JP2000302928A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition having improved heat-resistance and wax-remover resistance while keeping various excellent properties such as scratch resistance, excellent adhesivity to urethane sealant and metal, flexibility, etc., and useful especially as exterior parts for automobile, etc. SOLUTION: The objective resin composition contains (A) an ethylene-based ionomer or an ethylene-unsaturated carboxylic acid copolymer, (B) a hydrocarbon-based thermoplastic elastomer and (C) a styrene-methacrylic acid copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improvement in heat resistance and the like of a resin composition used for automobile exterior parts and the like, and more particularly to excellent scratch resistance, excellent adhesion to urethane sealants and metals, and flexibility. The present invention relates to a resin composition having improved heat resistance and wax remover resistance while retaining other excellent properties.

[0002]

2. Description of the Related Art Soft vinyl chloride resin blended with carbon black has been widely used as a material for exterior parts such as side moldings of automobiles and sealing materials for window frames.
In recent years, thermoplastic resins, such as ionomer resins and resin compositions thereof, have been used in place of vinyl chloride resins.

[0003] Japanese Patent Publication No. 4-462 proposed by the present applicant.
No. 96 describes that a blend of an ionomer resin and a partially crosslinked olefin-based thermoplastic elastomer is a polymer composition suitable for automobile exterior parts and the like. JP-B 8-26195 describes a polymer composition comprising an ionomer resin, a partially crosslinked olefin-based thermoplastic elastomer, and an ethylene / α-olefin-based copolymer rubber.

[0004]

Automotive exterior parts such as side moldings and window frame sealing materials made of a polymer composition containing the above-mentioned ionomer resin have scratch resistance,
Although excellent in properties such as adhesiveness and flexibility to urethane sealants and metals, sometimes the heat resistance of molded products is insufficient, and it is also necessary to remove wax for protecting coated steel sheets before delivery. There is still a problem that whitening or spots may remain in the wax remover treatment.

Accordingly, it is an object of the present invention to provide a resin having improved heat resistance and wax remover resistance while retaining other excellent properties such as scratch resistance, excellent adhesion to urethane sealants and metals, and flexibility. It is an object of the present invention to provide a resin composition which is useful as a composition, particularly as an automobile exterior part.

[0006]

According to the present invention, (A)
A resin composition comprising an ethylene ionomer or an ethylene / unsaturated carboxylic acid copolymer, (B) a hydrocarbon thermoplastic elastomer, and (C) a styrene / methacrylic acid copolymer is provided. You. In the resin composition of the present invention, (A) an ethylene ionomer or an ethylene / unsaturated carboxylic acid copolymer is used in an amount of 50 to 90.
% By weight, (B) 50% of hydrocarbon-based thermoplastic elastomer
It is preferable that the styrene / methacrylic acid copolymer (C) is contained in an amount of 5 to 30% by weight.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION In the resin composition of the present invention, a styrene / methacrylic acid copolymer is selected as a modifying component, and is used as an ethylene ionomer or an ethylene / unsaturated carboxylic acid copolymer and a hydrocarbon type copolymer. It is characterized by being combined with a thermoplastic elastomer. In the present invention, this characteristic allows the two components (A) and (B) to have heat resistance while retaining other excellent properties such as scratch resistance, excellent adhesion to urethane sealants and metals, and flexibility. And the wax remover resistance can be significantly improved.

See the examples below. That is, in a conventional composition (Comparative Examples 1 and 2) comprising two components of an ethylene-based ionomer or an ethylene / unsaturated carboxylic acid copolymer and a hydrocarbon-based thermoplastic elastomer, a stain or luster was obtained by a wax remover treatment. Fall, etc.,
In addition, heat resistance is insufficient, but according to the present invention, by blending the styrene / methacrylic acid copolymer with the above resin composition, defects such as stains and delustering during wax remover treatment are obtained. And the heat sag temperature can be improved.

