JP2000143896A - Preparation of functionalized elastomer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an elastomer composition which is soft, has a rubbery or leather-like appearance and is improved in adhesion to various materials, paintability, weathering resistance, mechanical properties and the like. SOLUTION: There is provided a process for preparing a functionalized elastomer composition wherein a crosslinkable elastomer (A) is incorporated into a thermoplastic resin (B) which is functionalized and partial or complete dynamic vulcanization is carried out. Alternatively, a crosslinkable elastomer (A) and a thermoplastic resin (B) are subjected to partial or complete dynamic vulcanization and then a thermoplastic resin (B) previously functionalized is added thereto.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an olefin-based thermoplastic elastomer composition having excellent adhesion to other resins and raw materials and excellent paintability. More specifically, the present invention relates to a method for producing an olefin-based thermoplastic elastomer composition which can provide an olefin-based thermoplastic elastomer composition having excellent balance between physical properties such as mechanical strength, weather resistance, adhesion, and coating properties.

[0002]

2. Description of the Related Art In recent years, olefin-based thermoplastic elastomer compositions have been widely used in various fields as an alternative to crosslinked rubber and the like because of their high flexibility, various molding processes and recyclability. . Above all, a composition by so-called dynamic crosslinking in which a radically crosslinkable olefin elastomer and a thermoplastic resin having no radically crosslinkable properties such as polypropylene are crosslinked while being melt-kneaded in a continuous or batch kneader in the presence of radicals. The product is a known product, and has been used for applications such as automobile parts because the heat resistance, oil resistance, compression set and the like are remarkably improved by crosslinking an elastomer component.

[0003] However, since the olefin-based thermoplastic elastomer composition does not have a polar group in its structure, it generally has poor adhesiveness and paintability, and has other types of resins such as rubber, metal, and the like. It is difficult to combine and use the material, which is an obstacle to the development of applications. Accordingly, attempts have been made to modify the olefin-based thermoplastic elastomer composition with a compound having a carboxyl group to impart adhesiveness and coatability.

JP-A-2-283743 discloses a thermoplastic elastomer composition in which an ethylene / α-olefin copolymer rubber obtained by graft-polymerizing a carboxyl group or an acid anhydride group and a crystalline polyolefin are dynamically crosslinked. Although described, the physical properties balance between flexibility, mechanical strength and adhesiveness is insufficient. In addition, Japanese Patent Application Laid-Open No. 1-25949
In the publication, an ethylene-propylene-non-conjugated diene copolymer rubber, an olefin-based plastic and an unsaturated carboxylic acid are dynamically crosslinked, and there is a description of an olefin-based thermoplastic elastomer composition further containing an amine. There was a problem that the weather resistance was poor due to the presence of the non-conjugated diene.

[0005] Further, such a crosslinkable elastomer,
In the method for producing a functionalized elastomer composition, which partially or completely undergoes dynamic crosslinking while functionalizing the thermoplastic resin, an improved adhesion can be obtained, but the functionalization of the thermoplastic resin component is sufficient. In some cases, effects such as adhesion may not be sufficiently exhibited, and improvement is required.

[0006]

SUMMARY OF THE INVENTION In view of such circumstances, an object of the present invention is to provide a thermoplastic elastomer composition which does not have the above-mentioned problems and is excellent in adhesiveness and coatability. Things.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, functionalized (1)
(B) A method for producing a functionalized elastomer composition, in which (A) a crosslinkable elastomer is added to a thermoplastic resin to partially or completely dynamically crosslink. Or (2) after partially or completely dynamically crosslinking (A) the crosslinkable elastomer and (B) the thermoplastic resin, and further adding the previously functionalized (B) thermoplastic resin. This was achieved by using a method for producing an elastomer composition.

