporate C) and 15 or the mineral oil softener (d), ethylene-α- Olefin copolymer rubber (,) and polyolefin resin (b) total amount 100 parts c) and 15
or (d) up to 100 parts by weight, preferably sfx to 10θ heavy parts.

Furthermore, the present invention Kj? The polyolefin resin (It) to be mixed as necessary after the dynamic heat treatment is the same resin as the polyolefin resin (b) added during the dynamic heat treatment, namely ethylene, propylene, butene-11.
Hexene-75-methyl-7-pentene, etc./-
Homopolymers of olefins, copolymers of one or more thereof, or copolymers of α-olefins with other polymerizable monomers of 13 molar or less, such as ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers Polymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylate copolymer, ethylene-
Examples include methyl methacrylate copolymers, etc., which are resinous polymeric substances. These polyolefin resin values) melt index (A8TM-D-Saw 3g-
AkT, /? (17, however, propylene polymer is 230υ)! ~ioo, particularly 10~SO is preferred. When adding polyolefin resin both during and after dynamic heat treatment, add polyolefin resin (b
) and the polyolefin resin (1) may be of the same type or different types.

To prepare the thermoplastic elastomer in the present invention,
Ethylene/α-olefin copolymer rubber (a)/(70
0 to 30 parts by weight of polyolefin resin (b) θ to 30 parts by weight, and if necessary further mixed with peroxide non-crosslinked rubber (c) and/or mineral oil softener (a) 0 to θ parts by weight. Approximately O per 100 parts by weight of the blend made of
, OS--% by weight, preferably 0. /flIshiO3S
Partial crosslinking may be carried out by blending a crosslinking agent in an amount of % by weight and dynamically heat-treating the mixture.

Dynamic heat treatment here means kneading in a molten state.

The crosstalk is preferably performed in a closed type device, and preferably under an atmosphere of an inert gas such as nitrogen or carbon dioxide gas. That temperature is usually.

~gotX, preferably /70~λ1Iot::, kneading time is usually 1-20 minutes, preferably f-1/~/θ minutes.

The crosslinking agents used for partial crosslinking in the present invention include organic peroxides, sulfur, phenolic vulcanizing agents,
Examples include oximes and polyamines, but among these, from the viewpoint of the physical properties of the thermoplastic elastomer obtained,
Organic peroxides and phenolic vulcanizing agents are preferred crosslinking agents.

Examples of the phenolic nitrifier used in the present invention include alkylphenol formaldehyde resins, triazine-formaldehyde resins, and melamine-formaldehyde resins.

Furthermore, the organic peroxides used in the present invention include:
dicumyl peroxide, di-tart-butyl peroxide, S,S-dimethyl-,2,5-bis(tart-
butylperoxy)hexane, co, S-dimethylco,
S-bis(tart-butylperoxy)hexyne-3
, he/-bis(1θrt-butylperoxyisopropyl)benzene, he/-bis(tart-butylperoxy)-3゜3 is monotrimethylcyclohexane, n-butyl-11, dervis(tsrt-butylperoxy)parerate, di Examples include benzoyl peroxide, tert-butyl peroxybenzoate, etc.
Among them, bisperoxide compounds are preferred due to their slightly unpleasant odor and high scorch stability, and 1,3-bis(t8
rt-butylperoxyisopropyl)benzene is most suitable.

In addition, during partial crosslinking heat treatment, P-quinonedioxime, p
, p'-dibenzoylquinonedioxime-lz, and polyfunctional vinyl monomers such as divinylbenzene (DVB), diethylene glycol methacrylate, and polyethylene diglycol methacrylate, resulting in more uniform and relaxed properties. It is preferable to incorporate these crosslinking aids and polyfunctional vinyl monomers, since a crosslinking reaction can be realized. In particular, divinylbenzene (DVB) is most preferred because it has a homogeneous crosslinking effect upon heat treatment and can yield a thermoplastic elastomer with well-balanced fluidity and physical properties.

