CN1085566C - Metal plate coated with resin and production method thereof - Google Patents
Metal plate coated with resin and production method thereof Download PDFInfo
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- CN1085566C CN1085566C CN96102592A CN96102592A CN1085566C CN 1085566 C CN1085566 C CN 1085566C CN 96102592 A CN96102592 A CN 96102592A CN 96102592 A CN96102592 A CN 96102592A CN 1085566 C CN1085566 C CN 1085566C
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- resin
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- steel plate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—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 for applying particular liquids or other fluent materials
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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
- B32B15/085—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 comprising polyolefins
Abstract
The present invention relates to a kind of resin coating metal plate particularly the resin coating steel plate which possesses not only the characteristics of superior machining, but also high resistance to wearing, compression, as well as anti-blackening during pressing, anti-corrosion, painting and earth properties; and the manufacturing of such kind of resin-coating metal plate particularly the resin coating steel plate. The resin coating metal plate is characterized in that the resin coating formed on the surface of metal plates has a dry weight of 0.2~2.5 g/square meter, the resin coating contains 5~30wt% of silicon dioxide particles, 0.5~20wt% of ball-shaped polyethylene wax particles, and 1~20wt% from solid portion of organic aziridine compound, which primarily contains a kind of polyethylene resin copolymer lactoprene associating with groups of free ions between molecules.
Description
The present invention relates to the good wearability of tool, processability, add man-hour anti-melanism, stampability, corrosion resistance and colouring property resin-coating metallic plate, particularly resin coated steel sheet and prepare the particularly method of the steel plate of resin-coating of this resinous coat metallic plate.
The metallic plate that uses as household appliances or construction material purpose has obtained using widely such as surface treated steel plate such as the steel plate of electrogalvanizing, the galvanized steel plain sheet of hot dipping stain and aluminium sheet and corrosion resistant plate together.Among them, must carry out chromate is handled or parkerized zinc plate surface is handled steel plate so far widely mainly as household appliances with such as the various members such as base plate of stereo set, machine element, electronic cooker.But the user becomes more and more higher to the aspect that requires of the various film properties of these surface-treated steel plates recently.
For example, under situation about using under the unsheltered state, need corrosion resistance, ground connection performance (earth properties) at surface treated steel plate even the anti-finger mark that when by last finger mark, also can not grip one's attention, to the chemical resistance of alkali, solvent etc. and resistance tocrocking etc.In addition, under their need situation that repressed processing or punching press handle, need lubricity, resistance to marring, metal deep drawing processability, anti-mould abrasiveness, stampability, to the anti-melanism of processing the back slidingsurface, to the oil resistivity of quick-drying oil etc.
In addition, under the situation that the surface-treated steel plate is transported with the product of the dish rolling or the form of become opening by its producer, they are generally by transportations such as trucies.Under the situation of dish rolling, can wear and tear, under the situation of become opening, at the interior steel plate of putting on another of packing wearing and tearing or scratch can appear on surface of steel plate, due to both vibrations when transporting.This scratch is a kind of defective, reveals into black that part of becoming of scratch.This defective is called as wearing and tearing, and it causes that the value of goods of surface treated steel plate is destroyed and makes the user can not be with its problem of using as goods.
Above-mentioned various needs can not be satisfied by the steel plate of handling through chromate or parkerized conventional inorganic surfaces is handled.For this reason, the steel plate of resin molding that proposed many coatings that constitute by a certain organic resin film as described below recently.
For example, at first, Japanese Patent Application Publication 62-50480 discloses by the steel plate that zinc is electroplated being carried out chromate and has handled, form then by the vistanex of carboxylation and epoxy resin and form and contain the steel plate that zinc that organic film of colloidal silica obtains is electroplated thereon, organic film has improved corrosion resistance, colouring property, solvent resistance, alkali resistance and anti-finger mark, secondly, Japanese Patent Application Publication 64-73083 discloses by the olefinically unsaturated compounds that can gather and has joined the ethylidene-α that contains colloidal sol, in the beta-unsaturated carboxylic acid copolymer resin with they emulsion polymerisations, thereby and after the polymerization of the handled liquid with crosslinked polymer of preparation is finished, this liquid coated through what chromate was handled and on the steel plate of zinc plating, improves cementability, anti-finger mark, marresistance, corrosion resistance waits the surface treated steel plate that obtains.
The 3rd, Japanese patent laid-open publication gazette 5-54823 discloses and has carried out chromate by the steel plate after zinc is electroplated and handle, thus coat in the above then the organic material of the ethene-ethylidene copolymers of unsaturated carboxylic acids resin that contains colloidal silica and tool aziridinyl resin liquid, be dried and form that cross linking membrane improves colouring property, corrosion resistance, chemical-resistant and marresistance and the steel plate that has been coated with resin that obtains.
The 4th, Japanese Patent Application Publication 6-246229 discloses by carrying out chromate through the steel plate that zinc is electroplated and has handled and utilize ethene and a kind of α, comprises band 60-80% and improves the steel plate that has been coated with organic double compound that anti-melanism obtains by the resin molding of the ethene ionomer resin of the carboxyl of sodium ion neutralization when keeping superior corrosion resistance thereby β-ethylidene unsaturated carboxylic acid forms one onboard as key component.
In addition, the 5th, Japanese patent laid-open publication gazette 5-13829 discloses the steel plate of resinizing of the good pressing mold performance of tool that obtains by the resin that comprises fluorine particle and silica granule as forming of key component with the epoxy resin of acroleic acid esterification on the steel plate that zinc is electroplated.
Above-mentioned first to the third prior art to a certain extent to improving at the required aspect of performance of user that no shielding status uses such as corrosion resistance, colouring property, anti-finger mark etc.Also the marresistance aspect that the carrying by the user is caused has caused effect to a certain degree.But, because these steel plates that have been coated with resin are wanting in the hardness and the lubricity of film, the resin molding that particularly causes owing to the slip between steel plate that has been coated with resin and the mould in bending process and the deep drawing processing in compression process is peeled off from steel plate and electrodeposited coating is stripped from the problem that adheres to product or amass the material of the melanism on mould that produces so not have so far to solve.Equally, for wear resistence, abrasive generation between the steel plate that is difficult to prevent under extreme pressure, to cause by vibration.
In the 4th kind of prior art, the vinyl of tool carboxyl is ion-exchange polymerization and being neutralized and the barrier effect of generation tree adipose membrane by ionic sodium, has strengthened the melanism of zinc coating under corrosive environment like this, promptly in the anti-melanism of not damaging under the corrosion resistance.Also have, it thinks that the marresistance on film surface can obtain certain raising by the ionomer of resin Composition in resin is incompatible.Yet its anti-melanism and wear resistence are not obtain any improvement when compression process.
