JP2021059643A - Olefinic polymer composition, crosslinked olefinic polymer composition, molding and component for automobile - Google Patents

Abstract

To provide an olefinic polymer composition having excellent adhesion to a polar resin without impairing moldability and designability of the resin.SOLUTION: An olefinic polymer composition contains 0.01-10 pts.mass of polyethyleneimine (B) having a weight average molecular weight (Mw) of 110,000 to 400,000 with respect to 100 pts.mass of an olefinic polymer (A). The olefinic polymer (A) preferably contains 1-100 pts.mass of a propylene-based polymer (A-1) and 99-0 pts.mass of an olefinic rubber (A-2). (The total amount of the propylene-based polymer (A-1) and the olefinic rubber (A-2) is 100 pts.mass.) A crosslinked olefinic polymer composition is obtained by subjecting the olefinic polymer composition to dynamic heat treatment in the presence of 0.005-3 pts.mass of an organic peroxide (D) with respect to 100 pts.mass of the olefinic polymer (A).SELECTED DRAWING: None

Description

The present invention relates to an olefin polymer composition. More specifically, an olefin-based polymer composition containing polyethyleneimine, a crosslinked olefin-based polymer composition obtained by dynamically heat-treating the olefin-based polymer composition in the presence of an organic peroxide, and a crosslinked olefin-based polymer composition thereof. The present invention relates to a molded product obtained by extrusion molding an olefin polymer composition, and an automobile part containing the molded product.

Olefin-based polymers have good mechanical properties, heat resistance, solvent resistance, oil resistance, chemical resistance, and other properties, and are therefore widely used as raw materials for manufacturing industrial parts such as automobiles and electrical equipment, and daily necessities. Has been done.

In such applications, it is required to have excellent adhesion (adhesiveness) with other members. For example, in an automobile interior member such as a window molding, adhesion (adhesive strength) with a urethane-based adhesive when flocking is required. However, olefin-based polymers such as polypropylene do not have a polar group in the molecule and are chemically inert, so that they do not have good adhesion to other resins. For this reason, proposals have been made for improving the adhesion of olefin-based polymers.

For example, Patent Document 1 describes a synthetic resin molded body formed by bonding a urethane-based rubber to a substrate via a terminal isocyanate urethane prepolymer having a number average molecular weight of 500 to 100,000, wherein the substrate is an olefin-based rubber. A synthetic resin molded body composed of a polyolefin-based polymer resin and a modified thermoplastic elastomer containing a diene polymer having a hydroxyl group or a hydrogenated product thereof is disclosed.

Further, in Patent Document 2, as an olefin-based polymer composition having excellent adhesiveness to a polar resin, 100 parts by weight of the olefin-based polymer (A) has an average molecular weight measured by a light scattering method. An olefin-based polymer composition containing 0.1 to 30 parts by weight of 3 to 100,000 polyethyleneimine (B) is disclosed.

In these Patent Documents 1 and 2, the adhesiveness of the olefin polymer is improved by blending an additive.

JP-A-2002-187209 Japanese Unexamined Patent Publication No. 2001-002857

In recent years, there has been an increasing desire for users to have an aesthetic sense and a sense of luxury for automobiles. For this reason, in addition to the conventionally required adhesion to other parts (adhesive strength), it is also required to improve the design as an aesthetic interior member in an automobile.
In such a situation, Patent Documents 1 and 2 have the following problems.

In the method described in Patent Document 1, DOTOL (dioctyltin dilaurate), which is a tin catalyst, is added in order to enhance compatibility with a polar resin together with a polyhydroxypolyolefin oligomer having a hydroxyl group in an olefin polymer. Adhesive strength was insufficient with this method. In addition, it is desirable to avoid the use of trisubstituted tin compounds (organic tin compounds) contained in DOTOL from the viewpoint of toxicity.

Further, in the method described in Patent Document 2, low molecular weight polyethyleneimine (polyethyleneimine having a molecular weight of 3 to 100,000) is added to improve the adhesion to the polar resin, but the composition is made by adding low molecular weight polyethyleneimine. In addition to the extremely high fluidity of the product, which deteriorates the moldability, there is a problem that low molecular weight components bleed out on the surface of the molded product, the surface of the molded product becomes sticky, and as a result, the designability deteriorates.

Focusing on the above-mentioned problems in the prior art, the present invention has an olefin-based polymer composition and a crosslinked olefin-based polymer having excellent adhesion to a polar resin without impairing the molding processability and designability of the resin. It is an object of the present invention to provide a composition.

As a result of diligent studies to solve the above problems, the present inventor blended polyethyleneimine having a specific weight average molecular weight with the olefin polymer without impairing the molding processability and designability of the base resin. In addition, they have found that an olefin-based polymer composition having excellent adhesion to a polar resin can be obtained, and have completed the present invention.