That is, the present invention provides (1) a functionalized elastomer composition, in which (A) a crosslinkable elastomer is added to a functionalized (B) thermoplastic resin to partially or completely dynamically crosslink. Manufacturing method. (2) A functionalized elastomer obtained by partially or completely dynamically cross-linking (A) a crosslinkable elastomer and (B) a thermoplastic resin, and further adding (B) a thermoplastic resin which has been previously functionalized. A method for producing the composition. (3) (A) is an ethylene / α-olefin copolymer rubber produced using a metallocene-based catalyst, comprising ethylene, an α-olefin having 3 to 12 carbon atoms, and optionally a non-conjugated diene, The process for producing a functionalized elastomer composition according to (1) or (2), wherein B) is an olefin-based resin. (4) The method for producing a functionalized elastomer composition according to any one of (1) to (3), wherein the functionalization is performed by a compound containing an acid anhydride group, a glycidyl group or a carboxylic acid group or a derivative thereof. (5) The functionalization is performed by a compound containing an ethylenically unsaturated group and at least one of an acid anhydride group, a carboxylic acid group and a glycidyl group or a derivative thereof (1).
The method for producing the functionalized elastomer composition according to any one of (1) to (4). (6) A functionalized elastomer composition obtained by the method for producing a functionalized elastomer composition according to (1) to (5).

Hereinafter, the present invention will be described in detail. In the present invention, the crosslinkable elastomer (A) is, for example, a polystyrene-based, polyolefin-based, polyester-based, polyurethane-based, 1,2-polybutadiene-based, polyvinyl chloride-based, or the like, and particularly preferably a polyolefin-based thermoplastic elastomer. .

Among the above-mentioned polyolefin-based thermoplastic elastomers, ethylene / α-olefin copolymer rubber is particularly preferable, for example, ethylene and carbon number 3-20.
More preferably, an ethylene / α-olefin copolymer rubber comprising 6 to 12 α-olefins is exemplified. Examples of the α-olefin having 3 to 20 carbon atoms include propylene, butene-1, pentene-1, hexene-1,
4-methylpentene-1, heptene-1, octene-
1, nonene-1, decene-1, undecene-1, dodecene-1 and the like. Among them, hexene-1, 4-methylpentene-1 and octene-1 are preferred, and octene-1 is particularly preferred. Octene-1 is excellent in softening effect even in a small amount, and the obtained copolymer is excellent in mechanical strength.

The polyolefin elastomer suitably used in the present invention is preferably produced by a known metallocene catalyst or Ziegler catalyst, and most preferably produced by a metallocene catalyst. Generally, a metallocene-based catalyst is composed of a cyclopentadienyl derivative of a group IV metal such as titanium or zirconium and a co-catalyst, and is not only highly active as a polymerization catalyst, but also has a higher polymer yield than a Ziegler-based catalyst. Has a narrow molecular weight distribution, and the distribution of the comonomer α-olefin having 3 to 20 carbon atoms in the copolymer is uniform. For this reason, the polymer obtained by the metallocene catalyst method has a more uniform crosslink,
Shows excellent rubber elasticity.

The (A) polyolefin elastomer suitably used in the present invention preferably has an α-olefin copolymerization ratio of 1 to 60% by weight, more preferably 10 to 50% by weight, and most preferably. 20 to 45% by weight. When the copolymerization ratio of the α-olefin exceeds 50% by weight, the hardness, tensile strength, etc. of the composition are greatly reduced,
On the other hand, if it is less than 1% by weight, the hardness of the composition is high and the mechanical strength tends to decrease.

The density of (A) is 0.8 to 0.9 g / cm.
It is preferably in the range of ³ . By using a polyolefin-based elastomer having a density in this range,
A thermoplastic elastomer composition having excellent flexibility and low hardness can be obtained. The polyolefin-based elastomer used in the present invention preferably has a long-chain branch. The presence of the long-chain branch enables the density to be lower than the ratio (% by weight) of the copolymerized α-olefin without lowering the mechanical strength. Hardness and high strength elastomer can be obtained. The olefin elastomer having a long chain branch is described in US Pat. No. 5,278,272 and the like.

