US3871896A - Precoated metal sheets and manufacture thereof - Google Patents

Precoated metal sheets and manufacture thereof Download PDF

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Publication number
US3871896A
US3871896A US294917A US29491772A US3871896A US 3871896 A US3871896 A US 3871896A US 294917 A US294917 A US 294917A US 29491772 A US29491772 A US 29491772A US 3871896 A US3871896 A US 3871896A
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parts
resin
weight
sheet
melamine
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US294917A
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English (en)
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Tadashi Matsudaira
Minoru Namiki
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Kansai Paint Co Ltd
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Kansai Paint Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B05D7/16—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies using synthetic lacquers or varnishes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a non-planar shape
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2701/00—Coatings being able to withstand changes in the shape of the substrate or to withstand welding
    • B05D2701/10—Coatings being able to withstand changes in the shape of the substrate or to withstand welding withstanding draw and redraw process, punching
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/03—3 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/748—Releasability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2398/00—Unspecified macromolecular compounds
    • B32B2398/10—Thermosetting resins
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31511—Of epoxy ether
    • Y10T428/31515—As intermediate layer
    • Y10T428/31522—Next to metal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y10T428/31681—Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y10T428/31688—Next to aldehyde or ketone condensation product
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y10T428/31692—Next to addition polymer from unsaturated monomers