In the resin composition of the present invention, styrene
The improvement in the heat resistance and the wax remover resistance of the resin composition due to the incorporation of the methacrylic acid copolymer was found as a phenomenon as a result of a number of experiments, and the reason for this is still unknown, but it is not clear. The inventors presume as follows.

The base (A) of the resin composition of the present invention
It is believed that an ethylene-based ionomer or an ethylene-unsaturated carboxylic acid copolymer and (B) a hydrocarbon-based thermoplastic elastomer form an interpenetrating network (IPN). (C) Styrene compounded in the present invention
Methacrylic acid copolymer has good heat resistance of itself,
Affinity with component (A) via a carboxyl group in the molecule,
It is believed that the resin composition of the present invention has improved heat resistance and wax remover resistance because it has an affinity for the component (B) via the polystyrene segment.

In the resin composition of the present invention, (A) 50 to 90% by weight of an ethylene ionomer or an ethylene / unsaturated carboxylic acid copolymer, (B) 50 to 10% by weight of a hydrocarbon thermoplastic elastomer, (C) It is preferable to contain the styrene-methacrylic acid copolymer in an amount of 5 to 30% by weight. That is, if the amount of the (C) styrene / methacrylic acid copolymer is below the above range, the heat resistance and the wax remover resistance are insufficiently improved, while if the amount exceeds the above range, the resin composition becomes hard. Inconveniences such as poor elongation are likely to occur. When the mixing ratio of the components (A) and (B) is out of the above range,
Either the scratch resistance, the excellent adhesiveness to urethane sealants and metals, or the flexibility tends to decrease as compared with those in the above range.

[(A) Ethylene ionomer or ethylene / unsaturated carboxylic acid copolymer] (A-1) The ethylene ionomer used in the present invention is ethylene and unsaturated carboxylic acid as essential components, and as an optional component. It is an ionically crosslinked polymer derived from other unsaturated monomer components, wherein at least a part of the unsaturated carboxylic acid is neutralized with a cation.

The ethylene / unsaturated carboxylic acid copolymer serving as the base polymer of the ionomer has an ethylene component of 85 to 99 mol%, particularly 90 to 98 mol%, an unsaturated carboxylic acid component of 1 to 15 mol%, Particularly, those containing 2 to 10 mol%, and other unsaturated monomer components in addition to ethylene and unsaturated carboxylic acid, are contained in an amount of 0 to 15 mol%.
The copolymerization may be carried out at a molar ratio of, particularly, 0 to 10 mol%. Further, as long as the sum satisfies the above conditions, two or more kinds of unsaturated carboxylic acid component units may be used.

As the unsaturated carboxylic acid component, for example,
Acrylic acid, methacrylic acid, ethacrylic acid, fumaric acid,
Examples thereof include maleic acid, maleic acid monomethyl ester, maleic acid monoethyl ester, and maleic anhydride, and acrylic acid or methacrylic acid is particularly preferable.

Other unsaturated monomer components include, for example, acrylic esters such as methyl (meth) acrylate, ethyl (meth) acrylate, isobutyl (meth) acrylate, and n-butyl (meth) acrylate; Examples include methacrylic acid esters and vinyl acetate.

Examples of the metal cation in the ethylene / unsaturated carboxylic acid copolymer ionomer include alkali metals such as lithium, sodium and potassium, alkaline earth metals such as magnesium and calcium, and transition metals such as zinc. The degree of neutralization by metal ions is not particularly limited, but those having an average degree of neutralization of 10 mol% or more, preferably 15 to 80 mol% are suitable.

As the ionomer, 190 ° C., 216
Melt flow rate at 0 g load (JIS K72
It is preferable to use those having a viscosity of 0.01 to 100 g / 10 min, particularly about 0.1 to 50 g / 10 min.

