CN1370189A - Prepn. of aqueous urethane resin compsn. - Google Patents
Prepn. of aqueous urethane resin compsn. Download PDFInfo
- Publication number
- CN1370189A CN1370189A CN00811866.3A CN00811866A CN1370189A CN 1370189 A CN1370189 A CN 1370189A CN 00811866 A CN00811866 A CN 00811866A CN 1370189 A CN1370189 A CN 1370189A
- Authority
- CN
- China
- Prior art keywords
- weight
- water
- prepolymer
- steel plate
- resin
- 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.)
- Granted
Links
Images
Classifications
-
- 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
Landscapes
- 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
Disclosed are a method for preparing an aqueous urethane resin composition, a method for preparing an aqueous lubricant urethane resin composition, and a surface treatment method of steel plates. The aqueous urethane resin composition is prepared by reacting polyester polyol, diisocyanate, dimethyl propionic acid or dimethyl butyric acid, and amino to give a prepolymer, dispersing the propolymer in water, introducing into the water-dispersed prepolymer a chain extender, and adding the aqueous polyurethane resin solution with a curing agent. The dimethyl propionic acid or dimethyl butyric acid serves as a hydrophilic moiety for water dispersion. The aqueous lubricant uretane resin composition is prpared from the aqueous urethane resin composition in combination with a wax mixture of fluorine resin-modified polyethylene wax and polyethylene wax, colloidal silica and a coupling agent. This lubricant resin composition is coated at a thickenss of 0.5-5.0 (m on a chromated, electroplated steel plate which is then baked at 110-200 (c and quenched in water.
Description
Background of invention
1. invention field
The present invention relates to a kind of method that is used to prepare aqueous polyurethane resin composition, this polyurethane resin composition is suitable as the binder resin solution of coating steel plate, the invention still further relates to a kind of preparation and contain the method for the polyurethane resin composition of water lubricating and the purposes of these two kinds of compositions.More particularly, the present invention relates to a kind of method for preparing aqueous polyurethane resin composition, this polyurethane resin composition has multinomial good physicals, comprise solidity to corrosion, clagging, chemical resistance, workability and surface friction performance, and be suitable as a kind of adhesive resin that is used to be coated with functional steel plate.In addition, the invention still further relates to a kind of polyurethane resin composition that contains water lubricating that contains aqueous polyurethane resin, this polyurethane resin composition can significantly improve the performance of steel plate aspect solidity to corrosion, chemical resistance, deep-draw ductility, aftertreatment outward appearance and the surface friction performance, and can make steel plate be processed to product under the condition of not having oil.In addition, the invention still further relates to the surface treatment of the electroplating steel plate of chromating.
2. to the description of prior art
For being used for film coating, requiring film flexibility, adhesivity, surface friction characteristic, chemical resistance and the recoatability that aqueous resins has good solidity to corrosion, represents with workability and can in conventional application, use steel plate.
Up to the present, multiple solvent-borne type or water type steel plate coating resin have been developed.About functional steel plate, conventional coating resin can be speciallyyed permit communique No.Hei.5-138120 referring to Japan.In this referenced patent, with solidifying agent, for example various aminated compoundss, ammonia resin and isocyanate compound have been mentioned the modification derivant of bisphenol-type epoxy resin, multi-functional Resins, epoxy, Synolac, esters resin, acrylic resin, urethane resin and above-mentioned resin together.But this patent is not described above-claimed cpd in detail, and only is simply to enumerate.In addition, their use range is too wide, can't distinguish out the performance of resin.
Use the surface of the electroplating steel plate of various resin film coating chromatings to be well known in the art with the process for treating surface that is used for various objectives.Japan special permission communique No.Hei.5-138120,4-44840,3-71836,3-39485,3-16726 and 3-270932 disclose the lubricant solution that is used for steel plate.But, mention in detail at the blackening phenomena of deep draw post-treatment parts and the base resin of arborescens solution without any the place.
Japan special permission communique No.Hei.5-3052668 discloses urethane resin and has had purposes aspect the highly corrosion proof discontinuous coating in formation.A kind of fluorochemicals and poly simple knot compound are used as the lubricant use and are coated on the steel plate by the use electrostatic method.But what electrostatic method obtained is non-continuous film, and this film is undesirable on solidity to corrosion.
Korean patent application No.96-39091 and 97-73554 have described fluorine resin modified polyethylene wax, and this polyethylene wax is used for the steel plate of anti-fingerprint.Because this kind anti-finger print steel plate only is used to carry out the processing technology of rudimentary machinery usually,, therefore when being carried out the deep draw technology, they can go wrong as crooked and boring.
Korean patent application No.97-73554 discloses a kind of ethylene-propylene acid resin that is used to be coated with the silica modification of anti-finger print steel plate.This kind resin has good workability, stability of solution, physicals, and as storage stability and chemical resistance, but when considering its snappiness, its workability is not good.
Preferably under the condition of not having oil, process the steel plate that is coated with lubricating resin.In the time must removing pollutent in the course of processing or after machining, be damaged in order to prevent resin coating, should be coated with chemical resistance, as the resin solution of alkali resistance and solvent resistance excellent lubrication.
Being provided for the chemical resistance of computer fittings and transparent household electrical appliance accessory and the demand of anti-blackening constantly increases.The long-term cleaning that therefore, need after processing, keep the surface.
The present invention's general introduction
Therefore, an object of the present invention is to provide a kind of preparation aqueous polyurethane resin method for compositions, this polyurethane resin composition can be coated on the steel plate thinly, has good anti-finger printing, recoatability and solidity to corrosion and has the consistency fabulous with other additives.
Another object of the present invention provides the method that a kind of preparation contains the polyurethane resin composition of water lubricating, and the feature of said composition is to have deep rolling performance, process defect reduction, blackening improvement and the resistance to chemical attack of not having oil.
Another purpose of the present invention provides the surface method that a kind of polyurethane resin composition of using this kind to contain water lubricating is handled the electroplating steel plate of chromating.
According to first embodiment of the present invention, a kind of aqueous polyurethane resin method for compositions that is used to prepare is provided, this method comprises the following steps: that (1) prepares a kind of aqueous polyurethane resin solution through the following steps: (a) make 100-150 weight part polyester polyol, 30-50 weight part vulcabond, 5-15 weight part neopentanoic acid or acid dimethyl and 3-10 portions of amine by weight were reacted 5-6 hour down at 55-85 ℃, obtain the prepolymer of a kind of NCO free-radical contents in the 2-8% scope, described neopentanoic acid or acid dimethyl are as the hydrophilic segment in the water-dispersion; (b) this prepolymer is dispersed in the water under 30-40 ℃; (c) under 25-30 ℃, introduce a kind of chain extension agent in the prepolymer of water-dispersion, this chain extension agent is selected from the group of being made up of dibasic alcohol, trivalent alcohol and diamines, the mode of introducing is 30 for the reaction mol ratio of described chain extension agent of control and NCO residue to obtain molecular weight, 000-100,000 final product; (2) add end-blocking isocyanide type or aziridine type solidifying agent in this aqueous polyurethane resin solution, the amount that is added is the 3-15 weight % of resin solid content.
