CN1186189C - Resin coated metal plate with good machinability and thermal stability - Google Patents
Resin coated metal plate with good machinability and thermal stability Download PDFInfo
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- CN1186189C CN1186189C CNB011100931A CN01110093A CN1186189C CN 1186189 C CN1186189 C CN 1186189C CN B011100931 A CNB011100931 A CN B011100931A CN 01110093 A CN01110093 A CN 01110093A CN 1186189 C CN1186189 C CN 1186189C
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08L61/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08L61/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- 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
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
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- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
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- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
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Abstract
A resin-coated metal sheet with good workability and heat resistance wherein the resin coating layer comprises a matrix resin having in the molecule at least either active hydrogen or functional groups, an organic lubricant, and two crosslinking agents capable of reacting with the matrix resin. The first crosslinking agent reacts with the matrix resin to such an extent as to impart sufficient scratch resistance. In the final high-temperature short-time baking step, the second crosslinking agent remaining intact crosslinks the resin coating layer, making it compact and preventing it from getting soft. Thus it is possible to make workability and heat resistance compatible with each other.
Description
Technical field
The present invention relates to a kind of sheet metal and method for making thereof and method of lacquering, relate in particular to a kind of sheet metal, its manufacture method and method of lacquering with good workability and stable on heating coated with resins.
Background technology
The sheet metal, particularly steel plate galvanized that are used for household electric appliances, OA utensil and building aspect not only need to possess following characteristic, for example corrosion-resistant, but painting, anti-fingerprint, but with screen printing, and can have good workability, anti-scratch in the course of processing.The steel plate of coated with resins is in harmony can satisfy this demand.They are through chromate treating, to guarantee to carry out resin-coating with steel plate galvanized.
Resin coating is normally formed by the matrix organic resin of the band functional group that is mixed with linking agent.The crosslinked resin coating that makes is hard and closely knit.In the matrix organic resin but also add silicon-dioxide or suchlike material to improve its solidity to corrosion and scuff resistance.In coating too admixture organic lubricant (wax) to improve workability and slip.The softening temperature of lubricant is 80-140 ℃, decides with the temperature that adds the mould in man-hour.
But the coating of resin-coated steel plate (tack after application or the silk screen printing) difference, it does not improve with the increasing of functional group's number of linking agent reaction along with keeping in the resin coating.This is the cause that reacts to each other owing to the linking agent that contains in unreacted functional group in the resin coating and the later coating of brushing.As for the situation that contains organic lubricant (wax) in the resin coating, because wax contains functional group hardly, therefore but the more little then coating of content of wax is good more, satisfy workability (slip) but and the usual method of the conflicting requirement of coating be, the amount of linking agent in the control resin coating is so that make the quantity of the unreacted functional group that keeps in the matrix resin and the amount phase equilibrium of organic lubricant.
Simultaneously, after application or silk screen printing, cure 20-30 minute to obtain hard filming usually at 130-160 ℃.Yet, trended towards adopting higher stoving temperature (about 200 ℃) modern age and cured the time (1-5 minute) to raise the efficiency than short.The steel plate of consequently common resin-coating is heated to 200 ℃ or when above, if resin's crosslinkage is low, then can run into the problem of resin coating deliquescing.When wax deliquescing and fusing, the deliquescing of easier generation resin coating.After the resin coating deliquescing, make the film curing above it after outward appearance of poor quality, and reduce with the clinging power of steel plate, binding property wherein also reduces.A kind of resin coating like this in the performance test of strictness, will make paint film and it together peel off.Therefore, as present good performance and clinging power after desiring to make film curing above the resin coating, then resin coating must have better thermotolerance.
A kind of to improve stable on heating possibility method be the linking agent quantity that increase to add in the matrix resin, thereby make coating harder and tightr, and will make paint film at high temperature the amount of the organic lubricant that reduces of clinging power be reduced to minimum.Can realize workability deteriorates.Can be thereby the amount that increases linking agent makes that coating is highly cross-linked with improved heat resistance to a certain degree, the amount that keeps organic lubricant (wax) simultaneously is in a fixed level, so that keep good workability.Improve stable on heating this method and run into the shortcoming that balance linking agent quantity and lubricant quantity encounter difficulties.Moreover, there is this possibility, promptly do not contain enough unreacted functional groups in the resin coating, when curing at last and the reaction of the linking agent in the paint film.But this causes bad coating.In these cases, found to make workability (slip), but the method that coating and thermotolerance are taken into account mutually..
Summary of the invention
Of the present invention finishing is in view of the above, and it relates to resin-coating sheet metal, its production method and using method thereof.But this resin-coating sheet metal has as the equally good workability of resin-coating steel plate, erosion resistance coating and scratch resistance.It also has good thermotolerance, cures to paint film and silk screen die and finally solidifies thereby can carry out high temperature.Therefore, but this good thermotolerance causes good coating.
The present invention has following aspect:
The aspect has resin-coated sheet metal for 1. 1 kinds, and it has good workability and thermotolerance, it is characterized in that described resin coating includes:
A kind of matrix resin has at least in its molecule or reactive hydrogen or functional group;
0.5-20 a kind of organic lubricant of weight %;
A kind of first linking agent can react with described matrix resin;
A kind of second linking agent can react with described matrix resin; Wherein said second linking agent and described matrix resin begin the temperature of crosslinking reaction, begin the temperature height of crosslinking reaction than described first linking agent and described matrix resin; With
Described resin coating contains the reaction product of described matrix resin and described first linking agent, also contain 1-20 weight % untouched in fact moving, not with described second linking agent of described matrix resin reaction, and do not contain not untouched moving described first linking agent with the matrix resin reaction in fact;
Wherein, the amount of first and second linking agents must respectively be 1-20 weight % in the resin coating, and its total amount is not more than 30%, in solid.
Aspect 2. is had a resin-coated sheet metal as what aspect 1 limited, it is characterized in that described first linking agent 130 ℃ or the reaction of following beginning linking agent, and described second linking agent is 135 ℃ or above beginning crosslinking reaction.