As the automotive exterior parts, an ionomer of an ethylene / methacrylic acid copolymer, particularly an ionomer whose metal species is zinc, is suitable. This ionomer is excellent in the above-mentioned various properties when used in a resin composition.

(A-2) In the present invention, an ethylene / unsaturated carboxylic acid copolymer, that is, an acid group-containing copolymer that has not been neutralized with metal cations, can be used in place of the ionomer described above. .

As the ethylene / unsaturated carboxylic acid copolymer, those having the same composition as that described for the ionomer as the base polymer are preferably used. Particularly preferred ethylene / unsaturated carboxylic acid copolymers are ethylene / methacrylic acid copolymers or ethylene / acrylic acid copolymers.

As the ethylene / unsaturated carboxylic acid copolymer, the melt flow rate at 190 ° C. under a load of 2160 g is 0.1 to 100 g / 10 min, especially 0.5 to 5 g.
It is preferable to use one having about 0 g / 10 minutes.

It has already been pointed out that the ionomer used in the present invention has an ionic cross-linking structure. However, in this ionomer, the cationic cross-linking of the unsaturated carboxylic acid unit forms a hard segment of the polymer chain and the ethylene unit forms a soft segment. It is believed that it acts to form an IPN structure and to impart scratch resistance, adhesion, and flexibility. In the case of the ethylene / acid copolymer, it is recognized that the hydrogen bond of the unsaturated carboxylic acid unit acts as a hard segment of the polymer chain, and the same advantages as the ionomer are achieved. Needless to say, in the present invention, the ionomer and the ethylene / unsaturated carboxylic acid copolymer may be used in combination.

[(B) Hydrocarbon-based thermoplastic elastomer] The hydrocarbon-based thermoplastic elastomer used in the present invention has a polymer chain formed of a hydrocarbon, and has a hard segment and a soft segment in the polymer chain. By doing so, the function as an elastomer is exhibited.

Specific examples of the hydrocarbon-based thermoplastic elastomer include a partially crosslinked olefin-based thermoplastic elastomer and a styrene-based thermoplastic elastomer, but are not limited to this example.

(B-1) Partially Crosslinked Olefin Thermoplastic Elastomer The partially crosslinked olefin thermoplastic elastomer used as the component (B) in the present invention comprises an ethylene / α-olefin copolymer rubber and a polyolefin resin as essential components. And at least one of them is partially crosslinked. Also in this partially crosslinked olefin-based thermoplastic elastomer, the crosslinked portion becomes a hard segment,
On the other hand, the non-crosslinked portion becomes a soft segment to exhibit elastomeric properties.

Examples of the ethylene / α-olefin copolymer rubber used as a raw material of the partially crosslinked olefin-based thermoplastic elastomer include ethylene-propylene copolymer rubber, ethylene-propylene-nonconjugated diene tertiary to multi-component copolymer rubber, and ethylene-propylene copolymer rubber. Butadiene copolymer rubber, ethylene-1-
A substantially amorphous elastomer containing ethylene and an α-olefin having 3 to 14 carbon atoms as a main component, such as butene copolymer rubber and ethylene-1-butene-non-conjugated diene multicomponent copolymer rubber, or a mixture thereof.

Here, the non-conjugated diene is dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, dicyclopentadiene, methylene norbornene,
-Ethylidene-2-norbornene and the like, dicyclopentadiene, methylenenorbornene, 5-ethylidene-
2-norbornene is preferred.

Among these copolymer rubbers, ethylene-propylene copolymer rubber and ethylene-propylene-nonconjugated diene copolymer rubber are preferred. In particular, those having a molar ratio of ethylene units to propylene units (ethylene / propylene) of 50/50 to 90/10, particularly 55/45
Of ethylene-propylene-non-conjugated diene copolymer rubber, especially ethylene-propylene-ethylidene norbornene copolymer rubber, which has excellent heat resistance, tensile properties and rebound resilience. It is preferable in that an elastomer can be obtained.