According to second embodiment of the present invention, a kind of method that is used to prepare the polyurethane resin composition that contains water lubricating is provided, this method comprises the following steps: that (1) prepares a kind of aqueous polyurethane resin solution by following step: (a) make 100-150 weight part polyester polyol, 30-50 weight part vulcabond, 5-15 weight part neopentanoic acid or acid dimethyl and 3-10 portions of amine by weight were reacted 5-6 hour down at 55-85 ℃, obtain the prepolymer of a kind of NCO free-radical contents in the 2-8% scope, described neopentanoic acid or acid dimethyl are as the hydrophilic segment in the water-dispersion; (b) this prepolymer is dispersed in the water under 30-40 ℃; (c) under 25-30 ℃, in the prepolymer of water-dispersion, introduce a kind of chain extension agent, this chain extension agent is selected from the group of being made up of dibasic alcohol, trivalent alcohol and diamines, the mode of introducing is 30 for the reaction mol ratio of described chain extension agent of control and NCO residue to obtain molecular weight, 000-100,000 final product; (2) add end-blocking isocyanide type or aziridine type solidifying agent in this aqueous polyurethane resin solution, the amount that is added is the 3-15 weight % of resin solid content; (3) add in this resin solution that to contain proportional be 1: 0.3-1: 0.7 the fluorine resin modified polyethylene wax and the mixture of polyethylene wax, the amount that is added is the 5-30 weight % of resin solid content, the proportion of described fluorine resin modified polyethylene wax is in the 0.98-1.02 scope, size of particles is at the 0.1-1.5 mu m range, the molecular weight of described polyethylene wax is 1,500-3,000 scope, size of particles is at the 0.05-1.0 mu m range; (4) add a kind of colloidal silica in the resin solution that step (3) is obtained, the amount that is added is the 10-30 weight % of resin solid content; (5) in the resin solution that step (4) is obtained, add a kind of coupling agent, this coupling agent is selected from by the silane coupling agent that contains epoxy group(ing), amido and/or acryl and contains phosphorus and/or group that the titanium coupling agent of amido is formed, and the amount that is added is the 0.1-0.5 weight % of resin solid content gross weight; (6) with pure water this resin solution being diluted to final resin solid content is 10-30 weight %.
According to the 3rd embodiment of the present invention, a kind of treatment process of electroplating steel plate surface of chromating is provided, its polyurethane resin composition that comprises the following steps: to contain water lubricating is coated on a kind of with 4-200mg/m with the dry coating thickness of 0.5-5.0 μ m
2On the steel plate galvanized of chromium amount chromating, under 110-200 ℃ steel temperature, toast steel plate, and in water, make steel plate quenching.
Simple description to accompanying drawing
Fig. 1 is schematic cross section with the steel plate of the polyurethane resin composition coating that contains water lubricating of the present invention of expression.
Detailed description of the present invention
The present invention is absorbed in a kind of method for preparing the aqueous polyurethane resin composition. Aqueous polyurethane resin composition of the present invention can be coated on the steel plate with the thickness that is as thin as 0.3-0.7 μ m. Except having good thin coating, corrosion resistance, film pliability, steel plate adhesiveness, suface friction, chemical resistance and recoatability, this aqueous polyurethane resin composition also shows and the good compatibility that is generally used for the different additive in the steel plate coating composition.
Prepare through the following steps aqueous polyurethane resin composition of the present invention: prepare a kind of urethanes prepolymer, this prepolymer is dispersed in water, make prepolymer and the reaction of a kind of cahin extension agent of aqueous dispersion obtain a kind of aqueous polyurethane resin solution, and in this aqueous polyurethane resin solution, add a kind of curing agent.
For obtaining this urethanes prepolymer, make the reaction of PEPA, vulcabond, neopentanoic acid or acid dimethyl and amine. Owing to its hydrophily, neopentanoic acid or acid dimethyl play a role in the aqueous dispersion of prepolymer afterwards.
As example, but not as restriction, the PEPA that is fit to use in the preparation of urethanes prepolymer is the PEPA of poly-adipic acid fourth two ester groups, and its molecular weight is in 500 to 3,000 scope. If the molecular weight of PEPA is lower than 500, the pliability of the film that obtains is too low, can not obtain good machinability. On the other hand, if the molecular weight of PEPA is higher than 3,000, the pliability of the film that obtains is too high, can not be used to be coated with steel plate.
Take the gross weight of prepolymer reactant as the basis, the use amount of preferred polyester polyalcohol is the 100-150 weight portion, more preferably the 120-130 weight portion. For example, when the content of PEPA was lower than 100 weight portion, resulting film was very hard, so that it will peel off in the steel plate process. On the other hand, when the content of PEPA was higher than 150 weight portion, the pliability of the film that obtains was very high, so that it will be out of shape in process.
The vulcabond that formation has the prepolymer of urethane groups is selected from the group that is comprised of '-diphenylmethane diisocyanate (MDI), toluene di-isocyanate(TDI) (TDI), IPDI (IPDI) and composition thereof, take the gross weight of prepolymer reactant as the basis, the addition of vulcabond is the 30-50 weight portion, and preferably its addition is 35-40 weight portions. For example, when the addition of vulcabond was lower than 30 weight portion, the urethane ester content in the main chain was excessively low, caused film to lack pliability. Therefore, add man-hour, resin will peel off and clagging poor. On the other hand, the content of vulcabond is higher than 50 weight portions and will causes common film properties deteriorated, comprises xanthochromia and chemical resistance reduction occur.
For obtaining better film, should very accurately calculate vulcabond and many pure mol ratios, the theoretical NCO% that makes prepolymer is in the scope of 2-8%.In this, vulcabond can be the mixture of simplification compound or two kinds or multiple compound.When the prepolymer polymerization, when the theoretical NCO residue content of main chain end was lower than 2%, the poor stability of solution caused film hardness to reduce.According to envrionment conditions, it is too sticking that film becomes, and causes its workability deteriorates.On the other hand, when the theoretical NCO content of end surpasses 8%, peel off, thereby be not suitable for coating owing to film will become very crisp.Therefore, the content of keeping the NCO free radical has guaranteed that in the scope of 2-8% chain extends to the urethane resin with needed molecular weight from prepolymer.
Based on the gross weight of prepolymer reactant, the hydrophilic neopentanoic acid (DMPA) that the water-dispersion of prepolymer is played a role or the usage quantity of acid dimethyl (DMBA) are the 5-15 weight part, preferred 8-10 weight part.Its carboxylic acidity can be dispersed in the water prepolymer.If the content of hydrophilic segment is lower than 5 weight parts, prepolymer can not fully disperse in water, cause to obtain needed aquifer coating solution.On the other hand, the hydrophilic segment content that is higher than 15 weight parts will damage solidity to corrosion, chemical resistance and the clagging (recoatability) of film.
Based on the gross weight of prepolymer reactant, be the 3-10 weight part as the usage quantity that makes prepolymer amine of the neutralizing agent of solubilising in water, more preferably identical amount with the equivalent of hydrophilic segment.
Can cause step in the reaction of synthetic prepolymer and add amine.But, because amine is neutralizing agent still not, still the catalyzer of the polyurethane reaction between polyester polyol and the vulcabond preferably causes step in the polymerization of prepolymer and adds the about 60% of usage quantity, and the reaction end of rest part before being dispersed in prepolymer in the water adds.Operable amine is any primary, second month in a season and tertiary amine, and its example comprises n-Butyl Amine 99, diethylamine, triethylamine, trolamine and quadrol, preferred triethylamine.Except having good water solubilising potentiality, because the boiling point of triethylamine is low to moderate 90 ℃, its another advantage is that it can not remain on the steel plate after being coated on resin solution on the steel plate.
When the add-on of amine is lower than 3 weight parts, can not obtain enough solubilisings.On the other hand, when the add-on of amine is higher than 10 weight parts, its catalysis will be strengthened, and cause unwanted side reaction to be caused significantly.
Make reactant under agitation condition, react to each other 5-6 hour, have the prepolymer of carboxylic group and terminal isocyanide (NCO) functional group with preparation at 55-80 ℃.
At the terminal point of polyreaction, the temperature of keeping reactant is 30-40 ℃, adds entry simultaneously under agitation condition, to disperse reactant.