That is, the gist of the present invention lies in the following [1] to [6].

[1] Olefin-based polymer composition containing 0.01 to 10 parts by mass of polyethyleneimine (B) having a weight average molecular weight (Mw) of 110,000 to 400,000 with respect to 100 parts by mass of the olefin-based polymer (A). Stuff.

[2] The olefin-based polymer (A) contains 1 to 100 parts by mass of the propylene-based polymer (A-1) and 99 to 0 parts by mass of the olefin-based rubber (A-2) (however, the propylene-based weight). The total amount of the coalescence (A-1) and the olefin-based rubber (A-2) is 100 parts by mass), the olefin-based polymer composition according to [1].

[3] The olefin-based polymer composition according to [2], which further contains 10 to 200 parts by mass of the rubber softening agent (C) with respect to 100 parts by mass of the olefin-based polymer (A).

[4] The olefin-based polymer composition according to any one of [1] to [3] is used as an organic peroxide (0.005 to 3 parts by mass) based on 100 parts by mass of the olefin-based polymer (A). A crosslinked olefin polymer composition obtained by dynamically heat-treating in the presence of D).

[5] A molded product obtained by extrusion molding the crosslinked olefin-based polymerization composition according to [4].

[6] An automobile part including the molded product according to [5].

According to the present invention, it is possible to provide an olefin-based polymer composition and a crosslinked olefin-based polymer composition having excellent adhesion to a polar resin without impairing molding processability and designability.
Since the olefin-based polymer composition and the crosslinked olefin-based polymer composition of the present invention have excellent adhesion to the polar resin, they can be advantageously used in applications such as forming a composite molded product by directly bonding with the polar resin. it can.

Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to the following description, and can be arbitrarily modified and carried out without departing from the gist of the present invention. In addition, in this specification, when a numerical value or a physical property value is put before and after using "~", it is used as including the value before and after that.

In the present invention, the "unit" in the olefin-based polymer (A) refers to a structural unit derived from the olefin formed in the olefin-based polymer (A) obtained as a result of polymerization of the olefin as a raw material. For example, the "propylene unit" is a unit per propylene produced as a result of the polymerization of propylene.
The content of each unit in the olefin polymer (A) can be determined by infrared spectroscopy.

[Olefin-based polymer composition]
The olefin-based polymer composition of the present invention has 0.01 to 10 parts by mass of polyethyleneimine (B) having a weight average molecular weight (Mw) of 110,000 to 400,000 with respect to 100 parts by mass of the olefin-based polymer (A). Is contained.

<Olefin-based polymer (A)>
Examples of the olefin-based polymer (A) used in the olefin-based polymer composition of the present invention include homopolymers or copolymers of α-olefins which are monomers. As the olefin polymer (A), a resin-like polymer can be used, an elastomer-like polymer can be used, or a mixture thereof can be used.

Examples of the α-olefin used as a raw material for the olefin polymer (A) may be a linear α-olefin or a branched α-olefin. Specifically, ethylene, propylene, 1-butene, 1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1- Penten, 3,3-dimethyl-1-butene, 1-heptene, methyl-1-hexene, dimethyl-1-pentene, trimethyl-1-butene, ethyl-1-pentene, 1-octene, methyl-1-pentene, Dimethyl-1-hexene, trimethyl-1-pentene, ethyl-1-hexene, methylethyl-1-pentene, diethyl-1-butene, propyl-1-pentene, 1-decene, 1-methylnonen, 1-dimethyloctene, Examples thereof include 1-trimethylheptene, 1-ethyloctene, methylethyl-1-heptene, diethyl-1-hexene, 1-dodecene and 1-hexadodecene. One of these may be used alone, or two or more thereof may be used in combination. A linear α-olefin having 2 to 10 carbon atoms is preferable, and a linear α-olefin having 2 to 4 carbon atoms is more preferable. Specific examples thereof include ethylene, propylene and 1-butene.

The olefin-based polymer (A) used in the olefin-based polymer composition of the present invention includes 1 to 100 parts by mass of the propylene-based polymer (A-1) and 99 to 0 parts by mass of the olefin-based rubber (A-2). (However, the total amount of the propylene-based polymer (A-1) and the olefin-based rubber (A-2) is 100 parts by mass).

The propylene-based polymer (A-1) in the present invention is a polymer in which the content of the propylene monomer in the polymer is 60 mol% or more, preferably 70 mol% or more, more preferably 85 mol% or more. is there.

