JPS59198141A - Thermoplastic polyester multilayer coated metallic laminate - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to thermoplastic polyester multilayer coated metal laminates. More specifically, the present invention relates to a thermoplastic polyester multilayer coated metal laminate having excellent water resistance and having an epoxy resin interposed between a metal body and a thermoplastic polyester coating layer.

Thermoplastic resins such as polyethylene and vinyl chloride are coated on the inner and outer surfaces of metal pipes and the surfaces of metal plates for the purpose of preventing metal rust, improving appearance, and improving food hygiene. These resins have a problem that the strength of the coating is low, and the coating is easily damaged when subjected to impact during transportation or storage, or during operations such as bending, caulking, and connection.

As one of the means to solve these problems, crystallinity 2
Metal body coated with 0% or less polyethylene terephthalate polymer (JP-A-51-17988), 200-3
Techniques for coating thermoplastic polyester have been proposed, such as a method of coating a metal body heated to 50 DEG C. with a polymethylene terephthalate polymer (Japanese Unexamined Patent Publication No. 148755/1982). However, when a metal body coated with thermoplastic polyester is brought into contact with water, phenomena have been observed in which the adhesive strength decreases over a short period of time, causing the adhesive to peel off from the adhesive surface, or the resistance to external forces such as impact strength to decrease dramatically. Served. Therefore, the actual situation is that it cannot be used as an inner coating material for water pipes or for applications that are exposed to wind and rain. Therefore, the present inventors investigated ways to improve the water resistance of thermoplastic polyester-coated metal laminates, and found that by interposing an epoxy resin between the thermoplastic polyester coating layer and the metal body, the water resistance was significantly improved. Furthermore, the inventors have discovered that the adhesive strength is also improved, and have arrived at the present invention.

The present invention provides a thermoplastic polyester multilayer coated metal with excellent water resistance and adhesive strength, characterized by laminating a thermoplastic polyester (13) on a metal body via an epoxy resin (Δ). The present invention provides a laminate.

The metal bodies used in the present invention include steel, stainless steel, copper,
It is a metal body such as lead, zinc, aluminum, nickel, etc.
It includes all shapes such as plate-shaped bodies, tube bodies, linear bodies, and rod-shaped bodies. The metal body is preferably one that has been subjected to treatments such as decabbing, degreasing, and pickling before being coated with the epoxy resin (A) described below, and may also be subjected to surface treatment such as chemical conversion treatment. .

The epoxy resin (Δ) used in the present invention is a polymolecular compound containing two or more highly reactive epoxy groups in the molecule, a Lewis base, an inorganic base, a primary amine, a primary amine, and an amide. salt-based curing agents, Lewis acids, phenols, etc.
It is a composition consisting of an acidic curing agent such as carboxylic acid and carboxylic acid anhydride, and various curing agents such as thiocol and alcohol. As a multimolecular compound containing two or more highly reactive epoxy groups in the molecule (hereinafter referred to as an epoxy compound), diglycidyl ethers of various molecular weights consisting of bisphenol 8 and epic 1"l ruhydrin are usually used. , other epoxy compounds such as butyl glycidyl ether, 1.4-butanediol diglycidyl ether,
Vinyl cyclohexene dioxite, decyl glycicyl ether, dicycloaliphatin cycloter dieboxy, 2,2-his(p-(2,3-epoxypropoxy) phenylcope 1'I pan, polyphenol formaldehyde 11 (2,3-epoxypropyl)ether, poly-0-cresol formaldehyde poly(
2,3-epoxypropyl) ether, 1,3-bis-(2,3-coniboxypropyl) Hensen, 2,2-
His(4-(2,3-epoxypropoxy)-3,5-
cyflomophenyl]propane, tetrakis(2,3-epoxypropoxy)diphenyl-methane, epoxidized polybutadiene, 2.4.4'-1-lis(2,3-
epoxypropoxy)-hyphenyl, linoleic acid diglycidyl ether, bis(2,3-epoxycyclopentyl) ether, epoxydicyclopentenylphenylglycidyl ether, l-liglycidyl-p-aminophenol, 3,4-epoxy Cyclohexylmethyl-(3,4-epoxy)cyclohexane carboxylate, epoxidized soybean oil, and the like can also be used. Specific examples of the curing agent include polymethylenediamine, diethylenetetramine, triethylenetetraminetanolamine, menthanediamine, N-aminoethylpiperacine, 1,3-diaminocyclohexane, isophoronediamine, m-xylylene). aliphatic amines such as mino and tetrac l:I l:l-p xylenecyamine, aromatic amines such as m-phenylenediamine, 4,4'-menthanediamine, noaminodiphenyl sulfone, hendicine and diaminodiphenyl ether;
Tetramethylguanidine, triethanolamine, N,
Tertiary amines such as N'dimethylpiperazine, N-methylpiperazine, pyridine, pyrazine, hensyldimethylamine, 2-(dimethylaminomethyl)phenol and 2,4.6-tris(dimethylaminomethyl)phenol, piperidine and secondary amines such as morpholine, 3,
3'-dimethyl-4,4'-diamino-dicyclohexylmethane, 3,9-bis(3-aminopropyl)-2.
4,8.10-Tetraoxospiro-C 5,5) Alicyclic polyamines such as undecane and those modified with butyl glycidyl ether, Cardura E, acrylonitrile, xylenecyamine, etc., polyamide 1ζ, urea, monomethylol Urea, urea resin, melamine, xamethoxymethylmelamine, triallyl cyanoate, novolak, resol, phthalic acid, -amine benzoic acid, maleic acid, succinic anhydride, citraconic anhydride, iconic anhydride, maleic anhydride , pyromellitic anhydride, phthalic anhydride, trimellitic anhydride, and the like. Among these, aromatic amines, tertiary amines, secondary amines, alicyclic polyamines, and modified products thereof are preferred from the viewpoint of durability of adhesive strength.

