JP3314454B2 - Method for producing polyolefin-based composite material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the production of a polyolefin composite material having excellent mechanical strength, tactile sensation, abrasion resistance, moldability, paintability, weather resistance and oil resistance and exhibiting good soft resin properties. About the method.

[0002]

2. Description of the Related Art Conventionally, as a polyolefin-based thermoplastic elastomer, those mainly composed of polypropylene and ethylene-propylene-based rubber have been widely known. However, this elastomer has no polar group in its molecular structure. Poor oil resistance was mentioned as a disadvantage. In order to remedy this drawback, a composite of polypropylene and acrylonitrile-butadiene rubber (hereinafter referred to as NBR) has been invented. This composite is excellent in oil resistance, but has a diene in its molecular structure and thus has an ozone resistance. , Ie, poor weather resistance, was mentioned as a disadvantage. Further, the polypropylene-based thermoplastic elastomers mentioned here have low strength properties, so that their use in parts requiring strength has been limited.

On the other hand, urethane-based thermoplastic elastomers are high-performance thermoplastic elastomers having excellent strength properties and excellent oil resistance, weather resistance, abrasion resistance and the like. However, this elastomer has high melt viscosity and poor moldability,
There are also problems such as high cost.

Some blends of a thermoplastic polyolefin resin and a thermoplastic urethane elastomer have already been studied. For example, JP-A-61-271351, JP-A-55-118943, or JP-A-54-86.
No. 52 describes a composition comprising a polyolefin resin, a thermoplastic polyurethane elastomer, and an acid-containing polyolefin. However, this material is hard to use as a soft material,
In addition, the flexibility was poor. Although the moldability was improved over the thermoplastic polyurethane elastomer, it was still not a satisfactory material.

[0005]

SUMMARY OF THE INVENTION The present invention provides a method for producing a polyolefin-based composite material which is excellent in tactile sensation, abrasion resistance, molding processability, paintability, weather resistance, oil resistance and exhibits good soft resinous properties. The purpose is to provide.

[0006]

Means for Solving the Problems The present inventors have made intensive studies in view of the above-mentioned situation, and as a result, completed the present invention. That is, the present invention provides a thermoplastic polyurethane elastomer.
-100 parts by weight of thermoplastic polyolefin resin
Not less than 3 parts by weight and not more than 50 parts by weight;
5 to 80 parts by weight of a terpolymer plasticizer and
For 100 parts by weight of thermoplastic polyolefin resin,
Graft-modified with unsaturated carboxylic acids or their derivatives
Acid thermoplastic polyolefin 5 parts by weight or more and 150 parts by weight or less
The production of the resin composition comprising from below, after melting the pre-thermoplastic polyurethane elastomer, this was mixed with other ingredients, a process for producing a polyolefin composite material comprising kneading. The details of the present invention are described below.

The thermoplastic polyolefin resin used in the present invention includes low-density polyethylene, medium-density polyethylene, high-density polyethylene, a copolymer of ethylene and α-olefin, polybutene, poly-4-methylpentene-1,
Examples include polypropylene-based resins. As a polypropylene resin, for example, polypropylene homopolymer,
Examples include a propylene / ethylene block copolymer having an ethylene content of 3% by weight or more and 45% by weight or less and a propylene / ethylene random copolymer having an ethylene content of 0.5% by weight or more and 10% by weight or less. The thermoplastic polyolefin resin used here is not particularly limited, but a polypropylene resin is preferably used from the viewpoint of heat resistance. Such a thermoplastic polyolefin-based resin is preferably mixed in an amount of 3 to 50 parts by weight, more preferably 5 to 30 parts by weight, based on 100 parts by weight of the thermoplastic polyurethane elastomer. When this amount is less than 3 parts by weight, no remarkable effect is exerted on the moldability,
If the amount exceeds 50 parts by weight, the properties as a soft material may be impaired, and the high strength properties of the thermoplastic urethane elastomer may be significantly reduced.

[0008] The thermoplastic polyurethane elastomer used in the present invention is not particularly limited. Examples thereof include polycaprolactone-based polyurethane, polycarbonate-based polyurethane, polyether-based polyurethane, and polyester-based polyurethane.
More than one species is used. These thermoplastic polyurethane elastomers are commercially available (for example, Miraxtran manufactured by Pandex Nippon Milactran Co., Ltd. manufactured by Dainippon Ink and Chemicals, Takelac manufactured by Takeda Pharmaceutical Co., Ltd.).
These are used as appropriate.

