JP3193406B2 - Modified thermoplastic elastomer composition having good coatability and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION Thermoplastic elastomers are used as structural materials in a wide range of industrial fields such as automotive materials, home appliances and construction. The present invention relates to a thermoplastic elastomer composition having excellent coatability. More specifically, the present invention relates to a modified thermoplastic elastomer composition having good coatability, which can be applied with a polyurethane coating without requiring a pretreatment such as a primer treatment or a corona treatment, and a method for producing the same.

[0002]

2. Description of the Related Art Polyolefin-based thermoplastic elastomers have excellent moldability such as injection molding and sheet molding, and are used in a wide range of fields as structural materials. These thermoplastic elastomer moldings may be used unpainted,
Depending on the application, it is often necessary to paint the shaped body. The polyolefin-based thermoplastic elastomer is a composition mainly composed of a non-polar polymer made of polyolefin as a raw material. Therefore, if it is intended to apply the coating directly to the coating, the coating film easily peels off because of low affinity with the coating. There's a problem.

[0003] Therefore, it is generally practiced to apply a so-called primer treatment for applying a material having an affinity for both the polyolefin-based thermoplastic elastomer and the paint, such as chlorinated polyolefin, to a molded product and then apply the paint. Have been done. Also, coating is performed after the surface properties are improved by corona treatment or the like to improve the affinity with the paint.

[0004] However, the primer is expensive and contains a large amount of organic solvent, so that a step for recovering or removing the organic solvent is required. The problem is that this step is performed at a high temperature and requires a long time. In addition, methods for improving the surface properties such as corona treatment are limited in shape, and have problems such as expensive equipment investment. Therefore, if a thermoplastic elastomer that does not require such a primer treatment or corona treatment at the time of coating can be obtained, the process can be shortened,
This brings advantages such as reduction in capital investment.

With respect to simple polyolefin resins such as polyethylene and polypropylene, as a method for improving the coating properties of polyurethane coatings, it is difficult to improve the affinity between polyolefin resins and polyurethane coatings by graft modification with a hydroxyl group-containing compound. As is already known, such attempts have been rare in special compositions such as thermoplastic elastomers.

[0006] Japanese Patent Application Laid-Open No. 1-2590 discloses improvement of coatability of a special composition such as a thermoplastic elastomer.
47. Here, a thermoplastic elastomer composition obtained by dynamically heat-treating a mixture of a peroxide-crosslinked polyolefin-based copolymer rubber, an olefin-based plastic and a monomer having at least one amino group with an organic peroxide is used. A method of blending a saturated carboxylic acid derivative under heating is disclosed.

Further, Japanese Patent Application Laid-Open Nos.
No. 259049 discloses a thermoplastic elastomer composition obtained by dynamically heat-treating a mixture comprising a peroxide-crosslinked polyolefin copolymer rubber, an olefin plastic and an unsaturated carboxylic acid or a derivative thereof with an organic peroxide. A method of blending the above-mentioned amino group-containing monomer under heating is disclosed. However, in these, the improvement of coating properties is not sufficient, and compounds having a low boiling point and harmfulness such as allylamine, acrylamide and diethylenetriamine are used.

JP-A-64-85206 discloses that peroxide-crosslinked polyolefin copolymer rubber, olefin plastic and unsaturated epoxy monomer or unsaturated hydroxy monomer are dynamically heat-treated with an organic peroxide. Although a thermoplastic elastomer composition has been disclosed, its effect is adhesion to metals and the like, and there is no indication of paintability such as whether or not it can be painted without primer treatment. Further, as shown in the examples, the present inventors have investigated the suitability of this composition for polyurethane coating, and as a result, sufficient paintability could not be obtained without primer treatment.

[0009]

DISCLOSURE OF THE INVENTION The present invention is a modified thermoplastic having excellent coating properties, which allows sufficient polyurethane coating without primer treatment without significant reduction in mechanical properties such as breaking strength and breaking elongation. The purpose is to develop elastomers.

