JPH03197134A - Laminate of metallic body and ultra-molecular weight polyethylene and manufacture thereof - Google Patents

Abstract

PURPOSE:To extraordinarily improve the durability and abrasion resistance in the anticorrosive layer of a metallic body by laminating ultra-molecular weight polyethylene on the surface of an anticorrosion-treated metallic body via a basic material. CONSTITUTION:A laminate of a metallic body and ultra-molecular weight polyethylene is made such that the ultra-molecular weight polyethylene is laminated on the surface of an anticorrosion-treated metallic body via a basic material. The material of the metallic body is pure iron, carbon steel, special steel, cast iron, cast steel, aluminum, magnesium, zinc, nickel, chrome, lead, or alloys of these materials, and the like. For the basic materials, there is used synthetic resin such as thermoplastic resin, thermosetting resin or the like, or sheet materials consisting of rubber or the like, metallic materials such as metal plate, wire gauze, or the like, and fiber materials such as cloth, non-woven fabric, lumber, paper, or the like, and FRP board or the like. Since the ultra-molecular weight polyethylene is noncohesive, it is difficult to adhere it in ordinary heat bonding or by the use of an adhesive agent or the like. Accordingly, the lamination is usually effected via a basic material which is capable of adhering by heat bonding or an adhesive agent.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a laminate of a metal body and ultra-high molecular weight polyethylene, and a method for producing the same. More specifically, it is a laminate of a metal body and ultra-high molecular weight polyethylene in which ultra-high molecular weight polyethylene is laminated on the surface of a metal body that has been subjected to anti-corrosion treatment via a base material, and the durability and abrasion resistance of the anti-corrosion layer are In addition to maintaining its anticorrosion effect over a long period of time, it also improves the non-stick properties, abrasion resistance, impact resistance, and stress cracking resistance (ESCR) of ultra-high molecular weight polyethylene.
The present invention relates to a laminate that takes advantage of properties such as chemical resistance, and a method for manufacturing the same.

[Prior Art] Conventionally, there has been a method of preventing corrosion on the surface of metal bodies such as metal plates, metal pipes, hoppers, shooters, tanks, etc. by applying anticorrosive paints such as epoxy paints and acrylic paints, anticorrosive linings, plating, etc. Coated steel pipes, which are metal pipes treated with paint, anticorrosive lining, anticorrosive asphalt, etc., and coated with resins such as polyethylene, have been proposed (
For example, Special Publication No. 53-4880).

However, during the storage, transportation, and mixing of powder and granular materials such as slurries, feed, and fertilizers, not only chemical corrosion but also significant abrasion occurs, and metal bodies simply coated with the above anticorrosive layer are not susceptible to such physical abrasion. Because it is weak against the earth, it is easily damaged and has poor durability.

Therefore, if the anti-corrosion layer is damaged, the metal will corrode or wear away, resulting in thinning and loss of mechanical strength. Rust may peel off and get mixed into feed, etc., or feed additives may remain attached to the corroded parts. There are problems such as contamination of the next feed etc. when changing the product. In addition, conventional coatings in which a metal body with a corrosion protection layer is coated with a resin are usually extrusion coated with a relatively fluid resin such as polyethylene by extrusion molding, and the coating layer has a wear-resistant It has the disadvantages of lack of strength and durability.

On the other hand, ultra-high molecular weight polyethylene has superior properties such as non-adhesiveness, abrasion resistance, impact resistance, low temperature resistance, and ESCR compared to general polyethylene and other synthetic resins, but it has high viscoelasticity when melted and has no fluidity. Due to its poor properties, it not only cannot be coated onto a metal body by conventional extrusion molding, but it is also difficult to heat-seal, and since it is non-adhesive, there is no suitable adhesive for bonding it.

Therefore, in the past, mechanical methods using screws, rivets, etc. had to be used.

However, with the lining method using screws, etc., it is difficult to prevent corrosion of the screw holes, and it has not been possible to form an anti-corrosion layer that provides both corrosion resistance and wear resistance.

In addition, due to the difference in thermal expansion coefficient between the metal body and the ultra-high molecular weight polyethylene, the ultra-high molecular weight polyethylene layer becomes undulating due to temperature changes, which creates a gap between the metal body layer and the problem that substances accumulate. have.

