JPH0350703B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an anti-slip polyolefin molded article. In more detail, it has excellent anti-slip effect,
The present invention also relates to a polyolefin molded product equipped with a non-slip material that has excellent heat resistance and abrasion resistance. Polyolefin molded products have weather resistance, chemical resistance,
Because it has excellent water resistance and is inexpensive, it is currently widely used in place of molded products made of wood or metal. However, although this polyolefin molded product has the above-mentioned excellent properties, it has the drawbacks of low frictional resistance and easy slippage.
For example, if a pallet used for transporting or storing cargo is made from this polyolefin molded product, slipping may easily occur between the cargo and the pallet or between the pallets, causing the cargo to collapse when being transported. There is danger. As a method for preventing slippage of polyolefin molded products, a method is used in which a vulcanized product of ethylene copolymer rubber with high frictional resistance is adhered to polyolefin molded products to prevent slipping (Japanese Patent Publication No. 15269/1983).
Low-density polyethylene, ethylene-vinyl acetate copolymer, styrene-butadiene-styrene block copolymer, or a blend of ethylene propylene rubber and linear low-density polyethylene are welded to polyolefin molded products as anti-slip materials. Method of stopping (Japanese Patent Publication No. 41505, 1982, 1983)
90957) is proposed. However, in the former method, the adhesive strength between the vulcanized rubber and the polyolefin molded product is not good, and it cannot be said that it is an economically inexpensive method. In addition, in the latter method, the adhesive strength of the anti-slip material to the polyolefin molded product, especially the polypropylene molded product, is poor, and furthermore, the heat resistance and abrasion resistance of the non-slip material itself attached to the polyolefin molded product are poor, and the coefficient of friction is small. It has drawbacks such as insufficient effectiveness as an anti-slip material. The inventors of the present invention have conducted intensive studies to overcome the drawbacks of these conventional techniques and to develop a new technology that effectively prevents the slippage of polyolefin molded products. The present invention was completed based on the discovery that this object can be achieved by attaching a stopper to a polyolefin molded product. That is, the present invention provides monoolefin copolymer rubber
An anti-slip material made of a thermoplastic elastomer composition (A) formed by dynamically heat-treating (a) and a polyolefin plastic (b) and partially crosslinked is adhered to a polyolefin molded product (B). related to polyolefin molded products. The thermoplastic elastomer composition used as an anti-slip material in the present invention is obtained by dynamically heat-treating a monoolefin copolymer rubber (a) and a polyolefin plastic (b) to partially crosslink them. Details of the method for preparing such partially crosslinked thermoplastic elastomer compositions are described in, for example, Japanese Patent Publication No. 53-34210 and Japanese Patent Publication No. 56-15741. That is, as the monoolefin copolymer rubber (a), for example, ethylene-propylene copolymer rubber,
Amorphous random rubber-like copolymers mainly composed of olefins, such as ethylene-propylene-nonconjugated diene copolymer rubber and ethylene-butadiene copolymer rubber, which are kneaded by heating in the presence of an organic peroxide. A rubber-like material is used that is crosslinked and has reduced fluidity or no longer flows. When copolymerizing non-conjugated dienes, dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, ethylidene norbornene, etc. are used, and among these non-conjugated diene copolymer rubbers, ethylene-propylene -5-ethylidene-1-norbornene copolymer rubber is preferred because it provides a thermoplastic elastomer with excellent heat resistance, tensile properties, and impact resilience. And Mooney viscosity ML ₁₊₄ (100℃)
Copolymer rubbers having a molecular weight of about 10 to 170, preferably about 40 to 80 are generally used. The polyolefin plastic (b) is a polyolefin plastic that is thermally decomposed by heating and kneading in the presence of an organic peroxide to reduce its molecular weight and increase the fluidity of the resin, specifically isotactic polypropylene. , copolymers of propylene and small amounts of other α-olefins, such as propylene-ethylene copolymers, propylene-1-butene copolymers, propylene-1-
Hexene copolymer, polyptene, propylene-4
-Methyl-1-pentene copolymer and the like are generally used. These polyolefin plastics are generally used having a melt index (at 230 DEG C.) of about 0.1 to 50, preferably about 5 to 20. The blending ratio of monoolefin copolymer rubber (a) and polyolefin plastic (b) is determined to maintain excellent physical properties of the resulting thermoplastic elastomer, particularly good heat resistance, abrasion resistance, and friction resistance. It is preferable that the amount of the polyolefin plastic component (b) is 10 to 60 parts by weight, particularly 15 to 50 parts by weight, based on 100 parts by weight of the components (a) and (b) in the composition. In addition, in the present invention, the total amount of monoolefin copolymer rubber (a) and polyolefin plastic (b) is
(c) Mineral oil softener and/or (d) Peroxide non-crosslinked hydrocarbon rubber material per 100 parts by weight.