Further, the polyolefin-based elastomer is
It is desirable to have a melting point peak of DSC above room temperature. When it has a melting point peak, the form is stable in the temperature range below the melting point, the handleability is excellent, and the stickiness is small. Further, the melt index of the polyolefin-based elastomer used in the present invention is 0.01 to 100 g.
/ 10 minutes (190 ° C., 2.16 kg load) are preferably used, and more preferably 0.2 to 20 g /
10 minutes. If the amount exceeds 100 g / 10 minutes, the crosslinking property of the thermoplastic elastomer composition is insufficient, and the crosslinking rate of the thermoplastic elastomer composition is too low.
If it is less than 01 g / 10 minutes, the fluidity is poor and the processability is undesirably reduced.

(A) used in the present invention may be a mixture of a plurality of types. In such a case, it is possible to further improve the workability in each molding method. In the present invention, the thermoplastic resin (B) is not particularly limited as long as it is compatible with or homogeneously dispersed with (A). For example, polystyrene-based, polyphenylene ether-based, polyolefin-based, polyvinyl chloride-based, polyamide-based, polyester-based, polyphenylene sulfide-based, polycarbonate-based, polymethacrylate-based, or a mixture of two or more of them can be used. . In particular, an olefin resin such as a propylene resin is preferable as the thermoplastic resin.

Specific examples of the propylene resin most preferably used in the present invention include homo isotactic polypropylene, propylene and other α-olefins such as ethylene, butene-1, pentene-1 and hexene-1. Examples include an isotactic copolymer resin with olefin (including block and random). At least one or more thermoplastic resins (B) selected from these resins are (A) and (B)
Is used at a composition ratio of 1 to 99 parts by weight based on a total of 100 parts by weight. Preferably 5 to 90 parts by weight, more preferably 2
0 to 80 parts by weight, most preferably 20 to 70 parts by weight. If the amount is less than 1 part by weight, the fluidity and processability of the composition are reduced, and if it exceeds 99 parts by weight, the flexibility of the composition is insufficient, which is not desirable.

The melt index of the propylene resin used in the present invention is 0.1 to 100 g / 10.
Min (230 ° C., 2.16 kg load) is preferably used. If it exceeds 100 g / 10 minutes, the heat resistance and mechanical strength of the thermoplastic elastomer composition will be insufficient, and if it is less than 0.1 g / 10 minutes, the fluidity will be poor and the moldability will be reduced, which is not desirable. .

In the present invention, the functionalization is to bond a compound having a reactive group with the component (A) or the component (B). Compounds which are more preferred by functionalization are compounds which have an ethylenically unsaturated group and also have a reactive group. Examples include acid anhydride groups, glycidyl groups,
A compound having a carboxylic acid group, a nitrile group, a hydroxyl group, an amino group, a sulfonic acid group, an ester group, or the like as a reactive group, and among them, an acid anhydride group, a glycidyl group, and a carboxylic acid group are more preferable. Preferred are those having an ethylenically unsaturated group.

Maleic acid, halogenated maleic acid, fumaric acid, phthalic acid, itaconic acid, citraconic acid, cis-4
-Cyclohexene-1,2-dicarboxylic acid, endo-cis-bicyclo (2,2,1) -5-heptene-2,3-
Examples include dicarboxylic acids and the like, anhydrides, esters, amides, imides, and metal salts of these dicarboxylic acids.Acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid and the like and esters of these monocarboxylic acids, for example, acrylic acid Examples include methyl, methyl methacrylate, ethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, amide, imide, and metal salts. Furthermore, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2
-Hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, 3-hydroxy-2-phenoxypropyl acrylate, 3-hydroxy -2-phenoxypropyl methacrylate, sodium 2-methyl-2-propene-1-sulfonate, methacrolein, methacrylamide,
Metharyyl chloride, N-methylol acrylamide, acrylonitrile and the like are also exemplified.

