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WO2001098392A1 - Preparation d'une composition de resine urethane aqueuse - Google Patents

Preparation d'une composition de resine urethane aqueuse Download PDF

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Publication number
WO2001098392A1
WO2001098392A1 PCT/KR2000/000657 KR0000657W WO0198392A1 WO 2001098392 A1 WO2001098392 A1 WO 2001098392A1 KR 0000657 W KR0000657 W KR 0000657W WO 0198392 A1 WO0198392 A1 WO 0198392A1
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WO
WIPO (PCT)
Prior art keywords
weight
prepolymer
resin composition
aqueous
parts
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2000/000657
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English (en)
Inventor
Yong-Gyun Jung
Chan-Sup Park
Chang-Sae Byen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Posco Holdings Inc
Original Assignee
Pohang Iron and Steel Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Pohang Iron and Steel Co Ltd filed Critical Pohang Iron and Steel Co Ltd
Priority to CNB008118663A priority Critical patent/CN1146617C/zh
Priority to PCT/KR2000/000657 priority patent/WO2001098392A1/fr
Priority to JP2002504346A priority patent/JP2004501252A/ja
Publication of WO2001098392A1 publication Critical patent/WO2001098392A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • C23C28/3225—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only with at least one zinc-based layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer

Definitions

  • the present invention relates to a method for preparing an aqueous urethane resin composition suitable as a binder resin solution for coating steel plates, a method for preparing an aqueous lubricant urethane resin composition, and use of such compositions. More particularly, the present invention relates to a method for preparing an aqueous urethane resin composition superior in various physical properties, including corrosion resistance, paint adhesion, chemical resistance, processability, and surface friction properties and suitable as a binder resin for coating functional steel plates.
  • the present invention is concerned with an aqueous lubricant urethane resin composition containing the aqueous urethane resin, which can give a great contribution to improving the steel plate in corrosion resistance, chemical resistance, deep drawability, postprocessing appearance, and surface friction properties as well as enables the steel plate to be processed into products under an oil-less condition. Further, the present invention relates to surface treatment of chromated, electroplated steel plates. 2. Description of the Prior Art To be useful for thin film coating, an aqueous resin is required to possess excellent corrosion resistance, coating flexibility in terms of processability, adhesiveness to ' steel plates, surface friction characteristics, chemical resistance, and overcoatability as well as to be used in general uses.
  • a conventional coating resin can be referred to Japanese, Pat. aid-Open Publication No. Hei. 5-138120.
  • bisphenol type epoxy resins, multi- functional epoxy resins, alkyd resins, ester resins, acryl resins, urethane resins, and modified derivatives thereof are mentioned along with curing agents such as various amine compounds, animo resins, and isocyanate compounds.
  • curing agents such as various amine compounds, animo resins, and isocyanate compounds.
  • Japanese Pat. Laid-Open Publication No. Hei. 5- 3052668 discloses use of a urethane resin in forming a non-continuous coat highly resistant to corrosion.
  • a simple combination of a fluorine compound and polyethylene is used as a lubricant and applied to a steel plate by use of an electrostatic method.
  • an electrostatic method results in non-continuous films which are unfavorable in terms of corrosion resistance.
  • Korean Pat. Appl'n. Nos. 96-39091 and 97-73554 describe polyethylene waxes modified with fluorine resins with an application for steel plates resistant to fingerprinting. Since such fingerprinting-resistant steel plates are usually developed to undergo low machining techniques such as bending and drilling, a problem occurs when deep drawing techniques are applied to them.
  • Korean Pat. Appl'n. No. 97-73554 discloses a silica-modified ethylene-acryl resin for coating fingerprinting-resistant steel plates. This resin is superb in workability, solution stability, physical properties such as storage properties, and chemical resistance, but poor in processability when its flexibility is taken into account.
  • Lubricant resin-coated steel plates are preferably processed without using oils.
  • a lubricant resin solution superior in chemical resistance such as alkali resistance and solvent resistance is applied in order to prevent the resin coating from being damaged.