In the present invention, in addition to the thermoplastic elastomer, fillers such as carbon black, clay, talc, calcium carbonate, heavy calcium carbonate, kaolin, diatomaceous earth, silica, alumina, asbestos, graphite, and glass fiber, and phenyl-α- Naphthylamine, 2,6-ditertiary-butylphenol, tetrakis[methylene (3,!
Antioxidants such as (di-tart-butyl-hydroxyphenyl)probionate and other additive components can be blended.

These fillers and additives may be added during the preparation stage of the thermoplastic elastomer, or may be added after the preparation.

In the present invention, "partially crosslinked" does not mean that the composition after crosslinking is crosslinked to the extent that it does not lose its properties as a thermoplastic elastomer. Partially crosslinked thermoplastic elastomers are preferred.

Measurement of Gel Content Approximately 100 Mg of a sample pellet of thermoplastic elastomer was weighed and added to yocc of cyclohexane in a closed container.
After being immersed for 4tt at 3υ, the sample was taken out and dried. The weight of this dry residue minus all insoluble fillers, pigments, etc. is the corrected final weight after drying (Y). On the other hand, the weight of cyclohexane-soluble components other than the ethylene/α-olefin copolymer and polyolefin resin, such as mineral oil, plasticizers, cyclohexane-soluble rubber components, and insoluble fillers and pigments, was subtracted from the weight of the sample pellet. Initial weight corrected to 0
Set to 0.

Here, the ethylene ionomer resin used in the present invention is an ethylene/α,β-unsaturated carboxylic acid copolymer (0)
Or ethylene/α,β-unsaturated carboxylic acid/α,β
- A portion of the carboxylic acid groups of the unsaturated carboxylic acid ester copolymer (II), usually j to zaoq6, are neutralized with metal ions.

In the present invention, the proportion of ethylene units in the ethylene copolymer component (D or (1)) before neutralization is usually about 7 to 9 days, preferably about 7 to 9 degrees. , α,β-unsaturated carboxylic acid units are customary O,S~/j moles, preferably 1 to 6 moles.

Further, the proportion occupied by the α,β-unsaturated carboxylic acid ester units is usually θ to 10 mol, preferably θ to 6 mol.

Further, among the carboxylic acid groups in the copolymer of 0) or (It) above, the proportion of carboxylic acid groups that are neutralized by metal ions (degree of neutralization) is usually s-go%, preferably 10 to 10%. 3%.

The content ratio of ethylene units in the above ethylene copolymer is
If it exceeds 75 molt, the oil resistance and scratch resistance of the resulting polymer composition will decrease, while if it is less than 75 molt, the flexibility of the resulting polymer composition will decrease.

Furthermore, if the content of α,β-unsaturated carboxylic acid in the ethylene copolymer is less than o3 molt, the oil resistance, scratch resistance and adhesive properties of the resulting polymer composition will be impaired; The heat resistance of the composition decreases.

If the degree of neutralization of carboxylic acid groups by metal ions is less than z%, the oil resistance and scratch resistance of the polymer composition will decrease,
On the other hand, if it exceeds tty%, the compatibility with the thermoplastic elastomer will be poor, and as a result, not only will crosstalk be impaired, but a polymer composition with satisfactory physical properties will not be obtained.

The unsaturated carboxylic acid ester unit has the role of imparting flexibility to the ethylene ionomer resin and improving compatibility with the olefinic thermoplastic elastomer, but the unsaturated carboxylic acid ester unit in the copolymer When the content of units exceeds 10 molty, the heat resistance of the resulting polymer composition decreases.

The α,β-unsaturated carboxylic acids constituting the above copolymer include acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, maleic anhydride, etc. having 3 to 3 g carbon atoms.
α,β-unsaturated carboxylic acids are used, and α,β-
Examples of unsaturated carboxylic acid esters include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, inbutyl acrylate, butyl methacrylate, dimethyl phthalate, and other unsaturated α,β-unsaturated carboxylic acids with a carbon number of D to S. Carboxylic acid esters are used. Among these, particularly preferred α/β-unsaturated carboxylic acids are acrylic acid and methacrylic acid, and a preferred ester is inbutyl acrylate.