Excessive when the viscosity of reactant, can't be dispersed in the water or when requiring to promote water-dispersion, with before the water-dispersion, add a kind of solvent, as acetone or N-Methyl pyrrolidone (NMP), the add-on of solvent is the 10 weight % that are lower than the reactant gross weight.In this, consider the physicals of solution, can use solvent separately or be used in combination.Consider environmental problem, the add-on of preferred solvent is the least possible.When adding this kind solvent, the viscosity of resin solution reduces, in water dispersible and film coated raising.
After this, in the prepolymer of water-dispersion, add chain extension agent, with synthetic aqueous urethane resin.When becoming completely water, reactant adds chain extension agent.With with the identical equivalent charging chain extension agent of equivalent of the NCO% of remnants.When considering to have difference between theoretical NCO% and the actual NCO% time, preferably add the amount and the fully reaction of 90% rather than 100% chain extension agent.In increasing chain process, the abstraction reaction sample and by infrared (IR) spectroscopic analysis to determine whether to add remaining amount.
As an example, but as restriction, chain extension agent can be selected from dibasic alcohol, ethylene glycol, 1 for example, 4-butyleneglycol and 1,6-hexylene glycol, diamines, for example quadrol and isophorone diamine, trivalent alcohol, for example a kind of in the TriMethylolPropane(TMP) or two kinds.Temperature of reaction maintains 25-30 ℃.
Temperature of reaction must be enough low, so that the NCO group of prepolymer do not react with water, but temperature of reaction also must be enough high, can carry out so that react.
When using dibasic alcohol or trivalent alcohol, (OH) reactive behavior with NCO is low, preferably keeps reaction and carries out about 24 hours or longer owing to hydroxyl.On the other hand, when using diamines, because the high reaction activity between amine and the isocyanide group, reacting completely approximately needs 1 hour.The target selection chain extension agent that can use according to the finished product.
By accurately controlling the NCO group remaining in the prepolymer and the mol ratio of chain extension agent, determine the final molecular weight of resin.The molecular weight of urethane resin of the present invention is in 30,000 to 100,000 scope.It is poor that molecular weight is lower than the chemical resistance of 30,000 urethane resin, and molecular weight is higher than 100,000 urethane resin in coating after drying excessive velocities and therefore make the coating workability not good.Therefore, by means of chain extension agent, obtained molecular weight 30,000-100 is in 000 the scope and have an aqueous solution of the urethane resin of high resistance to chemicals corrodibility and film coating.
Though the polyurethane resin solution that is obtained by step (1) has good chemical resistance, when it is in alkaline condition, for example skimming processes condition following time, still may have problems.Usually, because alkalescence than the more fragile resin of acidity, therefore finds that the resin of trace is decomposed.For improving the chemical resistance and the surface physical properties of film, used a kind of aziridine type or end-blocking isocyanide type solidifying agent, based on total resin solid content, the usage quantity of solidifying agent is 3-15 weight %.For example, if the amount of solidifying agent is lower than 3 weight %, then can not obtain needed alkali-proof improvement.On the other hand, if the amount of solidifying agent is higher than 15 weight %, the clagging of film, stability of solution, appearance suffer damage as gloss and workability.
In the aqueous polyurethane resin composition, add additive, for example a kind of lubricant, colloidal silica and coupling agent are used for the urethane resin that contains water lubricating of steel plate with preparation, but said composition is in no oil degree of depth machinability, reduce process defect, improve blackening and chemical resistance aspect excellent property.This preparation process is at room temperature carried out.
As for lubricant, it is the mixture of fluorine resin modified polyethylene type wax and polyethylene wax.When being used in combination, the improvement that fluorine resin modified polyethylene type wax and polyethylene wax compare the physicals of using every kind of material to make resin solution separately is bigger.But having added the degree of depth machinability of the resin solution that contains water lubricating of polyethylene wax and fluorine resin modified polyethylene type wax and alkali resistance and stability of solution is improved.
Conventionally, only be used as lubricant by the fluorine resin polytetrafluoroethylene (PTFE) type wax of stirring preparation and the mixture of polyethylene wax.Because the proportion of fluorine resin particle is on up to 1.6 magnitude, therefore conventional lubricant mixture has and can not be used for the homodisperse problem of low-viscosity aqueous resin system of film coating.When the aqueous resins system with routine was coated on the steel plate, fluorine-containing wax was in the position nearer apart from steel plate, and this causes oilness variation and resin adhesivity deficiency.
On the contrary, fluorine resin modified polyethylene type wax has the proportion of 0.98-1.02, wherein the combination of the particle of the particle of fluorine resin type wax and polyethylene wax is that meticulous fluorine resin type wax particle is modified, surround the polyethylene wax particle with tangible linkage force, thereby improved the oilness and the physicals of the polyurethane resin composition that contains water lubricating.
With reference to Fig. 1, show the structure of the film on the electroplating steel plate that is coated on chromating.In fluorine resin modified polyethylene type wax, diameter is that the fluorine resin type wax particle of 0.1-1.5 μ m surrounds and is combined on the low spherical ethylene type wax particle of proportion.Therefore, the proportion of fluorine resin modified polyethylene type wax is very low, even cause it still to have enough flotabilities on wet film.In addition, fluorine resin modified polyethylene type wax has been given full play to the performance characteristic of utilizing its ball effect to fluorine resin.Therefore, because the effect of fluorine resin modified polyethylene type wax, even after carrying out degree of depth mechanical workout, steel plate still can be kept its cleaning surfaces.About with the consistency of aqueous solution, the molecular weight of preferably polyethylene type wax is 1,500-3, between 000, diameter is between 0.05-1.0 μ m.
Different with the fluorine modified polyethylene type wax on the upper strata that mainly is distributed in film shown in Figure 1, since the adhesive resin of polyethylene wax and lubricated resin solution has good consistency and in adhesive resin good dispersibility, polyethylene wax is evenly dispersed in the resin molding.Therefore, polyethylene wax has guaranteed the uniform workability of steel plate.In addition, even mold temperature improves, its high-melting-point (120-130 ℃) also can be kept the existence of wax, and steel plate can be processed continuously.
Preferably in wax mixture, the weight ratio of fluorine resin modified polyethylene type wax and polyethylene wax is in 1: 0.3 to 1: 0.7 scope.Based on fluorine resin modified polyethylene type wax, if the weight ratio of polyethylene wax is lower than 0.3, then can not fully show the effect of polyethylene wax, cause continuous workability deteriorates.On the other hand,, then mainly show the physicals of polyethylene wax if weight ratio is higher than 0.7, but and degree of depth machinability variation.
Based on the weight of resin solid content, the amount of the wax mixture of adding is 5-30 weight % and preferred 10-15 weight %.For example, if the amount of the wax mixture that adds is lower than 5 weight %, the surface friction performance of resin solution obtains improvement to a certain degree, but but degree of depth machinability variation.On the other hand,, but do not observe the further improvement of degree of depth machinability if the amount of the wax mixture that adds is higher than 30 weight %, and resin solution generation physicals, comprise the problem that recoatability and solidity to corrosion reduce.
For improving corrosion proof purpose,, use the colloidal silica of 10-30 weight % based on the weight of resin solid content.The colloidal silica that is lower than 10 weight % can not bring the abundant effect of solidity to corrosion aspect.On the other hand, if the amount of colloidal silica is higher than 30 weight %, but the big silicon-dioxide of hardness will produce negative influence and cause clumsy blackening phenomena at process zone degree of depth machinability.
Usefully contain the silane coupling agent of epoxy, amine and/or acryloyl group among the present invention and contain the titanium coupling agent of amine groups.Coupling agent has the raising film toughness, thereby improves the function of the workability of gloss and steel plate, also has the silicon-dioxide of making homodisperse in film, thereby improves corrosion proof function.Based on the weight of resin solid content, the usage quantity of coupling agent is 0.1-0.5 weight %.