[0010]

SUMMARY OF THE INVENTION The present invention relates to a thermoplastic elastomer composition comprising a polyolefin resin and a partially crosslinked olefin polymer rubber, which has good coatability of a polyurethane coating, and comprises: Crosslinked olefin polymer rubber 30 ply
The amount% or more, and less than 80 wt% (B1) pre unsaturated hydroxy compound hydroxyl group-containing polyolefin-based becomes modified with compound resin or (B2) in advance hydroxyl group-containing polyolefin-based resin and polyolefin comprising modified with an unsaturated hydroxy compound (B) 2 composed of resin
A thermoplastic elastomer composition comprising 0% by weight or more and less than 70% by weight , wherein the concentration of hydroxyl groups in the composition is 7 × 10 ^-3 mmol / g or more, and good paintability is provided. A modified thermoplastic elastomer composition, [2] (B1) a polyolefin resin of a hydroxyl group-containing polyolefin resin previously modified with an unsaturated hydroxy compound, wherein the polyolefin resin is isotactic polypropylene;
The modified thermoplastic elastomer composition having good coatability according to the above [1], which is a syndiotactic polypropylene, a propylene-ethylene block copolymer, or a propylene-ethylene random copolymer, [3] an olefin-based polymer rubber or olefin the system the polymer rubber and poly olefin resin kneaded together with an organic peroxide in the presence of an unsaturated hydroxy compound, composition obtained by performing graft modification and cross-linking with the unsaturated hydroxy compound of olefin polymer rubber, (B1) a hydroxyl group-containing polyolefin resin previously modified with an unsaturated hydroxy compound, or (B2) a hydroxyl group-containing polyolefin resin and a polyolefin resin previously modified with an unsaturated hydroxy compound , A) Partially crosslinked olefin polymer Beam 30 double
% Or more and less than 80% by weight (B) polyolefin-based tree
Thermoplastic consisting of 20% by weight or more and less than 70% by weight of fat
An elastomer composition, and hydroxy in the composition;
A method for producing a modified thermoplastic elastomer composition having good coatability, characterized in that the concentration of the hydroxyl group is 7 × 10 ⁻³ mmol / g or more ; [4] an olefin polymer rubber or an olefin polymer rubber; A composition obtained by kneading a polyolefin-based resin with an organic peroxide in the absence of an unsaturated hydroxy compound, and crosslinking the olefin-based polymer rubber,
(B1) a hydroxyl group-containing polyolefin resin previously modified with an unsaturated hydroxy compound or (B2)
A hydroxyl group-containing polyolefin resin and a polyolefin resin modified in advance with an unsaturated hydroxy compound are blended, and (A) 30% by weight or more and less than 80% by weight of a partially crosslinked olefin polymer rubber; resin 20 wt% or more, and a thermoplastic elastomer composition comprising less than 70 wt%, and the ratio of the composition
A method for producing a modified thermoplastic elastomer composition having good coatability, wherein the concentration of the droxyl group is at least 7 × 10 ⁻³ mmol / g ; [5] (A) an olefin polymer rubber or an olefin polymer; (B1) a united rubber and a polyolefin resin
A hydroxyl group-containing polyolefin resin previously modified with an unsaturated hydroxy compound or (B2) a hydroxyl group-containing polyolefin resin and a polyolefin resin previously modified with an unsaturated hydroxy compound,
Kneading with an organic peroxide in the presence of an unsaturated hydroxy compound, and graft-modifying and crosslinking the olefin polymer rubber with the unsaturated hydroxy compound, (A) 30% by weight or more of partially crosslinked olefin polymer rubber , 80 weight
% And (B) 20% by weight or more of the polyolefin resin,
Thermoplastic elastomer composition comprising less than 70% by weight
And the concentration of hydroxyl groups in the composition is 7 × 1
0 method for producing ^-3 mmol / paintability, characterized in that g or more to satisfactory modified thermoplastic elastomer composition, and [6] and an olefin polymer rubber or olefin polymer rubber and a polyolefin resin (B1 A) a hydroxyl group-containing polyolefin resin previously modified with an unsaturated hydroxy compound, or (B2) a hydroxyl group-containing polyolefin resin previously modified with an unsaturated hydroxy compound and a polyolefin resin in the absence of an unsaturated hydroxy compound. It is obtained by kneading with an organic peroxide underneath and crosslinking the olefin polymer rubber.
(A) 30% by weight or less of partially crosslinked olefin polymer rubber
Above, less than 80% by weight and (B) polyolefin resin 20
Thermoplastic elast consisting of at least 70% by weight
And a hydroxyl group in the composition.
The object of the present invention has been solved by developing a method for producing a modified thermoplastic elastomer composition having good coatability, characterized in that the concentration is 7 × 10 ⁻³ mmol / g or more .