[Problems to be Solved by the Invention] In order to solve the above problems, the present invention provides a laminate and a method for manufacturing the same, which were developed as a result of intensive studies. This greatly improves wear resistance and wear resistance.

The second purpose is to eliminate the gap between the metal body and the ultra-high molecular weight polyethylene due to the difference in coefficient of thermal expansion, and to eliminate the accumulation of residue.

[Means for Solving the Problems] The invention of claim (1) of the present invention provides a metal body, characterized in that ultra-high molecular weight polyethylene is laminated on the surface of a metal body that has been subjected to anti-corrosion treatment via a base material. and ultra-high molecular weight polyethylene, and the invention of claim (2) is characterized in that the ultra-high molecular weight polyethylene is laminated and integrated on the surface of a metal body that has been subjected to anti-corrosion treatment via a base material. It is a method for producing a laminate of a metal body and ultra-high molecular weight polyethylene, and the invention of claim (3) is characterized in that a laminate in which a base material and ultra-high molecular weight polyethylene are laminated in advance is used ( 2) A method for producing a laminate of a metal body and ultra-high molecular weight polyethylene.

The metal bodies of the present invention include metal plates, metal tubes, hoppers,
Shooters, tanks, cases, feeders, take-ups, trippers, scrapers, various conveyors such as screw conveyors and chain conveyors, buckets, elevators such as packet elevators, rollers,
Examples include, but are not limited to, propellers, hoists, car dampers, pallets, containers, rods, fittings, valves, flanges, and the like.

It improves the durability and abrasion resistance of the anticorrosion layer on the anticorrosion-treated metal body, retaining its anticorrosion effect over a long period of time, and also improves the non-adhesiveness, abrasion resistance, impact resistance, and stress resistance of ultra-high molecular weight polyethylene. cracking resistance (ESCR),
Any metal body can be used if it is desired to impart properties such as chemical resistance.

The materials of these metal bodies are steel and non-ferrous metal materials such as pure iron, carbon steel, special steel, cast iron, cast steel, aluminum,
Magnesium, zinc, nickel, chromium, lead, or alloys thereof.

These metal bodies may be subjected to known surface treatments such as degreasing, pickling, sandblasting, and electrolytic treatment before being subjected to anticorrosion treatment.

The coating material for anticorrosion treatment of the present invention can be inorganic and/or organic. Inorganic materials include various metals or their alloys, ceramics, coatings, coatings, linings, etc., and materials include oil-based paints, cellulose derivatives, etc. There are paints, synthetic resin paints, synthetic resin emulsion paints, baking paints, etc. In addition to the organic substances, fire retardants, flame retardants,
Some contain anticorrosive agents, fillers, pigments, stabilizers, etc.

Widely used coating materials for anti-corrosion treatment include oil-based compound paints, oil-based anti-rust paints, various lacquers and enamels, synthetic resin compound paints, synthetic resin anti-rust paints, epoxy resin paints, unsaturated polyester paints, There are polyurethane paints, vinyl chloride paints, alkyd paints, various latex paints, acrylic paints, etc.

The base materials used in the present invention include sheet materials made of synthetic resins such as thermoplastic resins and thermosetting resins, rubber, etc., metal materials such as metal foils, metal plates, and wire meshes, cloth, nonwoven fabrics, woven fabrics, wood, Fiber materials such as paper, FRP boards, etc. can be used.

Thermoplastic resins used for the base material include homopolymers such as low, medium, and high density polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, and others whose main component is ethylene or propylene. copolymers with α-olefins, ethylene-vinyl acetate copolymers or saponified products thereof, copolymers with ethylene-unsaturated carboxylic acids or derivatives thereof, etc., which have α-olefins such as ethylene or propylene as the main component. Polyolefin resins containing copolymers with other polar monomers, polystyrene resins, polyacrylic resins, polyvinyl chloride resins, polyvinylidene chloride resins, nylon-6, nylon-6/6, nylon-11, Nylon-12, polyamide resins such as aromatic polyamides, polycarbonate resins, cellulose resins, polyethylene terephthalate,
Polyester resins such as polybutylene terephthalate, fluorine resins such as polytetrafluoroethylene, polyimide resins, polyamideimide resins, polyether resins, etc.
Examples include ether ketone resin, polyether sulfone resin, polysulfone resin, polyphenylene sulfide resin, and polyacetal resin.