  • a method for preparing an aqueous urethane resin composition comprising the steps of: (1) producing an aqueous polyurethane resin solution by (a) reacting 100-150 parts by weight polyester polyol, 30-50 parts by weight diisocyanate, 5-15 parts by weight dimethyl propionic acid or dimethyl butyric acid, and 3-10 parts by weight amine at 55-85 °C for 5-6 hours to give a prepolymer ranging, in NCO radical content, from 2 to 8%, said dimethyl propionic acid or dimethyl butyric acid serving as a hydrophilic moiety for water dispersion; (b) dispersing the prepolymer at 30-40 °C in water; and (c) introducing into the water-dispersed prepolymer a chain extender selected from the group consisting of glycol, triol and diamine at 25-30 °C in such a way that the reaction mole ratio between said chain extender and NCO residues
  • a method for preparing an aqueous lubricant urethane resin composition comprising the steps of: (1) producing an aqueous polyurethane resin solution by (a) reacting 100-150 parts by weight polyester polyol, 30-50 parts by weight diisocyanate, 5-15 parts by weight dimethyl propionic acid or dimethyl butyric acid, and 3-10 parts by weight amine at 55-85 °C for 5-6 hours to give prepolymer ranging, in NCO radical content, from 2 to 8%, said dimethyl propionic acid or dimethyl butyric acid serving as a hydrophilic moiety for water dispersion; (b) dispersing the prepolymer at 30-40 °C in water; and (c) introducing into the water-dispersed prepolymer chain extender selected from the group consisting of glycol, triol and diamine at 25-30 °C in such a way that the reaction mole ratio between said chain extender and NCO residues
  • a surface treatment of chromated, electroplated steel plates comprising the steps of: coating, on an zinc-electroplated steel plate chromated at a chrome amount of 4-200 mg/m 2 , the aqueous lubricant urethane resin composition at a dry coating thickness of 0.5-5.0 ⁇ m, baking the steel plate at a steel temperature of 110-200 °C, and quenching the steel in water.
  • Fig. 1 is a schematic cross section showing a steel plate coated with the aqueous lubricant urethane resin composition of the present invention.
  • the present invention contemplates a method for preparing an aqueous urethane resin composition.
  • the aqueous urethane resin composition according to the present invention can be coated on steel plates to a thickness as thin as 0.3-0.7 ⁇ m.
  • the aqueous urethane resin composition shows excellent compatibility with various additives which are usually used in plate steel coating compositions .
  • the aqueous urethane resin composition of the present invention is prepared by preparing a urethane prepolymer, dispersing the prepolymer in water, reacting the water-dispersed prepolymer with a chain extender to give an aqueous urethane resin solution, and adding a curing agent to the aqueous urethane resin solution.
  • polyester polyol, diisocyanate, dimethyl propionic acid or dimethyl butyric acid, and amine are reacted.
  • the dimethylpropionic acid or dimethyl butyric acid plays a role in the water dispersion of the prepolymer, later.
  • a polyester polyol suitable for use in the preparation of the urethane prepolymer is a polybutylene adipate-based polyester polyol ranging, in molecular weight, from 500 to 3,000. If the polyester polyol has a molecular weight less than 500, the resulting film is too low in flexibility to expect good processability. On the other hand, if the polyester polyol has a molecular weight more than 3,000, the resulting film has too high flexibility to be used for coating steel plates.
  • the polyester polyol is used at an amount of 100-150 parts by weight based on the total weight of the prepolymer reactants, and more preferably at an amount of 120-130 parts by weight.
  • the polyester polyol content is less than 100 parts by weight, the resulting film is so hard that it may be peeled off while the steel plate is processed.
  • the polyester polyol content is more than 150 parts by weight, the resulting film is so flexible that it may be pushed around upon processing.
  • the diisocyanate which is forming a prepolyme having urethane group, is selected from the group consisting of diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), isophorone diisocyanate
  • MDI diphenylmethane diisocyanate
  • TDI tolylene diisocyanate
  • diisocyanate content when the diisocyanate content is below 30 parts by weight, the backbone contains too small urethane content, so that the film lacks flexibility. Thus, upon processing, the resin is peeled off and is poor in paint adhesion.
  • diisocyanate content more than 50 parts by weight brings about a deterioration in general film properties, including yellowing occurrence and chemical resistance reduction.
  • the mole ratio of the diisocyanate to the polyol is so precisely calculated as that a theoretical NCO % of the prepolymer is within the range of 2-8 %.
  • the diisocyanate may be a single compound or a mixture of two or more species.
  • the theoretical NCO residue content at the end of the backbone is below 2 % upon prepolymer polymerization, poor solution stability occurs, resulting in a decrease in film hardness. According to circumstances, the film becomes too sticky, so that its workability is poor.
  • a theoretical NCO content at the end exceeds 8 %, the film is unsuitable as coating because it becomes so brittle that peeling occurs.
  • the maintenance of the NOC radical content within the range of 2-8 % guarantees the chain extension from the prepolymer to polyurethane resins with desired molecular weights .