Among these, maleic anhydride, maleic acid, itaconic anhydride, itaconic acid, citraconic anhydride,
Glycidyl methacrylate and 2-hydroxyethyl methacrylate are preferably used. More preferred are maleic anhydride, maleic acid and glycidyl methacrylate. These compounds can be used alone or in combination of two or more.

In addition to the compounds described above, vinyl aromatic compounds such as styrene and α-methylstyrene can be used in combination as long as the properties of the olefin-based thermoplastic elastomer composition are not impaired. Further, a compound obtained by further reacting the compound used for the functionalization with a reagent that does not impair the effect of the present invention may be used.

The amount of functionalization is from 0.01 to 10 parts by weight, preferably from 0.05 to 10 parts by weight, more preferably from 0 to 10 parts by weight based on 100 parts by weight of the total of (A) and (B). 0.1 to 5 parts by weight. If the amount is less than 0.01 part by weight, the adhesiveness of the composition is insufficient, which is not preferable. Even when the amount exceeds 10 parts by weight, the effect of improving the adhesiveness is hardly increased as compared with the amount less than 10 parts by weight.

The functionalized elastomer composition provided by the present invention is characterized in that the composition or a part of the composition is partially reacted with a radical initiator such as an organic peroxide or a radical initiator and a crosslinking assistant. It is necessary to crosslink properly or completely. Here, specific examples of the radical initiator preferably used include 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane and 1,1-bis (t-hexylperoxy). ) -3,
3,5-trimethylcyclohexane, 1,1-bis (t
-Hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-
Bis (t-butylperoxy) octane, n-butyl-
Peroxy ketals such as 4,4-bis (t-butylperoxy) butane and n-butyl-4,4-bis (t-butylperoxy) valerate; di-t-butyl peroxide, dicumyl peroxide , T-butylcumyl peroxide, α, α'-bis (t-butylperoxy-m-isopropyl) benzene, α, α'-bis (t-
Butylperoxy) diisopropylbenzene, 2,5-
Dialkyl peroxides such as dimethyl-2,5-bis (t-butylperoxy) hexane and 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3; acetyl peroxide, isobutylene Luper oxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5
Diacyl peroxides such as trimethylhexanoyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide and m-trioil peroxide; t-butylperoxyacetate, t-butylperoxyisobutyrate, t -Butyl peroxy-2-ethylhexanoate, t-butyl peroxy laurate, t-butyl peroxy benzoate, di-t-butyl peroxy isophthalate, 2,
Peroxyesters such as 5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxymaleic acid, t-butylperoxyisopropyl carbonate, and cumylperoxyoctate; and t-butyl Hydroperoxides such as hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide and 1,1,3,3-tetramethylbutyl peroxide Can be mentioned.

Among these compounds, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, di-t-butyl peroxide, dicumyl peroxide, 2,5-dimethyl -2,5-bis (t-butylperoxy) hexane and 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3 are preferred.

These radical initiators are (A) 100
0.02 to 3 parts by weight, preferably 0.05 to 3 parts by weight
Used in an amount of １1 part by weight. If the amount is less than 0.02 parts by weight, the crosslinking is insufficient, and if it exceeds 3 parts by weight, the physical properties of the composition are not improved, which is not preferable. Further, as a crosslinking aid,
Divinylbenzene, triallyl isocyanurate, triallyl cyanurate, diacetone diacrylamide,
Polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, diethylene glycol dimethacrylate, diisopropenylbenzene,
P- quinone dioxime, P, P ^'- dibenzoyl quinone dioxime, phenylmaleimide, allyl methacrylate, N, ^{N'-m-phenylene} bismaleimide, diallyl phthalate, tetraallyloxyethane, 1,2-polybutadiene and the like are preferable Used. These crosslinking aids may be used in combination of two or more.