Hereinafter, the present invention will be described in detail. As the polyolefin resin in the present invention, isotactic polypropylene, syndiotactic polypropylene, high-density polyethylene, low-density polyethylene, linear low-density polyethylene, propylene-alpha-olefin block copolymer, propylene-alpha-olefin random copolymer , Poly-1-butene, poly-4-methyl-1-pentene and the like, and mixtures thereof. Of these, isotactic polypropylene, syndiotactic polypropylene, propylene-alpha olefin block copolymer, propylene-alpha olefin random copolymer and mixtures thereof are preferred, and propylene-ethylene block copolymer, propylene-ethylene random Copolymers and those containing them are more preferred.

It is also possible to replace a part of the polyolefin with a compound modified with a compound such as an unsaturated carboxylic acid, a derivative thereof or an unsaturated hydroxy compound. These compounds include maleic anhydride, acrylic acid, methacrylic acid, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxyethyl maleimide and the like.

The ethylene content of the propylene-ethylene block copolymer and the propylene-ethylene random copolymer is preferably 20 parts by weight or less. If the ethylene content exceeds 20 parts by weight, the heat resistance will decrease. In terms of balance between heat resistance and flexibility, the ethylene content of the propylene-ethylene block copolymer and the propylene-ethylene random copolymer is preferably from 3 to 15 parts by weight, more preferably from 5 to 10 parts by weight. It is.

The polyolefin resin has a lower reactivity with the unsaturated hydroxy compound than the olefin polymer rubber, and when kneading a mixture of the two with an organic peroxide together with the hydroxy compound, it is substantially graft-modified. It does not react with the hydroxy compound to a small extent. Therefore, in the present invention, a mixture obtained by kneading the mixture with a hydroxy compound may have a small amount of hydroxy compound graft modification, but this is also described in the category of polyolefin-based resin.

[0015] The partially crosslinked olefin polymer rubber (A)
As the raw material, ethylene-alpha olefin copolymer rubber, butadiene rubber, natural rubber, styrene-butadiene rubber and the like can be used, and ethylene-propylene copolymer rubber and ethylene-propylene-diene copolymer rubber are particularly preferable. preferable. Among these, those having a melt index of 1 or less are preferable from the viewpoint of the mechanical strength of the composition. The propylene content in these propylene rubbers is preferably 50% by weight or less from the viewpoint of crosslinking efficiency,
In consideration of flexibility as the rubber, the range of 25 to 45% by weight is particularly preferable.

In the present invention, the definition of partial cross-linking is that the weight of the residue of P-xylene-Soxhlet extraction (excluding the weight of filler such as filler) of the composition is 90% or less of the weight of the olefin polymer rubber. It means something.

In the present invention, (B1) a hydroxyl group-containing polyolefin resin used in the modified thermoplastic elastomer
Fatty or (B2) hydroxyl group-containing polyolefin
Consists of a mixture of resin and polyolefin resin
That the mixing ratio of the polyolefin resin (B) and olefinic polymer rubber, both total weight polyolefin resin
(B) That is, a hydroxyl group-containing polyolefin tree
Of resin (B1) or (B1) and polyolefin resin
It is necessary that the compound (B2) is not less than 20% by weight and less than 70% by weight. If the content of the polyolefin resin is less than 20% by weight, the heat resistance and the fluidity are lowered, and a flow mark is easily formed, which is not preferable. On the other hand, if it is more than 70% by weight, it lacks flexibility and loses its properties as an elastomer.