  • dimethyl propionic acid DMPA
  • dimethyIbutyric acid DMBA
  • hydrophilicity is used at an amount of 5-15 parts by weight based on the total weight of the prepolymer reactants and preferably at an amount of 8-10 parts by weight.
  • carboxylic acid enables the prepolymer to be dispersed in water. If -the hydrophilic moiety content is less than 5 parts by weight, the prepolymer is insufficiently dispersed in water so that a desired aqueous coating solution is not obtained.
  • a hydrophilic moiety content more than 15 parts by weight deteriorates the corrosion resistance, chemical resistance, and paint adhesion (overcoatability) of the film.
  • amine serving as a neutralizing agent to solubilize the prepolymer in water, amine is used at an amount of 3-10 parts by weight based on the total weight of the prepolymer reactants and more preferably at the same equivalent as that of the hydrophilic moiety.
  • amine may be added. However, since amine serves not only as neutralizing agent, but also as catalyst for the urethane reaction between ester polyol and diisocyanate, it is preferable that about 60 % of the amount to be used is added at the polymerization
  • initiation step of the prepolymer and the remainder is fed at the termination point of the reaction before the dispersing the prepolymer in water.
  • Available is any of primary, secondary, and tertiary amines, examples of which include n-butyl amine, diethyl amine, triethyl amine, triethanol amine, and ethylene diamine with preference to triethyl amine.
  • triethyl amine is advantageous in that since its boiling point is as low as 90 °C, it does not remain on the steel plate after coating the resin solution on the steel plate.
  • the reactants are allowed to react with each other at 55-80 °C for about 5-6 hours with stirring to produce prepolymers which have carboxyl groups and terminal isocyan (NCO) functional groups.
  • the reaction is maintained at 30-40 °C, while water is added with stirring, so as to disperse the reaction.
  • a solvent such as acetone or n- methylpyrrolidone (NMP) is added at an amount of less than 10 % by weight based on the total weight of the reactants, before the water dispersion.
  • the solvents may be used alone or in combination, in consideration of the physical properties of the solution. It is preferable that the solvent is added at as small an amount as possible in consideration of environment issues. When added with such a solvent, the resin solution is lowered in viscosity and increased in water dispersibility and thin film coatability.
  • a chain extender is added to the water- dispersed prepolymer to synthesize aqueous polyurethane resins .
  • the addition of the chain extender is executed at the point that the reactants form a complete aqueous phase.
  • the chain extender is fed at the same equivalent as that of the remaining NOC %.
  • 90 % rather than 100 % of the amount of the chain extender is added and sufficiently reacted.
  • a reaction sample is taken during the extension and analyzed by IR spectroscopy to determine whether the remaining amount is to be fed or not.
  • the chain extender is one or two selected from glycols, such as ethylene glycol, 1,4-butylene glycol and 1, 6-hexanediol, diamines, such as ethylene diamine and isophorone diamine, triols such as trimethylol propane.
  • glycols such as ethylene glycol, 1,4-butylene glycol and 1, 6-hexanediol
  • diamines such as ethylene diamine and isophorone diamine
  • triols such as trimethylol propane.
  • the reaction temperature must be low enough not to react the NCO groups of the prepolymer to water, but high enough to proceed the reaction.
  • the reaction is preferably maintained for about 24 hours or longer because the reactivity between hydroxy (-OH) and NCO is low.
  • diamines when used, it takes about 1 hour for the reaction to be completed because of high reactivity between amine and isocyan groups .
  • the chain extender may be selected depending on the targets where the final product is applied. By precisely controlling the mole ratio between the NCO groups remaining in the prepolymer and the chain extender, the final molecular weight of the resin is determined.
  • the urethane resin of thin invention is determined to range, in molecular weight, from 30,000 to 100,000.
  • a urethane resin with a molecular weight of less than 30,000 is poor in chemical resistance while a urethane resin with a molecular weight of more than 100,000 is too rapidly dried after being coated and thus, poor in coating workability.
  • a urethane resin with a molecular weight of more than 100,000 is too rapidly dried after being coated and thus, poor in coating workability.
  • the urethane resin solution obtained by the step(l) may be problematic when it is under an alkali condition like a degreasing process condition.
  • an aziridine type or block isocyan type curing agent is used at an amount of 3-15 % by weight based on the weight of the total resin solid content. For example, if the amount of the curing agent is below 3 % by weight, a desired improvement is not achieved in alkali resistance. On the other hand, if the amount of the curing agent is over 15 % by weight, the film is deteriorated in paint adhesion, solution stability, surface appearance such as gloss, and processability.