These crosslinking aids are used in an amount of 0.1 to 5 parts by weight, preferably 0.5 to 2 parts by weight, per 100 parts by weight of (A). If the amount is less than 0.1 part by weight, crosslinking is insufficient, and if it exceeds 5 parts by weight, the physical properties of the composition are not improved, and an excessive amount of a crosslinking aid remains, which is not preferable. In the present invention, in addition to the above-described components of the functionalized elastomer composition, other resins and elastomers may be added to such an extent that their characteristics are not impaired. For example, polyamide resin,
Polyphenylene ether resin, polystyrene resin,
Polyvinyl chloride resin, polyester resin, polyphenylene sulfide resin, polycarbonate resin, polyolefin resin, polymethacrylate resin, polyacetal resin, polyarylate resin, polysulfone resin, at least one vinyl aromatic compound A block copolymer consisting of a polymer block A mainly composed of: and a polymer block B mainly composed of at least one conjugated diene compound, or a block copolymer obtained by hydrogenating this block copolymer, styrene Ethylene-vinyl ester copolymers such as butadiene random copolymer and ethylene-vinyl acetate copolymer, ethylene-unsaturated carboxylic acid ester copolymers such as ethylene-ethyl acrylate copolymer, and ethylene-vinyl alcohol copolymer Coalescing, polybutadiene Polybutene, polyisobutene, and the like. More specifically, the polystyrene resin is
Rubber-modified styrene-based resin and / or non-rubber-modified styrene-based resin. Particularly, examples of rubber-modified styrene-based resin include impact-resistant polystyrene, ABS resin (acrylonitrile-butadiene-styrene copolymer), and AAS resin ( Acrylonitrile-acryl rubber-styrene copolymer), AES resin (acrylonitrile-ethylene propylene rubber-styrene copolymer) and the like. Here, in order to particularly improve chemical resistance, oil resistance, heat resistance, and the like, a polyamide-based, polyester-based, or polycarbonate-based thermoplastic resin is preferable.

The functionalized elastomer composition of the present invention can contain an inorganic filler, an organic filler, and a plasticizer to such an extent that the characteristics of the composition are not impaired. Examples of the inorganic filler used here include calcium carbonate, magnesium carbonate, silica, carbon black, carbon fiber, glass fiber, titanium oxide, clay, mica, talc, magnesium hydroxide, aluminum hydroxide, zinc oxide, and the like. . Further, examples of the organic filler include various organic fibers, wood flour, walnut shell flour, jute, kenaf, cellulose, lignin and the like. Examples of the plasticizer include phthalic acid esters such as polyethylene glycol and dioctyl phthalate (DOP). In addition, other additives, such as lubricants, organic and
Inorganic pigments, heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, flame retardants, silicone oils, antiblocking agents, foaming agents, antistatic agents, antibacterial agents and the like are also suitably used.

The method for producing a thermoplastic elastomer composition by dynamic crosslinking in the present invention can be carried out by using a melt kneader usually used for producing such a thermoplastic elastomer composition. In particular,
There are continuous kneaders such as a batch-type kneader such as a mixing roll, a Banbury mixer, and a pressure kneader, a single-screw extruder, and a twin-screw extruder.

Examples of the method for producing the functionalized elastomer composition of the present invention are as follows. (A) First, (B) a thermoplastic resin is functionalized, and (A) a crosslinkable elastomer is added. Or complete dynamic crosslinking or (b)
(A) After partially or completely dynamically cross-linking the cross-linkable elastomer and (B) the thermoplastic resin, further functionalize the pre-functionalized (B) thermoplastic resin-added elastomer composition. Manufacturing method, (a),
The production method (b) is particularly preferably used for selectively functionalizing the thermoplastic resin (B). On the other hand, when the functionalization is performed simultaneously with the dynamic crosslinking, the rubber component of the dispersion layer is mainly functionalized, so that the adhesive effect is insufficient.