Definitions

  • This invention relates to a precoated metal sheet and manufacture thereof, more particularly to a precoated metal sheet for producing shaped articles by metal working with a coating film formed thereon.
  • the base metal sheets to be used according to this invention are a wide variety of metal sheets which have heretofore been used, such as mild steel sheet. aluminum sheet, chromium-plated steel sheet. zinc-plated steel sheet, etc.
  • Employable as the compositions for forming the semi-hardened coating film are those containing as a binder a thermosetting resin, such as for example, (l) thermosetting acrylic resin containing hydroxyl group in the molecule and having. an acid value material thus precoated is then shaped after hardening
  • An object of the invention is to provide a precoated metal sheet from which shaped metal working products can easily be obtained free from cracking or peeling of the coating film.
  • Another object of the invention is to provide a precoated metal sheet for producing the shaped metal working products having hard coatings which are excellent in physical and chemical properties such as hardness, abrasion resistance, scratch resistance, strain resistance, chemical resistance, etc.
  • Another object of the invention is to provide a precoated metal sheet for producing shaped metal working products, which is free from blocking phenomenon even when placed in layers or rolled up.
  • Another object of the invention is to provide a method for producing a precoated metal sheet having the above excellent characteristics.
  • the precoated metal sheet of the invention comprises a base metal sheet, a coating film ofa thermosetting resin which is formed on the base metal sheet and cured to semi-hardened state having a tackiness of from 2.0 to g/cm width at a temperature of 25C and at a relative humidity of 75%, and a polyolefin sheet adhered to the above semi-hardened coating film.
  • a combination of a balance and constant speed peeling device is used as a tester.
  • a precoated metal sheet having semi-hardened state coating film is adhered to protective polyolefin sheet and pressed at a pressure of 0.2 kg/cm with a rubber roll having a hardness of 70 determined according to MS K 6301 5.1 (l).
  • the precoated metal sheet with a protective polyolefin sheet adhered thereto is left to stand at room temperature for 24 hours and cut into a piece 25 mm wide by about 20 cm long.
  • the protective sheet is peeled off about 1 to 2 cm long from the upper end of the specimen, which of 5 tov 20 and hydroxyl value of'lO to 70, parts by weight of this resin being used with 20 to 60 parts by weight of melamineformaldehyde resin and/or not more than 20 parts by weight of bisphenol A- epichlorohydrine type epoxy resin having an epoxy equivalent of 300 to 800; (2) alkyd-melamine resin comprising 100 parts by weight of alkyd resin modified with non-drying oil and/or non-drying oil fatty acid and having an oil length of 10 to 30 and 20 to 60 parts by weight of melamineformaldehyde resin; (3) bisphenol A-epichlorohydrine type epoxy resin having an epoxy equivalent of 800 to 4,000, 100 parts by weight of this resin being used with 20 to 60 parts by weight of butyletherified phenol-formaldehyde resin or with 20 to 60 parts by weight of-butyl-etherified urea-formaldehyde resin; and (4) oil free
  • Such coating 1 composition usually comprises 100 parts by weight of the thermosetting resin binder, not more than parts by weight of extender pigment, not more than 100 parts by weight of coloring pigment and, if desired, not more than 20 parts by weight of plasticizer. Solvents are added to the composition in such an amount that the resultant composition have a viscosity of 30 to 200 see, preferably 100 to 120 sec. (at 25C, Ford cup No. 4).
  • the solvents to be used may be any of a wide variety of those usually employable as solvent. Particularly preferable are mixed solvents comprising aromatic hydrocarbons and cyclohexanone, ethyleneglycol mono;
  • plasticizers to be are volatile plasticizers such as dimethylphthalate, diethylphthalate, triethyleneglycol monoethyl ether, diethyleneglycol monobutyl ether, etc. Solvents having a boiling point of more than 200C also serve as plastiple by using roll coater or curtain flow coater.
  • the coating composition to form a semi-hardened top coat film is applied to a thickness of about 5 to 50 microns whendried.
  • the baking conditions which may'vary depending on the kind of the coating compositions used, are usually a temperature of 70 to 190C and a baking time of about 30 to 90 seconds so as to produce a semihardened coating film having a thickness of 2.0 to 40 g/cm width, preferably 5 to g/cm width.
  • a polyolefin sheet is then applied over the coating film which has beensemi-hardened by baking. If the tackiness of the coating film is lessthan 2.0 g/cm width, the polyolefin sheet is liable to peel off from the coating film.
  • the polyolefin sheet will be torn when peeled off from the shaped metal product obtained by shaping the present metal sheet.
  • the polyolefin sheets to be used for this purpose are, for example, those of polyethylene, polypropylene and the like. Preferably, the sheet is usually about 0.02 to 0.2 mm in thickness.
  • the polyolefin sheet can be applied to achieve the desired results by placing the sheet over the semi-hardened coating film. Since the coating film is in the specific semi-hardened state, the polyolefin sheet can be adhered to the semihardened coating film without using any adhesive or tackifying agent, to such extent that it will not be peeled off while transported or shaped.
  • the polyolefin sheet After shaping of the precoated material, the polyolefin sheet can be peeled off satisfactorily without damaging the coating film.
  • the semi-hardened coating film permits a polyolefin sheet to be adhered thereto without using any adhesive or tackifying agent and that the sheet can be peeled off ideally without damaging the coating film.
  • the precoated metal sheet of this invention can be shaped by any desired working process.
  • the polyolefin sheet is then peeled off the semi-hardened coating film, and the coating film is thereafter baked for complete hardening.
  • the coating film on the precoated metal sheet of this invention being in semi-hardened state, is free from cracking or peeling even when the metal sheet is shaped.
  • the polyolefin film on the semi-hardened coating film protects the coating film from damage during shaping.
  • the product of this invention has another advantage of being free, for example, from damage when it is transported after shaping and before the semi-hardened coating film is completely baked for finishing, since the plastic film protects the semi-hardened coating film.
  • the metal working product thus obtained has a coating which is excellent in hardness, abrasion resistance, stain resistance, and chemical resistance and is free from any cracking or peeling as well as from all the drawbacks of the conventional precoating process, assuring full utilization of its advantages.
  • primer can be applied to the metal sheet prior to the application of the composition for forming semi-hardened coating film in order to improve adhesion property and corrosion resistance.
  • the primer may be a wide variety of those conventionally used.
  • coating compositions of the epoxy resin or vinyl resin type are chiefly used.
  • the composition of the epoxyresin type for instance, comprises 60 to 100 parts by weight of epoxy resin, not more than 40 parts by weight of melamine, urea or phenolic resin,
  • the coating composition of the vinyl type comprises 60 to parts by weight of vinyl chloride-vinyl acetate copolymer resin, not more than 40 parts by weight of epoxy resin, notmore than 40 parts by weight of phenolic resin, not more than ,50 parts by weight of extender pigment, not more than 50 parts by weight of rust-proofing pigment, and a suitable amount of solvent.