The metal ions that neutralize the carboxylic acid groups of the ethylene copolymer include metal ions having a valence of /-7, especially l, I, I, and IVA in the periodic table of elements.
and a metal ion having a valence of 1 to 3 from group Ⅰ, specifically, Na+, K+, L1+, C8+, Ag+
, Hg9Cu10, B, -++, Mg++, Ca10+,
Sr++, B1+10, ou++, c6++, H1++,
snn+1Pb-toshi1, e-1+, GO++, Nl+
+, zn++, A, -H+, kanto sho+ kan→Sc, Fa, Y, etc. are mentioned.

There is no problem even if these metal ions are a mixed component of more than one type, and even if they are a mixed component with ammonium ions. Among these metal ions, 1Tf
Kzrr++, N, + are preferred.

AST of ethylene ionomer resin used in the present invention
The melt index (/O?lX) measured according to M D /Co3t is usually o, i to ioo.

It is in the range of 11/lo order.

In the polymer composition of the present invention, the mixing ratio of the thermoplastic elastomer (A) and the ethylene ionomer resin (B) is such that the ethylene ionomer resin (B) is 70 parts by weight of the thermoplastic elastomer ((trans)ioozH). parts or more and less than 100 parts by weight, preferably lj to 100 parts by weight,
Particularly preferred is a range of 10 to 90 parts by weight. If the amount of the ethylene ionomer resin (B) is less than 10 parts by weight based on the weight of the thermoplastic elastomer (A), the oil resistance, scratch resistance, and surface gloss of the resulting polymer composition will not be sufficiently improved. sea bream. In view of the flexibility and heat resistance of the resulting polymer composition, the amount of the ethylene ionomer resin (B) to be blended is preferably less than 100 parts by weight based on the i o o parts by weight of (A).

It is preferable that the polymer composition of the present invention has a melt index (Ide θυ) of o, or to roll/loym, and a hardness (D) of 1oS-to.

The polymer composition of the present invention is prepared by triblending or melt blending the thermoplastic elastomer (A) and the ethylene ionomer resin (B) simultaneously or sequentially.

Tri-blends are mixed using various types of blenders such as Henschel mixers, tumbler mixers, and ribbon blenders, while melt blends are mixed using various blenders such as single-screw extruders, twin-screw extruders, pants (Lee mixers, etc.), and roll blenders. , they can be melted and mixed using various kneaders, etc.
There are particular restrictions on the mixing order.

The polymer composition of the present invention may also contain fillers, such as carbon black, to the extent that the performance of the composition of the present invention is not impaired.
Clay, talc, calcium carbonate, heavy calcium carbonate, kaolin, diatomaceous earth, silica, alumina, earth best, graphite, whiskers, metal powder, glass bulbs,
Glass fibers, carbon fibers, etc., coloring agents such as titanium oxide, zinc white, red iron, ultramarine blue, navy blue, azo pigments, nitrone pigments, lake pigments, phthalocyanine pigments, etc., or other additives such as known antioxidants, plasticizers, etc. It is also possible to add additives, heat stabilizers, weather stabilizers, antistatic agents, metal soaps, lubricants such as wax, flame retardants, and the like.

These fillers, colorants, and additives may be added at the stage of preparing the olefinic thermoplastic elastomer as described above, or may be added at the stage of preparing the polymer composition of the present invention. Furthermore, it is also possible to add a foaming agent to the composition of the present invention to form a foam.

(Effects of the present invention) By blending a specific amount of ethylene-based ionomer resin into an olefin-based thermoplastic elastomer, the polymer composition of the present invention achieves oil resistance, scratch resistance, and surface gloss that are lacking in thermoplastic elastomers. As a result, the polymer composition of the present invention has excellent flexibility, heat and cold resistance, and moldability, as well as excellent oil resistance, scratch resistance, and surface gloss.