Aspect 3. is had a resin-coated sheet metal as what aspect 1 limited, it is characterized in that described first linking agent is a kind of Resins, epoxy, and second linking agent is a kind of melamine resin.
Aspect 4. is had a resin-coated sheet metal as what aspect 1 limited, it is characterized in that described resin coating also contains the silicon-dioxide of 5-30 weight %.
The 5. 1 kinds of methods that are used to produce the sheet metal with good workability and stable on heating resin-coating in aspect is characterized in that described method comprises the following steps:
To form resin coating, described synthetics contains a kind of matrix resin, has at least in its molecule or reactive hydrogen or functional group with a kind of synthetics metallizing tree; 0.5-20 a kind of organic lubricant of weight %; With more than a kind of linking agent that can play crosslinking reaction with described matrix resin, wherein, the amount of various linking agents must respectively be 1-20 weight %, and its total amount is not more than 30%, in solid; With
The metal sheet that applies is heated and drying at a certain temperature, this temperature has the crosslinking reaction that minimum crosslinking reaction begins the temperature crosslink agent than a kind of in the described linking agent and begins the temperature height, but has crosslinking reaction that the highest crosslinking reaction begins the linking agent of temperature to begin temperature be low than another kind of in the described linking agent.
The method of the sheet metal of the production resin-coating that aspect 6. is limited as aspect 5 is characterized in that described heating and drying step are to carry out under 80-120 ℃ temperature.
The resin-coated sheet metal that has that each limited among the 7. couples of aspect 1-4 in aspect carries out the painted method, it is characterized in that described method comprises will be on the resin coating surface form paint film and heats this paint film, and its temperature is high enough to make and keeps untouched moving described linking agent to react in described matrix resin and the described resin coating.
The accompanying drawing summary
Fig. 1 is the diagram of DTA figure, and the initial residing temperature of crosslinking reaction is described.
Embodiment
Foregoing composition makes matrix resin carry out crosslinking reaction in two stages.In the fs, first linking agent makes crosslinking reaction proceed to a kind of like this degree, and promptly resin coating has enough scuff resistance energy in the stage afterwards.Subordinate phase (at high temperature the short period of time cures), in the fs, keep unreacted second kind of linking agent, be cross-linked to form resin coating closely with matrix resin, its anti-thermoplastic.Workability and thermotolerance are taken into account mutually.
For first kind of linking agent, the temperature of beginning crosslinking reaction preferably is necessary for 130 ℃ or be lower than this; For second kind of linking agent then be 135 ℃ or more than.The Resins, epoxy (as first linking agent) that low temperature is crosslinked and the combination of melamine resin (as second linking agent) suit.The initial crosslinking reaction temperature of these two kinds of linking agents is significantly different.
Aforesaid according to the sheet metal with good workability and stable on heating resin-coating of the present invention, described first linking agent is to occur with itself and the reacted form of described matrix resin, and second linking agent comes down to occur without the prototype that changes with it, and it does not react with described matrix resin.Aforementioned component can be understood with the following fact, and promptly two kinds of linking agents begin reaction with matrix resin under different temperature, or carries out this reaction process so that only first linking agent and matrix resin reaction.
The aforementioned component of resin-coating sheet metal is characterized in that resin coating before carrying out curing between high temperature, short time, wherein contains the reaction product of the matrix resin and first linking agent.Resin-coating sheet metal in the case also within the scope of the invention.Desirable situation is before curing between high temperature, short time, and first linking agent does not keep not the state of not being touched with the matrix resin reaction in fact.Resin coating ought add in this case and has good scratch man-hour.The situation of another hope be second linking agent before curing between high temperature, short time, still have the part of 1-20 weight %, keeping not intact state in fact with the matrix resin reaction.Resin coating can resist in the case effectively because first linking agent is curing softening that stage generation crosslinking reaction causes.
Above-mentioned resin coating can be chosen wantonly and contain silicon-dioxide.Above-mentioned organic lubricant preferred content in resin coating is 0.5-20 weight %.
The invention still further relates to foregoing production and have the method for good workability and stable on heating resin-coating sheet metal.Wherein, heating and drying step must carry out in the following manner, will guarantee matrix resin exactly and have between a kind of linking agent of the highest crosslinking reaction starting temperature crosslinking reaction does not take place in fact.Heating and the preferred temperature of exsiccant are 80-120 ℃.
Resin-coating metal sheet of the present invention also has other step, and the paint film that will form on the resin coating surface is heated to sufficiently high temperature, so that still keep staying intact linking agent reaction in matrix resin and the resin coating.This coating process also within the scope of the invention.
The sheet metal of resin-coating of the present invention is by metal sheet and scribble resin coating and form on its one side at least.Because resin coating is to be made of the crosslinked matrix resin of a kind of linking agent, is not bonded to piece when its form of coiling with heap is deposited.And because first cross-linking system makes resin coating have suitable hardness; Therefore and wherein contain a kind of organic lubricant, thereby give good solidity to corrosion and resistance to marring, be not easy to be scratched when adding man-hour (for example cutting, punching press and shaping) resin coating.In addition, owing to before curing, still contain the unreacted functional group of proper amt in the matrix resin, back when curing processing (curing 20-30 minute) under the usual conditions when painting in 130-160 ℃, but resin coating presents good coating.
In addition, when resin coating japanning (or silk screen printing) and in cure more usually for the short time when higher temperature is cured, it shows good thermotolerance, not deliquescing, and and the cohesiveness of metal sheet and paint film good.This is that it keeps not reacting before curing owing to contain second linking agent in the resin coating, and it begins to react when curing.Second cross-linking system also helps to make and cures paint film and have good surface appearance.To carry out in following about of the present invention being described in detail.
Matrix resin is not special the qualification, as long as it has reactive hydrogen and/or functional group, can react with linking agent.Its preferred example comprises the polyolefin resin of modification, urethane resin, acrylic resin, Resins, epoxy and vibrin.They can use separately, if they have the use that also can mutually combine of good consistency.Those are with longing for for environment protection that water dispersion or solution form occur.From workability, but scrape resistant and coating viewpoint, and modified polyolefin resin and urethane resin are desirable.If consider solidity to corrosion, the former is the most suitable.