The propylene-based polymer (A-1) is not particularly limited as long as it satisfies the above-mentioned propylene unit content, but is preferably a propylene copolymer; a propylene unit content of 60 to 98 mol%. Crystalline propylene / ethylene block copolymer with ethylene unit content of 2-40 mol%; crystalline propylene with propylene unit content of 90-99.5 mol% and ethylene unit content of 0.5-10 mol% -Ethylene random copolymer can be mentioned.

The propylene-based polymer (A-1) preferably has a melt flow rate (MFR; ASTM D 1238, 230 ° C., load 21.2 N) of 0.05 to 200 g / 10 minutes, more preferably 0.10. ~ 100 g / 10 minutes, more preferably 0.5-60 g / 10 minutes. By using a propylene-based polymer (A-1) having such an MFR, good moldability can be ensured.
Further, it is more preferable that the density (JIS K6922) of the propylene-based polymer (A-1) is in ^{the range of 0.85 to 0.92 g / cm 3.}

The propylene-based polymer (A-1) can be obtained by a known production method. The manufacturing method thereof includes, for example, JP-A-50-108385, JP-A-50-126590, JP-A-51-20297, JP-A-51-28189, JP-A-52-151691 and the like. It is disclosed in detail in the publications of the above, and the techniques described therein can also be used in the present invention.

Moreover, you may use the commercially available propylene-based polymer (A-1). For example, Prime Polypro (registered trademark) manufactured by Prime Polymer, Sumitomo Noblen (registered trademark) manufactured by Sumitomo Chemical Co., Ltd., polypropylene block copolymer manufactured by Sun Aroma, Novatec (registered trademark) PP manufactured by Japan Polypropylene Corporation, and Waymax (WAYMAX). (Registered Trademarks)), Moldell (Registered Trademarks) manufactured by Lyondell Basell, ExxonMobil PP manufactured by ExxonMobil, Versify (Registered Trademarks) manufactured by Dow Chemical Co., Ltd. Borearis PP, SEETEC PP manufactured by LG Chemical, A. et al. Schulman Inc. of ASI POLYPROPYLENE, INEOS Olefins & Polymers, Inc. of INEOS PP, Braskem manufactured by Braskem PP, SAMSUNG TOTAL PETROCHEMICALS Co., Ltd. of Sumsung Total, Sabic manufactured by Sabic (registered trademark) PP, TOTAL PETROCHEMICALS Co., Ltd. TOTAL PETROCHEMICALS Polypropylene , SK's YUPLENE (registered trademark) and the like.

One of these propylene-based polymers (A-1) may be used alone, or two or more thereof may be used in combination.

As the olefin-based rubber (A-2) used in the present invention, an amorphous elastic copolymer composed of an olefin having a crystallinity of 40% or less, preferably 30% or less can be used without limitation. For example, a copolymer of α-olefins having 2 to 10 carbon atoms such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene and 1-octene, or one or more of these α-olefins. Examples thereof include a copolymer of and non-conjugated diene. When the olefin rubber (A-2) contains propylene units, the propylene unit content is preferably less than 60 mol%.

Specific examples of the non-conjugated diene include dicyclopentadiene, 1,4-hexadiene, dicyclooctadiene, methylenenorbornene, and 5-ethylidene-2-norbornene. One of these may be used alone, or two or more thereof may be used in combination.

Specific examples of the olefin rubber (A-2) include ethylene / propylene copolymer rubber, ethylene / 1-butene copolymer rubber, ethylene / 1-octene copolymer rubber, and ethylene / propylene / 1-butene copolymer. Rubber, ethylene / propylene / non-conjugated diene copolymer rubber, ethylene / 1-butene / non-conjugated diene copolymer rubber, ethylene / 1-octene / non-conjugated diene copolymer rubber, ethylene / propylene / 1-butene / non-conjugated diene Copolymerized rubber and the like can be mentioned.

The olefin rubber (A-2) preferably has a melt flow rate (MFR; ASTM D 1238, 230 ° C., load 21.2 N) of 0.05 to 200 g / 10 minutes, more preferably 0.10 to 100 g. / 10 minutes. By using the olefin rubber (A-2) having such an MFR, good moldability can be ensured.

As the olefin rubber (A-2), a commercially available one can be used. For example, JSR EPR manufactured by JSR, Mitsui EPT manufactured by Mitsui Chemicals, Engage (registered trademark) manufactured by Dow Chemicals, Esplen (registered trademark) manufactured by Sumitomo Chemical, Keltan (registered trademark) manufactured by ARLANXEO, etc. Can be mentioned.

One type of these olefin rubbers (A-2) may be used alone, or two or more types may be used in combination.