The unsaturated hydroxy compound in the present invention is a compound having both an ethylenic double bond and a hydroxyl group in the same molecule, for example, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, Ethyl maleimide, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, triethylene glycol monoacrylate, triethylene glycol monomethacrylate,
Monoethylene and monomethacrylate or dipropylene glycol monoacrylate of polyethylene glycol such as tetraethylene glycol monoacrylate, tetraethylene glycol monomethacrylate,
Monopropylene and monomethacrylate of polypropylene glycol such as dipropylene glycol monomethacrylate, tripropylene glycol monoacrylate, tripropylene glycol monomethacrylate, tetrapropylene glycol monoacrylate, tetrapropylene glycol monomethacrylate, and monoacrylate or methacrylate of trimethylene glycol,
Monoacrylates and methacrylates of tetramethylene glycol, monoacrylates and methacrylates of ethylene glycol and propylene glycol copolymers, and monoallyl ethers of polyethylene glycol or polypropylene glycol such as diethylene glycol monoallyl ether and dipropylene glycol monoallyl ether; and And the like.

Among them, monoacrylates or monomethacrylates of polyethylene glycol and polypropylene glycol having a degree of polymerization ranging from 2 to 20 in terms of the graft reactivity and the balance between the strength of the composition obtained and the coatability, and the degree of polymerization of 2 Monoacrylate or methacrylate of trimethylene glycol having a degree of polymerization of from 2 to 20, monoacrylate and methacrylate of tetramethylene glycol having a degree of polymerization of from 2 to 20, and a copolymer of ethylene glycol and propylene glycol having a degree of polymerization of from 2 to 20 Monoacrylates and methacrylates are preferred.

In the present invention, when kneading together with the organic peroxide in the presence of the unsaturated hydroxy compound, the compounding amount is as follows: (a) the polyolefin resin and (b) the olefin copolymer rubber in a total of 100 parts by weight. For 0.
1 to 10 parts by weight is preferred, and a particularly preferred range is 1 to 5 parts by weight. If the amount is less than 0.1 part by weight, no effect is obtained. If the amount is more than 10 parts by weight, the composition obtained becomes non-uniform, resulting in deterioration of mechanical properties and deterioration of appearance.

When kneading with an organic peroxide in the presence of an unsaturated hydroxy compound, the thermoplastic resin obtained can be obtained regardless of whether the starting polyolefin resin is an unmodified polyolefin or a modified polyolefin resin having a hydroxyl group. By increasing the hydroxyl group concentration in the elastomer, the effect can be enhanced as compared with kneading in the absence.

In the present invention, it is possible to add a softening agent as required for improving the fluidity and the flexibility. As the softening agent, any of paraffin, naphthene and aromatic can be used, but it is preferable to use paraffin from the viewpoint of stability and color tone. Since the compounding amount varies depending on the purpose, it cannot be unconditionally determined, but generally, the amount is 0% with respect to the thermoplastic elastomer composition.
~ 200% by weight. When it is added in an amount of 200% by weight or more, it bleeds out and reduces the adhesion strength to the coating film.

Examples of the organic peroxide which can be used in the present invention include dibenzoyl peroxide, p-chlorobenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, 1,3-bis (t- Butylperoxy) isopropylbenzene, 2,5-bis (t-butylperoxy) -2,5-dimethylhexane, 2,5-bis (t-butylperoxy) -2,5-
Dimethyl-3-hexyne, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane,
T-butyl peroxybenzoate and the like may be mentioned, and these may be diluted with an inert substance such as a plasticizer or calcium carbonate. The compounding amount is a total of 100 (a) the crystalline polyolefin and (b) the olefin polymer rubber.
It is 0.05 to 3 parts by weight, preferably 0.2 to 1.5 parts by weight based on parts by weight.

The olefin polymer rubber is partially crosslinked by kneading with an organic peroxide regardless of the presence or absence of an unsaturated hydroxy compound, thereby improving heat resistance. Also, when an unsaturated hydroxy compound is present, it is almost selectively graft-polymerized to the olefin polymer rubber, and
It is considered to be a partially crosslinked olefin polymer rubber (A) .

For the purpose of improving the crosslinking efficiency of these organic peroxides, a compound having a plurality of unsaturated bonds in one molecule can be used in combination. Such compounds include, for example, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, ethylene glycol diacrylate and dimethacrylate, di or triacrylate of trimethylolpropane and di or trimethacrylate and the like. No.

The amount of these compounds varies depending on the amount of the organic peroxide, but is usually 3 parts by weight or less based on 100 parts by weight of the total of (a) the crystalline polyolefin and (b) the olefin polymer rubber. .