Modified polyolefin resin has functional group.Preferred functional group is carboxyl (polyolefin resin can be made ionomer resin with carboxy-modified).Modified polyolefin resin obtains with one or more the common monomer polymerization of choosing wantonly by being unsaturated carboxylic acid (for example (methyl) vinylformic acid, toxilic acid, fumaric acid and methylene-succinic acid) with alkene (ethene, propylene, and butylene) and ethene.Ethene is that the preferable amount of unsaturated carboxylic acid must be the 1-40 weight % of monomer total amount, so that the modification polyene olefine resin that makes contains functional group's (or carboxyl) of proper amt.If the carboxylic acid amount is less than 1 weight %, the polyolefin resin that then makes does not have enough functional groups, and therefore purpose of the present invention does not reach.And it is not easy to be made for the desirable water dispersion of environmental protection.On the contrary, the carboxylic acid amount surpasses 40 weight %, the formed resin coating of the modified polyolefin resin that makes, and its solidity to corrosion and water tolerance are bad.Preferred alkene is ethene, and preferred unsaturated carboxylic acid is (methyl) vinylformic acid.
Other copolymerizable monomers comprise (methyl) alkyl acrylate, for example (methyl) methyl acrylate, (methyl) ethyl propenoate and (methyl) propyl acrylate; Aromatic monomer, alpha-methyl styrene for example, chlorostyrene, and Vinyl toluene; (methyl) acrylate of hydroxyl, for example (methyl) Hydroxyethyl acrylate and (methyl) vinylformic acid hydroxypropyl ester; Amide monomer is N-methylol (methyl) acrylamide for example; Contain for example Racemic glycidol (methyl) acrylate of epoxy group(ing) (methyl) acrylate; (methyl) vinyl cyanide.But their monomers use or the use that mutually combines.Any have a hydroxyl, amide group, or the modified polyolefin resin of epoxy group(ing) can be with have can be mutually crosslinked with the linking agent of the functional group of their reactions.
The more necessary form with water dispersion (emulsion) of the polyolefin resin that contains carboxyl group that so obtains is used, or is using with the form of ionomer resin with alkali (for example ammoniacal liquor) or positive ion reaction back.Preferred positive ion be by lithium, sodium, potassium, magnesium, calcium, iron, aluminium, or the like the metal ion that forms, be what long for most wherein with sodium ion.They cause ionomer to improve corrosion stability and scuff resistance.
Urethane resin contains the reactive hydrogen that obtains from hydroxyl and amido.Can use the water dispersion (" Superflex " Dai-ichi Kogyo Seiyaku Co., Ltd. is produced) of commercial urethane resin.All may make the water dispersion of urethane resin with any following currently known methods.
(1) a kind of method is to comprise having the so-called base polyurethane prepolymer for use as of isocyanate end group, compound reaction with having amido or carboxyl and sulfonic group or carboxyl (for example aqueous solution of the basic metal of diamino monocarboxylic acid or ammonium salt) causes chain extension and emulsification to be carried out simultaneously in this method.
(2) a kind of method comprises polyisocyanate compound and polyol, has the compound of quaternary ammonium group and hydroxyl, has the compound reaction of epoxy group(ing) and hydroxyl, and reaction product is scattered in the water.
(3) a kind of method comprises that aromatic polyisocyanate or aliphatic diisocyanate and chainextender react mutually with polyester polyol or how pure in inert organic solvents, reaction product and the water that contains an amount of emulsifying agent is carried out mechanical stirring, and solution is steamed.
Polyester polyol is made through dehydration condensation by many alcohol (for example polyethers, polyoxyethylene glycol, polypropylene glycol, butyleneglycol and hexylene glycol they be tetrahydrofuran (THF), oxyethane, propylene oxide (being total to) polymers) and dicarboxylic acid (for example toxilic acid, Succinic Acid and hexanodioic acid).Many alcohol are polyester, polyacetal for example, and polyesteramide and polythioether are made by cyclic esters ring-opening polymerization.
The example of aromatic polyisocyanate is as 1,5-naphthalene diisocyanate, 4,4-diphenylmethanediisocyanate (MDI), phenylene diisocyanate, Xylene Diisocyanate and tolylene diisocyanate.
The example of aliphatic diisocyanate such as hexamethylene diisocyanate, and dicyclohexyl methane diisocyanate.
In the example of chainextender such as the above-mentioned many alcohol any and low-molecular-weight diamines (for example quadrol, propylene diamine, diethylenetriamine, hexamethylene-diamine and dimethylphenylene diamine).
The example of inert organic solvents such as tetrahydrofuran (THF), acetone, methylethylketone, ethyl acetate and toluene.
(4) a kind of method for making is to comprise the polyurethane-urea polyamines is made in base polyurethane prepolymer for use as and polyamines polyene (for example diethylenetriamine) reaction with end isocyanate group, and to wherein adding aqueous acid.Another kind of method for making is to comprise polyurethane-urea polyamines and epoxy chloropropane are carried out addition reaction, and adds aqueous acid in reaction product.
(5) a kind of method for making is to comprise above-mentioned polyurethane-urea polyamines or itself and alkyl isocyanate or epoxy chloropropane affixture, with the reaction of ring dicarboxylic anhydride, and reaction product is mixed with alkaline aqueous solution.
(6) a kind of method for making is to comprise above-mentioned polyurethane-urea polyamines or itself and epoxy chloropropane affixture, with sulfonic acid, lactonic acid, and the sodium salt of single halogenated carboxylic acid among whichever, or with (methyl) acrylate, vinyl cyanide, or the like reaction, with the reaction product hydrolysis, and hydrolyzate mixed with water.
(7) a kind of method for making comprises the base polyurethane prepolymer for use as (it is made by how pure and mild polyisocyanates) that will have terminal hydroxy group or isocyanato, make compound with diamine reactant with end amido, by means of emulsifying agent reaction product is scattered in the water, and it is joined in the water dispersion of polyisocyanates to increase molecular weight.