  • the primer is applied to such a thickness as to form an approximately 0.5 to 10 micron thick coating when dried and the coating is baked at a temperature of to 250C for 20 to 60 seconds, whereby it is completely baked and hardened. If baking for hardening is insufficient, the coating will have poor adhesion to the metal sheet; hence the need for complete baking and hardening.
  • FIG. 1 is a photograph showing the surface of can obtained in Example 1.
  • EXAMPLE 1 An aluminum sheet of 0.5 mm in thickness was degreased and its surface was subjected to conversion coating with Bonderite 722 (Trade mark, product of Nippon Parkerizing Co., Ltd., Japan). Bonderite 722" is mixture comprising phosphoric acid, chromic acid and sodium fluoride as principal ingredients. The sheet was then coated by a roll coater with an epoxy type coating composition given in Table 1 below as a primer and then with a thermosetting acrylic coating composition given in Table 1 below for a top coat, respectively followed by baking. The primer was fully hardened by baking, whereas the top coat was baked to semihardened state of a tackiness of 20 g/cm width.
  • Bonderite 722 is mixture comprising phosphoric acid, chromic acid and sodium fluoride as principal ingredients.
  • the sheet was then coated by a roll coater with an epoxy type coating composition given in Table 1 below as a primer and then with a thermosetting acrylic coating composition given in Table 1 below for a top coat, respectively followed by
  • a 17 micron thick polyethylene film was then applied over the resulting coating, and the product was shaped into a square can by stamping.
  • the polyethylene sheet was thereafter peeled off, with the result that the coating surface was found to be free from any cracking and peeling.
  • Thev shaped article obtained was baked at a temperature of 200C for 10 minutes to effect complete hardening.
  • the surface of the resulting product, as the photograph of FIG. 1 shows, is free from any cracking or peeling. Further the coating obtained had the properties listed in Table 2.
  • COMPARISON EXAMPLE 1 The same aluminum sheet was coated with exactly the same primer and top coat forming composition and baked in the same manner as in Example 1, except that the top coat was also completely baked and hardened. The resulting product was then shaped into a square can by stamping, with the result that, as shown in the photograph of FIG. 2, marked cracking and apparent peeling were observed. The properties ofits coating are set forth in Table 2 below.
  • COMPARISON EXAMPLE 2 A shaped article was prepared by conducting the same treatment as in Example 1 and using the same primer as in Example 1, except that a coating composi- .5 tion presently used for precoated metal was applied to form a top coat, the coating composition comprising 160 parts of a 50% Xylol solution of acrylic copolymer(copolymer of styrene, n-butyl acrylate, hydroxyethyl methacrylate and acrylic acid in a weight ratio of 70 l5 2), 40 parts of U-van 20 SA (Trade mark, butylated melamine resin, product of Mitsui Toatsu Co., Ltd., Japan), 80 parts of titanium oxide, parts of Solvesso 100 (Trade mark, mixed solvent of the aromatic hydrocarbons, product of ESSO Standard Oil Co., U.S.A.), and 30 parts of B-ethoxy-ethyl acetate.
  • the coating obtained had the properties shown in Table 2 below.
  • EXAMPLE 2 A zinc-plated iron sheet, 0.3 mm in thickness, was degreased, with its surface thereafter subjected to'conversion coating with Bonderite 3300 (Trade mark, product of Nippon Parkerizing Co., -Ltd., Japan): Bonderite 3300 is principally zinc phosphate.
  • the sheet was coated by a curtain flow coater with a vinyl type coating composition given in Table 1 below as a primer and with a thermosetting aminoalkyd type coat- EXAMPLE 3 l0 Can-Super (Trade mark, 0.24 mm in thickness,
  • chromium-plated steel sheet product of Shin Nihon Seitetsu Co. Ltd., Japan
  • an acrylic coating composition by a roll coater and set to semihardened state having a tackiness of 28 g/cm width in 15 the same manner as in Example 1.
  • the sheet thus treated was then shaped in to a cylindrical cup by a press.
  • the film adhered was a polyethylene sheet, 17 microns in thickness.
  • the composition of the coating material is'shown in Table 1 below, and coating condi- 20 tions and properties of the coating as determined by testing are given in Table 2 below.
  • the coating had very excellent properties as in Example 1.
  • Example 1 Example 2
  • Example 3 1. Primer Epikote 1007 80 Vinylite VMCH" 90 (Epoxy resin, product parts (Vinyl resin, parts of Shell Chemical product of Union Co., U.S.A.) Carbide Corp.. U.S.A.) Resin Beckamine P-354" 40 Epikote 828" l0 (Butylated urea resin, parts (Epoxy resin, parts product of Dainihon product of Shell Ink Chemical Co., Ltd., Chemical Co., U.S.A.) Japan) Pigment Zinc chromate 20 Titanium dioxide 40 parts parts parts Solvesso 100" Xylol 140 (Trade mark, defined parts parts Solvent in Comparison Example 2) B-ethoxyethyl acetate 65 Isophorone 140 parts (Ketone solvent, parts product of Union Carbide Corp, USA) Total 270 Total 420 parts parts 2v Top coat forming C omp.
  • Cymel 300" 10 (Trade mark, parts melamine resin, product of American Cyanamid Co., U.S.A.)
  • Example 2 Pigment Titanium 80 Titanium 80 Titanium I 80 dioxide parts dioxide parts dioxide parts Plasti- Dimethyll5 Triethylene Diethylene 30 cize'r phthalate parts glycol parts glycol parts monoethyl A monobutyl ether ether Solvesso 2S Solvesso Solvesso 30 I00" parts I00" parts I00 parts (Trade mark, (Trade mark, (Trade mark, defined in defined in defined in Comparison Comparison Comparison Example 2) Example 2) Example 2) Solvent B-ethoxy- 2S Butanol l0 B-ethoxy- 25 ethyl parts parts ethyl parts acetate acetate.
  • Example 3 Coating and baking conditions Baking temp. 200C 200C 200C 150C Primer Baking time 40 sec. 40 sec. 40 sec. 30 sec. coat Dry coating 3 p. 3 p. 3 tr 7 p. thickness Baking temp. 100C 200C 250C C 180C Top coat for semi- Baking time 60 sec l0 min. 60 sec. sec. 40 sec. hardening Dry coating thickness 25 a 25 p. 25 a 40 p. 10 p.
  • a glass ring (about mm in inner diameter and mm in height) was placed on the coating in snug-fit contact therewith and completely sealed with vaseline or paraffin.
  • a 5% aqueous solution of acetic acid was poured into the ring to approximately one hall its height and the ring was covered with a glass plate.
  • the specimen was retained in horizontal position and left to stand at room temperature for 6 hours.
  • the ring was then removed from the specimen, which was thereafter dried in the indoor air for 1 hour. Subsequently, the state of the coating was inspected.
  • a precoated metal sheet for producing a metal working product which comprises a base metal sheet, a coating film of a thermosetting resit. hich is formed on the base metal sheet and cured to semi-hardened state having a tackiness of from 2.0 to g/cm width at a temperature of 25C and at a relative humidity of 75% and a polyolefin sheet removably adhered to the above semi-hardened coating film; said base metal sheet being one species selected from the group consisting of mild sheet, aluminum sheet, chromium-plated 5 steel sheet and zinc-plated steel sheet; said thermosetting resin being one species selected from the group consisting of l. thermosetting acrylic resin containing hydroxyl 2.
  • alkyd-melamine resin comprising parts by weight of alkyd resin modified with non-drying oil and/or non-drying oil fatty acid and having an oil length of 10 to 30 and 20 to 60 parts by weight of melamine-formaldehyde resin,
  • bisphenol A-epichlorohydrine type epoxy resin having an epoxy equivalent of 800 to 4,000 100 parts by weight of this resin being used with 20 to 60 parts by weight of butyl-etherified phenolformaldehyde resin or with 20 to 60 parts by weight of butyl-etherified urea-formaldehyde resin, and
  • oil free polyester-melamine resin comprising 100 parts by weight of oil free polyester having an acid value of 5 to 20 and hydroxyl equivalent of 400 to 1,300 and 20 to 60 parts by weight of melamineformaldehyde resin modified with an aliphatic monoalcohol having from 1 to 4 carbon atoms.