(d) 5 to 100 parts by weight can also be added. This mineral oil-based softener (c) usually weakens the intermolecular forces of rubber during roll processing, making processing easier, and helps disperse carbon black, white carbon, etc., and hardens vulcanized rubber. It is a high boiling point petroleum fraction used for the purpose of reducing stiffness and increasing flexibility and elasticity, and is classified into paraffinic, naphthenic, aromatic, etc. The peroxide non-crosslinked hydrocarbon rubber material (d) includes, for example, polyisobutylene, butyl rubber, propylene-ethylene copolymer rubber containing 70 mol% or more of propylene, propylene-1-butene copolymer rubber, and atactic polypropylene. A hydrocarbon-based rubbery substance that does not crosslink or lose fluidity even when mixed with peroxide and kneaded under heat. Among these, polyisobutylene, butyl rubber, and propylene-1-butene copolymer are preferred. Partial crosslinking by dynamic heat treatment is about 0.05 to 1.0% by weight, preferably about 0.1% by weight, based on 100 parts by weight of the material to be treated.
Add ~0.5% by weight of an organic peroxide, typically dicumyl peroxide, ditert-butyl peroxide, 1,3-bis(tert-butylperoxide isopropyl)benzene, etc., and mix the used organic peroxide using various kneading equipment. has a half-life of 1
Temperatures such as about 150-280℃, such that the
This is preferably carried out by kneading under melting conditions at about 170 to 240°C for about 1 to 20 minutes, preferably about 3 to 10 minutes. The partially crosslinked thermoplastic elastomer obtained preferably has a density of 0.87 to 0.90 g/cm ³ . The thermoplastic elastomer composition (A) used in the present invention may contain fillers such as calcium carbonate, calcium silicate, clay, kaolin, talc, silica, diatomaceous earth, etc., within a range that does not impair fluidity and rubber properties. Mica powder, asbestos, alumina, barium sulfate, aluminum sulfate, calcium sulfate, basic magnesium carbonate, molybdenum disulfide, graphite, glass fiber, glass bulb, shirasu balloon, carbon fiber, etc. or coloring agent,
For example, carbon black, titanium oxide, zinc white, red rose, ultramarine blue, navy blue, azo pigment, nitroso pigment, lake pigment, phthalocyanine pigment, etc. can be blended. The thermoplastic elastomer composition can be molded using equipment used for normal thermoplastics, such as extrusion molding, calendar molding, and injection molding, and can be molded into any shape such as a belt, string, plate, or block as an anti-slip material. is formed into. In addition, the polyolefin constituting the molded article (B) of the present invention includes polypropylene, polyethylene, polybutene-1, poly-4-methyl-1-pentene, ethylene-propylene copolymer, ethylene-
Examples include vinyl acetate copolymers or mixtures thereof, among which Rockwell hardness (R
Hardness according to scale ASTM D785) is 80 or more,
Preferably, a polyolefin mainly composed of polypropylene having a hardness of 90 or more, or polyethylene having a Rockwell hardness of 40 or more, preferably 50 or more. In addition, the polyolefin constituting this molded product (B) may contain antioxidants, ultraviolet absorbers, heat stabilizers, antistatic agents, flame retardants, crosslinking agents, blowing agents, dyes, pigments, and organic or inorganic additives as necessary. Fillers may also be added. The polyolefin molded product (B) can be molded using any conventional molding method such as injection molding, extrusion molding, blow molding, vacuum molding, rotational molding, or cast molding, and can be used to form pallets, plates, containers, bottles, etc. Or it can be molded into a desired molded product such as a pipe. Furthermore, the molded product (B) may be a non-foamed product or a foamed product. In the present invention, the thermoplastic elastomer composition (A)