Examples of the polyolefin resin having a hydroxyl group (B1) include isotactic polypropylene, syndiotactic polypropylene, high-density polyethylene, low-density polyethylene, linear low-density polyethylene, propylene-alpha-olefin block copolymer, Ethylene and one or more compounds selected from polyolefins such as propylene-alpha-olefin random copolymers, poly-1-butene, poly-4-methyl-1-pentene, vinyl esters and unsaturated carboxylic acid derivatives; And those obtained by graft-modifying an unsaturated hydroxy compound in the presence of an organic peroxide or the like to one or more resins selected from olefin resins such as a copolymer of the above. Here, the unsaturated hydroxy compound is the same as described above, and all of them are feasible.

Other usable polyolefin resins having a hydroxyl group other than those described above include ethylene-vinyl alcohol copolymer, hydrolyzate of ethylene-vinyl ester, copolymer of ethylene and the above-mentioned unsaturated hydroxy compound. Coalescing (which may include other monomers having no hydroxyl group) and the like, and these can be used in combination with a resin graft-modified with an unsaturated hydroxy compound.

Of these, one or more selected from isotactic polypropylene, syndiotactic polypropylene, propylene-ethylene block copolymer, propylene-ethylene random copolymer, vinyl ester and unsaturated carboxylic acid derivative A copolymer of a compound and ethylene and a mixture thereof, in which the above unsaturated hydroxy compound is graft-modified in the presence of an organic peroxide or the like, ethylene-vinyl alcohol copolymer, hydrolysis of ethylene-vinyl ester And a copolymer of ethylene and the above-mentioned compound having a hydroxyl group (which may contain another monomer having no hydroxyl group), and a mixture thereof.

Particularly, those obtained by graft-modifying a propylene-based polymer such as isotactic polypropylene, syndiotactic polypropylene, propylene-ethylene block copolymer, and propylene-ethylene random copolymer with an unsaturated hydroxy compound are most preferable.

The ethylene content of the propylene-ethylene block copolymer and the propylene-ethylene random copolymer is preferably 20 parts by weight or less. If the ethylene content exceeds 20 parts by weight, the heat resistance will decrease. In terms of balance between heat resistance and flexibility, the ethylene content of the propylene-ethylene block copolymer and the propylene-ethylene random copolymer is preferably from 3 to 15 parts by weight, more preferably from 5 to 10 parts by weight. It is.

Generally, it is obtained by kneading a hydroxy compound.
Hydroxyl-containing polyolefin resin and polyole
Polyolefin resin composed of fin resin (B
The hydroxyl group concentration in the hydroxyl group-containing polyolefin-based resin in 2) is determined by mixing a polyolefin and an olefin-based polymer rubber with an organic peroxide in the presence of an unsaturated hydroxy compound and having a hydroxyl group-containing polyolefin-based resin. Higher concentration, such a high concentration of hydroxyl group-containing polyolefin resin
The presence of (B1) is required.

In order to develop the adhesion strength of the coating film, the hydroxyl group concentration of the modified thermoplastic elastomer composition as a whole should be at least 7 × 10 ⁻³ mmol / g, preferably at least 20 × 10 ³ mmol / g.
A concentration of 10 ⁻³ mmol / g or more, particularly 40 × 10 ⁻³ mmol / g or more, is required for achieving high coating film adhesion strength.

[0034] In modified thermoplastic elastomer composition of the present invention, incorporated into the modified thermoplastic elastomer obtained by kneading together with an organic peroxide Oh olefin polymer rubber in the presence or absence of unsaturated hydroxy compound The amount of the polyolefin-based resin (B1) having a hydroxyl group is based on 100 parts by weight of the modified thermoplastic elastomer.
It is 1 to 30 parts by weight, preferably 5 to 15 parts by weight. 1
If the amount is less than 30 parts by weight, there is no effect of exhibiting the adhesion strength of the coating film.
Flexibility is reduced.

In order to reduce the flow mark at the time of injection molding, the weight average molecular weight of the polyolefin resin component used as a raw material of the modified thermoplastic elastomer composition is preferably 100,000 or more, particularly preferably 2,000,000 or more.
It is more than 100,000. When a molded article is partially applied, the appearance of the molded article is impaired due to the occurrence of flow marks, and a portion having low coating film adhesion strength is formed, and the coating film may be peeled off therefrom.