In addition, as the thermosetting resin of the base material, epoxy resin,
Examples include phenolic resins, urethane resins, urea resins, and melamine-unsaturated polyester resins.

Examples of the base rubber include polybutadiene, polyisoprene, neoprene rubber, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, styrene-butadiene copolymer, styrene-acrylonitrile copolymer, and styrene-propylene copolymer. Synthetic rubbers such as acrylonitrile-butadiene copolymer, butyl rubber, polyurethane rubber, chlorosulfonated polyethylene, chlorinated polyethylene, fluororubber, thiocol, and natural rubber may be mentioned.

The base metals include iron, aluminum, copper, zinc,
Examples include metal foils, metal plates, wire meshes, and punching plates made of metals such as brass and nickel.

Examples of the base fabric include tape yarns made of the thermoplastic resin, non-woven fabrics and woven fabrics of fibers such as monofilament, mesh canes, split films made by cutting the above resin films into fine pieces, and synthetic fibers such as vinylon and tetron. ,
It includes woven fabrics made of natural fibers such as cotton, silk, and linen, woven fabrics made of inorganic fibers such as glass fibers, carbon fibers, and metal fibers, mats, and felts.

The paper used as the base material is not particularly limited, and includes, for example, kraft paper, wrapping paper such as roll paper, thin paper such as glassine paper,
Paperboard and other Western papers, Japanese paper such as shoji paper, or synthetic paper such as polystyrene paper and vinylon paper are used.

For the FRP board as the base material, thermoplastic resin fibers, nonwoven fabrics, woven fabrics, carbon fibers, glass fibers, natural fibers, ceramic fibers, metal fibers, etc. are used as reinforcing fibers,
Examples of the matrix resin include those using the above-mentioned thermoplastic resins and thermosetting resins.

Examples of the base material include natural wood, improved wood processed from natural wood, plywood, laminated wood, fiberboard, and particle board.

Further, as the base material of the present invention, a sheet made of the above-mentioned thermoplastic resin mixed with a filler can also be used.

These fillers include calcium carbonate, magnesium carbonate, calcium sulfate, calcium sulfite, calcium silicate, clay, diatomaceous earth, talc, alumina, silica sand, glass powder, iron oxide, metal powder, antimony trioxide, graphite, silicon carbide, Silicon nitride, silica, boron nitride, aluminum nitride, wood powder, carbon black, mica, glass plate, sericite, pyrophyllite, aluminum flakes,
Examples include graphite, shirasu balloons, metal balloons, glass balloons, pumice, glass fibers, carbon fibers, graphite, whiskers, metal fibers, asbestos, organic fibers, and glass fibers.

The amount of the filler blended varies depending on the purpose of use, application, etc., but is usually blended in a range of 5 to 1000 parts by weight per 100 parts by weight of the thermoplastic resin. Further, foams and crosslinked bodies of the above-mentioned thermoplastic resins can be similarly used as the base material.

The ultra-high molecular weight polyethylene used in the present invention preferably has an intrinsic viscosity of 8 dl/g or more in a solution of decalin at 135°C, and is produced by a medium-low pressure polymerization method using an ordinary catalyst such as Ziegler. In addition to ethylene homopolymers, ethylene and small amounts of other α-olefins, such as propylene, butene-1, pentene-1,
hexene-1, octene-1,4-methyl-pentene-
1, etc., modified products of the polymer, and mixtures thereof.

The ultra-high molecular weight polyethylene used in the present invention is preferably in the form of a sheet or film (hereinafter abbreviated as sheet),
The manufacturing method thereof is not particularly limited, and may be a method using a screw extruder, a ram extruder, or a compression molding machine, or a method in which a block molded by these methods is shaved to a predetermined thickness.

The laminate of the present invention is produced by applying the above-mentioned anti-corrosion coating material to a metal body such as a metal plate or a metal tube by plating, coating, lining, etc., and then applying ultra-high molecular weight polyethylene through a base material. is coated.

That is, as mentioned above, since ultra-high molecular weight polyethylene is non-adhesive, it is difficult to adhere it using ordinary heat fusion or adhesives.