Acrylic resin is to be obtained by the one or more polymerizations in the following monomer.
(methyl) acrylate of carboxylic (methyl) vinylformic acid and hydroxyl, for example (methyl) Hydroxyethyl acrylate and (methyl) Propylene glycol monoacrylate; Acid amides is N-methylol (methyl) acrylamide for example; Contain for example 2-glycidyl (methyl) acrylate of epoxy group(ing) (methyl) acrylate; (methyl) alkyl acrylate is (methyl) methyl acrylate for example, (methyl) ethyl propenoate and (methyl) propyl acrylate; Aromatic polymer is vinylbenzene, alpha-methyl styrene, chlorostyrene and Vinyl toluene for example; And (methyl) vinyl cyanide.The acrylic resin that makes contains carboxyl, hydroxyl, amide group or epoxy group(ing) as functional group.
Available Resins, epoxy comprises having epoxy group(ing) any known Resins, epoxy as functional group.Applicable vibrin comprises the vibrin with carboxyl and hydroxy functional group.They comprise glyptal resin, phthalic acid resin, m-phthalic acid resin, maleic acid resin, aliphatic polyester resin and oxygen acid resin.
The present invention needs two or more or two kinds of linking agents, so that form resin coating.The present invention need must be by above-mentioned matrix resin at the resin coating on the resin-coating metal sheet; Two kinds of linking agents, they begin to carry out crosslinking reaction with described matrix resin under different temperature; Formed with organic lubricant.Resin coating still before high temperature cures, must contain and the crosslinked matrix resin of first linking agent after heating and drying; And second linking agent keeps not reacting, and it begins to react in the time of will curing at high temperature subsequently.Matrix resin may not always need all crosslinked.The part matrix resin can keep intact, because first linking agent is not a large amount of excessive interpolations usually.
Above-mentioned composition mode makes suitably crosslinked with first linking agent, and contains the resin coating of organic lubricant, presents good workability, solidity to corrosion, but anti-scratch and coating before heating between the high temperature short-term is cured.When heating is carried out curing between high temperature, short time, in resin coating, carry out the subordinate phase of crosslinking reaction, prevent the resin coating deliquescing.Paint film is solidified on resin-coated surface equably.Thereby obtain to have the solidified paint film of good appearance.In addition, when curing between high temperature, short time, in resin coating, carry out further crosslinked so that matrix resin is more strong.This just prevents that organic lubricant from moving with melted state, therefore prevents to reduce the clinging power of resin coating and metallic surface and the fusible any disadvantageous effect in the attenuating resin coating.
Make crosslinking reaction various methodologies be arranged respectively at two stages.A kind of possible method is to heat to use electron beam irradiation subsequently.Wish most to carry out first crosslinking reaction at low temperatures, and second crosslinking reaction does not take place, and carry out second crosslinking reaction under high temperature, this temperature generally is about 200 ℃, is used for curing between high temperature, short time.
The present invention uses the linking agent of two kinds (or more), it is inequality that they and matrix resin begin to carry out the temperature of crosslinking reaction, in these linking agents, have a kind of first linking agent that is called of minimum beginning temperature of reaction, be called second linking agent and have the highest beginning temperature of reaction person.But heat drying do not carry out as yet contains the compound that first linking agent and matrix resin reaction generate in the resin coating film that high temperature cures, and second linking agent maintenance unreacted; But wherein do not contain the compound that the reaction of any second linking agent and matrix resin generates, and keep unreacted first linking agent.
In other words, the fs of crosslinking reaction is to have first linking agent that minimum reaction begins temperature to carry out, and the subordinate phase of crosslinking reaction is to have second linking agent that the highest reaction begins temperature to carry out.Therefore can draw as drawing a conclusion, resin coating (before curing between high temperature, short time) contains the product of first linking agent and matrix resin reaction generation, and second linking agent keeps unreacted.Say that ideally it does not contain the spawn that keeps unreacted first linking agent and second linking agent and matrix resin reaction to generate.But, from the character of chemical reaction and opinion must have a kind of inevitable situation.Second linking agent reacts with matrix resin in the fs of crosslinking reaction by halves, or first linking agent partly keeps unreacted.This situation is not excluded from outside the scope of the present invention, and is non-existent but it is regarded as " in fact ".In addition, may there be following situation, in resin coating, contains the reaction product of the intact matrix resin of part, matrix resin and first and second linking agents, or the reaction product of first and second linking agents.This situation also is within the scope of the present invention.
Reaction beginning temperature is that the mixture (at room temperature making film forming shape) with matrix resin and linking agent adds heat determination in differential thermal analyzer.It is defined as the temperature that matrix resin and linking agent begin to carry out thermopositive reaction, and indicated temperature rises.DTA graphic representation and reaction beginning temperature diagrammatically are shown.
The more necessary linking agent that is a kind of 135 ℃ or above beginning crosslinking reaction of second linking agent of beginning crosslinking reaction under comparatively high temps.Definite temperature changes to some extent, and it depends on that first linking agent begins the temperature that crosslinked temperature and paint film form in final step.For example it comprises melamine resin and end capped isocyanic ester.Melamine resin and hydroxyl and carboxyl reaction, and the also reactive hydrogen by containing in the carbamate, hydroxyl, epoxy group(ing) or the like and urethane reaction.Their commercial product comprises " Suminal M40W " and " SumimarM50W " and " Cymel 303 " of Mitsui Saitech company limited of Sumitomo chemistry company limited.
End capped isocyanic ester is a kind of compound that its isocyanate group is contained the chemicals sealing of reactive hydrogen.Through heating, it discharges end-caps and becomes active.It can be used as first linking agent, and it begins crosslinked under lower temperature.With selecting suitable compounds, the active isocyanate group in TDI and the MDI blocked polyisocyanates compound for example, temperature that can the sustained release closing compound.Because the high thermal dissociation temperature of Fatty Alcohol(C12-C14 and C12-C18) (for example methyl alcohol, ethanol, ethylene glycol butyl ether) (be in some cases 180 ℃ or more than), so be applicable to the closing compound of making second linking agent, second linking agent begins to react when high temperature cures.Other kind of an end-caps comprises for example mouth-hexanolactam of lactan; Phenols is phenol and cresols for example; Oximes is methyl ethyl ketoxime and hexamethylene oxime for example; The active compound that contains methylene radical is dimethyl malonic ester and ethyl acetoacetic acid for example.Their thermal dissociation temperature subtracts the end (reducing to about 110 ℃) by above-listed order.Consider their crosslinking temperature, from first to second linking agent must be done suitable selection.