The Mooney viscosity M of the copolymer rubber
L _{1 + 4} (100 ° C.) is preferably from 10 to 250, particularly preferably from 40 to 160, and if it is less than 10, only a composition having poor tensile properties can be obtained, while if it exceeds 250, the fluidity of the composition becomes poor. Further, the iodine value (degree of unsaturation) of the copolymer rubber is preferably 16 or less, and within this range, a thermoplastic elastomer having a good balance between fluidity and rubber properties can be obtained.

Examples of the polyolefin resin serving as the other raw material of the partially crosslinked olefin-based thermoplastic elastomer include ethylene, propylene, 1-butene, 1-pentene and 1-pentene.
Hexene, 2-methyl-1-propene, 3-methyl-1
-Pentene, 4-methyl-1-pentene, 5-methyl-
Examples thereof include homopolymers of olefins such as 1-hexene, copolymers of two or more of them, and copolymers of the above-mentioned olefins with 15 mol% or less of other polymerizable monomers. Other polymerizable monomers include vinyl acetate, methyl methacrylate, ethyl acrylate, and the like.

These polyolefin resins are preferably crystalline resins obtained from the polymerization of one or more monoolefins by either the high-pressure method or the low-pressure method, which resins are isotactic or syndiotactic. It may have a tick structure.

The polyolefin resin used in the present invention comprises 2
The melt flow rate at 30 ° C. and a load of 2160 g is preferably in the range of 0.1 to 50 g / 10 min, particularly preferably 5 to 20 g / 10 min. Further, those having a degree of crystallinity determined by X-ray diffraction of 40% or more are preferred.

Particularly preferred polyolefin resins in the present invention are peroxide-decomposable olefin-based plastics. Peroxide-decomposable olefin-based plastics are olefin-based plastics that are mixed with peroxide, kneaded under heating, thermally decomposed to reduce the molecular weight, and increase the fluidity of the resin.For example, isotactic polypropylene and propylene And other small amounts of α-
Copolymer with olefin, for example, propylene-ethylene copolymer, propylene-1-butene copolymer, propylene-1-hexene copolymer, propylene-4-methyl-
Examples thereof include 1-pentene copolymer.

As the polyolefin resin, peroxide
With degradable olefin plastic or in Peru
Instead of oxide decomposition type olefin plastic,
Use of oxide cross-linked olefin plastic
Can also. Peroxide-crosslinked olefin plastic
Is mixed with peroxide and kneaded under heating
Olefins that reduce the fluidity of the resin by crosslinking
Plastics, for example polyethylene, especially density
Is 910 to 940 kg / m ³Of low density polyethylene or medium
Density polyethylene can be used.

In the production of the olefin-based thermoplastic elastomer, it is desirable to coexist with a mineral oil-based softening agent.
Mineral oil-based softeners are usually used in rubber roll processing to reduce the intermolecular force of the rubber to facilitate roll processing, and carbon black compounded as a filler.
It is used for the purpose of facilitating the dispersion of white carbon, etc., and increasing the flexibility and elasticity by reducing the hardness of the vulcanized rubber, and generally has a high boiling point, such as paraffinic naphthenic or aromatic. Oil fraction is used. Among them, particularly, the viscosity index (VI) is 80 or more, preferably 100
To 150, most preferably in the range of 110 to 140.

The olefinic thermoplastic elastomer is a peroxide-crosslinked olefinic copolymer rubber 90 to 1
0 parts by weight, especially 90 to 40 parts by weight, olefin-based plastic 10 to 90 parts by weight, especially 10 to 60 parts by weight (where the two components are selected to be 100 parts by weight),
And (c) 0-100 parts by weight of a mineral oil-based softener, particularly 3
乃至 60 parts by weight, prepared by dynamically heat treating and partially crosslinking in the presence of an organic peroxide.