The 5th kind of prior art relates to the technology about the steel plate of lubricatedization that is used to strengthen press process performance purpose, and the generation that suppresses melanism material and wearing and tearing when compression process can be actually played in hope.But the surface that is used as the fluorinated resin particle of lubricant is nonactive, is difficult to inside or surface chemistry bonding with resin molding.Therefore, when coating applied in handle by electrolytic deposition coating, powder coated etc. surperficial the time, just have the problem of the sticking retaining of film (colouring) aspect.In addition, be used as at Wax particles under the situation of lubricant, when the coating resin film and when carrying out drying, under the high situation of its heating-up temperature, thus the particle in the resin molding will deliquescing raise the film surface and solidified, cause the decline of colouring property and corrosion resistance.Therefore, the drying and the film-forming temperature of resin molding are limited to below the softening point, thereby cause the problem that can not reach with enough film-strengths.
For solving the particularly problem of the steel plate of resin-coating of above-mentioned metallic plate about conventional resin-coating, the present invention has accused and has finished.The purpose of this invention is to provide not only have wear resistence and also have excellent lubrication, marresistance, stampability, such as compacting processing characteristics and punching performances such as the anti-melanism that adds man-hour, character such as corrosion resistance, colouring property, ground connection performance, the metallic plate of the resin-coating of the well balanced property between above-mentioned these character of tool in addition, resin-coating steel plate particularly, and the metallic plate that this resin-coating of preparation the is provided method of the steel plate of resin-coating particularly.
According to the present invention, the metallic plate of resin-coating is provided, it is characterized in that having formed coating weight and be 0.2 to 2.5g/m on the surface of metallic plate
2Resin molding (with dry weight basis), described resin molding contains the organic compound of tool aziridinyl of silica granule, 0.5-20% (weight) spherical polyethylene Wax particles and the 1-20% (weight) of 5-30% (weight) in solid-state part, this resin mainly is included in the intermolecular polyolefin copolymer resin emulsion that is linked to each other by ion beam.
According to the present invention, the method of the metallic plate of preparation resin-coating also is provided, it comprises: be coated with the organic compound of the spherical polyethylene wax pellets of silica granule that its solid portion of last layer contains 5-30% (weight), 0.5-20% (weight) and the tool aziridinyl of 1-20% (weight) and mainly be included in the aqueous resins coating of the intermolecular polyene copolymer resin fat liquor that is linked to each other by ion beam at metal sheet surface, metallic plate is heated, with the coating drying, forming coating weight at metal form face is 0.2-2.5g/m
2Resin molding.
Below, will generally as metallic plate situation of the present invention be described with steel plate.
In the present invention, the intermolecular polyolefin copolymer resin emulsion that is linked to each other by ion beam is used as the resin Composition in the resinous coat.Here used polyolefin copolymer resin preferably contains the unsaturated carboxyl group of ethylidene of 1-40% (weight) and can contain the alkene one ethylidene copolymers of unsaturated carboxylic acids resin of (methyl) acrylate ester component, and it is by the ionomer polymerization and to be crosslinked agent crosslinked so that HMW to be provided.
Above-mentioned by ion beam intermolecular continuous polyolefin copolymer resin emulsion can be by preparation tool carboxyl polyolefin copolymer the first step, with second step of the olefin copolymer ionomer polymerization that obtained with the ionomer resin that is obtained is formed the 3rd of HMW go on foot and obtain.
At the organic compound of the silica granule, spherical polyethylene wax pellets and the tool aziridinyl that in the intermolecular polyolefin copolymer resin emulsion that links to each other by ion beam, add scheduled volume that so obtain to form aqueous resins coating.According to the present invention, this aqueous resins coating is coated onto the surface of metallic plate, metallic plate is heated to predetermined plate temperature makes coating dry and form resin molding, with and obtained not only have wear resistence but also had good film properties such as processability, the anti-melanism that adds man-hour, stampability, corrosion resistance, colouring property isoequilibrium.
In the intermolecular polyolefin copolymer resin emulsion that links to each other by ion beam of preparation, at first will explain the first step of preparation copolymer.Under 200-300 ℃ temperature and the atmospheric condition of 1000-2000, will comprise alkene as first kind of monomer, as the 1-40% (weight) of second kind of monomer but ethylidene unsaturated carboxylic acid and as the monomer mixture of the third monomer of the copolymerization of needs adding copolymerization and prepare the polyolefin copolymer resin emulsion of providing carboxyl in aqueous dispersion.
Used ethylidene unsaturated carboxylic acid serves as better for well with (methyl) acrylic acid with for example (methyl) acrylic acid, maleic acid, fumaric acid, itaconic acid etc.Wherein, preferably use (methyl) acrylic acid.As for alkene, generally preferably use such as aromatic ethylene compounds such as styrene or such as aliphatic alpha-olefins such as ethene and propylene.Therefore, used in the present invention preferred olefin copolymer resin can comprise for example ethene-(methyl) acrylic copolymer resin, styrene-(methyl) acrylic copolymer resin, ethene-styrene (methyl) acrylic copolymer resin etc.
In the present invention, except above-mentioned first kind and second kind of monomer, also can use the third monomer as needs, for example a kind of two kinds or multiple: such as (methyl) ethyl acrylate, (methyl) methyl acrylate, (methyl) acrylate such as (methyl) propyl acrylate, such as styrene, styrene monomer such as vinyltoluene and chlorostyrene, such as (methyl) acrylic acid hydroxy alkyl esters such as hydroxy-ethyl acrylate and (methyl) hydroxypropyl acrylates, replace (methyl) acrylamide such as N-such as N-methylol (methyl) acrylamides, epoxy radicals and (methyl) acrylonitrile of containing (methyl) acrylate such as (methyl) glycidyl acrylate etc.
In this polyolefin copolymer resin, when ethylidene unsaturated carboxylic acid component during more than 40% (weight), even be used as film formation material by ion beam at the intermolecular polyolefin copolymer resin emulsion that links by what emulsification ionomer step and macromolecule formation step obtained later on, the resin-coated steel plate that is obtained does not have enough corrosion resistances yet.On the other hand, in the polyolefin copolymer resin, when the undersaturated carboxyl acid component of ethylidene is less than 1% (weight), just be not suitable for using the inventive method, be difficult to obtain required polyolefin copolymer resin aqueous dispersion or the aqueous dispersion that obtains.
In the aqueous dispersion, share the mixture of water or water and hydrophilic organic solvent.Used hydrophilic organic solvent comprises for example such as rudimentary aliphatic alcohols such as methyl alcohol, ethanol and propyl alcohol, such as glycol ethers such as EGMEs, such as glycol esters such as ethylene glycol ethyl ethers acid esters, such as ethers such as oxolane and dioxane, dimethyl formamide, diacetone alcohol or the like.