Another aspect of the present invention is to knead a polyolefin resin (B1) or (B2) having a hydroxyl group and an olefin polymer rubber together with an organic peroxide in the presence or absence of an unsaturated hydroxy compound. And a thermoplastic elastomer composition obtained by crosslinking an olefin polymer rubber. Here, as the polyolefin-based resin having a hydroxyl group, the olefin-based polymer rubber, the unsaturated hydroxy compound, and the organic peroxide, any of those described above can be used.

The method for producing the modified thermoplastic elastomer composition is as follows: (A) a polyolefin resin, an olefin polymer rubber (unsaturated hydroxy compound if necessary) and an organic peroxide are mixed in advance with a Henschel mixer or the like. A modified thermoplastic elastomer prepared by kneading with a kneading device such as a Banbury mixer, a kneader, a single-screw extruder, a twin-screw extruder, and simultaneously performing cross-linking of an olefin copolymer rubber and graft reaction of an unsaturated hydroxy compound. (B) The polyolefin resin having a hydroxyl group is kneaded with a kneading device such as a Banbury mixer, a kneader, a single-screw extruder, a twin-screw extruder, and the like.

In another embodiment of the present invention,
Polyolefin resin having hydroxyl group (B1)
Or (B2) , an olefin polymer rubber (unsaturated hydroxy compound if necessary) and an organic peroxide are previously mixed with a Henschel mixer or the like, and then a Banbury mixer.
The modified thermoplastic elastomer composition is prepared by kneading with a kneading device such as a kneader, a single screw extruder or a twin screw extruder, and simultaneously performing the crosslinking reaction of the olefin copolymer rubber and the graft reaction of the unsaturated hydroxy compound.

In the present invention, in order to promote the reaction between the hydroxyl group in the composition and the urethane paint, a catalyst for the reaction between the hydroxyl group and the isocyanate group such as an organic tin compound or a tertiary amine can be added. Examples of such catalysts include organic tin compounds such as dibutyltin dilaurate, dibutyltin dimaleate, dibutyltin dioctylmalate, tetramethylethylenediamine,
N, N-dimethylbenzylamine, N, N-dimethylaniline, N, N-dialkylethanolamine, 1,4
-Diazabicyclo [2,2,2] octane, 1,8-diazabicyclo [5,4,0] -7-undecene, N, N
-Tertiary amines such as dimethylaminopyridine.

In the present invention, a filler such as a filler, carbon black, a pigment and the like can be added as required.

[0041]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto. In addition, the measuring method in an Example is as follows. MFR JIS K7210 (load 2.16 kg 230 ° C) HLMFR JIS K7210 (load 21.6 kg 230 ° C) Tensile breaking strength JIS K6301 hydroxyl group content Polyolefin resin and partially crosslinked olefin polymer rubber in the modified thermoplastic elastomer composition The hydroxyl group concentration of each component was determined by extracting a polyolefin-based resin (propylene resin) with p-xylene using Soxhlet, cooling to room temperature, and measuring the hydroxyl group concentration of the precipitate by infrared absorption spectrum.
The hydroxyl group concentration in the rubber component was determined by calculating the hydroxyl group concentration of the entire elastomer, and subtracting the hydroxyl group concentration in the propylene resin therefrom. Test conditions A 2 mm thick injection molded flat plate was used as a sample. The paint is a two-pack polyurethane paint (R-27) manufactured by Nippon Bee Chemical Co., Ltd.
1) was used. The peel test was performed with a width of 10 mm and a peeling of 180 degrees.