Dynamic heat treatment means kneading in a molten state. Examples of the organic peroxide used for the dynamic heat treatment include dicumyl peroxide, di-tert-butyl peroxide, and 2,5-dimethyl-2,5-di- (te
rt-butylperoxy) hexane, 2,5-dimethyl-
2,5-di (tert-butylperoxy) hexane-3,
1,3-bis (tert-butylperoxyisopropyl)
Benzene, 1,1-bis (tert-butylperoxy)-
3,3,5-trimethylcyclohexane, n-butyl-
4,4-bis (tert-butylperoxy) valerate,
Benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, te
rt-butyl peroxybenzoate, tert-butyl perbenzoate, tert-butyl peroxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, tert-butyl cumyl peroxide and the like. The amount of the organic peroxide is 0.05 to 3% by weight, preferably 0.1 to 3% by weight, based on the total amount of the above components.
It is chosen to be in the range of 1 to 1% by weight. In the partial crosslinking treatment with the organic peroxide, a peroxy crosslinking auxiliary such as sulfur, p-quinonedioxime, p, p'-dibenzoylquinonedioxime, N-methyl-N, N'-m-phenylenedimaleimide, or Contains multifunctional methacrylate monomer such as divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, acrylic methacrylate, and multifunctional vinyl monomer such as vinyl butyrate or vinyl stearate can do. With such a compound, a uniform and mild crosslinking reaction can be expected. The amount of such a crosslinking aid or polyfunctional vinyl monomer is preferably in the range of 0.1 to 2% by weight, particularly 0.3 to 1% by weight, based on the whole object to be treated. In order to promote the decomposition of organic peroxides, tertiary amines such as triethylamine, tributylamine, 2,4,6-tris (dimethylamino) phenol, aluminum, cobalt, vanadium, copper, calcium, zirconium,
Decomposition accelerators such as naphthenates such as manganese, magnesium, lead and mercury can also be used. As the kneading device, it is preferable to use a non-open type device, and it is preferable to perform kneading in an atmosphere of an inert gas such as nitrogen or carbon dioxide.
The kneading is carried out at a temperature at which the half-life of the organic peroxide used is less than 1 minute, usually 150 to 280 ° C., preferably 17 ° C.
The heat treatment may be performed at 0 to 240 ° C. for 1 to 20 minutes, preferably 3 to 10 minutes.

In the olefin-based thermoplastic elastomer, the copolymer rubber and the polyolefin resin are partially crosslinked by the above-mentioned dynamic heat treatment. As a result, the content (gel content) of the insoluble matter in the hot toluene is usually 3%. To 80% by weight, especially 5 to 60% by weight. Further, since the composition is partially crosslinked, the melt flow rate of the composition (230 ° C., 2160 g load) is generally 0.01 to 10
It is in the range of 0 g / 10 min, particularly 0.05 to 50 g / 10 min, and the moldability is extremely good.

(B-2) Styrene-based thermoplastic elastomer The styrene-based thermoplastic elastomer includes at least two polymer blocks A mainly derived from a styrene-based monomer and at least one polymer block A mainly derived from a conjugated diene compound. A block copolymer obtained by hydrogenating a block copolymer consisting of two polymer blocks B is used. Also in this elastomer, the styrene-based unit becomes a hard segment, and the hydrogenated conjugated diene unit becomes a soft segment, so that the elastomer-like characteristics are also exhibited.

This block copolymer comprises at least two polymer blocks A mainly composed of a styrene monomer,
A block copolymer comprising at least one polymer block B mainly composed of a conjugated diene compound or a block copolymer obtained by hydrogenating the block copolymer.
It is obtained by hydrogenating a vinyl aromatic compound-conjugated diene compound block copolymer having a structure such as A, BABA, ABAABA or the like.

Examples of the styrene monomer constituting the block copolymer include styrene, α-methylstyrene,
Examples thereof include vinyl toluene and p-tert-butylstyrene, and among them, styrene is preferable. As the conjugated diene compound, for example, butadiene, isoprene,
One or more kinds are selected from 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like,
Among them, butadiene, isoprene and a combination thereof are preferred.