The method of adhering the anti-slip material formed by molding the polyolefin to the polyolefin molded product (B) is as follows: (1) Melt the surface of the molded product (B) and the surface of the non-slip material using hot air or a heating plate; Hot air bonding method (2) in which the two are pressed together while they are in a molten state; Extrusion bonding method (3) in which the anti-slip material is extruded from an extruder into a strip, string, etc., and then pressed onto the surface of the molded product (B) and welded. ) An insert injection molding method in which a non-slip material is fixed in a mold, molten polyolefin is injected into the mold, and the heat of fusion is used to weld the molded product (B) and the non-slip material. For example, However, insert injection molding is usually used. The anti-slip material formed by molding the thermoplastic elastomer composition used in the present invention has excellent heat resistance and abrasion resistance, and also has a large coefficient of friction and strong adhesive strength to polyolefin molded products. The product exhibits excellent anti-slip properties and is characterized by being able to maintain its anti-slip properties for an extremely long period of time. EXAMPLES Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to the following examples. The various physical properties described in the examples were measured using the following measurement methods. Hardness, T _B , E _B : 25℃ according to JIS K-6301
Measured under constant temperature. Friction coefficient (sliding angle): Install a non-slip material sheet with a thickness of 2 mm and a length and width of 250 mm on the surface plate, and place a sheet of anti-slip material on it with a thickness of 2 mm and a length and width of 80 mm.
A sheet made of polyethylene or polypropylene with a diameter of 1.0 mm was placed thereon, and a load of 1 kg was applied to the sheet. From this state, one side of the surface plate
The angle at which the sheet, which was pulled up and placed at a constant speed of 100 mm/min, starts to slide (angle with respect to the horizontal plane) was measured, and the average value of three measurements was shown. Taper wear: Measured in accordance with JIS K-7204. Heating deformation rate: Compliant with JIS K-6723 (loading: 4.5Kg/cm ² , 10Kg/cm ² , heating temperature
90°C) 180° peel strength: Using a test piece with a length of about 250 mm in which a non-slip material with a width of 20 mm and a thickness of 2 mm is welded to the base material, half of the non-slip material in the length direction of the non-slip material is welded to the base material. With the peeled anti-slip material folded back 180 degrees, one end of the anti-slip material and base material was fixed to the chuck of a testing machine, and the anti-slip material was peeled off at a constant speed of 50 mm/min at a constant temperature of 20°C. It was peeled off from the base material, the force required for peeling was read, and the average value was expressed in kg/cm. Reference Example 1 (Preparation of thermoplastic elastomer composition) Ethylene-propylene-5-ethylidene-1-
Norbornene ternary copolymer rubber [ethylene content 80
Mol%, iodine number 13, Mooney viscosity ML ₁₊₄ (100
°C) 150] 40 parts (weight, same below), polypropylene (density 0.91 g/cm ³ , melt index 13) 45
and 15 parts of paraffinic process oil were kneaded for 5 minutes at 180° C. using a Banbury mixer in a nitrogen atmosphere, and then passed through a roll to produce pellets using a sheet cutter. 0.5 parts of 1,3-bis(tert-butylperoxyisopropyl)benzene was added to 100 parts of the pellets, mixed in a Henschel mixer, and then extruded at 210°C using an extruder in a nitrogen atmosphere to form a partially crosslinked thermoplastic. Elastomer () was manufactured. Reference example 2 Ethylene-propylene-5-ethylidene-2-