To carry out the polymerization of emulsification ionomer at the polyolefin copolymer resin that the first step obtains then.The polymerization of this emulsification ionomer is generally carried out with suitable cation and required ammoniacal liquor under 80-300 ℃ temperature and the atmospheric condition of 1-20.In the ionomer polymerization of pressurization,, preferably unite use amine from emulsification and resin property.
For cation, metal ion preferably.For example, particularly preferably use such as lithium, potassium, magnesium, zinc, sodium, calcium, iron and aluminium plasma.
For by the present invention form on the surface of steel plate tool wear resistence and processability, the anti-melanism that adds man-hour, stampability, corrosion resistance and can on the well balanced resin molding of bag property, need the resin Composition in the resinous coat is partial cross-linked to reach high molecular weight.
Therefore according to the present invention, thereby further partial cross-linked to obtain the intermolecular olefin copolymer resin that links to each other by ion beam be possible with the resin of ionomer polymerization by crosslinking agent.Here, crosslinking agent is not specifically limited, and the crosslinking agent that is fit to all can use, as long as these crosslinking agents can utilize the carboxyl of resin to come crosslinked.Therefore, described crosslinking agent comprises for example methylol compound, amines, epoxides, titanium compound etc.Cross-linking reaction is preferably under 30-200 ℃ temperature and the atmospheric pressure condition of normal pressure to 20 carries out.
Steel plate according to resin-coating of the present invention can obtain like this: will contain the organic compound of the tool aziridinyl of the spherical polyethylene Wax particles of silica granule, 0.5-20% (weight) of 5-30% (weight) and 1-20% (weight) at solid portion, and the intermolecular aqueous resins coating by the continuous polyolefin copolymer resin emulsion of ion beam that mainly comprises acquisition like this is coated on the metallic plate, metallic plate is heated to predetermined temperature, with the coating drying, be formed on that weight is 0.2-2.5g/m after the dry tack free of metallic plate
2Resin molding.
As described, be used for aqueous resins coating of the present invention contains 1-20% (weight) tool aziridinyl at solid portion organic compound, when this cold coating is painted on the steel plate and after heating and drying, it is crosslinked and form the resin molding with high crosslink density to be had the organic compound of aziridinyl as resin Composition intermolecular by the continuous olefin copolymer resin of ion beam.So the resin molding that obtains has increased substantially hardness, toughness and hear resistance.
The organic compound that is used for tool aziridinyl of the present invention comprises the trimethylolpropane tris (β-aziridinyl propionic ester) that for example is expressed from the next.
Be expressed from the next three-2,4,6-(1-a word used for translation propyl group)-1,3,5-triazines:
With three (1-(2-methyl) aziridinyl) the phosphinidyne oxygen that is expressed from the next:
As being shown below, the organic compound of above-mentioned tool aziridinyl reacts:
Therefore the resin molding that forms the tool high crosslink density thereby the copolymer resin of described compound of result and tool carboxyl plays cross-linking reaction has greatly strengthened the hardness of the resin molding that obtains, high toughness and hear resistance, has suppressed the vibrations that caused by the slip with used mould when the steel plate with resin-coating of the present invention carries out compression process and punching press and handles and because the softening of the resin molding that the generation of the heat of mould causes.In addition, corrosion resistance and chemical-resistant have also obtained enhancing.
Be used for cold coating of the present invention, if the amount at the organic compound of solid portion tool aziridinyl is less than 1% (weight), so not only with can not rise as the carboxyl in the above-mentioned copolymer resin enough cross-linking reactions and also as described in the carboxyl meeting and be used in compression process or the defatting step of punching press after handling in alkali compounds in ionic sodium and ionic potassium react make as described in film be hydrophily and greatly damaged its corrosion resistance and colouring property.On the other hand, when the amount of organic compound surpassed 20% (weight), the crosslink density of film excessively improved, and the hardness of film excessively raises, its as a result film can not follow the processing deformation that compression process etc. causes well and be full of cracks etc. takes place, reduced corrosion resistance and colouring property.Specifically, in the present invention, the amount of the organic compound of tool aziridinyl preferably is in the scope of 5-10% (weight) at solid portion in cold coating.
Be used for cold coating of the present invention contains 5-30% (weight) at solid portion silica granule.Silica granule can provide institute the resin molding superior corrosion resistance that obtains and colouring property effectively, further improves the hardness of resin molding, and the generation of the wearing and tearing that caused by vibration when being controlled at transportation, adds man-hour to the scratch of film, generation of melanism or the like.But, when in the cold coating when the amount of solid portion silica granule is less than 5% (weight), the corrosion resistance of the resin molding that is obtained and colouring property just can not get enough enhancings, also just can not reach the enough hardness of film.Therefore, just can not control wear resistence and add man-hour the scratch of film and the generation of melanism.On the other hand, when its amount surpassed 30% (weight), the hardness of resin molding strengthened significantly but silica granule occupies the excessive raising of ratio in resin molding cause the degeneration of resin molding film forming character and cause be full of cracks in film, has destroyed corrosion resistance.
In addition, silica granule play a part to improve film coefficient of friction, reduce lubricity, add the grinding agent that increases of wearing and tearing that cause mould man-hour and the service life of accelerating mould.Specifically, the amount of silica granule is preferably in the scope that accounts for solid portion 5-20% (weight) in cold coating.
For farthest bringing into play the effect of aforesaid silica granule, the particle diameter of silica granule is preferably in 1 to 200nm the scope.The particle diameter of silica granule is more little, and the corrosion resistance of described film improves many more.The use of silica granule use close and good bonding of resin molding and further strengthen the corrosion resistance of resin molding, from the viewpoint of this fact, the particle diameter of silica granule is more little then good more.Yet even use fines, above-mentioned effect correspondingly specifically is not enhanced.Therefore, in the present invention, 1nm or bigger silica granule particle diameter generally are to have satisfied the demand.On the other hand, when the particle diameter of silica granule becomes big, for example, when use was called as the silica of tool 40 to 20nm particle diameters of particle of chain type silica, the colouring property of resin molding had obtained very big enhancing.But if particle diameter surpasses 200nm, the surface of resin becomes coarse, thereby can not form careful resin molding.In addition, silica granule has worked to increase grinding agent, causes the decline of processing characteristics.Specifically, in the present invention, for example, under the situation that corrosion resistance seems important, the particle diameter of silica granule is preferably in 4 to 20nm the scope according to the performance of required film.Under the important situation of colouring property, then be preferably in 40 to 200nm the scope.
This silica granule generally is exactly usually said colloidal silica.In the present invention, the example of the commodity of Shi Yonging has SNOWTEX XS, SS, 40, N, UP (being produced by NISSANCHEMICAL INDUSTRIES LTD.).