The olefin-based polymer (A) used in the present invention is 1 to 100 parts by mass of the above-mentioned propylene-based polymer (A-1) and 99 to 0 parts by mass of the olefin-based rubber (A-2) (however, the propylene-based polymer). The total amount of (A-1) and the olefin-based rubber (A-2) is preferably 100 parts by mass), but the propylene-based polymer (A-1) and the olefin-based rubber (A) are preferably mixed. The content ratio of -2) is more preferably propylene-based polymer (A-1): olefin-based rubber (A-2) = 1 to 60:99 to 40 in terms of mass ratio, and even more preferably 10 to 50. : 90 to 50.

<Polyethyleneimine (B)>
The polyethyleneimine (B) blended in the olefin polymer composition of the present invention has a weight average molecular weight (Mw) of 110,000 to 400,000 (110,000 to 400,000), preferably 120,000 to 120,000. It is 350,000. If the weight average molecular weight (Mw) of the polyethyleneimine (B) used is less than the above lower limit, bleed-out occurs, and if it exceeds the above upper limit, the physical property balance of the obtained molded product tends to be deteriorated.

In the present invention, the weight average molecular weight (Mw) of polyethyleneimine (B) is a value measured by the GPC method. For example, polyethyleneimine (B) used in the following examples is prepared under the following conditions by the following apparatus. It was measured.
Equipment: Tosoh HLC-8320 manufactured by Tosoh Corporation
Column: Tosoh TSKgel GMPWxl (7.5 mm ID x 30 cm L x 2) manufactured by Tosoh Corporation
Detector: RI
Mobile phase: 0.5 M acetic acid aqueous solution + 0.2 M sodium nitrate aqueous solution Flow rate: 1.0 mL / min Injection: 100 μL
Column temperature: 40 ° C
Reference material: Monodisperse PEG / PEO

Polyethyleneimine (B) can be produced by a known method. Examples of the production method include a method of ring-opening polymerization of ethyleneimine using carbon dioxide, hydrochloric acid, hydrobromic acid, p-toluenesulfonic acid, aluminum chloride, boron trifluoride, etc. as a catalyst, and a method of ring-opening polymerization of ethylene chloride and ethylenediamine. Examples thereof include a method of synthesizing by a condensation reaction and a method of heating oxazolidone-2.

Commercially available products of polyethyleneimine (B) can also be used. Examples of commercially available products include Epomin manufactured by Nippon Shokubai Co., Ltd. and Lupasol manufactured by BASF Japan Ltd.

The content of polyethyleneimine (B) in the olefin-based polymer composition of the present invention is 0.01 to 10 parts by mass, preferably 0, with respect to 100 parts by mass of the olefin-based polymer (A). .1 to 5 parts by mass. If the content of polyethyleneimine (B) in the olefin polymer composition is less than the above lower limit, the adhesiveness is inferior, and if it exceeds the above upper limit, bleed-out may occur.

<Rubber softener (C)>
The olefin-based polymer composition of the present invention contains the above-mentioned olefin-based polymer (A) and polyethyleneimine (B), but preferably further contains a softening agent for rubber (C).

Examples of the rubber softening agent (C) used in the present invention include process oils called paraffin-based and naphthen-based process oils among mineral oil-based rubber softeners. In addition to these, white oil, mineral oil, oligomers of ethylene and α-olefin, low molecular weight polybutadiene, paraffin wax, liquid paraffin and the like can be used. Among them, paraffin-based process oil is preferably used.

Examples of the softening agent (C) for rubber include NA solvent (isoparaffin-based hydrocarbon oil, trade name) manufactured by Nippon Oil & Fat Co., Ltd. and PW-90 (n-paraffin-based process oil, trade name) manufactured by Idemitsu Kosan Co., Ltd. Name), IP-solvent 2835 (synthetic isoparaffin-based hydrocarbon, 99.8% by mass or more of isoparaffin, trade name) manufactured by Idemitsu Petrochemical Co., Ltd., neothiosol (n-paraffin-based process) manufactured by Sanko Chemical Industry Co., Ltd. Oil, trade name). These may be used alone or in combination of two or more.

When the olefin-based polymer composition of the present invention contains the softening agent (C) for rubber, the content thereof is preferably 10 to 200 parts by mass with respect to 100 parts by mass of the olefin-based rubber (A-2). It is more preferably 20 to 150 parts by mass, and further preferably 30 to 100 parts by mass. When the content of the softening agent (C) for rubber is at least the above lower limit, the effect of imparting flexibility is sufficiently exhibited. Further, when the content of the softening agent (C) for rubber is not more than the above upper limit, there is no possibility that the original characteristics of the olefin polymer (A) are impaired.

<Other ingredients>
The olefin-based polymer composition of the present invention may contain other components other than the olefin-based polymer (A), polyethyleneimine (B) and the softening agent for rubber (C).