Can practical application will be considered and the lubricated polyurethane resin composition for preparing is used as functional coating resin solution for different purposes.Can use the solid content of the polyurethane resin composition of pure water sight-feed lubricator.For film coating, use pure water that lubricated polyurethane resin composition is diluted to solid content and be 10-30 weight %.If solid content not in 10-30 weight % scope, then can not obtain film coating with lubricated polyurethane resin composition easily.
So the aqueous polyurethane resin composition that obtains can be coated on the steel plate with the thickness that is as thin as 0.5-5.0 μ m, said composition also have good film coated, solidity to corrosion, film snappiness, adhesivity, surface friction performance, chemical resistance and recoatability to steel plate and be used in the consistency of steel plate usually with the different additive in the conventional coated material.
An example can using the polyurethane resin composition that contains water lubricating is that a chromium deposition amount is 4-200mg/m
2The steel plate galvanized of chromating, but the feature of resin combination wherein is no oil degree of depth mechanical workout, reduces process defect, blackening improvement and resistance to chemical attack.If the chromium deposition amount is lower than 4mg/m
2, the solidity to corrosion of steel plate is poor.On the other hand, surpass 200mg/m when the chromium deposition amount
2The time, solidity to corrosion is good, but causes the clagging variation.
Can use common coating process, the polyurethane resin composition that will contain water lubricating as roller painting or spraying method is coated on the galvanized steel plate.The polyurethane resin composition that preferably contains water lubricating with the thickness coating of 0.5-5 μ m after the drying.For example, when film thickness was lower than 0.5 μ m, it can not provide film lubrication and the workability level that needs.On the other hand, if build is higher than 5 μ m, can not obtain the extra improvement of workability.In addition, thick coating is easier sticking on the mould when degree of depth mechanical workout, increases the burden of the course of processing.
The heat that is provided in the bake process solidifies lubricated resin of the present invention.In this, when measuring steel billet temperature, storing temperature is determined in 110-200 ℃ scope.The resin that is lower than in temperature on 110 ℃ the steel plate can not fully solidify, and causes its chemical resistance to suffer damage.And coating may keep moist state.On the other hand, 200 ℃ or higher temperature, steel plate generation physical deformation.After the baking, in water with steel plate quenching.
The present invention may be better understood with reference to the following example, and the following example is used to explain the present invention, should not be interpreted as limiting the present invention.Embodiment
Embodiment 1
The preparation of polyurethane resin composition
In embodiment 1-1 to 1-6 and comparative example 1-1 to 1-12, repeat the following step, with the preparation polyurethane resin composition, difference is that the usage quantity of every kind of composition is as shown in table 1.
It below is description to the cited polyurethane resin composition preparation of embodiment 1-5.
In a reactor, under nitrogen atmosphere, stirring condition, making 120 gram molecular weights is 2,000 the polyvalent alcohol that is purchased poly-hexanodioic acid fourth two ester groups, the '-diphenylmethane diisocyanate that 40 gram weight ratio is 2: 1: the mixtures of diisocyanates of isophorone diisocyanate, 8 gram acid dimethyls and 6 gram triethylamines one reacted 5 hours, and acquisition NCO content is 3% prepolymer.
Employed '-diphenylmethane diisocyanate, isophorone diisocyanate, acid dimethyl and triethylamine are one-level reagent.Initial period in the prepolymer polyreaction adds 3 gram triethylamines, and remaining 3 grams add at termination phase.
After this, when the temperature of keeping reactor is 35 ℃, in reactant, adds 12 gram N-Methyl pyrrolidone and, add 284 gram distilled water during this period to disperse prepolymer by the mixing that stirs.
When holding temperature is 25 ℃, in the reactant of water-dispersion, slowly add 8 grams as 1 of chain extension agent, the 4-butyleneglycol also left standstill 24 hours, obtain a kind of aqueous polyurethane resin solution, the adding weight ratio is respectively 7% and 0.2% aziridine type solidifying agent and γ-glycidoxypropyltrime,hoxysilane in this solution.
1,4-butyleneglycol and γ-glycidoxypropyltrime,hoxysilane are one-level reagent.The CX-100 that use is made by Zneca is as aziridine type solidifying agent.
After using pure water to be diluted to final solid content to be 20 weight %, by means of coating analog machine (coating simulator) (scraping strip coating machine) #3, thickness with 1.5 μ m will be coated on the steel plate galvanized of chromating according to the aqueous polyurethane resin composition that following table 1 cited condition prepares, the thick 0.8mm of steel plate, its zinc deposition is 20g/m
2, the chromic salt deposition is 50mg/m
2In a self-emptying stove, under 160 ℃ temperature, toast steel plate then and use water quenching, on steel plate, form film.
For comparing, the steel plate galvanized that will be coated on chromating respectively from three types the aqueous film coating resin that Korea S POSCO buys forms film, and the thickness of every block plate is 0.8mm, and its zinc deposition is 20g/m
2, the chromic salt deposition is 50mg/m
2In comparative example 1-13, use epoxy acrylate, in comparative example 1-14, use polyether-modified urethane resin, in comparative example 1-15, use acetate acrylic resin.The solid content of every kind of comparative resin is 20 weight %.
The physicals of the film that test forms on steel plate under following condition.
＜solidity to corrosion 〉
In salt solution spraying tester, estimate solidity to corrosion according to JIS Z 2731 with initial white corrosion (whitecorrosion) time of origin.
Solidity to corrosion is estimated (time) ◎ (excellent): 120 hours or longer, and zero (good): 85-100 hour △ (bad): 70-85 hour, * (poor): be lower than 70 hours
＜chemical resistance 〉
1. solvent resistance
The gauze that use is soaked in methyl ethyl ketone (MEK) is the wiping coatingsurface 20 times and the dissolving of filming by the bore hole evaluation repeatedly.
2. alkali resistance
Make under the employed conventional degreasing condition in field at household electrical appliance, steel plate sample to coating sprays degreasing and dipping degreasing, every kind of situation all uses the aqueous alkaline skim soln 60 ℃ of following degreasings 150 seconds, the washing secondary is also air-dry, measures the aberration (Δ E) of degreasing front and back then by color difference meter.Estimate according to following standard:
Alkali resistance is estimated (Δ E) ◎ (excellent): 0.5 or lower, zero (good): 1.0 △ (bad): 1.1-2.0, * (poor): 2.0 or higher
＜frictional coefficient 〉
After using the low viscosity lubricant applying, by one-sided friction testing instrument (one-sidedfriction tester), at 0.27kg/cm
2Under pressure, the no deep-fried twisted dough sticks spare, with the frictional coefficient of 1 meter/minute drawing speed measure sample.Estimate according to following standard:
Frictional coefficient is estimated (μ) ◎ (excellent): 0.12 or littler, zero (good): 0.075-0.085 △ (bad): 0.085-0.095, * (poor): 0.15 or bigger
＜workability 〉
After using the low viscosity lubricant applying, in a thin plate molding test machine, sample is carried out 5 secondary cup moldings (cup molding), change drawing ratio (DR) simultaneously.At least successfully to carry out the maximum drawing ratio numerical Evaluation workability of 3 secondary cup moldings.◎ (excellent): DR 1.95 or bigger, zero (good): DR 1.90-1.95 △ (bad): DR 1.90-1.80, * (poor): DR 1.80 or littler
＜membrane property 〉
For the urethane resin of measuring table 1 coating adhesive power to steel plate, a kind of heat cured trimeric cyanamide paint spay-coating is being coated with on the steel plate of resin, obtaining dry back thickness is the film of 25 μ m, then 150 ℃ of cured film.After carrying out following processing, the characteristic of evaluated for film:
A. initial adherence power: after the curing, film was at room temperature left standstill 24 hours, at 1mm
With carry out the crosscut test under the condition of 100 scales (1mm and 100 scales).