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  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
US294917A 1971-10-11 1972-10-04 Precoated metal sheets and manufacture thereof Expired - Lifetime US3871896A (en)

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JP46080405A JPS5229349B2 (enrdf_load_stackoverflow) 1971-10-11 1971-10-11

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Cited By (13)

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US3960979A (en) * 1974-12-24 1976-06-01 E. I. Du Pont De Nemours And Company High solids can coating compositions based on epoxy resin crosslinking agent, flexibilizing polyol, co-reactive acid catalyst, and surface modifier
US3993841A (en) * 1974-02-08 1976-11-23 Toagosei Chemical Industry Co., Ltd. Steel plate coated with thermosetting phenol resin and bisphenol A type epoxy resin
US4018848A (en) * 1974-12-24 1977-04-19 E. I. Du Pont De Nemours And Company High solids can coating compositions based on epoxy resin, crosslinking agent, flexibilizing polyol, co-reactive acid catalyst, and surface modifier
US4032678A (en) * 1974-09-12 1977-06-28 Bethlehem Steel Corporation Coated sheet metal and method of forming products therefrom
US4073776A (en) * 1975-01-28 1978-02-14 Schenectady Chemicals, Inc. Tackifiers for elastomers
FR2387170A1 (fr) * 1977-04-11 1978-11-10 Parker Ste Continentale Procede de fabrication d'un corps de boite
FR2462267A1 (fr) * 1979-07-30 1981-02-13 Dow Corning Recipients metalliques revetus sur leurs surfaces interieures d'une composition d'organosiloxane durcie et procede pour leur fabrication
US4289811A (en) * 1980-02-21 1981-09-15 Celanese Corporation Stable aqueous dispersions of mixed resins and process for use as coating compositions
EP0427561A3 (en) * 1989-11-10 1992-01-08 Somar Corporation Method of fabricating bent metal body with resin coating
WO2002072285A3 (de) * 2001-03-13 2003-06-26 Inst Polymerforschung Dresden Beschichtete aluminiumhalbzeuge und/oder -bauteile und verfahren zu ihrer herstellung
US20070049677A1 (en) * 2005-08-26 2007-03-01 Xerox Corporation Novel thick undercoats
US9530109B2 (en) * 2010-09-28 2016-12-27 International Business Machines Corporation Iterative pattern generation algorithm for plate design problems
CN108611189A (zh) * 2016-12-09 2018-10-02 丰益(上海)生物技术研发中心有限公司 一种控制油脂中双酚a和烷基酚的精炼工艺