Beginning the first crosslinked linking agent more necessary in low temperature is at 130 ℃ or the crosslinked linking agent of following beginning.Preferred example is can be at the Resins, epoxy of crosslinked at low temperature.Resins, epoxy contains epoxide group, the reactive hydrogen phase reaction of it and hydroxyl, hydroxyl and amine.Commercial Resins, epoxy example comprises " EX-313 ", " EX-314 ", " EX-321 ", " EX-421 ", " EX-512 ", " EX-521 ", " EX-147 ", " EX-810 " and " EX-614 ", (is included in " Denacol " series of Nagase chemistry company limited; " RikabondEX-8S " and " Rikabond AP-355B " with Chuo Rika Industrial Co., Ltd.
The use that can combine with additional linking agent of first and second linking agents, it has the intermediary of occuping reaction beginning temperature, and only needs it that the present invention is not had adverse influence.When first linking agent uses or second linking agent can use the additive-crosslinking agent when using.The example of this additive-crosslinking agent comprises methylol compound, and amine compound, epoxy compounds are used for crosslinked and contain the compound of aziridine group at high-temperature.
The amount of first and second linking agents must respectively be 1-20 weight % in the resin coating, and its total amount is not more than 30 weight % (in solid).Ideal situation is that second linking agent must be touched in resin coating in maintenance, does not react with matrix resin; And first linking agent must exist with the form with the back compound that produces of matrix resin reaction in resin coating.
If the amount of second linking agent is less than 1 weight %, then resin-coated poor heat resistance, and deliquescing when high temperature cures.Preferred amounts be 2 weight % or more than.If second cross-linked dosage is greater than 20 weight %, then resin-coated solidity to corrosion is poor before high temperature cures.If first cross-linked dosage is less than 1 weight %, then resin-coated solidity to corrosion and scuff resistance are poor.If first cross-linked dosage is greater than 20 weight %, then resin coating is excessive hard is easy to break when adding that therefore corrosion stability is poor man-hour.The preferred upper limit is 10 weight %.
If the total amount of two kinds of linking agents (with the additive-crosslinking agent) surpasses 30 weight %, because too much linking agent keeps unreacted, the resin coating corrosion stability is poor.
According to the present invention, resin coating must contain organic lubricant as an important component, so it has good lubricity and protects man-hour itself to exempt to be scratched when adding.Preferred organic lubricant amount is 0.5-20 weight %.The organic lubricant amount does not produce and improves workability and scratch-resistant effect less than 0.5 weight %.The organic lubricant amount surpasses 20 weight % and does not produce any adjection, but the stage of curing behind japanning or silk screen printing has the opposite effect to resin-coated thermotolerance.
The example of organic lubricant comprises polyolefin-wax (for example polyethylene, polyoxyethylene and polypropylene), fluorocarbon resin (for example tetrafluoroethylene, fluorinated ethylene propylene, polyvinylidene difluoride (PVDF)), and paraffin.In these examples polyethylene wax be long for because its oilness is good.The lubricant median size of being made up of annular particles is that 0.1-3 μ m person is for more desirable.Particle diameter can not produce it fully less than the wax of 0.1 μ m and improve the anti scuffing effect.Particle diameter greater than the wax of 3 μ m can not be in resin coating homodisperse.It is preferred within 80-140 ℃ of scope that polyethylene wax should have softening temperature.Softening temperature is lower than 80 ℃, flows and therefore to make deteriorated workability, softening temperature be higher than 140 ℃, the poor lubricity of wax when adding man-hour wax.
The polyethylene wax of being made up of annular particles is commercial to be gathered, its trade name is " Daijef E-17 " (Goou Kagaku Co., Ltd.), " KUE-5 " " KUE-1 ", " KUE-8 " (Sanyo Chemical Industries, Ltd.), " W-100 ", " W-200 ", " W-300 ", " W-400 ", " W-500 ", " W-640 " and " W-700 " (are included in MitsuiKagaku Co., Ltd.) in " Chemipearl " series), " Elepon E-200 " (Niccachemical co., Ltd.).
Resin coating can randomly contain silicon-dioxide, and its quantity is that 5-30 weight % (in solid) helps to improve solidity to corrosion and anti scuffing.Silica volume does not produce desirable effect less than 5 weight %.Silica volume breaks when making during greater than 30 weight % resin coating dry, thereby causes solidity to corrosion to reduce.
Silicon-dioxide may be spheroidal particle or chain particle.Spheroidal particle serves as preferred to have median size 1-200nm.Superfine silicon-dioxide can prevent resin coating embrittlement, therefore helps solidity to corrosion, but makes resin-coated composition unstable.Crossing thick silicon-dioxide makes resin coating be difficult to form.Preferred particle diameter is 4-20nm.Colloid silica and aerosol silicon-dioxide can address this need.More suitable commercial silica is that " XS ", " SS ", " 40 ", " N " and " UP " are included in Nissan Chemical Industries, the colloid silica in Ltd. " Snowtex " series.
Resin-coating sheet metal of the present invention is that above-mentioned constituent is mixed, and the mixture of making is applied on the metal sheet and with the coating drying make.Be used for resin-coated mixture and be water dispersion and linking agent with matrix resin, organic lubricant mixes mutually with above-mentioned optional silicon-dioxide and to make.(longing for water dispersion (or emulsion) form as mentioned above) from the viewpoint consideration matrix resin of environmental protection.The component (they do not have adverse influence to the present invention) that the mixture that makes can be sneaked into optional interpolation is diluting solvent, anti, levelling agent, antifoam agent, permeate agent, emulsifying agent, film coalescence aid, dyestuff and pigment, thickening material, organo-silicon coupling agent and do not contain the resin of functional group and reactive hydrogen for example.