B. water-fast adhesive power: in boiling water, soak after 30 minutes, the solidified sample is carried out horizontal stroke
Cut test.
C.6mm dust is made every effort to overcome the adhesive power after the gloomy processing (Erichsen Processing): at 1mm
After crosscut under the condition of 100 scales, the solidified sample is carried out the 6mm dust make every effort to overcome
Gloomy processing.
D. impact resistance: make the height of heavy 1 kilogram ball-type pendulum from 50 centimetres in distance sample
Drop down onto on the sample of solidified crosscut, then, adhesive tape is sticked to the sample dorsal part also
Remove to estimate the coating adhesive power.
Membrane property is estimated
◎ (excellent): no scale, zero (good): 1-2 scale
△ (bad): 3-5 scale, * (poor): 6 or more scales
Table 1
| The embodiment numbering | Resin combination | Performance | Remarks | |||||||||||||
| Polyvalent alcohol Mw | Polyvalent alcohol content (part) | Hydrophilic segment (part) | Vulcabond NCO (part) | ??NC ??O％ | Solidifying agent (weight %) | Solidity to corrosion | ???????? (2)Film | Chemical resistance | Workability | Frictional coefficient | ||||||
| ??a | ???b | ???c | ??d | |||||||||||||
| The embodiment of the invention | ???1-1 | ???500 | ????150 | ????15 | ????40 | ???8 | ????15 a | ??○ | ?◎ | ?◎ | ??○ | ?○ | ???◎ | ??○ | ??○ | |
| ???1-2 | ???700 | ????100 | ????12 | ????30 | ???6 | ????13 a | ??◎ | ?◎ | ?◎ | ??◎ | ?◎ | ???◎ | ??◎ | ??◎ | ||
| ???1-3 | ???1000 | ????130 | ????10 | ????50 | ???2 | ????10 a | ??◎ | ?◎ | ?◎ | ??◎ | ?◎ | ???◎ | ??◎ | ??◎ | ||
| ???1-4 | ???1000 | ????130 | ????10 | ????45 | ???3 | ????10 a | ??◎ | ?◎ | ?◎ | ??◎ | ?◎ | ???◎ | ??◎ | ??◎ | ||
| ???1-5 | ???2000 | ????120 | ????8 | ????40 | ???3 | ????7 b | ??◎ | ?◎ | ?◎ | ??◎ | ?◎ | ???◎ | ??◎ | ??◎ | ||
| ???1-6 | ???3000 | ????120 | ????5 | ????35 | ???4 | ????3 b | ??○ | ?◎ | ?◎ | ??○ | ?○ | ???○ | ??○ | ??◎ | ||
| The comparative example | ???1-1 | ???400 | ????150 | ????15 | ????50 | ???8 | ????15 a | ??△ | ?◎ | ?○ | ??○ | ?△ | ???△ | ??× | ??△ | |
| ???1-2 | ???3500 | ????110 | ????10 | ????30 | ???2 | ????5 a | ??△ | ?○ | ?○ | ??△ | ?△ | ???○ | ??△ | ??△ | ||
| ???1-3 | ???1500 | ????50 | ????8 | ????30 | ???5 | ????10 a | ??○ | ?◎ | ?○ | ??○ | ?○ | ???○ | ??× | ??○ | ||
| ???1-4 | ???1500 | ????160 | ????10 | ????35 | ???3 | ????7 b | ??○ | ?◎ | ?○ | ??△ | ?△ | ???○ | ??× | ??× | ||
| ???1-5 | ???1000 | ????130 | ????3 | ????30 | ???6 | ????7 a | ??- | ?- | ??- | ???- | ??- | ????- | ??- | ???- | Can not make aqueous resins | |
| ???1-6 | ???2000 | ????120 | ????17 | ????40 | ???3 | ????10 a | ??× | ?○ | ?× | ??△ | ?× | ???× | ??△ | ??○ | ||
| ???1-7 | ???1000 | ????140 | ????13 | ????25 | ???3 | ????10 a | ??○ | ?◎ | ?○ | ??△ | ?× | ???◎ | ??× | ??△ | ||
| ???1-8 | ???1000 | ????140 | ????13 | ????55 | ???3 | ????10 a | ??△ | ?◎ | ?△ | ??△ | ?△ | ???× | ??△ | ??○ | Yellow | |
| ???1-9 | ???2000 | ????120 | ????10 | ????30 | ???1 | ????5 a | ??◎ | ?○ | ?○ | ??△ | ?× | ???○ | ??× | ??○ | Solvent stability is not good | |
| ???1-10 | ???2000 | ????120 | ????10 | ????30 | ???9 | ????5 a | ??○ | ?◎ | ?◎ | ??◎ | ?◎ | ???△ | ??× | ??× | Viscosity is excessive | |
| ???1-11 | ???3000 | ????110 | ????5 | ????35 | ???4 | ????2 a | ??○ | ?◎ | ?◎ | ??○ | ?○ | ???× | ??○ | ??◎ | ||
| ???1-12 | ??3000 | ????110 | ????5 | ????35 | ???4 | ????17 a | ??◎ | ?◎ | ?○ | ??△ | ?× | ???◎ | ??○ | ??◎ | Solvent stability is not good | |
| ???1-13 | Epoxy acrylate | ??◎ | ?◎ | ?◎ | ??○ | ?○ | ???△ | ??△ | ??○ | |||||||
| ???1-14 | Polyether-modified urethane resin | ??△ | ?◎ | ?◎ | ??◎ | ?◎ | ???△ | ??△ | ??△ | |||||||
| ???1-15 | Ethylene-acrylate | ??○ | ?◎ | ?◎ | ??◎ | ?◎ | ???◎ | ??△ | ??△ | |||||||
Note
1Part or % refer to weight part or the weight % based on the gross weight of the solid content of the finished product
Note
2A: end-blocking isocyanide type solidifying agent, b: aziridine type solidifying agent
Note
3A) initial adherence power, b) water-fast adhesive power, c) the 6mm dust is made every effort to overcome the adhesive power after the gloomy processing, d) shock-resistance.
The result of table 1 is described below: embodiment 1-1 to 1-6
In the steel plate sample that has been coated with the aqueous polyurethane resin composition for preparing according to condition of the present invention, measure good physicals.
Comparative example 1-1 and 1-2
When the molecular weight of employed polyvalent alcohol in the polyreaction at prepolymer is lower than condition and range of the present invention, cause workability and chemical resistance to reduce.If molecular weight surpasses condition and range of the present invention, the snappiness of film is excessive, is not suitable for using in the coating of steel plate.Comparative example 1-3 and 1-4
When the content of polyvalent alcohol was lower than the scope of the present invention's suggestion, the hardness of film was very big, and film peels off in the process of processing steel plate to cause.When polyester polyol content was higher than condition and range, the snappiness of film was excessive, is out of shape in the course of processing.Therefore, the content of the polyvalent alcohol scope that exceeds suggestion will be damaged workability.Comparative example 1-5 and 1-6
If the content of hydrophilic segment is lower than the lower limit of suggested range of the present invention, prepolymer can not fully disperse in water, causes to obtain needed aquifer coating solution.The upper limit that hydrophilic segment content is higher than this scope will be damaged the general property of film, comprise solidity to corrosion, chemical resistance and clagging.Comparative example 1-7 and 1-8
When the content of vulcabond be lower than condition and range of the present invention following in limited time, film lacks snappiness, this causes workability, aftertreatment adhesivity and suffers damage with the represented clagging of shock-resistance, and the content of vulcabond is higher than the upper limit of this condition and will causes yellow and chemical resistance to reduce.Comparative example 1-9 and 1-10
When the prepolymer polymerization, if the theoretical content of terminal NCO residue is lower than the lower limit of condition and range of the present invention, the bad stability of solution not only, and make workability and suffer damage with the represented clagging of shock-resistance.If the theoretical content of terminal NCO exceeds this condition and range, the film too thickness that becomes, and can not handle steel plate.Also cause bad chemical resistance.Comparative example 1-11 and 1-12
If the amount of solidifying agent is lower than the lower limit of condition and range of the present invention, can not obtain needed chemical resistance, particularly alkali-proof improvement.If the amount of solidifying agent is higher than the upper limit of this condition and range, the clagging of film, stability of solution, appearance suffer damage as gloss and workability.Comparative example 1-13 and 1-15
Chemical resistance, workability and the frictional behaviour of conventional resin are not good.