As other components, elastomers other than the olefin rubber (A-2), for example, a styrene elastomer and / or a hydrogenated product thereof can be blended. Styrene-based elastomers and / or their hydrogenated products include styrene / ethylene / butylene / styrene block copolymers, styrene / ethylene / propylene block copolymers, styrene / ethylene / propylene / styrene block copolymers, and styrene / ethylene. -Butylene random copolymer and the like can be mentioned.

In addition, any other compounding ingredients can be blended according to various purposes as long as the effects of the present invention are not significantly impaired. Such components include, for example, fillers, antioxidants, heat stabilizers, light stabilizers, UV absorbers, neutralizers, lubricants, fungicides, antiblocking agents, slip agents, dispersants, etc. Various additives such as colorants, flame retardants, antistatic agents, conductivity-imparting agents, metal inactivating agents, molecular weight modifiers, antibacterial agents, fungicides, fluorescent whitening agents, and thermoplastics other than the essential components. Examples include resin.

Examples of the thermoplastic resin other than the essential components include ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ethylene / methacrylic acid copolymer, ethylene / acrylic acid ester copolymer, and ethylene / methacrylic acid. Ester copolymer, polyphenylene ether resin, polyamide resin such as nylon 6, nylon 66, polyester resin such as polyethylene terephthalate and polybutylene terephthalate, polyoxymethylene homopolymer, polyoxymethylene copolymer such as polyoxymethylene copolymer , Polymethylmethacrylate-based resin and the like.

However, in order to obtain the effect of using the olefin polymer (A) more effectively, when the olefin polymer composition of the present invention contains a thermoplastic resin other than these essential components, the content thereof is , 10% by mass or less, particularly preferably 5% by mass or less, based on 100% by mass of the total resin components in the olefin polymer composition.

Examples of the filler include glass fiber, hollow glass ball, carbon fiber, talc, calcium carbonate, mica, potassium titanate fiber, silica, titanium dioxide, carbon black and the like.

[Crosslinked olefin polymer composition]
The crosslinked olefin polymer composition of the present invention is obtained by dynamically heat-treating the above-mentioned olefin polymer composition of the present invention in the presence of an organic peroxide (D).

<Organic peroxide (D)>
Examples of the organic peroxide (D) include 2,5-dimethyl-2,5-di (t-butylperoxy) hexane and 2,5-dimethyl-2,5-di (t-butylperoxy) hexin-3. , 1,3-bis (t-butylperoxyisopropyl) benzene, 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di ( Peroxybenzoyl) hexyne-3, dicumylperoxide and the like can be mentioned. One of these may be used alone, or two or more thereof may be used in combination.

Among these, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane or 2,5-dimethyl-2,5-di (t-butyl) in terms of low odor and scorch. Peroxy) hexyne-3 is preferred.

The amount of the organic peroxide (D) used is usually 0.005 to 3 parts by mass, preferably 0.05 to 2 parts by mass, based on 100 parts by mass of the olefin polymer (A) in the olefin polymer composition. Selected from a range. If the amount of the organic peroxide (D) used is not less than the above lower limit, the crosslinking reaction can proceed sufficiently, and if it is not more than the above upper limit, the appearance of the molded product such as the extruded appearance is not affected, and , Economically advantageous.

<Crosslinking aid>
In the present invention, a cross-linking aid can be used in combination with the organic peroxide (D) as a cross-linking agent.
The main cross-linking aids are sulfur, p-quinone dioxime, nitrosobenzene, diphenylguanidine, N-methyl-N-4-dinitrosoaniline, trimethylolpropane-N, N'-m-phenylenedi maleimide. Peroxy cross-linking aids, divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, polyfunctional methacrylate monomers such as allyl methacrylate, vinyl butyrate, Examples thereof include polyfunctional vinyl monomers such as vinyl stearate. By using the above compounds, a uniform and mild cross-linking reaction can be expected.

When a cross-linking aid is used, the amount used is usually 0.005 to 4 parts by mass, preferably 0.05 to 3 parts by mass, per 100 parts by mass of the olefin polymer (A) in the olefin polymer composition. It is selected from the range of. If the amount of the cross-linking aid used is not less than the above lower limit, the effect can be sufficiently obtained, and if it is not more than the above upper limit, it is economical.

[Method for Producing Olefin Polymer Composition and Crosslinked Olefin Polymer Composition]
In the olefin-based polymer composition of the present invention, the olefin-based polymer (A) and polyethyleneimine (B) are mixed and kneaded at a predetermined ratio with a softening agent for rubber (C) and other components used as necessary. Manufactured by For the production of the olefin polymer composition of the present invention, for example, a normal kneader such as a uniaxial extruder, a twin extruder, a Banbury mixer, a roll, a lavender, a plastograph, a kneader or the like is used. Of these, a twin-screw extruder is suitable.