The composition of the present invention is molded into m shapes by conventionally known molding methods such as injection molding, extrusion molding, compression molding, and calendar molding. Compared to elastomer molded products, it has excellent oil resistance, scratch resistance, and surface gloss, so when used as automobile parts such as bumpers, various moldings, and mudguards, it is suitable for use with gasoline and other solvents, as well as engine oil. ■ Resistant to being attacked by non-polar oils, ■ Resistant to scratches,
It has features such as a glossy surface and high commercial value, and is not only widely used in this field, but also for home appliance parts, sports parts such as roller skates, squeegees, racket grips, tarpaulins, curtain hoses, and belts. etc. K is also widely used.

The present invention will be explained in more detail by way of Examples below. The physical properties of the thermoplastic polymer compositions in the Examples were measured by the following methods.

(1) Basic physical properties A test piece was cut from a square plate with a thickness of JIB obtained by injection molding, and measured according to the following method.

Tensile properties: Measured according to JIS K-430/method.

Spring hardness: JIS K-430/JI listed
Measured using the 8^type method.

Permanent elongation: Measured by JIS K-430/method.

(Strain / θθchi) Heat-resistant temperature: Place the test piece in a constant temperature bath, and set the temperature of the bath to λOυ
The temperature is expressed as the temperature at which a needle of diameter θ, g++n with a load of 4 (?, ?) touches the sample by 0.71 m when the temperature is raised at a rate of 0.71 m.

Taper wear: JIS K-? − Measured according to 〇da.

Is the wear wheel O8-/? using 1ooo rotation with load iooog The subsequent abrasion loss was measured.

Oil resistance: Measured according to the method of JIS K-4jθ/.

(2) Injection molding method (A) Molding conditions Injection molding was performed using the following equipment and conditions.

Molding machine: Dynamelter (Kyo Seisakusho #) Molding temperature θθυ Injection pressure Kani-Next pressure / Jθ0~/32 Secondary pressure 00Kp/m2 Injection speed: Exhaust Large molding speed: 90 seconds/l Cycle gate: Direct gate (Land length: 10 fins, Width: 10 Il, Thickness: l fins) Molded product: Square plate (Length: 300 m + 11. Width/1011% Thickness: 38 II
I+) (B) Appearance Judgment Criteria for Molded Products (1) Flow Mark Rating: Judgment Criteria l Near 0- Marks are extremely numerous 2: Significantly seen on the entire surface of the molded product 3: Slightly seen on the entire surface of the book 4I : Slightly observed only on the opposite side of the gate; S-near 0-mark not observed at all (Surface gloss measured at an incident angle of 60° according to the method of ASTM D-123).

S: 70% or more cross lI: 90% to 70% cross 3 Nigelos are 0% Koochi~da 12 Gross is 10% to 20% /: Cross is less than 10% (3) Extrusion moldability (A) Molding conditions Cheeve was extruded using the following equipment and conditions.

Molding machine Hy011JIp extruder (manufactured by Toshiba Machine) Sugenyu: Dalmage Scrier L/D=mu Compression ratio 3. j Molding temperature: Knee 10 Die: Straight die (Die/core = 10, 10, 10, 0, ohm) Take-up speed = 6 m/2000 (B) Appearance criteria for molded products: The unevenness of the surface of the tube is determined according to the following S stage. It was evaluated by

Rating: Judgment criteria! r: The skin is extremely smooth, and the dust mite skin is smooth and the cross S% to IO%. Production) Ethylene content Omolti, iodine value 15. Ethylene zolobylene-ethylidene norbornene copolymer rubber (hereinafter referred to as RPDM) with Mooney viscosity MLI + J (10 (7 υ) l-〇
) 70 parts by weight, melt index (ASTM-
D-/ko8-1. ! Tλ30υ)/3, density O, delI
! /cIIh3 polypropylene (hereinafter abbreviated as pp) co-O superimposed part, polyisobutylene (vistanex MML-
100 (manufactured by Esso Inc., hereinafter abbreviated as PIB) and 7 parts by weight of ten-based process oil (hereinafter abbreviated as oil) were placed in a Banbury mixer in a nitrogen atmosphere.
After kneading for 5 minutes at tOυ, the mixture was passed through a roll and then cut into pellets using a sheet cutter. (Step 7) Next, 0.3 parts by weight of 3-bis(tart-butylberoxyisozorobyl)benzene (hereinafter abbreviated as peroxide A) was added to the pellet and 0.3 parts by weight of divinylbenzene (hereinafter abbreviated as DVB). The solution was preliminarily mixed with 5 parts by weight using a Henschel mixer, and the solution was uniformly adhered to the surface of the pellet.