A specific example of each method will be described with reference to an example of functionalization with maleic anhydride, wherein the component (A) is an ethylene / α-olefin copolymer, the component (B) is a propylene-based resin, and Manufacturing examples can be described through such processing steps as described above. That is, as an example of the method (a), a commercially available product or a polypropylene resin previously functionalized with maleic anhydride by a twin-screw extruder and an ethylene / α-olefin copolymer are mixed well and an extruder is used. Put in hopper. The radical initiator and the crosslinking assistant may be added together with the ethylene / α-olefin copolymer and the propylene-based resin from the beginning, or may be added in the middle of the extruder. The oil may be added from the beginning of the extruder or from the middle, or may be added separately from the beginning and the middle. A part of the ethylene / α-olefin copolymer and the propylene resin may be added in the middle of the extruder. When heated and melted and kneaded in an extruder, the ethylene / α-olefin copolymer and a radical initiator and a crosslinking aid undergo a crosslinking reaction, and furthermore, an oil or the like is added and the crosslinking reaction is performed by melt-kneading. After sufficient kneading and dispersion, take out from the extruder. It can be pelletized to obtain pellets of the functionalized elastomer composition according to the invention.

As an example of the method (b), ethylene · α
-Mix the olefin copolymer and the propylene-based resin well and put them into the hopper of the extruder. The radical initiator and the crosslinking assistant may be added together with the ethylene / α-olefin copolymer and the propylene-based resin from the beginning, or may be added in the middle of the extruder. The oil may be added from the beginning of the extruder or from the middle, or may be added separately from the beginning and the middle. A part of the ethylene / α-olefin copolymer and the propylene resin may be added in the middle of the extruder. When heated and melted and kneaded in an extruder, the ethylene / α-olefin copolymer and a radical initiator and a crosslinking assistant undergo a crosslinking reaction, and maleic anhydride, an ethylene / α-olefin copolymer and a propylene-based The resin reacts with the mixture, and the mixture is melted and kneaded by adding an oil or the like to make the crosslinking reaction and kneading dispersion sufficient, followed by extrusion and pelletizing. Further, a commercially available product or a polypropylene resin previously functionalized with maleic anhydride by a twin-screw extruder and pelletized pellets are mixed, extruded by a twin-screw extruder, pelletized and functionalized elastomer according to the present invention. A pellet of the composition can be obtained.

The elastomer composition according to the present invention is particularly effective during molding and processing as described below. (A) Polyamide resin, polyphenylene ether resin, polystyrene resin, polyvinyl chloride resin, polyester resin, polyphenylene sulfide resin, polycarbonate resin, polyolefin resin, polymethacrylate resin, polyacetal resin, polyarylate Resin, polysulfone resin, ABS resin, A
Multi-layer molding with AS resin, AES resin, etc .; multi-layer injection molding (two-color molding, insert molding, etc.), multilayer extrusion molding, multilayer blow molding, etc. (b) Olefin, styrene, urethane, ester, etc. Injection molding (two-color molding, insert molding, etc.), multilayer extrusion molding, multilayer blow molding, multilayer inflation molding, etc. (c) Polyamide, acrylic, urethane, etc. Coating with various paints such as ester, alkyd, cellulose, phenol, epoxy and amino. (D) Acrylic, cyanoacrylate, alkyd, cellulose, polyamide, phenol, ester, epoxy With various materials using various adhesives such as melamine, urea, synthetic rubber, etc. (e) Polyamide resin, polyf Phenylene ether resin, polystyrene resin, polyvinyl chloride resin, polyester resin, polyphenylene sulfide resin, polycarbonate resin, polyolefin resin, polymethacrylate resin, polyacetal resin, polyarylate resin, polysulfone resin Resin, ABS resin, A
Alloy materials with AS resin, AES resin, etc.