Norbornene ternary copolymer rubber [ethylene content 79
Mol%, iodine number 13, Mooney viscosity ML ₁₊₄ (100
°C) 90〕70 parts and 30 parts of the polypropylene of Reference Example 1
Pelletization and partial crosslinking were carried out in the same manner as in Reference Example 1 using the same procedure as in Reference Example 1 to produce a partially crosslinked thermoplastic elastomer (2). Reference example 3 Ethylene-propylene-5-ethylidene-2-
Norbornene ternary copolymer rubber [ethylene content 79
Mol%, iodine number 13, Mooney viscosity ML ₁₊₄ (100
°C) 90] 65 parts, 20 parts of the polypropylene of Reference Example 1, and 15 parts of the propylene-ethylene copolymer containing 50 mol% of propylene were pelletized and partially crosslinked in the same manner as in Reference Example 1. Thermoplastic elastomer () was manufactured. Examples 1 to 3 The thermoplastic elastomers prepared in Reference Examples 1 to 3 were press-molded to a thickness of 2 mm, a width of 200 mm, and a length of
A 200mm sheet was created and used as an anti-slip material sheet. (a) Heat fusion to polypropylene molded products Polypropylene [manufactured by Mitsui Petrochemical Industries, Ltd. Product name Mitsui Petrochemical Polypro SJ310 (melt index (230°C); 1.2 g/10 minute density; 0.91
g/cm ³ , Rockwell hardness R scale; 85)]
Thickness 2mm, length and width 200mm manufactured using
The above anti-slip material sheet is placed on a plate of 190mm in diameter.
Heat welding was carried out by press molding at 150 Kg/cm ³ at 150 Kg/cm 3 for 5 minutes. Table 1 shows various physical properties of the obtained anti-slip material. (b) Heat fusion to polyethylene molded product Polyethylene [Mitsui Petrochemical Co., Ltd. product name]
Hi-Zex 2200J (Melt Index (190)
°C); 5.5 g/10 minutes; density; 0.968 g/cm ³ ; Rockwell hardness R scale; 190℃, 150Kg/cm ³ 5
Heat welding was carried out by press molding under conditions of pressurization for minutes. Table 1 shows various physical properties of the obtained anti-slip material. Comparative Examples 1 to 2 Ethylene-α-olefin copolymer rubber [trade name: Tafmer P.0680 (density: 0.88,
Melt index (230°C); 0.44)] and 5 parts of linear low-density polyethylene [density; 0.93 g/cm ³ , melt index (230°C); 1.3] A mixture sheet (Comparative Example 1) or Ethylene-vinyl acetate copolymer [vinyl acetate content: 14%, density: 0.93
g/cm ³ , melt index (190° C.); 1.4] An anti-slip polyolefin molded article was produced in the same manner as in Examples 1 to 3, except that the sheet (Comparative Example 2) was used as the anti-slip material sheet. Table 1 shows various physical properties of the obtained anti-slip material. 【table】

Claims (1)

[Scope of Claims] 1. A non-slip product obtained by molding a thermoplastic elastomer composition (A) in which a monoolefin copolymer rubber (a) and a polyolefin plastic (b) are dynamically heat-treated and partially crosslinked. A slip-resistant polyolefin molded product made by adhering the material to the polyolefin molded product (B). 2 The thermoplastic elastomer composition is composed of about 40 to 90 parts by weight of monoolefin copolymer rubber (a) and 60 to 10 parts by weight of polyolefin plastic (b) (where (a) + (b) is
100 parts by weight) and (c) a mineral oil softener and/or (d) a peroxide non-crosslinked hydrocarbon rubber 5 to 100 parts by weight, which are partially crosslinked by heat treatment. The anti-slip polyolefin molded product described in item 1. 3. The anti-slip polyolefin molded article according to claim 1 or 2, wherein the polyolefin molded article (B) is a polypropylene molded article. 4. The anti-slip polyolefin molded article according to any one of claims 1 to 3, wherein the polyolefin molded article has a shape of a pallet, a container, a plate, a bottle, or a tube.