  • additives such as a lubricant, colloidal silica and a coupling agent are added to prepare an aqueous lubricant urethane resin composition for use in steel plates, which is superb in oil-less deep machinability, process- defective decrease, blackening improvement, and chemical resistance. This preparation is carried out at room temperature .
  • the lubricant it is a mixture of fluorine resin-modified polyethylene type wax and polyethylene wax.
  • the fluorine resin-modified polyethylene type wax and the polyethylene wax bring about a greater improvement in the physical properties of the resin solution than when each is used, alone.
  • the aqueous lubricant resin solution added with a combination of a polyethylene type wax and a fluorine resin-modified polyethylene type wax is improved in deep machinability as well as alkali resistance and solution stability.
  • the fluorine resin-modified polyethylene type wax in which fluorine resin type wax particles are associated with polyethylene type wax particles in such a way that fine fluorine resin type wax particles are modified to surround polyethylene wax particles with significant bonding forces, has a specific gravity of 0.98-1.02, so that the aqueous lubricant urethane resin composition is improved in lubricating ability and physical properties
  • the fluorine resin-modified polyethylene type wax In the fluorine resin- modified polyethylene type wax, fluorine resin type wax particles with a diameter of 0.1-1.5 ⁇ m surround and bind to globular ethylene type wax particles which are low in specific gravity. Therefore, the fluorine resin-modified polyethylene type wax is so low in specific gravity that it has sufficient floatability even on the wetted film. In addition, the fluorine resin-modified polyethylene type wax sufficiently exerts the properties characteristic to fluorine resins by virtue of the ball bearing effect. Thus, even after being subjected to deep machining processes, the steel plate can maintain its surface clean by virtue of the fluorine resin-modified polyethylene type wax. In regard to the compatibility with aqueous solutions, the polyethylene type wax preferably ranges, in molecular weight, from 1,500 to 3,000 with a diameter of 0.05-1.0 ⁇ m.
  • the polyethylene type wax is homogeneously distributed in the resin film, unlike the fluorine-modified polyethylene type wax which is prevalently distributed in the upper portion of the film as shown in Fig. 1.
  • the polyethylene type wax guarantees the uniform processability of the steel plate.
  • its high melting point 120-130 °C
  • the weight ratio of the fluorine resin- modified polyethylene type wax to the polyethylene type wax in the wax mixture ranges from 1:0.3 to 1:0.7.
  • the weight ratio of the polyethylene type wax is below 0.3 on the basis of the fluorine resin-modified polyethylene type wax, the effect of the polyethylene type wax is not sufficiently expressed so that the continuous workability becomes poor.
  • the weigh ratio is over 0.7, the physical properties of the polyethylene type wax are dominantly expressed while the deep machinability is poor.
  • the wax mixture is added at an amount of 5-30 % by weight and preferably at an amount of 10-15 % by weight. For instance, if the wax mixture is added at an amount of less than 5 % by weight, the resin solution is improved in surface friction properties to some degree, but the deep machinability is poor. On the other hand, if the wax mixture is added at an amount of more than 30 % by weight, no additional improvements are found in the deep mechinability and the resin solution suffers from the problems of being lowered in physical properties, including overcoatability and corrosion resistance.
  • colloidal silica is used at an amount of 10-30 % by weight based on the weight of the resin solid content. Less than 10 % by weight of colloidal silica cannot bring about a sufficient effect in the corrosion resistance. On the other hand, if the colloidal silica is present at an amount greater than 30 % by weight, silica, which is large in hardness, negatively affects the deep machinability and causes a scratchy blackening phenomenon on the processed regions.
  • silane coupling agents containing epoxy, amine and/or acryl groups and titanium coupling agents containing amine groups are useful in the present invention.
  • the coupling agents have the functions of increasing film strength so as to improve the gloss and processability of the plate as well as of uniformly dispersing the silica particles in the film so as to improve the corrosion resistance.
  • the coupling agent is used at an amount of 0.1-0.5 % by weight based on the weight of the resin solid content.
  • the lubricant urethane resin composition which is prepared in consideration of practical applications can be used as functional coating resin solutions for various purposes.
  • the solid content of the lubricant urethane resin composition may be controlled by use of pure water.
  • the lubricant urethane resin composition is diluted with pure water to a solid content of 10-30 % by weight. If the solid content is outside of the range of 10-30 % by weight, a thin film coating is not conveniently obtained with lubricant urethane resin composition.
  • the aqueous urethane resin composition thus obtained is superior in terms of thin film coatability, corrosion resistance, film flexibility, adhesiveness to steel plates, surface friction property, chemical resistance, and overcoatability as well as in terms of compatibility with various additives which are usually used in conventional coating materials for steel plates .