The number average molecular weight of the block copolymer is 10
The hydrogenated block copolymer has a melt flow rate (230 ° C., 2160
g load) is preferably in the range of 0.01 to 100 g / 10 minutes.

(C) Styrene / methacrylic acid copolymer In the present invention, styrene / methacrylic acid is added to (A) the ethylene ionomer or the ethylene / unsaturated carboxylic acid copolymer and (B) the hydrocarbon thermoplastic elastomer. By blending the copolymer, the heat resistance and the wax remover resistance can be improved.

In the styrene / methacrylic acid copolymer, the styrene component has a high affinity for the hydrocarbon elastomer, while the methacrylic acid component has a high affinity for the ionomer and the acid copolymer. It is believed that this leads to increased compatibility with the components. Further, since the styrene / methacrylic acid copolymer has good heat resistance itself, it is considered that this also contributes to the improvement of the heat resistance and the wax remover resistance of the resin composition.

In the styrene-methacrylic acid copolymer used in the present invention, the styrene component is preferably present in an amount of 98 to 60 mol%, particularly 95 to 70 mol%, while the methacrylic acid component is preferably present in a residual amount. When the amount of the styrene component is more than the above range, the affinity for the ionomer or the acid copolymer is reduced, and the effect of improving the heat resistance and the wax remover resistance is not recognized.

The styrene-methacrylic acid copolymer to be used preferably has a melt flow rate (230 ° C., 2160 g load) in the range of 0.01 to 100 g / 10 minutes.

[Resin Composition] The resin composition of the present invention comprises:
(A) 50 to 90% by weight, especially 60 to 85% by weight of an ethylene ionomer or an ethylene / unsaturated carboxylic acid copolymer, and (B) 50 to 10% by weight, especially 40 to 15% by weight of a hydrocarbon thermoplastic elastomer. 5 to 30% by weight, especially 10 to 25% by weight of (C) a styrene-methacrylic acid copolymer.

To prepare the resin composition of the present invention, the components (A), (B) and (C) may be dry-blended and / or melt-blended simultaneously or sequentially. Various mixers such as a Henschel mixer, a tumbler mixer, and a ribbon blender or a blender can be used for the dry blending. For the melt blending, a kneading device such as a single-screw or twin-screw extruder, a Banbury mixer, a roll, a kneader or the like can be used. It should be understood that the resin composition of the present invention has excellent compatibility, and there is no particular limitation in blending.

Fillers, reinforcing agents, coloring agents and the like can be blended within a range that does not impair the fluidity (moldability), flexibility and thermal adhesiveness of the resin composition. , Kaolin, talc, silica,
Diatomaceous earth, mica powder, asbestos, alumina, barium sulfate, aluminum sulfate, calcium sulfate, basic magnesium carbonate, molybdenum disulfide, graphite, glass fiber, glass sphere, shirasu balloon, carbon fiber, carbon black, titanium oxide, zinc oxide , Black and blue, navy blue, azo pigments, nitroso pigments, lake pigments, phthalocyanine pigments and the like.

The resin composition of the present invention further comprises a resin compounding agent known per se, a phenolic compound, a sulphite compound,
Known heat stabilizers such as phenylalkane-based, phosphite-based or amine-based stabilizers, antioxidants, weathering stabilizers, antistatic agents, metal soaps, lubricants such as waxes, and the like can be added.

These fillers, reinforcing agents, coloring agents, and other compounding agents may be added in advance at the stage of producing each of the resin components described above, or may be added at the stage of preparing the resin composition of the present invention. You may. Further, components such as a filler, a reinforcing agent, and a colorant can be blended in the resin composition of the present invention in the form of a masterbatch in which these are dispersed in a resin in advance.