The crosslinked olefin polymer composition of the present invention can be obtained by dynamically heat-treating such an olefin polymer composition in the presence of an organic peroxide (D). The crosslinked olefin-based polymer composition of the present invention may be produced by adding an organic peroxide (D) to the olefin-based polymer composition of the present invention mixed in advance, and the olefin-based polymer (A) and It may be produced by adding a predetermined amount of organic polymer (D) together with polyethyleneimine (B), a softening agent for rubber (C) used as needed, and other components, and performing dynamic heat treatment.

In the present invention, "dynamic heat treatment" means kneading in a molten state or a semi-molten state in the presence of the organic peroxide (D) which is a cross-linking agent. This dynamic heat treatment is preferably performed by melt-kneading, and as the mixing and kneading device for that purpose, for example, a non-open type Banbury mixer, a mixing roll, a kneader, a twin-screw extruder and the like are used. Among these, it is preferable to use a twin-screw extruder. A preferred embodiment of the manufacturing method using this twin-screw extruder is to supply each component to a raw material supply port (hopper) of a twin-screw extruder having a plurality of raw material supply ports to perform dynamic heat treatment.

The temperature at which the dynamic heat treatment is performed is usually 80 to 300 ° C, preferably 100 to 250 ° C. The time for performing the dynamic heat treatment is usually 0.1 to 30 minutes.

[Forming Method of Olefin Polymer Composition and Crosslinked Olefin Polymer Composition]
The molding method of the olefin-based polymer composition and the crosslinked olefin-based polymer composition of the present invention is not particularly limited, and for example, various molding methods such as injection molding, extrusion molding, hollow molding, and compression molding can be used to obtain the molded product. can do. Of these, extrusion molding is preferable. Further, it is also possible to obtain a molded product obtained by performing secondary processing such as laminating molding and thermoforming after performing these moldings.

[Molded parts and composite molded parts]
The molded product of the present invention is obtained by extrusion molding the crosslinked olefin polymer composition of the present invention.

In particular, the crosslinked olefin polymer composition of the present invention is excellent in adhesion to the polar resin, and therefore can be suitably used for use as a composite molded product with the polar resin. For example, a crosslinked olefin polymer composition in which a crosslinked olefin polymer composition and a polar resin are firmly adhered by molding a polar resin on a molded product made of the crosslinked olefin polymer composition of the present invention. A polar resin composite molded product can be easily obtained. In this case, the molded product made of the crosslinked olefin polymer composition is subjected to electrical treatment such as corona discharge, mechanical roughening, flame treatment, oxygen treatment or ozone treatment to have an affinity for the polar resin. By directly bonding with the polar resin without performing pretreatment such as pretreatment or primer treatment for improving the properties, a composite molded product having excellent adhesion to the polar resin can be obtained. As a method for producing such a composite molded product, for example, a molded product made of the crosslinked olefin polymer composition of the present invention is placed in a mold for manufacturing parts, and then a polar resin stock solution is poured into the mold to close the mold. , A method of simultaneously molding and adhering a polar resin and the like.

Polar resins applied to such composite molded bodies include urethane resin, urethane foam, melamine resin, benzoguanamine resin, urea resin, alkyd resin, acrylic resin, epoxy resin, epoxy ester resin, polyester resin, polyamide, and chloroprene rubber. , Nitrile rubber and the like. Among these, urethane resin, urethane foam, melamine resin, and alkyd resin are preferable.

The molded product made of the crosslinked olefin polymer composition of the present invention is a polar resin-based paint or adhesive, for example, a paint such as a urethane resin-based paint or an amino resin-based paint, a urethane resin-based adhesive, or an amino resin-based adhesive. Since it has excellent adhesion to agents and the like, it is also suitable for painting with such a paint and for adhering parts to each other using the above-mentioned adhesive.

In either case, the primer treatment and the surface treatment for improving the adhesion to the polar resin can be omitted, the processing apparatus and the manufacturing process can be reduced, and the manufacturing cost can be reduced.

[Use]
The molded product of the present invention or a composite molded product obtained by directly joining the molded product with a polar resin is a variety of industrial parts such as automobile parts, motorcycle parts, electrical equipment parts, daily necessities, building materials, office equipment, packaging materials, etc. It can be widely used for sports equipment, medical equipment, etc.
Of these, it is particularly suitable as an automobile part, and specifically, an automobile interior part such as an instrument panel, a center panel, a center console box, a door trim, a pillar, an assist grip, a steering wheel, and an airbag cover; Such as automobile exterior parts; automobile functional parts such as rack and pinion boots, suspension boots, constant velocity joint boots; and the like.