Used in the present invention cold coating also comprises the spherical polyethylene Wax particles that accounts for solid portion 0.5-20% (weight).Thereby this spherical polyethylene Wax particles strengthens the lubricity of the resin molding that obtains effectively and strengthens wear resistence and marresistance.The anti-melanism that this has further strengthened deep drawing processability, stampability and mould abrasiveness required when carrying out compression process and punching press processing and has added the slidingsurface in man-hour, thus give good processing characteristics.
Yet in described cold coating, when the amount of spherical polyethylene Wax particles was less than 0.5% (weight), the lubricity of the resin molding that obtains was not enough, can not obtain the enhancing and the satisfied processing characteristics of wear resistence and marresistance.On the other hand, when its amount surpassed 20% (weight), the resin mold that is obtained has enough lubricities but electrolytic deposition is coated with when using, during the coating of powder coated or screen printing mode, and the cohesive of the film that is coated with is poor.Its former one of solid be applied when cold coating, bake and when dry, thereby wax deliquescing and liquefaction and the cohesive of retrogradation reduction pigment on the interface between resin molding and pigment.Specifically, in the present invention, the amount of spherical polyethylene wax preferably accounts for the 1-10% (weight) of solid portion in cold coating.
In order farthest to bring into play the effect of aforesaid spherical polyethylene Wax particles, the particle diameter of Wax particles is preferably in the scope of 0.1 to 3 μ m.When the particle diameter of Wax particles during less than 1 μ m, the resin molding that obtains the good lubricating property of tool is impossible, and the enhancing that will obtain stampability, anti-mould abrasiveness and deep drawing processability on the basis of this resin molding and the Wax particles in this film also is impossible.
On the other hand, when particle grain size surpasses 3 μ m, be difficult to Wax particles is dispersed in the cold coating, can damage the cohesive of film in the resin molding that can not equably wax be disperseed to be obtained steel plate.In addition, also reduce cohesive through the film of method preparations such as electrolytic deposition coating, powder coated and serigraphy.
Specifically, in the present invention, the particle diameter of spherical polyethylene Wax particles is preferably between 0.3 to 1.0 μ m in cold coating.
In the present invention, the softening point of spherical polyethylene Wax particles is preferably in 80 to 140 ℃ of scopes.When its softening point is lower than 80 ℃, with deliquescing of mould temperature rising Wax particles and liquefaction, according to this when carrying out compression process or punching press on the surface that allowing of steel plate after resin-coated and mould slided and handle, generation reduces the liquid spillover that processing characteristics produces scratch or bonds with mould, greatly damages the outer existing of product thereby the material of melanism adheres to slipper.On the other hand, when softening point surpasses 140 ℃, stampability, anti-mould abrasiveness and deep drawing are not enhanced, can not obtain good processing characteristics thereby the lubricity of Wax particles is not enough.
In the present invention, the commodity of this spherical polyethylene Wax particles that is suitable for have DIEJETE17 (being made by GOO CHEMICAL LTD.), KUE-1, KUE-5 and KUE-8 (making) by SANYO KASEI INDUSTRIES LTD., CHEMIPEARLW-100 CHEMIPEARL W-200, CHEMIPEARL W-300, CHEMIPEARL W-400, CHEMIPEARL W-500, CHEMIPEARLW-640, CHEMIPEARL W-700 (making) and EREPON E-20 (making) by NIKKACHEMICAL LTD. by MITSU1 PETROLEUMCHEMICAL INDUSTRIES LTD..
According to the present invention, when aforesaid aqueous resins coating was coated on surface of steel plate and be heated with drying, it heated and drying under than the low plate temperature of the softening point in spherical polyethylene Wax particles footpath.Then, formed resin molding, in resin molding, kept the spherical of spherical polyethylene Wax particles simultaneously and the lubricity of the resin molding that obtains is further strengthened, thereby further strengthened the press processability and the punch process of the resin coated steel sheet that obtains.In addition, spherical by in resin molding, the spherical polyethylene Wax particles being maintained, Wax particles can be scattered in the resin molding more equably.In addition, on the surface of resin molding, the shared ratio regular meeting of surface area that is exposed on the Wax particles on the resin face reduces, thereby the covering of finishing that can easily reach resin molding obtains good resistance to abrasion and colouring property.
For forming conventional thermosetting resin film on the surface of steel plate, at high temperature carry out long time period bake and drying is necessary.But the cold coating that is used for the present invention is to coat the surface of metallic plate in the short time cycle and be heated and dry so that crosslinked according to this and form film at lower temperature, has formed the resin molding with tridimensional network like this.Resemble in prior art the high temperature long time period bake and drying be unnecessary.Therefore, according to the present invention, can prepare crosslinked resin-coated steel plate, and have the advantage that described steel plate can prepare on its production line by simple drying equipment.
For example, on the electrogalvanizing production line, cold coating prepares resin-coated steel plate by print roll coating device coating and by the drying that simple drying equipment carries out short cycle.Just as top described, because can produce, so expection can be saved the expense of writing by online mode and inexpensive equipment investment.
In the present invention, the coating weight of washing resin molding with respect to steel plate preferably can reach 0.2-2.5g/m in that dried film situation is following
2When the coating weight of resin molding is lower than 0.2g/m
2The time, cold coating can not be coated on the steel plate equably, can not sufficiently show good film properties and the wear resistance such as processability, anti-melanism, corrosion resistance, colouring isoequilibrium expected in addition.On the other hand, when the coating weight of resin molding greater than 2.5/m
2The time, as the ground connection performance of one of required property such as calculating hood, for example electric conductivity is just by impaired.In addition, in compression process, thereby the overburden amount of resin molding increases and to make the film of being stripped from adhere to and accumulate on mould, causes the inconvenience of pressing mold and improves producing cost.Go out from the viewpoint of reality, specifically, the coating weight of resin molding preferably is in 0.3 to 1.9g/m
2Scope.
Be not specifically limited for metallic sheet material used on the metallic plate by tool resin coating film of the present invention, but the example that can propose has zine plate or galvanized steel plain sheet, aluminium sheet, aluminium alloy plate, titanium plate or the like.Zine plate or galvanized steel plain sheet, aluminium sheet, aluminium alloy plate etc. preferably carry out generating processing such as chromate processing or phosphate treated etc.Specifically, preferably carrying out chromate handles.It can be any that cleaning-type (response type) chromate is handled, the application type chromate is handled and the electrolysis-type chromate is handled that used chromate is handled.
As mentioned above, according to the present invention, the water coating is applied to and heats with a short cycle at a lower temperature then on the steel plate and drying, can obtain the steel plate of the resin coating film of tool crosslinked resin film according to this.