Embodiment 2
Contain the preparation of the polyurethane resin composition of water lubricating
Add fluorine resin modified polyethylene wax in the polyurethane resin solution for preparing in embodiment 1-5: polyethylene wax is 1: 1 a mixture, the amount that adds is as shown in table 2 below, contain the polyurethane resin composition of water lubricating with preparation, the solid content of each embodiment is 20 weight %.As silica, using solid content is the Snowtex-n (Nissin chemical company, Japan) of 20 weight %.
Then, as embodiment 1, lubricated polyurethane resin composition is coated on the steel plate of chromating and measures its physicals.
＜solidity to corrosion 〉
In salt solution spraying tester, estimate solidity to corrosion according to JIS Z 2731 with initial white corrosion time of origin.
Solidity to corrosion is estimated (time) ◎ (excellent): 350 hours or longer, and zero (good): 300-350 hour △ (bad): 250-300 hour, * (poor): be lower than 250 hours
＜chemical resistance 〉
1. solvent resistance
The gauze that use is soaked in methyl ethyl ketone is the wiping coatingsurface 20 times and the dissolving of filming by the bore hole evaluation repeatedly.
2. alkali resistance
Make under the employed conventional degreasing condition in field at household electrical appliance, steel plate sample to coating sprays degreasing and dipping degreasing, every kind of situation all uses the aqueous alkaline skim soln to carry out under 60 ℃ 150 seconds, the washing secondary is also air-dry, measures the aberration (Δ E) of degreasing front and back then by color difference meter.Estimate according to following standard:
Alkali resistance is estimated (Δ E) ◎ (excellent): 0.5 or lower, zero (good): 0.6-0.8 △ (bad): 0.9-1.5, * (poor): 1.5 or higher
＜frictional coefficient 〉
After using the low viscosity lubricant applying, by one-sided frictiograph, at 0.27kg/cm
2Under pressure, the no deep-fried twisted dough sticks spare, with the frictional coefficient of 1 meter/minute drawing speed measure sample.Estimate according to following standard:
Frictional coefficient is estimated (μ) ◎ (excellent): 0.075 or littler, zero (good): 0.075-0.085 △ (bad): 0.085-0.095, * (poor): 0.095 or bigger
But＜degree of depth machinability 〉
In blank holding power is 30 tons, punching speed is 230 mm/min, under the condition of non-refuelling steel plate is carried out plane strain Elongation test (plain strain stretch testing) (PSST), measuring limit spring of arch (limit dome height) (LDH) then.Before applying lubricated resin, when introducing steel plate with low viscous lubricant, the LDH value that measures is 32-35mm.
But degree of depth machinability (mm) ◎ (excellent): 45 or bigger, zero (good): 42-45, △ (bad): 38-42, * (poor): 38 or littler
The outward appearance on＜the surface that processed 〉
On the surface of determining to have processed whether after the stretch bending test of blackening, measure aberration (Δ E) before and after the processing by color difference meter.Estimate according to following standard:
The outward appearance ◎ on the surface that has processed (excellent): 0.5 or littler, zero (good): 0.5-2.0, △ (bad): 2.0-4.0, * (poor): 4.0 or bigger.
Table 2
| The embodiment numbering | Composition (weight %) | Performance | Remarks | ||||||
| Lubricant | Silica | Solidity to corrosion | Chemical resistance | Frictional coefficient | But degree of depth machinability | Outward appearance | |||
| The embodiment of the invention | ?2-1 | ????5 | ????10 | ????○ | ????○ | ??○ | ????○ | ?○ | |
| ?2-2 | ????5 | ????20 | ????◎ | ????○ | ??○ | ????○ | ?○ | ||
| ?2-3 | ????10 | ????10 | ????○ | ????◎ | ??◎ | ????○ | ?◎ | ||
| ?2-4 | ????10 | ????15 | ????○ | ????◎ | ??◎ | ????◎ | ?○ | ||
| ?2-5 | ????15 | ????20 | ????◎ | ????◎ | ??◎ | ????◎ | ?◎ | ||
| ?2-6 | ????20 | ????20 | ????◎ | ????○ | ??◎ | ????◎ | ?◎ | ||
| ?2-7 | ????20 | ????30 | ????◎ | ????◎ | ??◎ | ????◎ | ?◎ | ||
| ?2-8 | ????25 | ????30 | ????◎ | ????◎ | ??◎ | ????◎ | ?○ | ||
| ?2-9 | ????30 | ????35 | ????◎ | ????◎ | ??◎ | ????◎ | ?○ | ||
| The comparative example | ?2-1 | ????3 | ????15 | ????○ | ????△ | ??× | ????× | ?× | |
| ?2-2 | ????32 | ????20 | ????△ | ????○ | ??◎ | ????◎ | ?◎ | ||
| ?2-3 | ????35 | ????20 | ????△ | ????△ | ??◎ | ????◎ | ?◎ | ||
| ?2-4 | ????20 | ????5 | ????△ | ????◎ | ??◎ | ????◎ | ?◎ | ||
| ?2-5 | ????20 | ????40 | ????◎ | ????◎ | ??△ | ????× | ?× | Scratch | |
As shown in table 2, be good with the physicals of all tests of the steel plate of lubricated resin solution coating prepared in accordance with the present invention.On the contrary, when lubricated resin solution contains when being lower than lubricant content as suggested in the present invention, the workability of steel plate is bad usually.When lubricated resin solution contains when being higher than lubricant content as suggested in the present invention, not only workability does not improve, and the solidity to corrosion of steel plate is variation also.Silica content is lower than needed scope suffers damage solidity to corrosion, and because silica has high rigidity, higher silica content will make steel plate add the blackening in man-hour and scratch occur.At latter event, but steel plate also shows bad degree of depth machinability.
Embodiment 3
In the present embodiment, measure of the influence of the weight ratio of polyethylene wax and fluorine resin modified polyethylene wax to the physicals of steel plate.
The polyurethane resin solution that contains water lubricating by preparation shown in the table 3.Employed polyethylene wax is bought from the Daedong of Korea S, is called PS-35, and its solid content is 26 weight %.The solid content of fluorine modified polyethylene wax is 25 weight %, for being purchased product.Every kind of resin solution that contains water lubricating all is used in the prepared resin combination of embodiment 5-2.As described in embodiment 2, but the degree of depth machinability and the aftertreatment outward appearance of the polyurethane resin composition that contains water lubricating that test so obtains.