When the epoxy resin (Δ) is broken down to the surface of the body, G1 is dissolved in a solvent, coated with -j, or coated directly or by cooling over ε. good.

Heat used in the present invention "IJ Mei+Moon 71 Polyester (1
3) refers to aliphatic glycols such as ethylene glycol, propylene glycol, 1.4 phthanesio 1-dipenyl glycol, polyoxyethylene glycol, polyoxypropylene glycol, Schiff 11 hexyl, etc. alicyclics such as xanthimethanol)
Aromatic 1-exoaromatic compounds such as nor, or these 2 (4 bows;) 1 or p, +)
' +:+ medium-oxy compounds, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, 7-uric acid, succinic acid, adipic acid, sebacic acid, undecadicarboxylic acid, etc. aliphatic dicarboxylic acid,
Hexahydride is a polyester formed from an alicyclic dicarboxylic acid such as 1-terephthalic acid or a dicarboxylic acid unit selected from two or more of these, and as long as it exhibits Lyoplasticity, a small amount of triol, maleic anhydride, I・It may be modified with a divalent or higher polyhydroxy compound such as a dicarboxylic acid or a polycarphonic acid.If necessary, a thermoplastic rubber or polyolefin modified with an unsaturated carboxylic acid or unmodified is added. You may.

Further, the polyester may be crystalline. Among them, copolyesters selected from terephthalic acid and isophthalic acid as dicarboxylic acids and ethylene glycol and neopentyl glycol as dihydroxy compounds have adhesive properties.
More preferred in terms of impact resistance.

The thermoplastic polyester multilayer coated metal laminate of the present invention can be obtained by the following method. For example, a method of preheating a metal body, coating the metal body with epoxy resin (A), and subsequently coating the layer (A) with heat-degradable polyester (B), or coating the metal body with epoxy resin (A). After coating the metal body, the metal body is heated, and the thermoplastic polyester (B) is coated on the layer (A).

Molding methods for coating thermoplastic polyester (B) on a body 1 coated with epoxy resin (△) include extrusion coating, 1-1 injection molding (insert molding), and powder molding (powder coating, fluidization). Examples include immersion, rotational molding, etc.) compression molding, etc.

Also, if necessary, a thermoplastic polyester (I3) layer -
Polyolefin, polystyrene, or polyvinyl chloride may be laminated on top.

The metal laminate coated with multiple layers of thermoplastic polyester of the invention can be obtained by the method described above, but in the past, thermoplastic polyester was coated directly onto the metal body without using an epoxy resin to form a laminate with adhesive strength sufficient for practical use. To get a body,
Preheat the metal object to at least 300°C! ; Whereas it was necessary to cover the plastic polyester - (
It is possible to obtain a laminated IM body with a level of adhesive strength that does not cause any practical soil problems even if the preheating density is reduced to 1/l (1°C) by applying an epoxy resin to the epoxy resin. It has the advantage of being able to

The thickness of the epoxy resin (Δ) coating layer and the pJL iJ plastic polyester (13) coating layer is adjusted as appropriate depending on the use of the metal laminate, but usually the thickness of both layers in total is 20μ or less (including heat treatment). plastic polyester layer 10μ or more), preferably 100μ or more”-(of which, thermoplastic polyester layer 101
If the coating is made thicker (1 or more), a coated metal laminate with excellent performance can be obtained.