  • the aqueous, lubricant urethane resin composition characterized by oil-less deep machinability, process-defective reduction, blackening improvement, and chemical resistance
  • the aqueous lubricant urethane resin composition can be coated on electroplated steel plates in an ordinary coating method such as a roll coating method or a spray method.
  • the aqueous lubricant urethane resin composition is coated at a thickness from 0.5 to 5 ⁇ m when it is dried. For instance, when the film thickness is below 0.5 ⁇ m, it cannot afford desired levels in film lubricating ability and workability. On the other hand, if a dry film thicker than 5 ⁇ m, no additional improvements in processability are obtained.
  • thick coats can be more feasibly attached to the mold upon . deep machining, incurring a load to the processing process.
  • the heat provided during a baking process cures the lubricant resin of the present invention.
  • the baking temperature is determined within the range of 110-200 °C as the plate temperature is measured.
  • the resin on the steel plate whose temperature is below 110 °C is not sufficiently cured so that it is deteriorated in chemical resistance. Also, the coat may remain undried.
  • the steel plate is physically transformed at 200 °C or higher. After baking, quenching the steel plate in water.
  • Example 1-5 The following was a description of the urethane resin composition preparation set forth in Example 1-5.
  • 120 g of a commercially available polybutyrene adipate based polyol with a molecular weight of 2,000, 40 g of diisocyanates mixture of 2:1 by weight ratio of diphenylmethane diisocyanate : isophorone diisocyanate, 8 g of dimethyl butyric acid, and 6 g of triethyl amine were reacted together at 65 °C for 5 hours under nitrogen atmosphere with stirring to give a prepolymer with an NCO content of 3 % .
  • Each of the used diphenylmethanediisocyanate, isophoronediisocyanate, dimethylbutyric acid, and triethylamine was a first grade reagent. 3 g of triethylamine was added in an initial stage of the prepolymer polymerization and the remaining 3 g at a termination stage.
  • reaction was added with 12 g of n- methylpyrrolidone and homogeneously mixed by stirring, during which 284 g of distilled water was added to disperse the prepolymer.
  • the water-dispersed reaction was slowly added with a 8 g of 1,4-butylene glycol, serving as a chain extender, and allowed to stand for 24 hours to give an aqueous polyurethane resin solution to which an aziridine type curing agent and r- glycidoxy propyl trimethoxy silane were added at amounts of 7 % by weight and 0.2 % by weight, respectively.
  • Both 1,4-butyrene glycol and r-glycidoxy propyl trimethoxy silane were first grade reagents.
  • the aqueous urethane resin composition prepared according to the condition listed in Table 1, below was coated on a chromated zinc- electroplated steel plate, which was 0.8 mm thick with a zinc deposition of 20 g/m 2 and a chromate deposition of 50 mg/m 2 , at a thickness of 1.5 ⁇ m with the aid of a coating simulator (bar coater) #3. Subsequently, the steel plate was baked at a temperature of 160 °C in an automatic discharging oven and quenched with water to form a film thereon.
  • aqueous thin film coating resins commercially available from POSCO, Korea, were respectively applied to chromated zinc-electroplated steel plates, each being 0.8 mm thick with a zinc deposition of 20 g/m 2 and a chromate deposition of 50 mg/m 2 , to form films.
  • Epoxy acrylate was used for Comparative Example 1-13, a polyether-modified urethane resin for Comparative Example 1-14, and an ethylene acryl resin for Comparative Example 1-15.
  • Each of the comparative resins had a solid content of 20 % by weight.
  • Corrosion resistance was evaluated as an initial white corrosion generation time in a brine water-spraying tester in accordance with JIS Z 2731.
  • a coated surface was scrubbed 20 times back and forth with a cotton gauze soaked in methyl ethyl ketone (MEK) and the dissolution of the coat film was evaluated by the naked eye.
  • MEK methyl ethyl ketone
  • a coated steel plate sample was subjected to spray degreasing and immerse degreasing, each at 60 °C for 150 sec by use of an aqueous alkali degreasing solution, washed twice with water, and air-dried, followed by measuring color differences ( ⁇ E) before and after the degreasing with the aid of a color difference meter. Evaluation was carried out according to the following criteria: Alkali Resistance Evaluation ( ⁇ E) ⁇ (excellent): 0.5 or less, O(good): 1.0 ⁇ (poor): 1.1-2.0, X (bad): 2.0 or greater.
  • Friction Coefficient Evaluation ( ⁇ ) ⁇ (excellent): 0.12 or less, O(good): 0.075-0.085, ⁇ (poor): 0.085-0.095, X(bad): 0.15 or greater.