In some cases, the thermoplastic polyurethane elastomer used in the present invention has hygroscopicity. In such a case, it is preferable to perform pre-drying at about 80 ° C. for about 4 hours as in the case of a normal hygroscopic polymer. If the pre-drying is not performed, foaming may occur during material molding.

The acid-containing thermoplastic polyolefin used in the present invention is added for the purpose of improving the compatibility between a polyolefin resin originally having poor compatibility and a thermoplastic polyurethane elastomer, and uniformly and finely dispersing the same.
This acid- containing thermoplastic polyolefin is an unsaturated carboxylic acid
Alternatively, a modified polyolefin obtained by grafting a derivative thereof to a polyolefin is used. In this case, as the polyolefin, high-density polyethylene, medium-density polyethylene, low-density polyethylene, polypropylene, polybutene, poly4-methylpentene-1, polyolefins such as a copolymer of ethylene and α-olefin, ethylene-propylene rubber, Polyolefin comprising ethylene-propylene-diene terpolymer rubber, butyl rubber, butadiene rubber, low-crystalline ethylene-propylene copolymer or low-crystalline ethylene-butene copolymer, or low-crystalline propylene-butene copolymer -Based thermoplastic elastomers, polyolefin-based elastomers such as polyolefin-based thermoplastic elastomers mainly comprising a blend of polypropylene and ethylene-propylene rubber, or ethylene-vinyl ester copolymers, ethylene-a Includes Lil ester copolymers such as, blends of various polyolefins mutual also included. On the other hand, unsaturated carboxylic acids or derivatives thereof and other functional vinyl monomers include, for example, acid anhydrides such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, sorbic acid, acrylic acid amide, methacrylic acid amide Amides, such as glycidyl acrylate, epoxy such as glycidyl methacrylate, 2-hydroxyester acrylate, 2-hydroxyester methacrylate, hydroxy compounds such as polyethylene glycol monoacrylate, sodium acrylate, sodium methacrylate, acrylic Metal salts such as zinc acid can be given, and they can be mixed with each other. Among them, acrylic acid, maleic acid and maleic anhydride give preferable results. When the above-mentioned monomers are used, they can be used simultaneously with various monomers such as styrene, vinyl acetate, acrylic ester, and methacrylic ester for graft copolymerization. Such an acid-containing thermoplastic polyolefin is commercially available (for example, Umex manufactured by Sanyo Chemical Industries, Ltd.). Further, the oxygen-thermoplastic polyolefin used, unsaturated carbo contained in the graft modified polyolefin
The amount of the acid or its derivative is preferably 0.05 to 20 parts by weight, more preferably 0.5 to 20 parts by weight, based on 100 parts by weight of the polyolefin. If this amount is less than 0.05 part by weight, the effect of addition is not recognized, and if it exceeds 20 parts by weight, moldability and thermal stability may be adversely affected.

It is necessary to select the mixing amount according to the type of the functional group and the amount of modification, but it is 5 parts by weight or more and 150 parts by weight or less based on 100 parts by weight of the thermoplastic polyolefin resin used.
It is more preferably from 10 to 120 parts by weight, and still more preferably from 10 to 100 parts by weight.
When the amount is less than 5 parts by weight, the effect of the addition is not recognized.
When the amount is more than the weight part, moldability and thermal stability may be adversely affected.

As the plasticizer used in the present invention, a polyester polymer plasticizer is used for the purpose of suppressing bleed out after molding of the obtained polyolefin-based composite material.
, And the it is desirable, the molecular weight generates a molding defect exceeds 10000 little effect of suppressing bleed-out is less than 700 molecular weight of the polyester polymer plasticizer used in this case is 700 to 10,000 Sometimes. The mixing amount is 5 parts by weight or more to 100 parts by weight of the thermoplastic polyurethane elastomer.
0 parts by weight or less, more preferably 10 parts by weight or more and 60 parts by weight or less. If the amount is less than 5 parts by weight, the properties of a soft resin and the moldability may be impaired, and if it exceeds 80 parts by weight, the mechanical strength may be significantly reduced.

[0013] or more thermoplastic polyolefin resin in the present invention, a thermoplastic polyurethane elastomer, non
A polyolefin-based composite material is manufactured by kneading an acid- containing thermoplastic polyolefin graft-modified with a saturated carboxylic acid or a derivative thereof and a plasticizer. Is characterized in that the above components are mixed and kneaded, whereby a composite having excellent strength properties is obtained.