Metal sheet is not special the qualification.It comprises zinc coating steel plate, steel plate galvanized, the steel plate that comprises zinc alloy, aluminium sheet, aluminium alloy plate and titanium plate.In order to obtain corrosion stability and adhesion preferably, give that resin layer carried out chromate treating before forming on paint film or metallic surface or phosphatizing is suitable.Chromate treating can be a response type, application type, or the electrolytic action type.
The resin coating that on metal sheet, forms, essential with for example roller coating of any known coating process, spraying, or the curtain rolling is coated with etc. and is used for the one or both sides that resin-coated constituent is applied to metal sheet with above-mentioned.Subsequently with coating heating and dry.Heating and drying step must hand over gather connection stage or first linking agent and begin to carry out more than the temperature of its crosslinking reaction in carrying out first.In other words, heating and drying step must not carry out or second linking agent does not begin to carry out below the temperature of crosslinking reaction in second cross-linking stage.This is because the subordinate phase of crosslinking reaction must be carried out when curing between the high temperature, short time as final step, therefore, as mentioned above, keeps good coating and workability simultaneously but resin coating presents good thermotolerance.But with regard to the person's character of chemical reaction, exist second linking agent partly with the possibility of matrix resin reaction.The resin-coating metal sheet that obtains with this sample loading mode also is acceptable in the present invention.
The definite of actual drying temperature must consider that the reaction of employed first and second linking agents begins temperature.Organic lubricant is that 70-130 ℃ drying temperature is preferred under the situation of polyethylene wax of spheroidal particle.In the case first linking agent of Shi Yonging more necessary in the said temperature scope, carry out crosslinked.In view of water base constituent is used for resin-coated situation, heating and exsiccant temperature are more longed within 80-120 ℃ of scope.
Resin coating must so form so that its thickness or weight (after the drying) are 0.2-2.5g/m
2If thin excessively, it will show its corrosion stability and scuff resistance by halves; If it is blocked up, it will be stripped from when adding man-hour.Consider that from the viewpoint of electroconductibility and weldability thickness is at 0.4-1.5g/m
2Close in needs within the scope.
The resin-coating metal sheet of Sheng Chaning can directly use at this point or use after application or silk screen printing according to the application of attempt as mentioned above.Usually cured 20-30 minute at 130-160 ℃ immediately after application or the silk screen printing.
Cure the stage in this routine, the crosslinked of subordinate phase proceeds to a certain degree.Therefore, filming of so making has good corrosion stability.Far and away, optimal results is cured paint film and was obtained in 1-5 minute in 200 ℃, and so subordinate phase is crosslinked carries out fully.So on the resin-coating metal sheet, in the short period of time, form and have good heat resistance and good paint film is possible.Because final baking step carries out being about 200 ℃, second linking agent must be the kind of carrying out crosslinking reaction in this temperature fast.Kind 135 ℃ or above beginning crosslinking reaction can satisfy this demand.Preferred example comprises melamine resin and the blocked isocyanate with high dissociation temperature.
Resin-coating metal sheet of the present invention is by metal sheet and scribble resin coating and form on its one side at least.Before final high temperature cured, matrix resin was in crosslinked state in this resin coating, and this is cross-linked to form in one of first cross-linking stage it and two kinds of linking agents.Because crosslinked, resin coating has suitable hardness; And wherein contain organic lubricant, it also has good corrosion stability and anti-scratch.Therefore the resin-coating metal sheet can cut with punching and resin coating is not destroyed.Moreover the matrix resin in the resin coating contained an amount of remaining functional group before final high temperature cures, when the resin-coating metal sheet carries out conventional application, (cured 20-30 minute in 130-160 ℃ simultaneously) but they help coating.
The metal sheet of resin-coating of the present invention is so to form, and before curing between high temperature, short time, contains another in two kinds of linking agents in the resin coating, and it is in unreacted state.When curing at last after the metal plate coating of resin-coating and with paint film, this linking agent begins to react in the subordinate phase of crosslinking reaction.Therefore, resin coating manifests good thermotolerance and not deliquescing, and is providing good adhesion between metal sheet and the resin coating and between resin coating and the paint film.And paint film has good surface appearance after curing.
Embodiment
Provide the following example so that the invention will be further described, but not as restriction.Can change these embodiments, but not break away from the spirit and scope of the present invention.
[test mode]
Following test mode is used for each embodiment.
(1) crosslinking reaction begins temperature
Matrix resin is mixed with linking agent, and under the room temperature mixture that makes being coated with into film on polyfluortetraethylene plate.In after the drying film sample being heated in differential thermal analyzer.DTA diagram as Fig. 1 provide the temperature that linking agent begins to react (℃).
(2) pencil scratch test (being used to measure pencil hardness)
According to JIS K5400, this test is to carry out on the metal sheet sample of resin-coating, and this sample is in 80 ℃ of dryings 1 minute, or has carried out curing between high temperature, short time (230 ℃ 50 seconds).Observe the scratch situation with magnifying glass, with evaluation pencil hardness grade.
(3) workability
On the metal sheet sample of resin-coating, carry out list with a toggle joint press and press test, observe the surface of pressing sample later, and by following standard rating.
5: almost not scratch, 4: slight scratch, 3: obviously scratch, 2: scar, 1: cracking.(4) corrosion stability
According to JIS Z2371, on the metal sheet sample of the resin-coating of edge sealing, spray the salt test.Cover 1% needed time representation corrosion stability of sample surfaces according to white rust.
(5) thermotolerance
The polyester lacquer is applied on the metal sheet sample of resin-coating, and film thickness is 20 μ m.Paint film was cured for 50 seconds in 230 ℃.The sample that will have the paint film that cured soaked in boiling water 1 hour, and the lattice in 1mm interval indentation formation 10 * 10 carries out the cross cut test subsequently.With the lattice number that retains (resin coating film and paint film the two number) expression thermotolerance.