Table 3
| The embodiment numbering | The weight ratio of PE wax * | Performance | Remarks | ||
| But degree of depth machinability | The aftertreatment outward appearance | ||||
| The comparative example | ??3-1 | ????0 | ????△ | ????○ | |
| ??3-2 | ????0.1 | ????△ | ????○ | ||
| ??3-3 | ????0.2 | ????△ | ????○ | ||
| The embodiment of the invention | ??3-1 | ????0.3 | ????○ | ????◎ | |
| ??3-2 | ????0.4 | ????○ | ????◎ | ||
| ??3-3 | ????0.5 | ????◎ | ????◎ | ||
| ??3-4 | ????0.6 | ????◎ | ????◎ | ||
| ??3-5 | ????0.7 | ????○ | ????○ | ||
| The comparative example | ??3-4 | ????0.8 | ????△ | ????△ | Solvent stability is not good |
*The weight ratio of polyethylene wax and fluorine resin modified polyethylene wax
As shown in table 3, but weight ratio fluorine resin modified polyethylene wax and the mixture of the polyethylene wax degree of depth machinability and the aftertreatment outward appearance that have improved steel plate within the scope of the invention.The content of polyethylene wax is lower than scope as suggested in the present invention and can not makes needed contribution to the machinability of steel plate in fluorine resin modified polyethylene wax itself or the wax mixture.Content at polyethylene wax is higher than under the situation of the scope of being advised, can not embody the effect owing to fluorine resin modified polyethylene wax.
As described above, the polyurethane resin composition that contains water lubricating that is used for film coating according to the present invention's preparation has many-sided good physicals, comprise solidity to corrosion, clagging, chemical resistance, workability and surface friction performance, and said composition is suitable as the adhesive resin that is used to be coated with functional steel plate.When the lubricated coating solution that contains aqueous polyurethane resin as thin film coated on steel plate the time, this solution can significantly improve solidity to corrosion, chemical resistance deep processing, aftertreatment outward appearance and the surface friction performance of steel plate, and can make steel plate be processed to product under the condition of not having oil.This no deep-fried twisted dough sticks spare causes saving skimming treatment, therefore economically with all be favourable on the environment.
Above described the present invention in illustrative mode, should be understood that, employed term is intended to be used for describe and unrestricted.Might improve and change the present invention according to above-mentioned instruction.Therefore, should be understood that, within the scope of the appended claims, can implement the present invention in the mode that is different from special description.
Claims (12)
1. one kind prepares the aqueous polyurethane resin method for compositions, and described method comprises the following steps:
(1) prepare a kind of aqueous polyurethane resin solution through the following steps:
(a) make 100-150 weight part polyester polyol, 30-50 weight part two isocyanic acids
Ester, 5-15 weight part neopentanoic acid or acid dimethyl and 3-10 portions of amine by weight exist
55-85 ℃ was reacted 5-6 hour down, obtains a kind of NCO free-radical contents at the 2-8% model
Prepolymer in enclosing, described neopentanoic acid or acid dimethyl are as water-dispersion
Hydrophilic segment;
(b) prepolymer is dispersed in the water under 30-40 ℃; With
(c) under 25-30 ℃, in the prepolymer of water-dispersion, add a kind of chain extension agent,
This chain extension agent is selected from the group of being made up of dibasic alcohol, trivalent alcohol and diamines, the mode of adding
For the reaction mol ratio of controlling described chain extension agent and NCO residue to obtain molecular weight is
30,000-100,000 final product;
(2) add end-blocking isocyanide type or aziridine type solidifying agent in described aqueous polyurethane resin solution, the amount that is added is the 3-15 weight % of resin solid content.
2. method that is used to prepare the polyurethane resin composition that contains water lubricating, described method comprises the following steps:
(1) prepare a kind of aqueous polyurethane resin solution through the following steps:
(a) make 100-150 weight part polyester polyol, 30-50 weight part two isocyanic acids
Ester, 5-15 weight part neopentanoic acid or acid dimethyl and 3-10 portions of amine by weight exist
55-85 ℃ was reacted 5-6 hour down, obtains a kind of NCO free-radical contents at the 2-8% model
Prepolymer in enclosing, described neopentanoic acid or acid dimethyl are as water-dispersion
Hydrophilic segment;
(b) prepolymer is dispersed in the water under 30-40 ℃; With
(c) under 25-30 ℃, in the prepolymer of water-dispersion, add a kind of chain extension agent,
This chain extension agent is selected from the group of being made up of dibasic alcohol, trivalent alcohol and diamines, the mode of adding
For the reaction mol ratio of controlling described chain extension agent and NCO residue to obtain molecular weight is
30,000-100,000 final product;
(2) add end-blocking isocyanide type or aziridine type solidifying agent in described aqueous polyurethane resin solution, the amount that is added is the 3-15 weight % of resin solid content;
(3) additional proportion is 1 in resin solution: 0.3-1: 0.7 the fluorine resin modified polyethylene wax and the mixture of polyethylene wax, the amount that is added is the 5-30 weight % of resin solid content, the proportion of described fluorine resin modified polyethylene wax is in the 0.98-1.02 scope, size of particles is at the 0.1-1.5 mu m range, the molecular weight of described polyethylene wax is 1,500-3,000 scope, size of particles is at the 0.05-1.0 mu m range;
(4) add a kind of colloidal silica in the resin solution that step (3) is obtained, the amount that is added is the 10-30 weight % of resin solid content;
(5) in the resin solution that step (4) is obtained, add a kind of coupling agent, described coupling agent is selected from by the silane coupling agent that contains epoxy group(ing), amido and/or acryl and contains phosphorus and/or group that the titanium coupling agent of amido is formed, and the amount that is added is the 0.1-0.5 weight % of resin solid content gross weight; With
(6) with pure water resin solution being diluted to final resin solid content is 10-30 weight %.
3. claim 1 or 2 described methods, wherein based on the weight of prepolymer reactant, the usage quantity of described polyester polyol is the 120-130 weight part.
4. claim 1 or 2 described methods, wherein based on the weight of prepolymer reactant, the usage quantity of described vulcabond is the 35-40 weight part.
5. claim 1 or 2 described methods, wherein based on the weight of prepolymer reactant, the usage quantity of the hydrophilic segment of described water-dispersion is the 8-10 weight part.
6. the described method of claim 2, wherein based on the weight of prepolymer reactant, the usage quantity of described wax mixture is the 10-15 weight part.
7. claim 1 or 2 described methods before it also is included in dispersion steps, add based on the acetone of 10 weight % of prepolymer reactant weight and/or the step of N-Methyl pyrrolidone solvent.
8. claim 1 or 2 described methods, wherein said polyvalent alcohol is that molecular weight is 500-3, the polyester polyol of 000 poly-hexanodioic acid fourth two ester groups.
9. claim 1 or 2 described methods, wherein said vulcabond is selected from the group of being made up of '-diphenylmethane diisocyanate, isophorone diisocyanate and tolylene diisocyanate.
10. claim 1 or 2 described methods, wherein said amine is triethylamine.
11. claim 1 or 2 described methods, wherein said chain extension agent is selected from by dibasic alcohol, for example ethylene glycol, 1,4-butyleneglycol and 1,6-hexylene glycol, diamines, for example quadrol and isophorone diamine, trivalent alcohol, for example group formed of TriMethylolPropane(TMP) and composition thereof.