(Example 1) <Composition A> Polypropylene homopolymer 40 parts by weight (MFR 0.5 g / 10 min or less, abbreviated as PP1) Ethylene propylene copolymer rubber 60 parts by weight (MFR 0.01 or less EPR 2-hydroxyethyl methacrylate 3 parts by weight (hereinafter abbreviated as HEMA) Paraffin-based process oil 15 parts by weight (hereinafter abbreviated as oil) The above mixture was kneaded at 180 ° C. with a Brabender mixer, and then 2,5-bis (t) -Butylperoxy) -2,5-
1 part by weight of dimethylhexane (hereinafter abbreviated as PO)
The mixture was kneaded for 0 minutes to produce a modified thermoplastic elastomer (composition A). <Composition B> 100 parts by weight of PP1 3 parts by weight of HEMA 0.4 part by weight of PO Also, the above mixture was mixed with a Brabender mixer for 180 parts.
The mixture was kneaded at 10 ° C. for 10 minutes to obtain a polypropylene resin having a hydroxyl group (composition B). 90 of the above composition A
Parts by weight and 10 parts by weight of the composition B were kneaded with a Brabender mixer at 180 ° C. for 5 minutes to obtain a modified thermoplastic elastomer composition.

(Example 2) 40 parts by weight of the composition B of Example 1 60 parts by weight of EPR 3 parts by weight of HEMA 15 parts by weight After kneading the above composition at 180 ° C. with a Brabender mixer, 1 part by weight of PO was added. And kneaded for 10 minutes to produce a modified thermoplastic elastomer composition.

(Example 3) In Example 1, the composition A
A modified thermoplastic elastomer composition was produced in the same manner as in Example 1, except that half of PP1 was changed to an ethylene propylene random copolymer (MFR 0.5 ethylene content 7%, hereinafter abbreviated as PP2).

(Example 4) In Example 1, the composition A
HEMA to polyethylene glycol monomethacrylate (a mixture of tetraethylene glycol monomethacrylate and pentaethylene glycol monomethacrylate)
A modified thermoplastic elastomer composition was prepared in the same manner as in Example 1 except that the composition was changed to.

Example 5 A thermoplastic elastomer composition was produced in the same manner as in Example 1 except that the HEMA of the composition A was not used.

(Example 6) <Composition C> 100 parts by weight of PP1 3 parts by weight of polyethylene glycol monomethacrylate 2 parts by weight of PO
After kneading for 0 minutes, a polypropylene resin having a hydroxyl group (composition C) was obtained. For 5 parts by weight of the composition C,
90 parts by weight of the composition A of Example 1 and 5 parts by weight of a propylene random copolymer (MFR 0.5 g / 10 min, ethylene content 3% by weight) were mixed with a Brabender mixer to give 18 parts.
The mixture was kneaded at 0 ° C. for 5 minutes to obtain a modified thermoplastic elastomer composition.

(Example 7) A thermoplastic elastomer composition was produced in the same manner as in Example 1 except that PP2 was used instead of PP1 and polyethylene glycol monomethacrylate was used instead of HEMA in composition A of Example 1. did.

Comparative Example 1 A thermoplastic elastomer composition was produced in the same manner as in Example 1 except that the HEMA of the composition A and the composition B were not blended.

Comparative Example 2 A thermoplastic elastomer composition was produced in the same manner as in Example 1 except that the HEMA of the composition B was not blended.

Comparative Example 3 In Example 1, the composition A
Only composition B was not blended.

Comparative Example 4 A modified thermoplastic elastomer composition was prepared by using 1.5 parts by weight of PO in the composition A of Example 1, and the physical properties of the composition were measured as it was. Table 1 shows the physical property values of the examples and comparative examples.

[0053]

[Table 1]

[0054]

According to the present invention, there is provided a modified thermoplastic elastomer composition which can be coated with urethane without a primer treatment. The primer treatment step can be omitted, the step can be shortened, and an expensive primer is not used. There are advantages such as. The modified thermoplastic elastomer composition of the present invention can be used in a wide range of fields such as interior and exterior of automobiles and home appliances.