The temperature, kneading time, shearing force, and other conditions at the time of kneading vary depending on the components used, but conditions sufficient for kneading are appropriately employed.

[0015] In the above method, there is no particular limitation on the manufacturing apparatus used, and a Banbury mixer, a kneader,
Any device such as an extruder and a roll kneader can be used. However, if the shearing force is too small, sufficient mixing is not performed, so that a device that gives a sufficient shearing force is preferably used.

The composite obtained as described above can additionally contain other types of synthetic elastomers and fillers typified by calcium carbonate, talc, carbon, barium sulfate and the like. In addition, stabilizers such as antioxidants, ultraviolet absorbers, antistatic agents, slip agents, flame retardants, pigments and the like may be added at all.

[0017]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited to these examples. In this example, the tensile strength was measured according to JIS K7311 by punching a 2 mm thick sheet into a dumbbell-shaped test piece.

Example 1 A polycaprolactone-based polyurethane (manufactured by Nippon Milactran Co., Ltd.) as a thermoplastic polyurethane elastomer preliminarily dried in an oven at 80 ° C. for 4 hours in a Brabender mixer having an internal volume of 100 cc and a set temperature of 180 ° C. 75 g of Miractran E580) was added and kneaded at 140 rpm for 6 minutes to melt the thermoplastic polyurethane elastomer. After that, polypropylene resin (Tosoh Polypro J5100A manufactured by Tosoh Corporation)
7 g, maleic anhydride-modified polypropylene (molecular weight: 4000, acid value: 52) as an acid-containing thermoplastic polyolefin
mgKOH / g, Sanyo Kasei Kogyo Co., Ltd. Umex 1
010) 3 g, polyester-based high molecular weight plasticizer as plasticizer (Adekaizer PN170 manufactured by Asahi Denka Kogyo KK)
15 g. Thereafter, the mixture was further kneaded at a rotation speed of 140 rpm for 6 minutes, then taken out and press-molded for 2 m.
The desired composition was obtained in a sheet having a thickness of m and the tensile strength was measured. Table 1 shows the results.

Example 2 A target composition was obtained by the same operation except that a polyether-based polyurethane (Milactran E385 manufactured by Nippon Milactran Co., Ltd.) was used in place of the thermoplastic polyurethane elastomer used in Example 1. The tensile strength was measured. Table 1 shows the results.

Comparative Example 1 A sample was produced in the same manner as in Example 1 except that a thermoplastic polyurethane elastomer, a polypropylene resin, an acid-containing thermoplastic polyolefin, and a plasticizer were all simultaneously charged into a Brabender mixer. Was measured. However, the kneading time was 6 minutes. Table 1 shows the results.

Comparative Example 2 A sample was produced in the same manner as in Example 2 except that a thermoplastic polyurethane elastomer, a polypropylene resin, an acid-containing thermoplastic polyolefin, and a plasticizer were all simultaneously charged into a Brabender mixer. Was measured. However, the kneading time was 6 minutes. Table 1 shows the results.

[0022]

[Table 1]

[0023]

As described above, the composite material produced according to the method of the present invention has excellent strength characteristics.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁷ Identification code FI C08L 67:00) C08L 67:00) (56) References JP-A-3-2311963 (JP, A) JP-A-3-247646 (JP, A) JP-A-2-160868 (JP, A) JP-A-4-214711 (JP, A) JP-A-4-239042 (JP, A) Evaluation and market of polymer additives and modifiers , Japan, CMC Co., Ltd., June 27, 1984, 2-5 Advances in Polymer and Rubber Additives, Japan, Chemical Industry Co., Ltd., March 15, 1976, 22-23 (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 1/00-101/16 C08J 3/20

Claims (1)

(57) [Claims] 1. A thermoplastic polyurethane elastomer 100
3 parts by weight of thermoplastic polyolefin resin to parts by weight
To 50 parts by weight, polyester-based high as plasticizer
5 to 80 parts by weight of the molecular plasticizer and the thermoplasticity
100 parts by weight of polyolefin resin, unsaturated
Acid-containing thermoplastics graft-modified with rubonic acid or its derivatives
Production of a composite material comprising 5 to 150 parts by weight of a reactive polyolefin, wherein a thermoplastic polyurethane elastomer is melted in advance, and then other components are mixed therein and kneaded. Method.