12. a method of handling the electroplating steel plate surface of chromating, it comprises the following steps: a kind of with 4-200mg/m
2Contain the urethane resin of water lubricating on the steel plate galvanized of chromium amount chromating with the dry coating thickness coating of 0.5-5.0 μ m, under 110-200 ℃ steel temperature, toast steel plate, and in water, make steel plate quenching.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/KR2000/000657 WO2001098392A1 (en) | 2000-06-22 | 2000-06-22 | Preparation of aqueous urethane resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1370189A true CN1370189A (en) | 2002-09-18 |
| CN1146617C CN1146617C (en) | 2004-04-21 |
Family
ID=19198233
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB008118663A Expired - Fee Related CN1146617C (en) | 2000-06-22 | 2000-06-22 | Prepn. of aqueous urethane resin compsn. |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP2004501252A (en) |
| CN (1) | CN1146617C (en) |
| WO (1) | WO2001098392A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100497506C (en) * | 2006-09-14 | 2009-06-10 | 华明扬 | Water-based polyurethane/epoxy copolymerized water-proof air-moisture-permeable antibacterial adhesive coating preparing method |
| CN101815735B (en) * | 2007-07-25 | 2012-10-17 | 氰特特种表面技术奥地利有限公司 | Self-crosslinking binders |
| CN104559717A (en) * | 2014-12-25 | 2015-04-29 | 澳达树熊涂料(惠州)有限公司 | Low-cost high-performance water-based two-component polyurethane coating and method for preparing same |
| CN108276762A (en) * | 2018-01-05 | 2018-07-13 | 武汉理工大学 | A kind of compound polyurethane material and preparation method for water lubriucated bearing |
| CN114645471A (en) * | 2022-03-04 | 2022-06-21 | 无锡市曼优丽新型复合材料有限公司 | Flame-retardant artificial leather and preparation method thereof |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002275656A (en) * | 2000-12-21 | 2002-09-25 | Furukawa Electric Co Ltd:The | Metal plate material for electric and electronic appliance and electric and electronic appliance using the same |
| KR100458984B1 (en) * | 2001-08-24 | 2004-12-03 | (주)나눅스 | Water dispersible polyurethane-colloidal silica nano composite materials and method for preparation thereof |
| JP4495543B2 (en) * | 2004-08-12 | 2010-07-07 | 日新製鋼株式会社 | Hot water soluble resin coated stainless steel sheet |
| CN100445332C (en) * | 2006-11-01 | 2008-12-24 | 淄博奥德美高分子材料有限公司 | Fluorine silicon modified aqueous polyurethane high polymer conductive emulsion |
| JP5344365B2 (en) * | 2008-08-26 | 2013-11-20 | 日本ポリウレタン工業株式会社 | Aqueous polyurethane dispersion and method for producing the same |
| CN102808148B (en) * | 2011-05-30 | 2016-03-30 | 比亚迪股份有限公司 | A kind of preparation method of touch screen surface anti-fingerprint film |
| JP5674605B2 (en) * | 2011-09-13 | 2015-02-25 | 日新製鋼株式会社 | Chemical conversion treated steel sheet and method for producing the same |
| JP5674606B2 (en) * | 2011-09-14 | 2015-02-25 | 日新製鋼株式会社 | Chemical conversion treated steel sheet and method for producing the same |
| CN103625034A (en) * | 2013-11-25 | 2014-03-12 | 江苏克罗德科技有限公司 | Self-lubricating high-corrosion-resistant aluminum-zinc coated steel plate and preparation method thereof |
| CN111944111B (en) * | 2019-04-30 | 2022-04-22 | 万华化学集团股份有限公司 | Aqueous self-extinction polyurethane dispersion, preparation method and composition thereof |
| CN112227083A (en) * | 2020-09-30 | 2021-01-15 | 京准化工技术(上海)有限公司 | Fabric water pressure resistance improver and preparation method thereof |
| KR102560656B1 (en) * | 2020-12-21 | 2023-07-26 | 주식회사 포스코 | Adhesive coating composition for electrical steel sheet, electrical steel sheet laminate, and method for manufacturing the electrical steel sheet product |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4301053A (en) * | 1980-01-29 | 1981-11-17 | General Electric Company | Polyurethane resin coating composition |
| JP2988958B2 (en) * | 1990-04-12 | 1999-12-13 | 三井化学株式会社 | Water-based polyurethane resin |
| DE4406159A1 (en) * | 1994-02-25 | 1995-08-31 | Bayer Ag | Aqueous polyester-polyurethane dispersions and their use in coating materials |
| DE19725297A1 (en) * | 1997-06-14 | 1998-12-17 | Basf Ag | Aqueous polyurethane dispersions made from polypropylene glycol with a low urea content |
| JPH11138096A (en) * | 1997-11-06 | 1999-05-25 | Nippon Steel Corp | Organic coated steel sheet for fuel tank |
-
2000
- 2000-06-22 WO PCT/KR2000/000657 patent/WO2001098392A1/en active Application Filing
- 2000-06-22 JP JP2002504346A patent/JP2004501252A/en active Pending
- 2000-06-22 CN CNB008118663A patent/CN1146617C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100497506C (en) * | 2006-09-14 | 2009-06-10 | 华明扬 | Water-based polyurethane/epoxy copolymerized water-proof air-moisture-permeable antibacterial adhesive coating preparing method |
| CN101815735B (en) * | 2007-07-25 | 2012-10-17 | 氰特特种表面技术奥地利有限公司 | Self-crosslinking binders |
| CN104559717A (en) * | 2014-12-25 | 2015-04-29 | 澳达树熊涂料(惠州)有限公司 | Low-cost high-performance water-based two-component polyurethane coating and method for preparing same |
| CN108276762A (en) * | 2018-01-05 | 2018-07-13 | 武汉理工大学 | A kind of compound polyurethane material and preparation method for water lubriucated bearing |
| CN114645471A (en) * | 2022-03-04 | 2022-06-21 | 无锡市曼优丽新型复合材料有限公司 | Flame-retardant artificial leather and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2001098392A1 (en) | 2001-12-27 |
| JP2004501252A (en) | 2004-01-15 |
| CN1146617C (en) | 2004-04-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1146617C (en) | Prepn. of aqueous urethane resin compsn. | |
| RU2404289C2 (en) | Coated steel plate | |
| CN1226359C (en) | Aqueous compositions and process for surface modification of articles by use of aqueous compositions | |
| CN1308647A (en) | Interpenetrating networks of polymers | |
| CN1172996C (en) | Water surface treatment agent for metal material and furface treated metal plate | |
| CN1743085A (en) | Surface treated metal board | |
| CN1345359A (en) | Coating composition capable of forming alkali-soluble lubricating film suitable for forming and use thereof | |
| JP4485377B2 (en) | Golf ball | |
| CN1718606A (en) | Water-based polyurethane emulsion, its mfg. method and use | |
| US7387821B2 (en) | Golf ball and process for preparing the same | |
| JP4303647B2 (en) | Golf ball | |
| JP4542024B2 (en) | Painted golf ball and manufacturing method thereof | |
| US6180714B1 (en) | Golf ball coating composition and coated golf ball | |
| CN1169885C (en) | Water-based metal surface treatment composition forming lubricating film with excellent maring resistance | |
| JP3969781B2 (en) | Aqueous urethane resin composition and aqueous metal surface treatment composition containing the same | |
| JP4163609B2 (en) | Surface-treated metal plate | |
| JP4533476B2 (en) | Fluorine resin-containing cationic electrodeposition coating and production method | |
| CN108699211B (en) | Polycarbonamide resins for metal coating applications | |
| CN114921168A (en) | Carbon-silicon nano material modified waterborne polyurethane emulsion, and synthesis method and application thereof | |
| CN113999586A (en) | Weather-resistant water-based polyurethane matte varnish | |
| KR101638794B1 (en) | Biomass-polymer polyurethane resin and method of manufacturing using the same | |
| KR19980052464A (en) | Preparation of aqueous lubricant resin solution and steel plate surface treatment method | |
| KR100262495B1 (en) | Polyurethane resin solution composition having good lubricating and workability and its uses for the preparation of surface treatment of steel plate | |
| JP4540595B2 (en) | Painted golf ball and manufacturing method thereof | |
| JP2000239690A (en) | Water-based metal surface treating composition for forming lubricating film excellent in scratch resistance |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20040421 |