The epoxy resin (A) and thermoplastic polyester (B) used in the present invention include pigments, dyes, fillers, reinforcing agents, plasticizers, heat stabilizers, ultraviolet absorbers, lubricants, Ge 1 as a fuel, antistatic 1 Additives such as oxidative agents and other polymers may be added to the extent that they do not impair the purpose of the present invention.

The thermoplastic polyester multilayer coated metal laminate of the present invention has superior adhesive strength and water resistance compared to conventional polyethylene terephthalate middle layer coated metal bodies, so it can be used for coated steel pipes and coated steel wires, especially for fisheries applications that require saltwater resistance. It is suitable as aquaculture wire mesh.

In addition, compared to a laminate coated only with polyolefin resin, the coated metal body of the present invention has a thermoplastic polyester layer as an adhesive layer, so the coating has excellent fracture resistance, and can be used, for example, as a coated steel pipe. Even if the coating is damaged during buried construction, etc., the coating will not break down to the 114 pipe surface (it has the advantage of a long service life as a steel pipe).

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 Bright iron plate (JIS G3141, 2+i++
X 200++mx200mm) was degreased with toluene, 50μ of an epoxy resin adhesive having the composition shown below (hereinafter abbreviated as P) was applied, and baked at 200mm for 20 minutes (=
Got 1.

Composition of epoxy resin adhesive: Evomic R30] 40 parts (epoxy resin manufactured by Niai Ishiura Chemical Industry) I3 K 32315 4
0 parts (phenol resin manufactured by Showa Union Gosei Co., Ltd.)

solids content, 50%) Turkinine 100 parts Butanol 20 parts Total 20
0 parts of the above epoxy resin; Place the pellets (abbreviated as ) so that the thickness is 1 mm,
Press bonding was carried out at 0° C. under a pressure of 50 kg/+ffl for 10 minutes to obtain a laminate having an iron plate/P/PET-H configuration.

The following tests were conducted on this laminate.

(1) Initial peel strength (PS-0) The laminate was cut into a 2 cm wide piece to prepare a test piece.

Peeling was performed at 90 degrees using an Instron tensile testing machine at a rate of 50 ni/min.

(2) Salt water resistance (21-A Peel strength after immersion in salt water (PS-D)
) After immersing a 2 cm wide test piece in 3% saline at 60°C for 7 days, the peel strength was determined in the same manner as the initial peel strength.

(2+ - B Peeling length after immersion in saline solution PS-L
) A test piece (20 × 200 × 20 × 20 × 20 × 20 × 20 × 20 × 20 × 20 × 20 × 20 × 20 × 20 × 20 × 20 × 20 × 20 × 20 × 20 × 20 × 20 × 20 × 20 × 20 × 20 × 20 × 20 × 20 × 20 × 200 × 20 × 200 × 200 × 1000% ) test pieces were soaked in a 3% saline solution at 60° C. for 7 days, and then the length of peeling from the cross-cut portions was measured.

The results are shown in Table 1.

Comparative Example 2 A test was carried out in the same manner as in Example 1 except that the epoxy resin adhesive was not used. The results are shown in Table 1.

Examples 2 to 4 Approximately 70μ of the adhesive P used in Example 1 was applied to a 1-inch steel pipe that had been subjected to the Plus 1 treatment and baked at 200°C for 40 minutes.

The adhesive-coated steel pipe was heated to a predetermined temperature (140°C).

180℃, 230℃), [η] is 1.3
Ethylene glycol and terephthalic acid 80 mo1
A polyester copolymer (hereinafter abbreviated as PET-C) consisting of isophthalic acid (20mol%) and isophthalic acid (20mo1%) was extruded and coated to a film thickness of 1mm at an extrusion resin temperature of 280℃ and an extrusion temperature of 1m/min, and cooled water was added. It was quenched by Evaluation was performed by the method shown in Example 1 below.

3 2 The results are shown in Table 1.

Comparative Examples 2 to 4 Tests were conducted in the same manner as in Examples 2 to 4, except that adhesive P was not used. The results are shown in Table 1.

Unexamined Japanese Patent Publication No. 59-198141 (5) mosquito Affair Wipe two Peng Baked　　　　　　　　　− H← Park princess Shoulder opening stomach vague 111mi <Be 1 ball Yoto )

Claims (1)

[Claims] (1) A thermoplastic polyester multilayer coated metal M-layer body, characterized in that a thermoplastic polyester (B) is laminated on a metal body via an epoxy resin (A).