Next, this pellet was placed in a nitrogen atmosphere using an extruder for 220 υ
An extruded thermoplastic elastomer (hereinafter abbreviated as thermoplastic elastomer A) was obtained.

Reference Example (manufacture of thermoplastic elastomer) In step 11 of Reference Example/, butyl rubber (rxrt-Oat manufactured by Japan Synthetic Rubber ■, ML1+) was used instead of PIBO.
5 (at 100)! I? A thermoplastic elastomer (hereinafter abbreviated as thermoplastic elastomer B) was obtained in the same manner as in Reference Example 1, except that , unsaturation degree/, O (hereinafter abbreviated as IIR) was used.

Example 1 Parts by weight of the thermoplastic elastomer Aioo obtained in Reference Example 1 and ethylene ionomer resin (Mitsui Polychemical ■ product, trade name Himilan/6S MI (/9)
0υ)! After mixing with 20 parts by weight of pellets of i// 0, density O, deda p/cm', ion type lZn type) (hereinafter abbreviated as ionomer resin A) in a tumbler blender, extrusion was carried out in an extruder at θ/θ°C. , the desired composition was obtained.

Examples 2 to 3 The same procedure as in Example 1 was conducted except that the amount of the ionomer resin added to 100 parts by weight of the thermoplastic elastomer A was changed as shown in Table 1.

Comparative Example 1 A test piece was prepared using only thermoplastic elastomer A and evaluated.

Comparative Example In Example 1, high-pressure low-density polyethylene (melt index (l?θ°C)) was used instead of ionomer resin B.
The same procedure as in Example 1 was carried out except that LDPK was used.

Comparative Example The same procedure as in Example 1 was carried out except that in place of thermoplastic elastomer A, the uncrosslinked rubber composition CI) obtained in the first step of Reference Example 1 was used.

In Example 1, Example 11 on the left, or U, ethylene-based ionomer resin (Mitsui Polychemical Co., Ltd.
Product, product name Himiran/! ;! ! .

MI (/waOυ) 10 g/10mls, density O
The same procedure as in Example 1 or Yo was performed except that 6 lamps 1//1 m', ion type INa type (hereinafter abbreviated as ionomer resin B) was used.

Example 6 Example 1 was carried out in the same manner as in Example 1, except that thermoplastic elastomer B obtained in Reference Example Y was used instead of thermoplastic elastomer A.

Table 1 shows the evaluation results of the compositions obtained in Example 1-6 and Comparative Example 1-2.

Reference Example 3 (Manufacture of thermoplastic elastomer) In the first step of Reference Example 1, the blending amount of PP was 30 layers, PIB and oil were not blended, and peroxide A and DVB were substituted in the first step. Niko, S-dimethylluko! -di(tert-butylperoxy)hexyne-
A thermoplastic elastomer (hereinafter abbreviated as thermoplastic elastomer C) was obtained in the same manner as in Reference Example 1 except that only o, yz parts of 3 (hereinafter referred to as peroxide B) were used.

Reference Example 2 (Manufacture of thermoplastic elastomer) In the first step of Reference Example 1, the amount of pp blended was 30 parts by weight,
A thermoplastic elastomer (hereinafter referred to as thermoplastic elastomer D) was prepared in the same manner as in Example 1, except that PIB was not blended and peroxide B was used instead of peroxide A in the first step.
) was obtained.

Examples 1 to g The same procedure as in Example 1 was carried out except that thermoplastic elastomer C obtained in Reference Example 3 was used in place of thermoplastic elastomer A.