  • thermosetting melamine paint was sprayed over a resin-coated steel plate to give a film 25 ⁇ m thick when it was dried, followed by curing the film at 150 °C. After the following treatments, the film was evaluated for its characteristics .
  • Primary Adhesion after the curing, the film was allowed to stand for 24 hours at room temperature and subjected to cross-cut testing under a condition of 1 mm and 100 scales.
  • Water-Resistant Adhesion after being immersed for 30 min in boiling water, a cured sample was subjected to cross-cut testing.
  • Adhesion after 6 mm Erichsen Processing After being cross-cut under a condition of 1 mm and 100 scales, a cured sample was allowed to undergo a 6 mm Erichsen processing.
  • Impact Resistance a ball type pendulum weighing 1 kg was allowed to fall down to a cured, cross-cut sample from a height 50 cm away from the sample, after which a tape was attached to the backside of the sample and removed to evaluate the coating adhesion.
  • Film Characteristics Evaluation ⁇ (excellent) no scales, 0 (good) : 1-2 scales ⁇ (poor) : 3-5 scales, X (bad) : 6 or more scales CO t c ⁇ o n en
  • Note 2 a: blockisocyan type curing agent, b: aziridine type curing agent Note 3 a) primary adhesion, b) water-resistant adhesion, c) adhesion after 6 mm Erichsen processing, d) impact resistance
  • Examples 1-1 to 1-6 Excellent physical properties were measured from the steel plate samples which were coated with the aqueous urethane resin composition prepared under the conditions of the present invention.
  • the polyol used in the prepolymer polymerization has a lower molecular weight than the condition range of the present invention, a decrease is brought about in processability and chemical resistance. If the molecular weight exceeds the condition range of the present invention, the film is too flexible to be suitable for use in steel plate coating.
  • Comparative Examples 1-3 and 1-4 When the content of polyol is lower than the range the present invention suggests, the film is so hard that it is peeled off while the steel plate is processed. When the polyester polyol content is more than the condition range, the film is so flexible that it is pushed around upon processing. Therefore, the polyol content outside of the suggested range results in deteriorating the processability.
  • hydrophilic moiety content is less than the lower limit of the range the present invention suggests, the prepolymer is insufficiently dispersed in water so that a desired aqueous coating solution is not obtained.
  • a hydrophilic moiety content more than the upper limit of the range deteriorates general film properties, including corrosion resistance, chemical resistance, and paint adhesion.
  • the film When the diisocyanate content is below the lower limit of the condition range of the present invention, the film lacks flexibility, which leads to a deterioration in processability, post-processing adhesion, and paint adhesion in terms of impact resistance while a diisocyanate content more than the upper limit of the condition causes yellowing and chemical resistance reduction.
  • the amount of the curing agent is below the lower limit of the condition range of the present invention, a desired improvement is not achieved in chemical resistance, especially, alkali resistance. If the amount of the curing agent is over the upper limit of the condition range, the film is deteriorated in paint adhesion, solution stability, surface appearance such as gloss, and processability.
  • Comparative Examples 1-13 and 1.-15 Conventional resins are poor in chemical resistance, processability and friction properties.
  • the urethane resin solution prepared in Example 1-5 was added with a mixture of 1:1 fluorine resin-modified polyethylene wax : polyethylene wax at the amounts indicated in Table 2, below, to produce aqueous lubricant urethane resin compositions, each having a solid content of 20 wt%.
  • silica Snowtex-n with a solid content of 20 % wt% (Nissin Chemical Co., Japan) was used.
  • the lubricant polyurethane resin compositions were coated on chromated steel plates as in Example 1 and assayed for physical properties .
  • Corrosion resistance was evaluated as an initial white corrosion generation time in a brine water-spraying tester in accordance with JIS Z 2731.
  • a coated surface was scrubbed 20 times back and forth with a cotton gauze soaked in methyl ethyl ketone and the dissolution of the coat film was evaluated by the naked eye.
  • a coated steel plate sample was subjected to spray degreasing and immerse degreasing, each at 60 °C for 150 sec by use of an aqueous alkali degreasing solution, washed twice with water, and air-dried, followed by measuring color differences ( ⁇ E) before and after the degreasing with the aid of a color difference meter. Evaluation was carried out according to the following criteria: Alkali Resistance Evaluation ( ⁇ E)
  • Friction Coefficient Evaluation ( ⁇ ) ⁇ (excellent): 0.075 or less, O(good): 0.075-0.085, ⁇ (poor): 0.085-0.095, X(bad): 0.095 or greater.