The resin composition of the present invention can be formed into various shapes by a molding method such as an injection molding method, an extrusion molding method, a compression molding method, or a calendar molding method. This resin composition has scratch resistance, adhesion to metal, surface gloss,
In addition to excellent flexibility, it has excellent heat resistance and wax remover resistance, making it ideal for use in automotive exterior parts such as side moldings and window frame sealing materials, and also for automotive interior parts and civil engineering It can also be used for various purposes such as building materials such as sheets for architectural use, skirting boards and handrails, sports goods, cases for optical and office equipment, stationery, toys, and daily necessities.

[0053]

Next, the present invention will be described specifically with reference to examples and comparative examples. The various polymers used as raw materials in Examples and Comparative Examples and methods for measuring physical properties of the obtained compositions are as follows.

1. Raw materials Various polymers shown in Table 1 were used.

[0055]

[Table 1]

2. Physical properties • MFR (Melt flow rate): JIS K7210
・ Test temperature 230 ° C, load 2160g ・ Hardness: JIS K7215, Shore D ・ Bending rigidity: JIS K7106 ・ Tensile properties: JIS K6301 Temperature: A test piece having a length of 100 mm, a width of 20 mm, and a thickness of 3 mm is horizontally held on a fixed table having a height of 100 mm, left in an oven heated to a constant temperature for 2 hours, and then is not fixed. The height of one tip was measured. The test was carried out from 80 ° C. to 110 ° C. in steps of 10 ° C. The measured values were graphed, and the temperature at which the tip hangs down by 20 mm was read as the heat sag temperature and used as an index of heat resistance.・ Wax remover resistance: 6 kg / cm ^{2 of} a water / kerosene mixture (kerosene concentration: 3 wt%) heated to 85 ° C. on an extruded sheet having a thickness of 0.6 mm using an automobile washing device.
And the appearance was observed.

Example 1 Zinc ionomer of ethylene / methacrylic acid copolymer (IONOMER), olefin-based thermoplastic elastomer (TPO), styrene / methacrylic acid copolymer (S /
MAA) and carbon masterbatch (CMB)
Were mixed at a weight ratio of 52: 18: 20: 10, and supplied to a screw type single screw extruder (screw diameter: 40 mm, dalmage screw, L / D = 28), and a barrel temperature of 200
The mixture was melt-kneaded at a temperature of 50 ° C. and a screw rotation speed of 50 min ⁻¹ . The various physical properties described above were measured for the obtained blend. Table 2 shows the results.

Comparative Example 1 In Example 1, the styrene-methacrylic acid copolymer component (S / MAA) was excluded, and the compounding ratio was IONOMER: T
Physical properties were measured in the same manner as in Example 1 except that PO: CMB was set to 72:18:10. Table 2 shows the results. The heat sag temperature was lower by 9 ° C. and the wax remover resistance was inferior to Example 1.

Example 2 In Example 1, an ethylene / methacrylic acid copolymer (E / MAA) was used instead of IONOMER, and TPO was used instead of TPO, and the mixing ratio was E / MAA: TPO.
: S / MAA: CMB = 50: 20: 20: 10
In the same manner as in Example 1, melt kneading was performed, and physical properties were measured. Table 2 shows the results.

Comparative Example 2 In Example 2, the mixing ratio was E / MAA: T except for the styrene / methacrylic acid copolymer component (S / MAA).
Physical properties were measured in the same manner as in Example 1 except that PO: CMB was set to 70:20:10. Table 2 shows the results. As compared with Example 2, the heat sag temperature was lower by 5 ° C., and the wax remover resistance was poor.

Example 3 Physical properties were measured in the same manner as in Example 1 except that TPS was used instead of TPO. Table 2 shows the results.