Comparative Example Disease A test piece was prepared using only the thermoplastic elastomer C obtained in Reference Example 3 and evaluated.

Examples D to I In Example 1, thermoplastic elastomer D obtained from the reference side disease was used as a substitute for thermoplastic elastomer A, and the type and amount of the ionomer resin were changed as shown in Table 2. The same procedure as in Example 1 was carried out except for this.

Example/J In Example 1, ethylene-based ionomer resin (Mitsui Polychemical ■ product,
Product name Himiran/RiOko, MI (790℃)/+97
The procedure was the same as in Example 1 except that 10 m, density (7193 l/m', ion type Zn type) (hereinafter abbreviated as ionomer resin 0) was used.

Comparative Example A test piece was prepared using only the thermoplastic elastomer D obtained in the reference case and evaluated.

Above are Examples 2 to 13. Table 2 shows the evaluation results of the compositions obtained in Comparative Examples D to D.

Reference example (manufacture of thermoplastic elastomer) In the first step of reference example 1, the amount of EPDM was changed to SO
A thermoplastic elastomer (hereinafter referred to as thermal A plastic elastomer E) was obtained.

In Examples 11A to 1 or 1, thermoplastic elastomer A
The same procedure as in Example Y or Weak was carried out except that thermoplastic elastomer E obtained in Reference Example 3 was used instead of.

As a comparative example, a test piece was prepared using only thermoplastic elastomer E and evaluated.

Reference Example 6 In the seventh step of Reference Example 1, the amount of EPDM was 70 parts by weight,
The blending amount of PP was 15 parts by weight, and instead of PIB and oil, ethylene-methacrylic acid copolymer (melt index (/?0r) 101/10m, density O,
Thermoplastic elastomer F (hereinafter referred to as thermoplastic elastomer ) was obtained.

Example/A-10 In Example 1, thermoplastic elastomer F obtained in Reference Example 6 was used in place of thermoplastic elastomer A, and the type and amount of ionomer resin were as shown in Table 3. The same procedure as in Example 1 was performed except for the following changes.

Comparative Example 2 A test piece was prepared using only the thermoplastic elastomer F obtained in Reference Example 6 and evaluated.

Table 3 shows the evaluation results of the compositions obtained in Examples Ivy to Ko θ and Comparative Examples 6 to 2.

Reference example ethylene/propylene/dicyclopentadiene ternary copolymer rubber (ethylene/propylene molar ratio t/here, M
L1+4 (at 100) / A o, iodine value 1
3) Bullet-shaped KP containing 1 part of 100Mf and 1 part of mineral oil softener (yo1gt of Idemitsu Petrochemicals pw-io)
DM (hereinafter abbreviated as RPDM-1) to parts by weight, ppco O heavy background parts VBo, 4' parts by weight, peroxide B O
, 25 parts by weight were premixed for 6Q seconds in a shell mixer, and this mixture was transferred to a twin screw extruder (W&PX manufactured by Warner).
L/D=:=tI3 (hereinafter abbreviated as a twin-screw extruder) was fed with a constant feeder and extruded at 210°C to obtain a thermoplastic elastomer (hereinafter abbreviated as thermoplastic elastomer 0).

Example 1: 10 parts by weight of the thermoplastic elastomer Gioo obtained in Reference Example were mixed with 10 parts by weight of ionomer resin A in a tumbler blender, and then extruded with an extruder at -10υ to obtain the desired composition. Ta.

Example 2 The same procedure as in Example 1 was carried out except that the amount of ionomer resin A was changed to the qo overlapping portion.

Comparative Example & A test piece was prepared using only thermoplastic elastomer G and evaluated.

Reference Example & In Reference Example 7, the blending amount of EPDM-1 was 70 parts by weight, the blending amount of PP was 20 parts by weight, and the new IcE
A thermoplastic elastomer (hereinafter referred to as thermoplastic elastomer H
) was obtained.