Therefore, it is important to laminate them using a base material that can be bonded by heat fusion or adhesive.

Further, in order to avoid poor adhesion between the base material and the ultra-high molecular weight polyethylene, it is preferable to use a laminated sheet in which the base material and the ultra-high molecular weight polyethylene are laminated in advance.

The method for manufacturing the laminated sheet is disclosed in Japanese Patent Application Laid-Open No. 60-155428.
Although detailed in the publication, the following adhesives (
(hereinafter referred to as the first adhesive).

By this method, it is possible to continuously and easily produce a laminated sheet containing ultra-high molecular weight polyethylene, which cannot be easily made thin using normal molding methods.

In addition, when manufacturing by the above-mentioned molding method or compression molding method, it is necessary to use the base material and/or the ultra-high molecular weight polyethylene, as well as when the base material itself has adhesive properties to ultra-high molecular weight polyethylene such as modified polyolefin. In resin,
If a base material and/or ultra-high molecular weight polyethylene that has been subjected to surface treatment such as flame treatment, corona discharge treatment, or plasma treatment, or modified with an acrylic acid compound to improve adhesion, the base material and ultra-high molecular weight polyethylene can be bonded together. can be firmly adhered.

The first adhesive may be epoxy-based, polyurethane-based,
Adhesives such as modified acrylic adhesives, cyanoacrylate adhesives, anaerobic adhesives, various hot melt adhesives, various emulsion adhesives, urea resin adhesives, melamine adhesives, phenolic adhesives, rubber adhesives, etc.
Olefins such as ethylene and unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride,
or a copolymer with its derivative, a copolymer of an olefin such as ethylene and a vinyl ester such as vinyl acetate,
Ionomers and polyolefins graft-modified with reactive monomers having unsaturated groups such as the above-mentioned unsaturated carboxylic acids are preferable.

Examples of the laminate of the present invention include: 1. Metal body (iron)/anticorrosive layer (antirust paint)/adhesive/
Base material (cotton cloth)/ultra high molecular weight polyethylene 2, carbon steel/galvanized/adhesive/polyester cloth/ultra high molecular weight polyethylene 3, carbon steel/epoxy paint/adhesive/rubber/ultra high molecular weight polyethylene 4, carbon steel/ Galvanized / Adhesive / Glass cloth / 1st
Examples include adhesive/ultra-high molecular weight polyethylene.

However, these are appropriately selected depending on the purpose, use, etc., and are not limited.

Further, there are no particular limitations on the method of laminating and integrating ultra-high molecular weight polyethylene on the surface of the anticorrosion-treated metal body via a base material. Preferably, a laminate sheet in which a base material and ultra-high molecular weight polyethylene are laminated in advance is used, and an adhesive (hereinafter referred to as a second adhesive) is used on the anti-corrosion layer to form the base of the ultra-high molecular weight polyethylene laminate. It is better to glue the material layers together. A simple and reliable method is to apply the second adhesive to the anticorrosive layer and the base material layer by a known method, and then laminate, cure, and bond them together.

Examples of the second adhesive used in the present invention include ebony-based, urethane-based, unsaturated polyester-based, phenol-based, resorcinol-based, urea-based, melamine-based, and rubber-based adhesives.

In the present invention, plasticizers, stabilizers, lubricants, vulcanizing agents, colorants, antistatic agents, cups, etc. are included in the ultra-high molecular weight polyethylene, the synthetic resin of the base material layer, the adhesive resin, etc., without departing from the gist of the invention. Conventional additives such as ring agents and flame retardants may be added as appropriate.

Claims (1) to (3) of the present invention include the following embodiments.

1. A laminate of a metal body and ultra-high molecular weight polyethylene, characterized in that ultra-high molecular weight polyethylene is laminated on the surface of a metal body that has been subjected to anti-corrosion treatment via a second adhesive, a base material and a first adhesive. If it is.

2. A combination of a metal body and ultra-high molecular weight polyethylene, characterized in that ultra-high molecular weight polyethylene is laminated and integrated on the surface of a metal body that has been subjected to anti-corrosion treatment via a second adhesive, a base material and a first adhesive. If it is a method of manufacturing a laminate.