Continuation of the front page (56) References JP-A-62-207344 (JP, A) JP-A-64-85206 (JP, A) JP-A-4-339814 (JP, A) (58) Fields investigated (Int) .Cl. ⁷ , DB name) C08L 23/00-23/36

Claims (6)

(57) [Claims] (A) Partially crosslinked olefin polymer rubber
30 wt% or more and less than 80 wt% and (B1) in advance unsaturated becomes modified with hydroxy compounds hydroxyl group-containing polyolefin-based resin or (B2) a hydroxyl group-containing polyolefin-based resin and an modified with advance unsaturated hydroxy compound Composed of polyolefin resin
(B) 20% by weight or more, 70% by weight of polyolefin resin
% Of a thermoplastic elastomer composition comprising:
A modified thermoplastic elastomer composition having good coatability, wherein the concentration of the hydroxyl group in the composition is 7 × 10 ⁻³ mmol / g or more. 2. The polyolefin resin of a hydroxyl group-containing polyolefin resin (B1) previously modified with an unsaturated hydroxy compound, wherein the polyolefin resin is isotactic polypropylene, syndiotactic polypropylene, propylene-ethylene block copolymer, propylene-ethylene. 2. The modified thermoplastic elastomer composition according to claim 1, which is a random copolymer. 3. A kneaded together with an organic peroxide olefin polymer rubber or olefin polymer rubber and poly olefin resin in the presence of an unsaturated hydroxy compound, grafted by an unsaturated hydroxy compound of olefin polymer rubber The composition obtained by performing the modification and the crosslinking includes (B)
1) blending a hydroxyl group-containing polyolefin resin previously modified with an unsaturated hydroxy compound, or (B2) a hydroxyl group-containing polyolefin resin previously modified with an unsaturated hydroxy compound and a polyolefin resin; ) Partially crosslinked olefin polymer rubber
30% by weight or more and less than 80% by weight (B) polyolefin
Heat of 20% by weight or more and less than 70% by weight
A thermoplastic elastomer composition, and a hydride in the composition;
A method for producing a modified thermoplastic elastomer composition having good coatability, wherein the concentration of a roxyl group is at least 7 × 10 ⁻³ mmol / g . 4. An olefin polymer rubber or an olefin polymer rubber and a polyolefin resin are kneaded with an organic peroxide in the absence of an unsaturated hydroxy compound,
The composition obtained by cross-linking the olefin-based polymer rubber is added to (B1) a hydroxyl group-containing polyolefin-based resin previously modified with an unsaturated hydroxy compound or (B1).
2) A hydroxyl group-containing polyolefin resin and a polyolefin resin previously modified with an unsaturated hydroxy compound are blended, and (A) a partially crosslinked olefin polymer rubber is contained in an amount of 30% by weight or more and less than 80% by weight. If, (B) a polyolefin resin 20 wt% or more, and a thermoplastic elastomer composition comprising less than 70 wt%, and the composition
The method for producing a modified thermoplastic elastomer composition having good coatability, wherein the concentration of the hydroxyl group is 7 × 10 ⁻³ mmol / g or more . 5. A olefin polymer rubber or an olefin polymer rubber and a polyolefin resin,
(B1) a hydroxyl group-containing polyolefin resin previously modified with an unsaturated hydroxy compound or (B2)
A hydroxyl group-containing polyolefin resin and a polyolefin resin previously modified with an unsaturated hydroxy compound are kneaded with an organic peroxide in the presence of the unsaturated hydroxy compound, and the olefin polymer rubber is grafted with the unsaturated hydroxy compound. Perform denaturation and crosslinking,
(A) 30% by weight or less of partially crosslinked olefin polymer rubber
Above, less than 80% by weight and (B) polyolefin resin 20
Thermoplastic elast consisting of at least 70% by weight
And a hydroxyl group in the composition.
A process for producing a modified thermoplastic elastomer composition having good coatability, wherein the concentration is 7 × 10 ⁻³ mmol / g or more . 6. An olefin polymer rubber or an olefin polymer rubber and a polyolefin resin, and (B1)
A hydroxyl group-containing polyolefin resin previously modified with an unsaturated hydroxy compound or (B2) a hydroxyl group-containing polyolefin resin and a polyolefin resin previously modified with an unsaturated hydroxy compound, in the absence of an unsaturated hydroxy compound (A) 30% by weight of a partially crosslinked olefin polymer rubber obtained by kneading with an organic peroxide and crosslinking the olefin polymer rubber.
Above, less than 80% by weight and (B) polyolefin resin 2
A thermoplastic elastomer comprising 0% by weight or more and less than 70% by weight.
Hydroxyl groups in a stoma composition and in the composition
The method for producing a modified thermoplastic elastomer composition having good coatability, characterized by having a concentration of 7 × 10 ⁻³ mmol / g or more .