Examples Koni - Koro 100 parts by weight of the thermoplastic elastomer H obtained in Reference Example t was mixed with the ionomer resin shown in Table 7 in the proportions shown in the same table using a tumbler blender, and then mixed with 100 parts by weight of the thermoplastic elastomer H obtained in Reference Example t.
The desired composition was obtained by extrusion at υ.

Example 2 In Example 2, instead of ionomer resin A, ethylene-based ionomer resin (Mitsui Polychemical side product,
Example λ except that product name Himilan/lθ/ Mz(1woυ)/, density O, Deda I/忤3, ion type Na-based) (hereinafter abbreviated as ionomer resin) was used.
I did the same as step 3.

A test piece was prepared using only the thermoplastic elastomer H obtained in Comparative Example and Reference Example and evaluated.

The evaluation results of the compositions obtained in Examples 21 to 2 and Comparative Examples g to D are shown in the @da table.

Reference Example 9 Ethylene/propylene/ethylidenenorbornene copolymer rubber (ethylene/propylene molar ratio 17s/co3, M
L, +, (10 (F:) / 6θ, iodine value / 5)
Mineral oil softener (Idemitsu Petrochemical Products p.
w-7O0) 70 parts by weight of oil-extended EPDM (hereinafter abbreviated as EPDM-, 7) blended with G02 and parts by weight of ppyo were mixed in a Banbury mixer for 3 minutes at lO'c, and then further mixed with sulfur. Added 0.5 parts by weight, parts by weight of tetraethylthiuram disulfide OOS, Corbis (benzothiazolyl) disulfide θ, - type bone part, and 2.0 parts by weight of zinc oxide, and kneaded for an additional S minute with tWOυ, passed through a roll, and cut into a sheet cutter. A pellet was manufactured using the above method to obtain a thermoplastic elastomer (hereinafter abbreviated as thermoplastic elastomer I).

Example code g Reference example! 1,100 parts by weight of the thermoplastic elastomer obtained in step 1 and parts by weight of ionomer resin A and O were mixed in a tumbler and extruded at 210 υ with an extruder to obtain the desired composition.

Example Cobb Example-g was carried out in exactly the same manner as in Example 2&, except that ionomer resin B was used in place of ionomer resin A.

Comparative Example 1θ A test piece was prepared using only thermoplastic elastomer I and evaluated.

Reference Example IO KPDM-J Parts by weight of RiO and parts by weight of PP301i were kneaded in a Banbury mixer at /lO°C for 3 minutes, and then a phenol curing resin (SP-10!r & Schenectaday Chemicals, hereinafter abbreviated as phenol curing agent) was added. B,
0 parts by weight and 1.0 parts by weight of zinc oxide were added and kneaded for further S minutes at /10υ, then passed through a roll and used a sheet cutter to produce a thermoplastic elastomer (hereinafter abbreviated as thermoplastic elastomer J). Obtained.

Example 30 The thermoplastic elastomer J/θθ heavy portion obtained in Reference Example IQ and 20 parts by weight of ionomer resin A were extruded using a tumbler mixer and an extruder at 10°C to obtain the desired composition.

Examples 31 to 3'A The same procedure as in Example 3θ was carried out except that the type and amount of the ionomer in Example 30 were changed as shown in Table 3.

Comparative Example/l A test piece was prepared using only the thermoplastic elastomer J obtained in Reference Example IQ and evaluated.

Table 3 shows the evaluation results of the compositions obtained in Examples, 2g~Jhiro, and Comparative Examples 1θ~/l.

Reference Example/l 100 parts by weight of EPDM and 30 parts by weight of oil were kneaded in a Banbury mixer in a nitrogen atmosphere at 110°C for 5 minutes, and then passed through a roll to produce pellets with a sheet cutter (first step). Next, the pellets and a solution prepared by dissolving and dispersing 0.3 parts by weight of Peroxide A in 0.3 parts by weight of D V BOOS were premixed using a tumbler blender, and the solution was uniformly adhered to the surface of the pellets. Next, this pellet is extruded with an extruder under a sulfuric acid atmosphere,
A thermoplastic elastomer (hereinafter referred to as thermoplastic elastomer) was obtained. (Step 1) 100 parts by weight of the thermoplastic elastomer obtained in Reference Example/l of Example 3 and 10 parts by weight of ionomer resin A were mixed in a tumbler blender and extruded at 10 υ with an extruder to obtain the desired composition. I got it.