Embodiment 1
The sample of the metal sheet of resin-coating is that (0.8mm is thick, 20g/m by the steel plate of electro-galvanizing
2Zinc) make, it is through chromate treating (15mg/m
2Chromium) as substrate.
Apply the resin coating that synthetics forms on the metal sheet.This synthetics is mixed and made into following component.
Ethylene-acrylic acid copolymer (containing 20 weight % vinylformic acid) is in the emulsion form as matrix resin.Carboxyl in the multipolymer is partly with the sodium hydroxide neutralization, so it has been converted into the ionomer resin of ionomer in advance.
The polyethylene wax of annular particles (median size is 0.6 μ m) has 100 ℃ of softening temperatures.Content in compound is 5 weight % (solid meters).
Colloid silica, median size are that 10-20nm (" Snowtex 40 " NissanChemical Industries.Ltd.) content in compound is 20 weight % (in solid).
Resins, epoxy is used for crosslinked at low temperature (it is 50 ℃ of beginning crosslinking reactions) NagaseChemicals, Ltd, " Denacol ES-313 ".Quantity (in the solid in synthetic) is shown in Table 1.
Melamine resin (in 140 ℃ of beginning crosslinking reactions) " Sumimal M40W " is selected from Sumitomo Chemical Co., Ltd.).Quantity (in the solid in the synthetics) is shown in Table 1.
Each synthetics that makes is applied on the one side of above-mentioned metal sheet with roller painting.With coating in 80 ℃ of (temperature of plate) heat dryings 1 minute.So make the sample of the steel board of resin-coating, have separately 1 the gram/square metre resin coating film.Evaluation result to them is shown in table 1.
Table 1
| Linking agent (weight %) | Pencil hardness | Thermotolerance | Corrosion stability (h) | Workability | |||
| Resins, epoxy | Ultraps | When drying | After curing | ||||
| Embodiment | 5 | 1 | 2H | 3H | 100 | 760 | 5 |
| 1 | 5 | 2H | 4H | 100 | 780 | 5 | |
| 5 | 5 | 2H | 4H | 100 | 740 | 5 | |
| 10 | 5 | 2H | 4H | 100 | 810 | 5 | |
| 15 | 5 | 3H | 4H | 100 | 790 | 5 | |
| 20 | 5 | 3H | 4H | 100 | 750 | 5 | |
| 5 | 10 | 2H | 4H | 100 | 720 | 5 | |
| 5 | 15 | 2H | 4H | 100 | 800 | 5 | |
| 5 | 20 | 2H | 4H | 100 | 770 | 5 | |
| Reference example | 5 | 0.5 | 2H | 2H | 63 | 760 | 5 |
| 5 | 25 | 2H | 4H | 100 | 450 | 4 | |
| 0.5 | 5 | H | 4H | 100 | 380 | 3 | |
| 25 | 5 | 3H | 4H | 55 | 600 | 5 | |
| Comparative Examples | - | 5 | F | 3H | 100 | 340 | 3 |
| - | 10 | F | 4H | 100 | 330 | 3 | |
| - | 15 | F | 4H | 100 | 280 | 3 | |
| 5 | - | 2H | 2H | 5 | 760 | 5 | |
| 10 | - | 2H | 2H | 8 | 780 | 5 | |
| 15 | - | 3H | 3H | 6 | 760 | 5 | |
| - | - | F | F | 3 | 260 | 3 | |
Embodiment 2
Except using Dai-ichi Kogyo Seiyaku Co., Ltd. Gong Ying " Superflex " urethane resin (the water dispersion form) replacement ethylene-acrylic acid copolymer is as beyond the matrix resin, repeat as the same step among the embodiment 1, with the steel plate sample of preparation resin-coating.Evaluation result to them is shown in table 2.
Table 2
| Linking agent (weight %) | Pencil hardness | Thermotolerance | Corrosion stability (h) | Workability | |||
| Resins, epoxy | Melamine resin | When drying | After curing | ||||
| Embodiment | 5 | 1 | 3H | 3H | 100 | 700 | 5 |
| 1 | 5 | 2H | 3H | 100 | 710 | 5 | |
| 5 | 5 | 3H | 4H | 100 | 680 | 5 | |
| 10 | 5 | 3H | 4H | 100 | 670 | 5 | |
| 15 | 5 | 3H | 4H | 100 | 700 | 5 | |
| 20 | 5 | 3H | 4H | 100 | 670 | 5 | |
| 5 | 10 | 3H | 4H | 100 | 700 | 5 | |
| 5 | 15 | 3H | 4H | 100 | 790 | 5 | |
| 5 | 20 | 3H | 4H | 100 | 750 | 5 | |
| Reference example | 5 | 0.5 | 3H | 3H | 68 | 700 | 5 |
| 5 | 25 | 3H | 4H | 100 | 380 | 4 | |
| 0.5 | 5 | H | 3H | 100 | 330 | 4 | |
| 25 | 5 | 3H | 4H | 60 | 550 | 5 | |
| Comparative Examples | - | 5 | H | 3H | 100 | 300 | 4 |
| - | 10 | H | 4H | 100 | 290 | 3 | |
| - | 15 | H | 4H | 100 | 210 | 3 | |
| 5 | - | 3H | 3H | 43 | 660 | 5 | |
| 10 | - | 3H | 3H | 28 | 680 | 5 | |
| 15 | - | 3H | 3H | 51 | 670 | 5 | |
| - | - | H | H | 18 | 220 | 4 | |
Claims (9)
1. one kind has resin-coated sheet metal, it is characterized in that described resin coating includes:
A kind of matrix resin has reactive hydrogen or functional group at least in its molecule;
0.5-20 a kind of organic lubricant of weight %;
A kind of first linking agent can react with described matrix resin;
A kind of second linking agent can react with described matrix resin; Wherein said second linking agent and described matrix resin begin the temperature of crosslinking reaction, begin the temperature height of crosslinking reaction than described first linking agent and described matrix resin; With
Described resin coating contains the reaction product of described matrix resin and described first linking agent, also contain 1-20 weight % untouched in fact moving, not with described second linking agent of described matrix resin reaction, and do not contain not untouched moving described first linking agent with the matrix resin reaction in fact;
Wherein, the amount of first and second linking agents must respectively be 1-20 weight % in the resin coating, and its total amount is not more than 30%, in solid.