[0033]

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In these examples and comparative examples, the test methods used for evaluating various physical properties are as follows. [1] Surface Hardness Four sheets having a thickness of 2 mm were piled up and evaluated according to ASTM D2240 using an A type or a D type in a 23 ° C. atmosphere. [2] Tensile breaking strength [kgf / cm ² ] Evaluated at 23 ° C. according to JIS K6251. [3] Tensile elongation at break [%] Evaluated at 23 ° C. according to JIS K6251. [4] Weather resistance Using a carbon arc type sunshine weather meter (manufactured by Suga Test Instruments), according to ASTM D1499, a black panel temperature of 63 ° C., a rainfall time of 18 minutes and an irradiation time of 120 were used.
And the tensile elongation retention [%] after continuously exposing the 2 mm-thick compression molded sheet for 500 hours. [5] Coating adhesion The surface of a 2 mm thick flat sheet was degreased with isopropanol and allowed to dry at room temperature. An epoxy-based paint was applied by spraying (coating thickness: about 100 microns) and left at room temperature for 10 minutes. Next, it was dried at 50 ° C. for 30 minutes with a hot air drier and left at room temperature for 3 days. According to JIS K5400, 100 cuts were produced by drawing 11 cuts each reaching the substrate surface with a razor at intervals of 1 mm in length and width. A cellophane pressure-sensitive adhesive tape was pressed thereon, and the tape was peeled off by pulling it in the direction of 180 ° with respect to the coating film surface, and the number of grids that did not peel off was measured. [6] Adhesion of Polyamide (PA) A flat plate of a polymer is formed by compression molding, and a flat plate of the elastomer composition of the present invention, which is separately formed by compression molding, is laminated and compression molded. The peeling strength at that time is evaluated in the following stages: ◎: not integrated and peeled, ○ strong to peel, △: slightly adhered, ×: easily peeled. [7] Adhesion of polyethylene terephthalate (PET) The adhesion is evaluated in the same manner as the adhesion of the polyamide. [8] Metal Adhesion A flat plate of the elastomer composition of the present invention is laminated on an aluminum plate having a thickness of 0.1 mm and compression molded together. The peel strength at that time is evaluated in the same manner as the polyamide adhesion.

The following components were used in the examples and comparative examples. <1> Ethylene / α-olefin copolymer Copolymer of ethylene and octene-1 (referred to as EOR) Produced by a method using a metallocene catalyst. Composition ratio of ethylene / octene-1 in the copolymer: 75/25 (weight ratio), density: 0.87 g / cm ³ , MFR: 0.5
(190 ° C. × 2.16 kg), Mw / Mn = 2.3, long chain branching, DSC melting point peak.

Ethylene-propylene-ethylidene norbornene copolymer (referred to as EPDM) It was produced by a method using a Ziegler catalyst. Propylene content: 28% by weight, iodine value 15, density: 0.8
7 g / cm ³ , MFR; 0.4 (190 ° C. × 2.16 k
g), having no long-chain branching and no DSC melting point peak. <2> Propylene resin (referred to as PP) Homo isotactic polypropylene, MFR15
(230 ° C. × 2.16 kg) MPP1: Admir QF305 manufactured by Mitsui Chemicals, Inc. is used. For this, a homopolypropylene functionalized with maleic anhydride and having a functionalization ratio of 0.2% by weight is used.

MPP2: maleic anhydride in a twin screw extruder,
A radical initiator, homopolypropylene, is added to produce anhydrous maleated PP. The functionalization rate is 0.17% by weight. <3> Softener Paraffin oil (referred to as MO) Diana Process Oil PW-90 (Idemitsu Kosan Co., Ltd.)
<4> Ethylenically unsaturated group-containing carboxylic acid derivative Maleic anhydride (referred to as MA) <5> Radical generator (referred to as POX) 2,5-dimethyl-2,5-bis (t-butylperoxy) ) Hexin-3 <6> Crosslinking aid divinylbenzene (referred to as DVB)

[0037]

Examples 1 to 6 and Comparative Examples 1 to 3 As an extruder, a twin screw extruder (40 mmφ, L /
D = 47) was used. As the screw, a double screw having a kneading portion before and after the injection port was used. EOR10
0 parts, 33 parts of PP, 0.5 parts of POX, and 1.3 parts of DVB were mixed together except for MO and then introduced into a twin-screw extruder (cylinder temperature: 220 ° C.). Subsequently, an injection port at the center of the extruder An MO in an amount corresponding to more than 60 parts was injected by a pump, and melt extrusion and pelletization were performed.