Not only wear resistence is good especially for the steel plate of the resin-coating of Huo Deing like this.And lubricity, marresistance, stampability, such as compacting processability and punch process such as the anti-melanism that adds man-hour, also have corrosion resistance, colouring property, ground connection performance etc. also very good.In addition, these character are well balanced.
Hereinafter the present invention will be described by the mode of embodiment, but the present invention is not subjected to the limitation of these embodiment.Below, as metallic sheet material, (coating weight of zinc is 20g/m to have used the steel plate of handling through chromate through electrogalvanizing
2, the coating weight of chromium is 20mg/m
2) relative evaluation between embodiment can be carried out.
In an embodiment, assessment item and assay method are as described below.In five evaluations, it is best estimating 5, is the poorest and estimate 1.
(1) corrosion resistance
With respect to the steel plate of the resin coating film that is obtained, on the dull and stereotyped of edge sealing and the material handled according to the Ericksen of JISZ23711, carry out the salt solution spray test, estimate during to appearance 1% white rust.It highly is 6mm that Ericksen releases.
(2) colouring property
Be applied on the resin-coated steel plate that is obtained by the melamine paint of spraying 20 μ m thickness.Afterwards, steel plate is baked at 150 ℃ immersed again in 30 minutes in the boiling water 1 hour.After steel plate shifted out 1 hour, with cutting knife at last 100 grid that carve the 1mm of mensuration.Carry out the herring bone disbonded test, with the number evaluation film cohesive of residue paint.
(3) dynamic friction coefficient
The lubricity of the resin coating film steel plate that obtains in order to estimate is calculated dynamic friction coefficient with the slip measurement measurement device by the load value that the lower slider of exerting pressure at 150kg causes.
(4) stampability
The stampability of the resin coating film steel plate that obtains in order to estimate carries out punch test with continuous punching press determinator under the condition that be at mold materials that SKD-11, mould are shaped as that 10mm square, clearance are 25%, drawing velocity is 80/minute and punching oil useless and comes it is estimated up to return altitude and reach 50 μ m.Observe the abrasion condition of mould after 1500000 punching presses with video oscilloscope and estimate anti-mould abrasiveness five stages.
(5) processability
The deep drawing press processability of the steel plate of the resin coating film that obtains in order to estimate etc. are carried out single compacting test by 80 tons of crank die arrangemenies and are come visual valuation scratch of the slidingsurface of product after the mold pressing in five stages, membrane (mould dragging) and anti-melanism.
(6) hardness of film
Carrying out the hardness of weighing with pencil hardness that pencil hardness test comes resin molding on the surface of steel plate of evaluating resin coating on the surface of the resin-coated steel plate that is obtained according to JISK5400.
(7) ground connection property
The surface of the steel plate of termination lead of analyzer (+,-) and the resin coating film that is obtained is contacted the resistance value of measuring slidingsurface gently.
(8) wear resistence
With PWO type flat flexural fatigue determinator cause wearing and tearing in case with visual valuation in the wear resistence of five Jie in the stage.
(9) resin molding intensity
For utilizing tension test just to measure the hot strength of film (temperature is 20 ℃ during mensuration for the wide 15mm of film, nip clearance 15mm), preparation thickness is the resin molding of 40 μ m.
Embodiment 1
Contain 0.5-50% (weight) thus the polyolefin copolymer of tool carboxyl of ethylidene unsaturated carboxylic acid component by the polymerization of NaOH ionomer and further form high-polymer molecular and prepare the intermolecular polyolefin copolymer resin emulsion that links to each other by ion beam by crosslinking agent.
The trimethylolpropane tris (β-aziridinyl propionic ester) of spherical polyethylene Wax particles and 10% (weight) that adds the particle diameter account for solid portion 10% (weight) and be the particle diameter of the softening point of 100 ℃ of tools of 10 to 20nm silica granule, 5% (weight) and 0.6 μ m in resulting emulsion prepares aqueous resins coating.
Thereby the heating to the surface of the steel plate of the electrogalvanizing of handling through chromium and under 90 ℃ temperature of this cold coating is obtained having 1g/m with dry
2The resin-coated steel plate of the coating weight of village's adipose membrane.
The corrosion resistance of the resin-coated steel plate that obtains like this and colouring property are listed in the table 1.
Table 1
| The content of ethylidene unsaturated carboxylic acid (weight %) | Corrosion resistance hr) | Colouring property (number of residue grid) | ||
| Dull and stereotyped | Ericksen | |||
| The present invention | 1 | 892 | 744 | 99 |
| 5 | 960 | 744 | 100 | |
| 10 | 984 | 792 | 100 | |
| 20 | 984 | 792 | 100 | |
| 40 | 888 | 792 | 100 | |
| Comparative example | 0.5 | The aqueous dispersion of difference | ||
| 45 | 420 | 360 | 82 | |
Embodiment 2
Contain 20% (weight) thus the polyolefin copolymer of tool carboxyl of ethylidene unsaturated carboxylic acid component by the polymerization of NaOH ionomer and further form high-polymer molecular and prepare the intermolecular polyolefin copolymer resin emulsion that links to each other by ion beam by crosslinking agent.
Add the particle diameter account for solid portion 10% (weight) and be 10 to 20nm silica granule in resulting emulsion, the spherical polyethylene Wax particles of 100 ℃ of softening points of the tool of 5% (weight) and 0.6 μ m particle diameter and the trimethylolpropane tris of 0.5-25% (weight) (β-aziridinyl propionic ester) (TAZM) prepare aqueous resins coating.
Be coated onto on the surface of the steel plate of the electrogalvanizing that chromium is handled this cold coating and heating and dry under 90 ℃ temperature, thereby obtain having 1g/m
2The steel plate of the resin-coating of the coating weight of resin molding.
The corrosion resistance of the steel plate of the resin-coating that obtains like this and colouring property are listed in the table 2.
Table 2
| Amount (weight %) (wt.%) | Hot strength (kg/m 2) | Corrosion resistance (hr) | Colouring property | Film hardness | Processing characteristics | ||
| Dull and stereotyped | Ericksen | ||||||
| The present invention | 0.5 | 722 | 888 | 768 | 100 | H | 4 |
| 1 | 766 | 888 | 768 | 100 | 2H | 5 | |
| 5 | 786 | 912 | 792 | 100 | 3H | 5 | |
| 10 | 780 | 960 | 816 | 100 | 3H | 5 | |
| 15 | 790 | 912 | 768 | 100 | 3H | 5 | |
| 20 | 812 | 912 | 744 | 100 | 4H | 5 | |
| Comparative example | 0.3 | 132 | 720 | 480 | 85 | HB | 2 |
| 25 | 890 | 624 | 96 | 36 | 5H | 1 | |
Example 3
Contain 20% (weight) thus the polyolefin copolymer of tool carboxyl of ethylidene unsaturated carboxylic acid component by the polymerization of NaOH ionomer and further form high-polymer molecular and prepare the intermolecular polyolefin copolymer resin emulsion that links to each other by ion beam by crosslinking agent.