2. as the resin-coated sheet metal that has that claim 1 limited, it is characterized in that described first linking agent 130 ℃ or the reaction of following beginning linking agent, and described second linking agent is 135 ℃ or above beginning crosslinking reaction.
3. as the resin-coated sheet metal that has that claim 1 limited, it is characterized in that described first linking agent is a kind of Resins, epoxy, and second linking agent is a kind of melamine resin.
4. as the resin-coated sheet metal that has that claim 1 limited, it is characterized in that described resin coating also contains the silicon-dioxide of 5-30 weight %.
5. a method that is used for the sheet metal of production resin-coating is characterized in that described method comprises the following steps:
To form resin coating, described synthetics contains a kind of matrix resin, has reactive hydrogen or functional group in its molecule at least with a kind of synthetics metallic sheet; 0.5-20 a kind of organic lubricant of weight %; With more than a kind of linking agent that can play crosslinking reaction with described matrix resin, wherein, the amount of various linking agents must respectively be 1-20 weight %, and its total amount is not more than 30%, in solid; With
The metal sheet that applies is heated and drying at a certain temperature, this temperature has the crosslinking reaction that minimum crosslinking reaction begins the temperature crosslink agent than a kind of in the described linking agent and begins the temperature height, but has crosslinking reaction that the highest crosslinking reaction begins the linking agent of temperature to begin temperature be low than another kind of in the described linking agent.
6. carry out the painted method to having resin-coated sheet metal, described resin coating includes:
A kind of matrix resin has reactive hydrogen or functional group at least in its molecule;
0.5-20 a kind of organic lubricant of weight %;
A kind of first linking agent can react with described matrix resin;
A kind of second linking agent can react with described matrix resin; Wherein said second linking agent and described matrix resin begin the temperature of crosslinking reaction, begin the temperature height of crosslinking reaction than described first linking agent and described matrix resin; With
Described resin coating contains the reaction product of described matrix resin and described first linking agent, also contain 1-20 weight % untouched in fact moving, not with described second linking agent of described matrix resin reaction, and do not contain not untouched moving described first linking agent with the matrix resin reaction in fact;
Wherein, the amount of first and second linking agents must respectively be 1-20 weight % in the resin coating, and its total amount is not more than 30%, in solid,
Described method comprises and will form paint film and heat this paint film on the resin coating surface that its temperature is high enough to make and keeps untouched not moving described linking agent reaction in described matrix resin and the described resin coating.
7. as the method that claim 6 limited, it is characterized in that described first linking agent 130 ℃ or the reaction of following beginning linking agent, and described second linking agent is 135 ℃ or above beginning crosslinking reaction.
8. as the method that claim 6 limited, it is characterized in that described first linking agent is a kind of Resins, epoxy, and second linking agent is a kind of melamine resin.
9. as the method that claim 6 limited, it is characterized in that described resin coating also contains the silicon-dioxide of 5-30 weight %.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000098864A JP3412690B2 (en) | 2000-03-31 | 2000-03-31 | Resin-coated metal sheet with excellent workability and heat resistance |
| JP98864/2000 | 2000-03-31 |
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| Publication Number | Publication Date |
|---|---|
| CN1315249A CN1315249A (en) | 2001-10-03 |
| CN1186189C true CN1186189C (en) | 2005-01-26 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011100931A Expired - Lifetime CN1186189C (en) | 2000-03-31 | 2001-03-30 | Resin coated metal plate with good machinability and thermal stability |
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| Country | Link |
|---|---|
| JP (1) | JP3412690B2 (en) |
| KR (1) | KR100399302B1 (en) |
| CN (1) | CN1186189C (en) |
| ID (1) | ID29714A (en) |
| MY (1) | MY140699A (en) |
| SG (1) | SG96609A1 (en) |
| TW (1) | TW521034B (en) |
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| US7618711B2 (en) | 2004-02-17 | 2009-11-17 | Kabushiki Kaisha Kobe Seiko Sho | Resin coated metal plate having excellent formability, weldability and corrosion resistance, and worked articles using the resin coated metal plate and method for manufacturing same |
| JP4551786B2 (en) * | 2004-02-17 | 2010-09-29 | 株式会社神戸製鋼所 | Resin-coated metal plate excellent in workability, weldability and corrosion resistance, processed product using the resin-coated metal plate, and production method thereof |
| JP4318610B2 (en) * | 2004-07-30 | 2009-08-26 | 株式会社神戸製鋼所 | Surface-treated metal plate |
| JP4659432B2 (en) * | 2004-10-25 | 2011-03-30 | 株式会社神戸製鋼所 | Resin-coated metal plate with excellent releasability and method for producing the same |
| JP5555008B2 (en) * | 2010-02-23 | 2014-07-23 | 株式会社神戸製鋼所 | Pre-coated aluminum plate for electronic equipment |
| JP5671402B2 (en) * | 2011-04-18 | 2015-02-18 | 株式会社神戸製鋼所 | Pre-coated aluminum plate for electronic equipment |
| CN102248824B (en) * | 2011-05-25 | 2013-03-27 | 葛爱民 | Household appliance printing panel producing method and household appliance printing panel produced thereby |
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| CA2249705C (en) * | 1997-11-12 | 2006-09-12 | Basf Corporation | High solids thermosetting compositions with dual cure mechanism |
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- 2001-03-23 TW TW090106896A patent/TW521034B/en not_active IP Right Cessation
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| ID29714A (en) | 2001-10-04 |
| JP2001277422A (en) | 2001-10-09 |
| CN1315249A (en) | 2001-10-03 |
| JP3412690B2 (en) | 2003-06-03 |
| TW521034B (en) | 2003-02-21 |
| MY140699A (en) | 2010-01-15 |
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