  • a steel plate sample was subjected to plain strain stretch testing (PSST) under the condition of a blank holding force 30 tons and a punch speed 230 mm/min without providing an oil and, then, measured for limit dome height (LDH) .
  • PSST plain strain stretch testing
  • LDH limit dome height
  • the steel plates coated with the lubricant resin solutions prepared according to the present, invention are excellent in all of the physical properties tested.
  • the steel plates are generally poor in processability.
  • the steel plates become poor in corrosion resistance.
  • a silica content lower than the desired range results in deteriorating the corrosion resistance while a higher silica content incurs blackening and scratching upon processing because silica has a large hardness. In the latter case, the steel plates show poor deep machine, as well.
  • Aqueous lubricant urethane resin solutions were prepared as indicated in Table 3.
  • the polyethylene wax used was one purchased from Daedong, Korea, identified as PS-35, which has a solid content of 26 wt%.
  • the fluorine-modified polyethylene wax was 25 wt% in solid content and commercially avariable.
  • Each of the aqueous lubricant resin solutions was applied to the resin composition prepared in Example 5-2.
  • the aqueous lubricant urethane resin compositions thus obtained were tested for deep machinability and post-processing appearance as in Example 2.
  • a mixture of fluorine resin-modified polyethylene wax and polyethylene wax which is within the weight ratio range of the present invention enhances the deep machinability and postprocessing appearance of the steel plate fluorine.
  • Resin-modified polyethylene wax alone or a wax mixture containing a polyethylene wax at a lower content than suggested by the present invention does not give a desirable contribution to the machinability of the steel plate.
  • the effect attributed to fluorine resin-modified polyethylene wax is not expressed.
  • the aqueous lubricant urethane resin composition for thin film coating prepared according to the present invention is superior in various physical properties, including corrosion resistance, paint adhesion, chemical resistance, processability, and surface friction properties and suitable as a binder resin for coating functional steel plates .
  • a lubricant coating solution containing the aqueous urethane resin when applied as a thin film to a steel plate, gives a great contribution to improving the steel plate in corrosion resistance, chemical resistance, deep machinability, post-processing appearance, and surface friction properties as well as enables the steel plate to be processed into products under an oil-less condition. This oil-less condition results in omitting a degreasing process, thereby bringing about a favor economically and environmentally.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Paints Or Removers (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

L'invention concerne un procédé de préparation d'une composition de résine uréthane aqueuse, un procédé de préparation d'une composition de résine uréthane lubrifiante aqueuse, ainsi qu'un procédé de traitement de surface de plaques d'acier. On prépare cette composition de résine uréthane aqueuse en faisant réagir du polyol de polyester, du diisocyanate, de l'acide propionique de diméthyle ou de l'acide butyrique de diméthyle et une amine de manière à obtenir un prépolymère. Ensuite, on disperse ce prépolymère dans l'eau, puis on introduit un allongeur de chaîne dans le prépolymère dispersé dans l'eau avant d'ajouter la solution de résine polyuréthane aqueuse avec un agent de durcissement. L'acide propionique de diméthyle ou l'acide butyrique de diméthyle tient lieu de groupe caractéristique hydrophile en vue d'une dispersion dans l'eau. La composition de résine uréthane lubrifiante aqueuse est préparée à partir de la composition de résine uréthane aqueuse en combinaison avec un mélange d'une cire de polyéthylène modifiée par une fluororésine et d'une cire de polyéthylène, d'une silice colloïdale et d'un agent de couplage. Cette composition de résine lubrifiante est appliquée à une épaisseur de 0,5-5,0 νm sur une plaque d'acier chromatée électrodéposée, laquelle est alors cuite à 110-200 °C et trempée dans l'eau. Outre ses propriétés supérieures en termes d'aptitude au couchage mince, de résistance à la corrosion, de souplesse de film, d'adhésion à la plaque, de frottement superficiel, de résistance chimique et d'aptitude au surcouchage, ladite composition de résine lubrifiante présente une excellente compatibilité avec de nombreux additifs habituellement utilisés.