Add the particle diameter account for solid portion 3-35%% (weight) and be 10 to 20nm silica granule in resulting emulsion, the trimethylolpropane tris (β-aziridinyl propionic ester) of the spherical polyethylene Wax particles and 10% (weight) of 100 ℃ of softening points of the tool of 5% (weight) and 0.6 μ m particle diameter prepares aqueous resins coating.
Be coated onto on the surface of the steel plate of the electrogalvanizing that chromium is handled this cold coating and heating and dry under 90 ℃ temperature, thereby obtain having 1g/m
2The steel plate of the resin-coating of the coating weight of resin molding.
The corrosion resistance of the steel plate of the resin-coating that obtains like this and colouring property are listed in the table 3.
Table 3
| Silica granule addition (weight %) | Corrosion resistance (hr) | Colouring property | Film hardness | Processing characteristics | Wear resistence | The power coefficient of friction | ||
| Dull and stereotyped | Ericksen | |||||||
| The present invention | 5 | 912 | 792 | 100 | 2H | 5 | 4 | 0.080 |
| 10 | 960 | 816 | 100 | 3H | 5 | 5 | 0.070 | |
| 15 | 960 | 840 | 100 | 3H | 5 | 5 | 0.065 | |
| 20 | 960 | 816 | 100 | 3H | 5 | 5 | 0.072 | |
| 25 | 936 | 792 | 100 | 3H | 5 | 5 | 0.100 | |
| 30 | 888 | 744 | 100 | 3H | 5 | 5 | 0.120 | |
| Comparative example | 3 | 520 | 240 | 66 | HB | 3 | 3 | 0.100 |
| 35 | 240 | 72 | 27 | 4H | 4 | 1 | 0.386 | |
Embodiment 4
Contain 20% (weight) thus the polyolefin copolymer of tool carboxyl of ethylidene unsaturated carboxylic acid component by the polymerization of NaOH ionomer and further form high-polymer molecular and prepare the intermolecular polyolefin copolymer resin emulsion that links to each other by ion beam by crosslinking agent.
Add the particle diameter account for solid portion 10% (weight) and be 4 to 400nm silica granule in resulting emulsion, the trimethylolpropane tris (β-aziridinyl propionic ester) of the spherical polyethylene Wax particles and 10 (weight) of 100 ℃ of softening points of the tool of 5% (weight) and 0.6 μ m particle diameter prepares aqueous resins coating.
Be coated onto on the surface of the steel plate of the electrogalvanizing that chromium is handled this cold coating and heating and dry under 90 ℃ temperature, thereby obtain having 1g/m
2The steel plate of the resin-coating of the coating weight of resin molding.
The corrosion resistance of the steel plate of the resin-coating that obtains like this and colouring property are listed in the table 4.
Table 4
| Silica granule addition (weight %) | Corrosion resistance (hr) | Colouring property | Film hardness | Processing characteristics | Wear resistence | The power coefficient of friction | ||
| Dull and stereotyped | Ericksen | |||||||
| The present invention | 4-6 | 960 | 816 | 100 | 3H | 5 | 5 | 0.070 |
| 10-20 | 960 | 816 | 100 | 3H | 5 | 5 | 0.065 | |
| 30-50 | 936 | 792 | 100 | 3H | 5 | 5 | 0.080 | |
| 40-200 | 912 | 792 | 100 | 3H | 5 | 5 | 0.098 | |
| Comparative example | 1 or littler | 936 | 792 | 95 | 2H | 4 | 4 | 0.080 |
| 200 or bigger | 240 | 72 | 27 | 4H | 2 | 2 | 0.146 | |
Embodiment 5
Contain 20% (weight) thus the polyolefin copolymer of tool carboxyl of ethylidene unsaturated carboxylic acid component by the polymerization of NaOH ionomer and further form high-polymer molecular and prepare the intermolecular polyolefin copolymer resin emulsion that links to each other by ion beam by crosslinking agent.
Add the particle diameter account for solid portion 10% (weight) and be 10 to 20nm silica granule in resulting emulsion, the trimethylolpropane tris (β-aziridinyl propionic ester) of the spherical polyethylene Wax particles and 10% (weight) of 100 ℃ of softening points of the tool of 0.3-2.5% (weight) and 0.6 μ m particle diameter prepares aqueous resins coating.
Be coated onto on the surface of the steel plate of the electrogalvanizing that chromium is handled this cold coating and heating and dry under 90 ℃ temperature, thereby obtain having 1g/m
2The steel plate of the resin-coating of the coating weight of resin molding.
The corrosion resistance of the steel plate of the resin-coating that obtains like this and colouring property are listed in the table 5.
Table 5
(notes)
*The punching press number of times is that (with ten thousand times is list to the punching press number of times that reaches when reaching 50 μ m of return altitude
| Wax particles addition (weight %) | Dynamic friction coefficient | Film hardness | Processing characteristics | Wear resistence | Stampability * | Colouring property | ||
| The punching press number of times | The mould wearing and tearing | |||||||
| The present invention | 0.5 | 0.085 | 2H | 5 | 5 | 150 | 5 | 5 |
| 1 | 0.070 | 3H | 5 | 5 | ＞150 | 5 | 5 | |
| 5 | 0.065 | 3H | 5 | 5 | ＞150 | 5 | 5 | |
| 10 | 0.065 | 3H | 5 | 5 | ＞150 | 5 | 5 | |
| 15 | 0.065 | 3H | 5 | 5 | ＞150 | 5 | 5 | |
| 20 | 0.065 | 4H | 5 | 5 | ＞150 | 5 | 4 | |
| Comparative example | 0.3 | 0.125 | H | 2 | 2 | 80 | 2 | 4 |
| 25 | 0.065 | 4H | 5 | 5 | ＞150 | 5 | 1 | |
The position)
For mould wearing and tearing, estimated the anti-mould abrasiveness after the punching press 1500000 times.
Embodiment 6
Contain 20% (weight) thus the polyolefin copolymer of tool carboxyl of ethylidene unsaturated carboxylic acid component by the polymerization of NaOH ionomer and further form high-polymer molecular and prepare the intermolecular polyolefin copolymer resin emulsion that links to each other by ion beam by crosslinking agent.
Add the particle diameter account for solid portion 10% (weight) and be 10 to 20nm silica granule in resulting emulsion, the trimethylolpropane tris (β-aziridinyl propionic ester) of the spherical polyethylene Wax particles and 10% (weight) of 100 ℃ of softening points of the tool of 10% (weight) and 0.1-3 μ m particle diameter prepares aqueous resins coating.