Hereinafter, specific embodiments of the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples as long as the gist of the present invention is not exceeded. The values of various production conditions and evaluation results in the following examples have meanings as preferable values of the upper limit or the lower limit in the embodiment of the present invention, and the preferable range is the above-mentioned upper limit or lower limit value. , The range specified by the combination of the values of the following examples or the values of the examples may be used.

[raw materials]
The raw materials used in the following examples and comparative examples are as follows.

<Component (A): Olefin polymer (A)>
<Propene polymer (A-1)>
(A-1a) Homopolypropylene Novatec (registered trademark) PP manufactured by Japan Polypropylene Corporation
Propene unit content: 100 mol%
MFR (230 ° C, 21.2N): 2.5g / 10 minutes Density (JIS K6922): 0.90g / cm ³
(A-1b) Ethylene-propylene random copolymer, manufactured by Dow Chemical Co., Ltd. Versify (registered trademark)
Propene unit content: 90 mol%
MFR (230 ° C, 21.2N): 8g / 10 minutes Density (JIS K6922): 0.87g / cm ³
<Olefin rubber (A-2)>
(A-2a) Ethylene 1-butene copolymer rubber Dow Chemical Co., Ltd. Engage (registered trademark)
Propene unit content: 0 mol%
MFR (230 ° C, 21.2N): 2.1 g / 10 minutes (A-2b) Ethylene propylene / non-conjugated diene rubber JSR JSRO EPR
Propene unit content: 30 mol%
MFR (230 ° C, 21.2N): 0.2g / 10 minutes

<Component (B): Polyethyleneimine (B)>
Polyethylenimine Nippon Shokubai Co., Ltd. Epomin P-1000
Weight average molecular weight (Mw): 125,000

<Component (C): Rubber softener (C)>
Paraffin oil Diana process oil PW-90 manufactured by Idemitsu Kosan Co., Ltd.

<Component (D): Organic peroxide (D)>
Kayaku Akzo Corporation Kayahexa AD40C
(A mixture of 40% by mass of 2,5-dimethyl-2,5-di (t-butylperoxy) hexane and 60% by mass of calcium carbonate)

<Other ingredients>
(X-1) Polyethylenimine BASF Japan Ltd. LupasolFG
Weight average molecular weight (Mw): 800
(X-2) Dioctyltin dilaurate (DOTDL)
TVS8501 manufactured by Nitto Kasei Co., Ltd.
(X-3) Polyhydroxy polyolefin Oligomer Polytail H manufactured by Mitsubishi Chemical Corporation
(X-4) Antioxidant BASF Japan Co., Ltd. Ilganox 1010
(X-5) Crosslinking aid Divinylbenzene Made by Nippon Steel Chemical Co., Ltd. DVB-570 (purity 60%)

[Evaluation method]
The evaluation method of the crosslinked olefin polymer composition in the following Examples and Comparative Examples is as follows.

<Peeling strength>
Using the crosslinked olefin polymer composition, a sheet having a thickness of 1 mm was formed at 220 ° C. using a press molding machine (hydraulic jack type heating / cooling press 200 × 200 mm, manufactured by Toyo Seiki Seisakusho). Solvent-based one-component moisture-curable urethane resin adhesive (solvent: toluene + methyl ethyl ketone + butyl acetate, non-volatile content: 47%, constituents: diphenylmethane diisocyanate / liquid polybutadiene polyol / polypropylene glycol / 2-ethyl-1 on the surface of the molded sheet , 3-Hexenediol = 33/39/19/8 (mass ratio)) is applied with a bar coater to a thickness of about 7 μm, and the adhesive is wet nylon tape (Polycotape manufactured by Okuda Sangyo Co., Ltd., Width 1.5 cm) was stacked. Then, it was dried in an oven at 80 ° C. for 2 minutes, and then air-dried at room temperature for 48 hours.
For the obtained test piece, the peel strength between the tape and the sheet was measured with reference to the ISO 8510-2: 1990 standard.
The adhesion between the crosslinked olefin polymer composition and the urethane resin was evaluated from this peel strength.

<MFR>
Using a melt indexer (model name "L220", manufactured by Tateyama Kagaku Kogyo Co., Ltd.), MFR was measured at a load of 2.12 N and a measurement temperature of 230 ° C.

<Bleed out>
Using the crosslinked olefin polymer composition, a sheet having a thickness of 2 mm was formed at 220 ° C. using a press molding machine (hydraulic jack type heating / cooling press 200 × 200 mm, manufactured by Toyo Seiki Seisakusho). Immediately after molding, the surface of the sheet was touched with a finger to evaluate the presence or absence of stickiness.