3. When the base material is selected from the group consisting of rubber, metal, FRP board, synthetic resin, wood, nonwoven fabric, woven fabric, and paper.

4. The second adhesive is selected from the group consisting of epoxy, urethane, unsaturated polyester, phenol, resorcinol, urea, melamine, and rubber adhesives.

[Examples] Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples unless it departs from the gist of the present invention.

Example 1 Thickness: 0.0mm by the method disclosed in Japanese Patent Application Laid-Open No. 60-155428.
Ultra-high molecular weight polyethylene made by laminating 3 ultra-high molecular weight polyethylene sheets (product name: Hi-Zex Million 240M, manufactured by Mitsui Petrochemicals Iil), polyester nonwoven fabric (thickness: 230 μm), and acid-modified polyethylene (thickness: 30 μm). The laminated sheet is made of carbon steel plate (SS) with a thickness of 3.2mm.
41) On top of the anti-corrosion layer (thickness 20 μm) that was cured by applying epoxy paint to (300 m x 30 cm),
Laminated with urethane adhesive.

As a result, the ultra-high molecular weight polyethylene layer was firmly adhered to the anticorrosive layer via the base material and the second adhesive, and the 180° peel strength of the ultra-high molecular weight polyethylene layer was 4.0 kg/cm². A taper type wear test (wearing wheel C8-10, load i, ooog 1 rotation speed, test piece rotation 70 rpm) was conducted, and the amount of wear was as small as 0.8 m, showing the original characteristics of ultra-high molecular weight polyethylene. .

Example 2 Thickness 3.2. , carbon steel plate (SS41) (30c++X
30 cm ), and before curing, a laminate of ultra-high molecular weight polyethylene and cotton cloth produced in the same manner as in Example 1 was pressed so that the cotton cloth and polyester paint were in close contact, and then cured. As a result of evaluating this laminate in the same manner as in Example 1, the peel strength was 4.2 kg.
/c-.

Comparative Example 1 The tapered abrasion test result of the carbon steel plate used in Example 1 was 79-g.

Comparative Example 2 The tapered abrasion test result of the carbon steel plate with the epoxy corrosion protection layer used in Example 1 was 70 g.

Examples 3 to 4 Table 1 shows the abrasion test results when the ultra-high molecular weight polyethylene laminate sheet of Example 1 was tested with different base materials and second adhesives.

Comparative Example 3 The peel strength of a laminate sheet using high-density polyethylene instead of the ultra-high molecular weight polyethylene of Example 1 was 4.2.
kg/c■, but the result of the taper type wear test was 8
It was mg.

Table 1 [Effects of the Invention] As described above, the present invention provides a laminate of ultra-high molecular weight polyethylene and a metal body, and a method for producing the same, in which a base material is applied to the surface of the metal body which has been subjected to anti-corrosion treatment. It is made of a laminate of a metal body and ultra-high molecular weight polyethylene, which are laminated with ultra-high molecular weight polyethylene. The non-stick properties of polyethylene,
Abrasion resistance, impact resistance, stress cracking resistance (ES
The present invention is extremely useful because it has been able to provide a laminate that has properties such as CR) and chemical resistance, and a method for producing the same.

In addition, by using a laminated sheet of ultra-high molecular weight polyethylene and a base material in advance, it is possible to use an ultra-high molecular weight polyethylene laminated sheet, which was previously difficult to thin, making it easier to handle and significantly reducing work during construction. Not only does this improve the properties of metal products, but it can also be easily applied at room temperature without the need for heating as in conventional methods, thereby preventing thermal deterioration of metal products and the like.

Claims (3)

[Claims] (1) A laminate of a metal body and ultra-high molecular weight polyethylene, characterized in that ultra-high molecular weight polyethylene is laminated on the surface of a metal body that has been subjected to anti-corrosion treatment via a base material. (2) A method for producing a laminate of a metal body and ultra-high molecular weight polyethylene, which comprises laminating and integrating ultra-high molecular weight polyethylene onto the surface of a metal body that has been subjected to anti-corrosion treatment via a base material. (3) The method for producing a laminate of a metal body and ultra-high molecular weight polyethylene according to claim (2), characterized in that a laminate in which a base material and ultra-high molecular weight polyethylene are laminated in advance is used.