PCT/KR2000/000657 2000-06-22 2000-06-22 Preparation d'une composition de resine urethane aqueuse Ceased WO2001098392A1 (fr)

Priority Applications (3)

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CNB008118663A CN1146617C (zh) 2000-06-22 2000-06-22 含水的聚氨酯树脂组合物的制备
PCT/KR2000/000657 WO2001098392A1 (fr) 2000-06-22 2000-06-22 Preparation d'une composition de resine urethane aqueuse
JP2002504346A JP2004501252A (ja) 2000-06-22 2000-06-22 水性ウレタン樹脂組成物の作製方法

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EP1219359A3 (fr) * 2000-12-21 2003-05-07 The Furukawa Electric Co., Ltd. Plaque métallique pour des instruments électriques/électroniques et appareils électriques/électroniques utilisant cette plaque
KR100458984B1 (ko) * 2001-08-24 2004-12-03 (주)나눅스 수분산 폴리우레탄-콜로이달 실리카 나노 복합재료 및그의 제조방법
CN102808148A (zh) * 2011-05-30 2012-12-05 比亚迪股份有限公司 一种触摸屏表面防指纹薄膜的制备方法
CN111944111A (zh) * 2019-04-30 2020-11-17 万华化学集团股份有限公司 一种水性自消光聚氨酯分散体和制备方法及其组合物
CN112227083A (zh) * 2020-09-30 2021-01-15 京准化工技术(上海)有限公司 一种织物耐水压提升剂及其制备方法
US20240301260A1 (en) * 2020-12-21 2024-09-12 Posco Co., Ltd Adhesive coating composition for electrical steel sheet, electrical steel sheet laminate and manufacturing method therefor

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JP4495543B2 (ja) * 2004-08-12 2010-07-07 日新製鋼株式会社 温水可溶型樹脂被覆ステンレス鋼板
CN100497506C (zh) * 2006-09-14 2009-06-10 华明扬 水性聚氨酯/环氧共聚防水透气透湿抗菌涂层胶的制备方法
CN100445332C (zh) * 2006-11-01 2008-12-24 淄博奥德美高分子材料有限公司 水性聚氨酯氟硅改性高分子导电乳液
EP2025694A1 (fr) * 2007-07-25 2009-02-18 Cytec Surface Specialties Austria GmbH Liants autoréticulants
JP5344365B2 (ja) * 2008-08-26 2013-11-20 日本ポリウレタン工業株式会社 水性ポリウレタン分散体及びその製造方法
JP5674605B2 (ja) * 2011-09-13 2015-02-25 日新製鋼株式会社 化成処理めっき鋼板およびその製造方法
JP5674606B2 (ja) * 2011-09-14 2015-02-25 日新製鋼株式会社 化成処理めっき鋼板およびその製造方法
CN103625034A (zh) * 2013-11-25 2014-03-12 江苏克罗德科技有限公司 自润滑高耐蚀性镀铝锌钢板及其制备方法
CN104559717B (zh) * 2014-12-25 2017-05-24 澳达树熊涂料(惠州)有限公司 一种低成本高性能的水性双组分聚氨酯涂料及其制备方法
CN108276762A (zh) * 2018-01-05 2018-07-13 武汉理工大学 一种用于水润滑轴承的聚氨酯复合材料及制备方法
CN114645471B (zh) * 2022-03-04 2024-10-01 无锡市曼优丽新型复合材料有限公司 一种阻燃人造革及其制备方法
CN116333273A (zh) * 2023-04-24 2023-06-27 江苏东邦科技有限公司 一种多元醇及用其制备的聚氨酯粘合剂及制备方法

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Publication number Priority date Publication date Assignee Title
EP1219359A3 (fr) * 2000-12-21 2003-05-07 The Furukawa Electric Co., Ltd. Plaque métallique pour des instruments électriques/électroniques et appareils électriques/électroniques utilisant cette plaque
US6797407B2 (en) 2000-12-21 2004-09-28 The Furukawa Electric Co., Ltd. Metallic plate material for electric/electronic instrument and electric/electronic instrument using same
KR100458984B1 (ko) * 2001-08-24 2004-12-03 (주)나눅스 수분산 폴리우레탄-콜로이달 실리카 나노 복합재료 및그의 제조방법
CN102808148A (zh) * 2011-05-30 2012-12-05 比亚迪股份有限公司 一种触摸屏表面防指纹薄膜的制备方法
CN111944111A (zh) * 2019-04-30 2020-11-17 万华化学集团股份有限公司 一种水性自消光聚氨酯分散体和制备方法及其组合物
CN111944111B (zh) * 2019-04-30 2022-04-22 万华化学集团股份有限公司 一种水性自消光聚氨酯分散体和制备方法及其组合物
CN112227083A (zh) * 2020-09-30 2021-01-15 京准化工技术(上海)有限公司 一种织物耐水压提升剂及其制备方法
US20240301260A1 (en) * 2020-12-21 2024-09-12 Posco Co., Ltd Adhesive coating composition for electrical steel sheet, electrical steel sheet laminate and manufacturing method therefor

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