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JP2000345105A (ja) * 1999-06-07 2000-12-12 Nippon Steel Corp カーテン安定性に優れるカーテンコーター用塗料及びカーテンコーターによる塗装製品の製造方法
JP2000345108A (ja) * 1999-06-07 2000-12-12 Nippon Steel Corp カーテン安定性に優れるカーテンコーター用塗料及びカーテンコーターによる塗装製品の製造方法
KR101292292B1 (ko) 2011-02-18 2013-08-05 포항공과대학교 산학협력단 강판용 도료 조성물 및 이를 이용한 표면처리강판

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US3993841A (en) * 1974-02-08 1976-11-23 Toagosei Chemical Industry Co., Ltd. Steel plate coated with thermosetting phenol resin and bisphenol A type epoxy resin
US4032678A (en) * 1974-09-12 1977-06-28 Bethlehem Steel Corporation Coated sheet metal and method of forming products therefrom
US3960979A (en) * 1974-12-24 1976-06-01 E. I. Du Pont De Nemours And Company High solids can coating compositions based on epoxy resin crosslinking agent, flexibilizing polyol, co-reactive acid catalyst, and surface modifier
US4018848A (en) * 1974-12-24 1977-04-19 E. I. Du Pont De Nemours And Company High solids can coating compositions based on epoxy resin, crosslinking agent, flexibilizing polyol, co-reactive acid catalyst, and surface modifier
US4073776A (en) * 1975-01-28 1978-02-14 Schenectady Chemicals, Inc. Tackifiers for elastomers
FR2387170A1 (fr) * 1977-04-11 1978-11-10 Parker Ste Continentale Procede de fabrication d'un corps de boite
FR2462267A1 (fr) * 1979-07-30 1981-02-13 Dow Corning Recipients metalliques revetus sur leurs surfaces interieures d'une composition d'organosiloxane durcie et procede pour leur fabrication
US4289811A (en) * 1980-02-21 1981-09-15 Celanese Corporation Stable aqueous dispersions of mixed resins and process for use as coating compositions
EP0427561A3 (en) * 1989-11-10 1992-01-08 Somar Corporation Method of fabricating bent metal body with resin coating
WO2002072285A3 (de) * 2001-03-13 2003-06-26 Inst Polymerforschung Dresden Beschichtete aluminiumhalbzeuge und/oder -bauteile und verfahren zu ihrer herstellung
US20040105972A1 (en) * 2001-03-13 2004-06-03 Dieter Lehmann Coated reshaped aluminum semi-finished products and/or components and method for the production thereof
DE10211512B4 (de) * 2001-03-13 2007-05-31 Leibniz-Institut Für Polymerforschung Dresden E.V. Verfahren zur Herstellung von beschichteten, umgeformten Aluminiumbauteilen und nach dem Verfahren hergestellte Aluminiumbauteile
US20070049677A1 (en) * 2005-08-26 2007-03-01 Xerox Corporation Novel thick undercoats
US7544452B2 (en) * 2005-08-26 2009-06-09 Xerox Corporation Thick undercoats
US9530109B2 (en) * 2010-09-28 2016-12-27 International Business Machines Corporation Iterative pattern generation algorithm for plate design problems
US10108913B2 (en) 2010-09-28 2018-10-23 International Business Machines Corporation Iterative pattern generation algorithm for plate design problems
CN108611189A (zh) * 2016-12-09 2018-10-02 丰益(上海)生物技术研发中心有限公司 一种控制油脂中双酚a和烷基酚的精炼工艺
CN108611189B (zh) * 2016-12-09 2023-02-21 丰益(上海)生物技术研发中心有限公司 一种控制油脂中双酚a和烷基酚的精炼工艺

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GB1407837A (en) 1975-09-24
JPS5229349B2 (enrdf_load_stackoverflow) 1977-08-01
JPS4845532A (enrdf_load_stackoverflow) 1973-06-29

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