Be coated onto on the surface of the steel plate of the electrogalvanizing that chromium is handled this cold coating and heating and dry under 90 ℃ temperature, thereby obtain having 1g/m
2The steel plate of the resin-coating of the coating weight of resin molding.
The corrosion resistance of the steel plate of the resin-coating that obtains like this and colouring property are listed in the table 6.
Table 6
(notes)
*The punching press number of times is the punching press number of times that return altitude reaches when reaching 50 μ m
| Wax particles addition (weight %) | Dynamic friction coefficient | Film hardness | Processing characteristics | Wear resistence | Stampability * | Colouring property | ||
| The punching press number of times | The mould wearing and tearing | |||||||
| The present invention | 0.1 | 0.085 | 3H | 5 | 5 | ＞150 | 5 | 5 |
| 0.3 | 0.065 | 3H | 5 | 5 | ＞150 | 5 | 5 | |
| 0.5 | 0.065 | 3H | 5 | 5 | ＞150 | 5 | 5 | |
| 1.0 | 0.065 | 3H | 5 | 5 | ＞150 | 5 | 5 | |
| 1.5 | 0.077 | 3H | 5 | 5 | ＞150 | 5 | 5 | |
| 3.0 | 0.085 | 3H | 5 | 5 | ＞150 | 5 | 4 | |
| Comparative example | ＜0.1 | 0.248 | H | 1 | 2 | 65 | 2 | 4 |
| 3.5 | 0.125 | 2H | 2 | 3 | 120 | 3 | 1 | |
For mould wearing and tearing, estimate the anti-mould abrasiveness after the punching press 1500000 times.
Embodiment 7
Contain 20% (weight) thus the polyolefin copolymer of tool carboxyl of ethylidene unsaturated carboxylic acid component by the polymerization of NaOH ionomer and further form high-polymer molecular and prepare the intermolecular polyolefin copolymer resin emulsion that links to each other by ion beam by crosslinking agent.
Add the particle diameter account for solid portion 10% (weight) and be 10 to 20nm silica granule in resulting emulsion, the trimethylolpropane tris (β-aziridinyl propionic ester) of the spherical polyethylene Wax particles and 10% (weight) of the tool 70-150 ℃ softening point of 10% (weight) and 0.6 μ m particle diameter prepares aqueous resins coating.
Be coated onto on the surface of the steel plate of the electrogalvanizing that chromium is handled this cold coating and heating and dry under 90 ℃ temperature, thereby obtain having 1g/m
2The steel plate of the resin-coating of the coating weight of resin molding.
The corrosion resistance of the steel plate of the resin-coating that obtains like this and colouring property are listed in the table 7.
Table 7
(notes)
*The punching press number of times is that (with ten thousand times is list to the punching press number of times that reaches when reaching 50 μ m of return altitude
| The softening temperature of Wax particles (℃) | Dynamic friction coefficient | Film hardness | Processing characteristics | Wear resistence | Stampability * | Colouring property | ||
| The punching press number of times | The mould wearing and tearing | |||||||
| The present invention | 80 | 0.068 | 3H | 5 | 5 | ＞150 | 5 | 5 |
| 100 | 0.064 | 3H | 5 | 5 | ＞150 | 5 | 5 | |
| 120 | 0.067 | 3H | 5 | 5 | ＞150 | 5 | 5 | |
| 140 | 0.072 | 3H | 5 | 5 | ＞150 | 5 | 5 | |
| Comparative example | 70 | 0.070 | 2H | 2 | 3 | 32 | 1 | 4 |
| 150 | 0.262 | 2H | 1 | 1 | 43 | 2 | 3 | |
The position)
For mould wearing and tearing, estimated the anti-mould abrasiveness after the punching press 1500000 times.
Embodiment 8
Contain 20% (weight) thus the polyolefin copolymer of tool carboxyl of ethylidene unsaturated carboxylic acid component by the polymerization of NaOH ionomer and further form high-polymer molecular and prepare the intermolecular polyolefin copolymer resin emulsion that links to each other by ion beam by crosslinking agent.
Add the particle diameter account for solid portion 10% (weight) and be 10 to 20nm silica granule in resulting emulsion, the trimethylolpropane tris (β-aziridinyl propionic ester) of the spherical polyethylene Wax particles and 10% (weight) of 100 ℃ of softening points of the tool of 10% (weight) and 0.6 μ m particle diameter prepares aqueous resins coating.
Be coated onto on the surface of the steel plate of the electrogalvanizing that chromium is handled this cold coating and heating and dry under 90 ℃ temperature, thereby obtain having the steel plate of resin-coating of the coating weight of 0.2-2.5g/m2 resin molding.
The corrosion resistance of the steel plate of the resin-coating that obtains like this and colouring property are listed in the table 8.
Table 8
| Coating weight (the g/m of resin molding 2) | Dynamic friction coefficient | Film hardness | Processing characteristics | Wear resistence | Corrosion resistance (hr) | Colouring property | The ground connection performance | ||
| Dull and stereotyped | Ericksen | ||||||||
| The present invention | 0.2 | 0.074 | 2H | 4 | 4 | 888 | 744 | 5 | 5 |
| 0.5 | 0.067 | 3H | 5 | 5 | 936 | 792 | 5 | 5 | |
| 1.0 | 0.064 | 3H | 5 | 5 | 960 | 816 | 5 | 5 | |
| 1.5 | 0.065 | 3H | 5 | 5 | 1032 | 912 | 5 | 5 | |
| 2.0 | 0.068 | 3H | 5 | 5 | 1260 | 936 | 5 | 4 | |
| 2.5 | 0.072 | 3H | 4 | 5 | 1380 | 936 | 5 | 3 | |
| Comparative example | ＜0.2 | 0.364 | B | 1 | 1 | 480 | 360 | 4 | 5 |
| 3.0 | 0.092 | 2H | 1 | 3 | 780 | 480 | 1 | 1 | |
Claims (12)
1. the metallic plate of resin-coating, it is characterized in that having formed on the surface of metallic plate coating weight is 0.2-2.5g/m
2The resin molding of (with dry weight basis), described resin molding in solid portion, contain the spherical polyethylene Wax particles of silica granule, 0.5-20% (weight) of 5-30% (weight) and 1-20% (weight) the organic compound of tool aziridinyl, mainly comprise the intermolecular polyolefin copolymer resin emulsion that links to each other by ion beam.
2. according to the metallic plate of the resin-coating of claim 1, the wherein said intermolecular polyolefin copolymer resin emulsion that is connected by ion beam is the polyene copolymer resin fat liquor that contains the ethylidene unsaturated carboxylic acid component of 1-40% (weight), and the alkene-ethylidene copolymers of unsaturated carboxylic acids resin that can contain (methyl) acrylate component therein is by the ionomer polymerization and be crosslinked agent and further be cross-linked into high-polymer molecular.