<Example 1>
Ingredients (A) to (C) are blended in the proportions shown in Table 1 (total of component (A) is 100 parts by mass), and (X-4) antioxidant is 0.1 parts by mass, (X-). 5) 0.4 parts by mass of the cross-linking aid was mixed, and the mixture was charged into a twin-screw extruder (“TEX30” manufactured by Japan Steel Works, L / D = 52.5, number of cylinder blocks: 14) in the same direction. The temperature of the upstream portion to the downstream portion was raised in the range of 120 to 210 ° C., melt kneading was performed, and pelletization was performed to produce an olefin polymer composition.
The obtained pellets and 0.6 parts by mass of the component (D) were put into a small kneader (Toyo Seiki Seisakusho "Laboplast Mill A", main body 20C-200, mixer R-60H), and the temperature was 180 ° C. and the screw rotation speed. The mixture was kneaded at 100 rpm for 8 minutes to prepare a crosslinked olefin polymer composition.
The peel strength of this crosslinked olefin polymer composition was evaluated. The obtained evaluation results are shown in Table-1.

<Examples 2 to 3>
The same procedure as in Example 1 was carried out except that the compounding composition was changed as shown in Table 1, and the peel strength was evaluated. For Example 2, MFR and bleed-out were also evaluated. The obtained evaluation results are shown in Tables 1 and 2.

<Comparative Examples 1-2>
As shown in Tables 1 and 2, pellets of the crosslinked olefin polymer composition were obtained from a twin-screw extruder in the same direction with the same composition as in Example 1 except that the component (B) was not added. .. In Comparative Example 2, the component (X-2) DOTDL and the (X-3) polyhydroxypolyolefin oligomer were further blended in the blending amounts shown in Table 1. The peel strength was evaluated using the obtained pellets. In Comparative Example 1, MFR and bleed-out were also evaluated.
The obtained evaluation results are shown in Tables 1 and 2.

<Comparative example 3>
In order to confirm the effect of the addition of low molecular weight polyethyleneimine on moldability and designability, component (X-1) low molecular weight polyethyleneimine was used instead of component (B), and the formulation shown in Table 2 was used. Pellets of the crosslinked olefin polymer composition were obtained in the same manner as in Example 2 except for the above.
The obtained crosslinked olefin polymer composition was evaluated for MFR and bleed-out. The obtained evaluation results are shown in Table-2.

[Discussion]
As shown in Table 1, Examples 1, 2 and 3 corresponding to the crosslinked olefin polymer composition containing the high molecular weight polyethyleneimine (B) of the present invention all contain (X-2) polyhydroxypolyolefin oligomer. It can be seen that it shows a higher peeling strength than Comparative Example 2 and has excellent adhesion to the urethane adhesive.
On the other hand, Comparative Example 1 did not use an adhesion component and had insufficient adhesion to the urethane adhesive.

Further, as shown in Table 2, Example 2 corresponding to the crosslinked olefin polymer composition containing the high molecular weight polyethyleneimine (B) of the present invention is compared with Comparative Example 1 not containing the high molecular weight polyethyleneimine (B). On the other hand, it can be seen that the fluidity and the molded appearance do not change.
On the other hand, in Comparative Example 3 to which (X-1) low molecular weight polyethyleneimine was added, the fluidity became extremely high, so that the extrusion moldability was deteriorated. Further, the low molecular weight component bleeds out on the surface of the molded product, and the appearance is deteriorated.

Claims (6)

An olefin polymer composition containing 0.01 to 10 parts by mass of polyethyleneimine (B) having a weight average molecular weight (Mw) of 110,000 to 400,000 with respect to 100 parts by mass of the olefin polymer (A). The olefin-based polymer (A) contains 1 to 100 parts by mass of the propylene-based polymer (A-1) and 99 to 0 parts by mass of the olefin-based rubber (A-2) (however, the propylene-based polymer (A)). -1) and the olefin-based rubber (A-2) have a total amount of 100 parts by mass), the olefin-based polymer composition according to claim 1. The olefin-based polymer composition according to claim 2, further comprising 10 to 200 parts by mass of the rubber softening agent (C) with respect to 100 parts by mass of the olefin-based polymer (A). The olefin-based polymer composition according to any one of claims 1 to 3 is obtained from 0.005 to 3 parts by mass of the organic peroxide (D) with respect to 100 parts by mass of the olefin-based polymer (A). A crosslinked olefin polymer composition obtained by dynamically heat-treating in the presence. A molded product obtained by extrusion molding the crosslinked olefin-based polymerization composition according to claim 4. An automobile part including the molded product according to claim 5.