[0062]

[Table 2]

[0063]

According to the present invention, (A) an ethylene ionomer or an ethylene / unsaturated carboxylic acid copolymer,
And (B) a hydrocarbon thermoplastic elastomer, and (C)
Includes styrene-methacrylic acid copolymer to improve heat resistance and wax remover resistance while retaining other excellent properties such as scratch resistance, excellent adhesion to urethane sealants and metals, and flexibility. The obtained resin composition was able to be obtained. Since this resin composition has the above properties, it is useful as an automobile exterior part or the like.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] May 24, 1999 (1999.5.2
4)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0013

[Correction method] Change

[Correction contents]

[0013] As the ethylene-unsaturated carboxylic acid copolymer as the base polymer of the ionomer, ethylene component is 85 to 99 mol%, in particular 90 to 98 mol%, Ingredient unsaturated carboxylic acids 1 to 15 mol% And especially 2 to 10 mol%, and 0 to 15 other unsaturated monomer components in addition to ethylene and the unsaturated carboxylic acid.
The copolymerization may be carried out at a molar ratio of, particularly, 0 to 10 mol%. Further, as long as the sum satisfies the above conditions, two or more kinds of unsaturated carboxylic acid component units may be used.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0022

[Correction method] Change

[Correction contents]

It has already been pointed out that the ionomer used in the present invention has an ionic cross-linking structure. However, in this ionomer, the cationic cross-linking of the unsaturated carboxylic acid unit forms a hard segment of the polymer chain and the ethylene unit forms a soft segment. It is believed that it acts to form an IPN structure and to impart scratch resistance, adhesion, and flexibility. In addition, ethylene / unsaturated calcium
Also in the case of the boric acid copolymer, the hydrogen bond of the unsaturated carboxylic acid unit acts as a hard segment of the polymer chain,
It is recognized that similar advantages as the ionomer have been achieved. Needless to say, in the present invention, the ionomer and the ethylene / unsaturated carboxylic acid copolymer may be used in combination.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0056

[Correction method] Change

[Correction contents]

2. Physical properties • MFR (Melt flow rate): JIS K7210
・ Test temperature 190 ° C, load 2160g ・ Hardness: JIS K7215, Shore D ・ Bending stiffness: JIS K7106 ・ Tensile properties: JIS K6301, No.3 test piece, pulling speed 200mm / min Temperature: A test piece having a length of 100 mm, a width of 20 mm, and a thickness of 3 mm is horizontally held on a fixed table having a height of 100 mm, left in an oven heated to a constant temperature for 2 hours, and then is not fixed. The height of one tip was measured. The test was carried out from 80 ° C. to 110 ° C. in steps of 10 ° C. The measured values were graphed, and the temperature at which the tip hangs down by 20 mm was read as the heat sag temperature and used as an index of heat resistance.・ Wax remover resistance: 6 kg / cm ^{2 of} a water / kerosene mixture (kerosene concentration: 3 wt%) heated to 85 ° C. on an extruded sheet having a thickness of 0.6 mm using an automobile washing device.
And the appearance was observed.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0058

[Correction method] Change

[Correction contents]

[0058] In Comparative Example 1 Example 1, Except the styrene-methacrylic acid copolymer component (S / MAA), the blending ratio Ionomer: TP
Physical properties were measured in the same manner as in Example 1 except that O: CMB was set to 72:18:10. Table 2 shows the results. The heat sag temperature was lower by 9 ° C. and the wax remover resistance was inferior to Example 1.

Claims (2)

[Claims] 1. A composition comprising (A) an ethylene ionomer or an ethylene / unsaturated carboxylic acid copolymer, (B) a hydrocarbon thermoplastic elastomer, and (C) a styrene / methacrylic acid copolymer. A resin composition. 2. (A) 50 to 90% by weight of an ethylene ionomer or an ethylene / unsaturated carboxylic acid copolymer, (B) 50 to 10% by weight of a hydrocarbon thermoplastic elastomer, and (C) styrene / methacrylic acid. 2. The resin composition according to claim 1, comprising 5 to 30% by weight of an acid copolymer.