3. according to the metallic plate of the resin-coating of claim 2, wherein said alkene is a kind of in ethene and the styrene at least.
4. according to the metallic plate of the resin-coating of claim 1, the particle diameter of wherein said silica granule is in 1 to 200nm scope.
5. according to the metallic plate of the resin-coating of claim 1, the particle diameter of wherein said spherical polyethylene Wax particles is in the scope of 0.1 to 3 μ m.
6. according to the metallic plate of the resin-coating of claim 1, the softening point of wherein said spherical polyethylene Wax particles is 80 to 140 ℃.
7. the method for preparing resin-coated metallic plate, comprise: be coated with silica granule, the spherical polyethylene Wax particles of 0.5-20% (weight) and the organic compound and the main aqueous resins coating of forming by the intermolecular polyolefin copolymer resin emulsion that links to each other by ion beam of the tool aziridinyl of 1-20% (weight) that the last layer solid portion contains 5-30% (weight) on the surface of metallic plate, metallic plate is heated, with the coating drying, forming coating on the surface of metallic plate heavily is 0.2-2.5g/m
2Resin molding.
8. according to the method for claim 7, the wherein said intermolecular polyene copolymer resin fat liquor that is connected by ion beam is the polyolefin copolymer village fat liquor that contains the ethylidene unsaturated carboxylic acid component of 1-40% (weight), and the alkene-ethylidene copolymers of unsaturated carboxylic acids resin that can contain (methyl) acrylate component therein is by the ionomer polymerization and be crosslinked agent and further be cross-linked into high-polymer molecular.
9. according to the method for claim 8, wherein said alkene is at least a in ethene and the styrene.
10. according to the method for claim 7, the particle diameter of wherein said silica granule is in 1 to 200nm scope.
11. according to the method for claim 7, the particle diameter of wherein said spherical polyethylene Wax particles is in the scope of 0.1 to 3 μ m.
12. according to the method for claim 7, wherein said metallic plate heats under than the low temperature of the softening point of spherical polyethylene Wax particles, and tool spherical polyethylene wax pellets in described resin molding has kept its spherical shape.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7014034A JP2759620B2 (en) | 1995-01-31 | 1995-01-31 | Resin-coated metal plate and method of manufacturing the same |
| JP14034/95 | 1995-01-31 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1135379A CN1135379A (en) | 1996-11-13 |
| CN1085566C true CN1085566C (en) | 2002-05-29 |
Family
ID=11849867
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96102592A Expired - Lifetime CN1085566C (en) | 1995-01-31 | 1996-01-31 | Metal plate coated with resin and production method thereof |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP2759620B2 (en) |
| KR (1) | KR0175961B1 (en) |
| CN (1) | CN1085566C (en) |
| MY (1) | MY132288A (en) |
| TW (1) | TW381108B (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4183558B2 (en) | 2003-05-26 | 2008-11-19 | ヤマウチ株式会社 | Heat press sheet |
| US9169406B2 (en) * | 2003-08-25 | 2015-10-27 | Dow Global Technologies Llc | Coating compositions |
| JP4398827B2 (en) * | 2004-02-06 | 2010-01-13 | 株式会社神戸製鋼所 | Resin coated metal plate |
| JP5355141B2 (en) * | 2009-02-24 | 2013-11-27 | 株式会社神戸製鋼所 | Chromate-free coating-coated hot-dip galvanized steel sheet with excellent adhesion between the plating surface and chromate-free coating and method for producing the same |
| WO2010101188A1 (en) * | 2009-03-04 | 2010-09-10 | 株式会社神戸製鋼所 | Resin-coated metallic material with excellent planar-direction thermal conductivity |
| JP5079037B2 (en) * | 2010-02-26 | 2012-11-21 | 住友軽金属工業株式会社 | Conductive pre-coated aluminum alloy plate for electrical or electronic equipment housing |
| JP5695430B2 (en) * | 2010-03-31 | 2015-04-08 | 株式会社神戸製鋼所 | Black metal plate |
| KR101424410B1 (en) * | 2010-08-31 | 2014-07-28 | 닛폰 파인 코팅스 카부시키카이샤 | Chromate-free coated metal plate |
| JP2013056441A (en) * | 2011-09-07 | 2013-03-28 | Sumitomo Light Metal Ind Ltd | Conductive precoated aluminum alloy plate |
| KR101762340B1 (en) | 2015-12-09 | 2017-07-27 | 주식회사 포스코 | Resin composition, the black resin coated steel sheet using the same, and the method of preparing the same |
| CN112048115B (en) * | 2019-06-06 | 2023-09-26 | 神华(北京)新材料科技有限公司 | Composite material of metal and polyolefin, preparation method and container thereof |
| WO2021207927A1 (en) * | 2020-04-14 | 2021-10-21 | Henkel Ag & Co. Kgaa | Sound deadener composition |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6292859A (en) * | 1985-10-18 | 1987-04-28 | Hitachi Ltd | Thin-film type thermal recording head |
| JPS63248872A (en) * | 1987-04-03 | 1988-10-17 | Nippon Shokubai Kagaku Kogyo Co Ltd | Composition for treating metallic surface |
| US4876160A (en) * | 1987-07-06 | 1989-10-24 | Nippon Steel Corporation | Organic composite-plated steel sheet |
-
1995
- 1995-01-31 JP JP7014034A patent/JP2759620B2/en not_active Expired - Fee Related
- 1995-12-29 TW TW084114138A patent/TW381108B/en not_active IP Right Cessation
-
1996
- 1996-01-05 MY MYPI96000043A patent/MY132288A/en unknown
- 1996-01-24 KR KR1019960001476A patent/KR0175961B1/en not_active IP Right Cessation
- 1996-01-31 CN CN96102592A patent/CN1085566C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6292859A (en) * | 1985-10-18 | 1987-04-28 | Hitachi Ltd | Thin-film type thermal recording head |
| JPS63248872A (en) * | 1987-04-03 | 1988-10-17 | Nippon Shokubai Kagaku Kogyo Co Ltd | Composition for treating metallic surface |
| US4876160A (en) * | 1987-07-06 | 1989-10-24 | Nippon Steel Corporation | Organic composite-plated steel sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| KR960028983A (en) | 1996-08-17 |
| KR0175961B1 (en) | 1999-03-20 |
| TW381108B (en) | 2000-02-01 |
| JP2759620B2 (en) | 1998-05-28 |
| JPH08207199A (en) | 1996-08-13 |
| MY132288A (en) | 2007-09-28 |
| CN1135379A (en) | 1996-11-13 |
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