The pellet (called TPV) and MPP
(Comparative Example: PP) was pellet-blended at the ratios shown in the table, and then extruded by a 30 mm twin-screw extruder. These pellets were kneaded with a roll, formed into a flat plate, and flat plates were prepared by compression molding, and used as test pieces having various physical properties. Table 1 shows the results.

[0039]

Comparative Example 4 As an extruder, a twin-screw extruder (40 mmφ, L / D = 47) having an inlet at the center of the barrel was used. As the screw, a double screw having a kneading portion before and after the injection port was used. EOR100, PP81
, 0.5 parts of POX, 1.3 parts of DVB and 0.1 part of maleic anhydride were mixed in a composition other than MO, and then introduced into a twin-screw extruder (cylinder temperature 220 ° C.). Of MO equivalent to 60 parts from the inlet at
Was injected by a pump to perform melt extrusion and pelletization. The total composition is adjusted to be the same as in Example 1. Table 1 shows the results.

[0040]

[Table 1]

[0041]

The molded article made of the olefinic thermoplastic elastomer composition obtained according to the present invention has a flexible and rubbery or leathery appearance, as well as adhesion to various materials, coating properties, weatherability, and mechanical properties. Excellent physical properties. The present invention provides an instrument panel, a lamp end rubber,
Interior and exterior parts for automobiles such as console boxes and shift knob grips, home appliances, light electrical appliance housings, various grips,
It can be widely used for various switches, various key tops, cushioning materials, rubber feet, hoses, tubes, etc.

Continued on the front page F term (reference) 4J002 AA015 AC04W BB005 BB05W BB065 BB075 BB12X BB14X BB15W BB15X BB185 BC02X BC025 BC04W BC055 BD03X BD035 BD05W BE035 BG005 BG05X BL01W BL013 BN0 005 CB0 005 CL00X CL005 CN01X CN015 CN035 EA048 EF046 EF076 EF116 EG016 EG056 EG086 EG096 EH076 EH106 EH108 EH136 EH146 EH148 EK007 EK017 EK037 EK047 EK0 050 ELF036 EL136 EL146 EP016 EP026 EP0 020 FD040 FD040 FD040 FD040 FD158 FD170 FD180 FD320 GN00 GQ00 4J011 AA05 PA54 PA64 PA65 PA66 PA76 PA88 PA95 PC02 QA02 QA03 QA05 QA06 QA07 QA08 QA09 QA13 QA19 QA20 QA24 QA34 QA35 QA37 QA39 QB16 RA07 BA02A07 ABAA07A02A07 EB09 EB10 EC02 EC03

Claims (6)

[Claims] 1. The functionalized thermoplastic resin (B) comprises:
(A) A method for producing a functionalized elastomer composition, which comprises adding a crosslinkable elastomer and partially or completely performing dynamic crosslinking. 2. A method wherein (A) a crosslinkable elastomer and (B) a thermoplastic resin are partially or completely dynamically crosslinked, and then a functionalized (B) thermoplastic resin is further compounded. A method for producing a functionalized elastomer composition. 3. An ethylene / α-olefin copolymer rubber produced by using a metallocene catalyst (A) in which the crosslinkable elastomer comprises ethylene and an α-olefin having 3 to 12 carbon atoms and, if necessary, a non-conjugated diene. The method for producing a functionalized elastomer composition according to claim 1, wherein (B) is an olefin-based resin. 4. The process for producing a functionalized elastomer composition according to claim 1, wherein the functionalization is carried out by a compound containing an acid anhydride group, a glycidyl group or a carboxylic acid group or a derivative thereof. 5. The functionalization according to claim 1, wherein the functionalization is carried out by a compound containing an ethylenically unsaturated group and at least one of an acid anhydride group, a carboxylic acid group and a glycidyl group or a derivative thereof. For producing a cured elastomer composition. 6. A functionalized elastomer composition obtained by the method for producing a functionalized elastomer composition according to claim 1.