Example JA In Example J, the blending amount of ionomer resin A was 41
The same procedure as in Example 3 was carried out except that the weight part of O was changed.

Example 32 The same procedure as Example J6 was carried out except that ionomer resin A was used in place of ionomer resin A.

Comparative Example/2 A test piece was prepared using only a thermoplastic elastomer and evaluated.

Example 3 & After mixing, the mixture was extruded using an extruder at λ/2 to obtain the desired composition.

Example 3q.

In Example 3g, an ionomer resin was used instead of ionomer resin A, and an ethylene-propylene copolymer (melt index (tqoυ)) of 3.o was used as the PPO base υ.
, density 0. ? lIp /arc', hereinafter M D P
Example 7 was carried out in exactly the same manner as in Example 7, except that G) was used.

Example θ In Example 39, ethylene-vinyl acetate copolymer (melt index (/θv)/
k, F'F vinyl acid content i/4'mt%, hereinafter EV
The same procedure as in Example 39 was carried out except that A) was used.

Example 1 In Example 39, high-density polyethylene (melt index (190°C) 1, density 0
．． 94 s l /lns or less anpg t omitted) ヲ用E71、■1 Doosan Tawara + 9OL 100 Hashi 2r Masuda Comparative Example/, 2 Reference Example/pp based on 100 parts by weight of the thermoplastic elastomer obtained in i After mixing only tio parts by weight, use an extruder to -
110 to prepare test pieces and evaluate them.

Table 6 shows the evaluation results of the compositions obtained in Example J-1I11 and Comparative Example 1-/3.

Claims (6)

[Claims] (1) (A) 100 parts by weight of a thermoplastic elastomer containing as essential components a polyolefin resin and an ethylene/α-olefin copolymer rubber, at least one of which is partially crosslinked, (B) ethylene A polymer composition prepared by mixing 10 parts by weight or more and less than 100 parts by weight of a based ionomer resin. (2) The polymer composition according to claim 1, comprising 15 to 99 parts by weight of (B) an ethylene ionomer resin mixed with 100 parts by weight of (A) thermoplastic elastomer. (3) The thermoplastic elastomer (A) is (a) ethylene/α-olefin copolymer rubber 100
~20 parts by weight (b) 0 to 80 parts by weight of polyolefin resin (here, (
a)+(b) is selected to be 100 parts by weight. ) and (c) a peroxide non-crosslinked hydrocarbon rubber-like material and (d) a mineral oil softener. A mixture consisting of 0 to 100 parts by weight of at least one component selected from mineral oil softeners is dynamically heat treated in the presence of a crosslinking agent. Partially crosslinked rubber composition (I) 10 obtained by
A composition of 0 to 30 parts by weight and 0 to 70 parts by weight of polyolefin resin (II) (provided that (b) contained in the final composition)
The total amount of (II) and (II) is 5 to 70 parts by weight per 100 parts by weight of the final composition.
parts by weight).
) or (2). (4) The polymer composition according to any one of claims (1) to (3), wherein the polyolefin resin is polypropylene. (5) The ethylene/α-olefin copolymer rubber is an ethylene-propylene copolymer rubber or an ethylene-propylene-nonconjugated diene terpolymer rubber. 4) The polymer composition according to any one of items 4). (6) Ethylene ionomer resin (B) is 75 to 99
．． 5 mol% ethylene units, 0.5-15 mol% α,
β-unsaturated carboxylic acid units and 0 to 10 mol% α, β
- The invention is made by neutralizing 5 to 80% of the carboxylic acid groups of an ethylene copolymer consisting of unsaturated carboxylic acid ester units with monovalent to trivalent metal ions. The polymer composition according to any one of items (1) to (5).