CN100368098C - Surface-treated metal sheets excellent in press dragging resistance and coil deformation resistance and process for producing the same - Google Patents
Surface-treated metal sheets excellent in press dragging resistance and coil deformation resistance and process for producing the same Download PDFInfo
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- CN100368098C CN100368098C CNB2005100906977A CN200510090697A CN100368098C CN 100368098 C CN100368098 C CN 100368098C CN B2005100906977 A CNB2005100906977 A CN B2005100906977A CN 200510090697 A CN200510090697 A CN 200510090697A CN 100368098 C CN100368098 C CN 100368098C
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Abstract
A surface-treated metal sheet having a coating film formed in an amount of 0.3 to 5.0 g/m<2> from a water-based organic/inorganic composite coating material which comprises: a lubricant comprising either (1) a polyolefin wax dispersion having a molecular weight of 6,000 to 15,000 or (2) a combination of a polyolefin wax dispersion (A) having a molecular weight of 6,000 to 15,000 and a polyolefin wax dispersion (B) having a molecular weight of 1,000 to 5,000; and colloidal silica of 5 to 35 wt.% on a solid basis. Also provided is a surface-treated metal sheet which has a first layer which is a coating film formed in an amount of 0.05 to 0.3 g/m<2> on a dry basis from a water-based organic/inorganic composite comprising a polyolefin wax dispersion having a molecular weight of 6,000 to 15,000 and a second layer which is a coating film formed in an amount of 0.5 to 5.0 g/m<2> on a dry basis from a water-based organic/inorganic composite comprising colloidal silica of 5 to 35 wt.% on a solid basis. The water-based organic/inorganic composite coating material with which these surface-treated metal sheets can be produced is further provided.
Description
The application is that application number is dividing an application of 02803860.6 patent application (denomination of invention: the surface-treated metal plate and the manufacture method thereof of resistance to compression system scratch property and anti-Texturized property excellence).
Technical field
The water-based organic/inorganic composite coating that the present invention relates to be applicable to the surface-treated metal plate and the manufacture method thereof of automobile, household electrical appliance and construction material etc. and can be used for obtaining described surface-treated metal plate, described surface-treated metal plate not only shows excellent performance such as corrosion resistance, adhesive force and solderability, and shows excellent resistance to compression system scratch property and anti-Texturized property.
The invention still further relates to surface-treated metal plate and manufacture method thereof that is applicable to automobile, household electrical appliance and construction material etc. and the water-based organic/inorganic composite coating that can be used for obtaining described surface-treated metal plate, described surface-treated metal plate not only shows excellent performance such as corrosion resistance, adhesive force and solderability, and shows excellent resistance to compression system scratch property and anti-continuous skimming wear.
The invention still further relates to the surface-treated metal plate that is applicable to automobile, household electrical appliance and construction material etc., show excellent performance such as corrosion resistance, adhesive force and solderability and keep resistance to compression system scratch property, improve simultaneously in the section bundling process because of reeling loose or the folding problem that causes the coiled material fragmentation of load, and be suppressed in the pressing process generation that breaks away from the adhering residue thing that film causes by lubricant.
Background technology
Surface treated steel plate of having developed so far such as plated steel sheet and hot-dip galvanized steel sheet are widely used for household electrical appliance, construction material and auto parts and components etc.These steel plates mostly through perchromate handle or phosphate treated to improve corrosion resistance and coating adhesion.
In addition, along with being that the no coatings applications of purpose increases recently to reduce step and to reduce cost, particularly in electrical equipment industry, performance requirement to the surface of steel plate presentation quality improves constantly, not only comprise corrosion resistance and coating adhesion, and comprise resistance to marring, anti-impression of the hand and condensation or the wetting sensitiveness that causes variable color.
Require required performance for satisfying the consumer, developed the coating metal plate that special resin base organic hybrid films is arranged on the deposited steel plating plate that chromate is handled.For example, Japan has examined and discloses a kind of production method with the surface treated steel plate that improves performance such as corrosion resistance and anti-impression of the hand among patent publications (disclosing) No.4-14191 (JP-A-4-14191), is wherein forming on the steel plate of chromium plating chromate coatings by add the organic hybrid films of certain detail seed lac body colloidal sol preparation in water-soluble organic resin.
Japanese unexamined patent publication No. publication (disclosing) No.3-39485 (JP-A-3-39485) discloses after carrying out the chromate processing on the steel plate of zinc-plated Base Metal, 0.3-3.0g/m
2Silica that is dispersed in the water soluble resin the comprising of dry weight coverage rate and glass transition temperature (Tg) are the coating of 40 ℃ or higher wax.And Japanese unexamined patent publication No. publication (disclosing) No.3-28380 (JP-A-3-28380) discloses on the steel plate of electrogalvanizing chromate and has handled the back by 0.5-4.0g/m
2The dry weight coverage rate comprise carboxylation polyvinyl resin and Teflon
TMThe lubricated coating steel plate that the coating of lubricant obtains.But, also develop surface treated steel plate with improvement lubricity by in organic film, adding kollag for satisfying for example requirement of press formability of the strong resistance to marring of consumer wants.For example, Japanese unexamined patent publication No. publication (disclosing) No.6-173037 (JP-A-6-173037) discloses the steel plate by the band lubricating film that adds silica and polyolefin-wax acquisition in ether/ester type polyurethane resin and epoxy resin.
Disclosed technology provides and has had the sheet material that the excellent properties balance comprises corrosion resistance, coating adhesion, anti-impression of the hand and variable color sensitiveness among Japanese unexamined patent publication No. publication (disclosing) No.4-14191 (JP-A-4-14191), at present as one of main material of household electrical appliance.Even but the surface treated steel plate of the organic film of this coating also shows cut, the scratch in the pressing operation process and the wearing and tearing in the Product transport process etc. in the cargo handling process sometimes.
By contrast, disclosed technique table reveals scratch or the wearing and tearing in the pressing operation process of low degree among Japanese unexamined patent publication No. publication (disclosing) No.3-39485 (JP-A-3-39485) and Japanese unexamined patent publication No. publication (disclosing) No.3-28380 (JP-A-3-28380), and disclosed technology even in violent operation as also still have excellent resistance to compression system under the press forming and abrade property among Japanese unexamined patent publication No. publication (disclosing) No.6-173037 (JP-A-6-173037).But, the surface of steel plate of producing by disclosed technology among Japanese unexamined patent publication No. publication (disclosing) No.3-39485 (JP-A-3-39485), Japanese unexamined patent publication No. publication (disclosing) No.3-28380 (JP-A-3-28380) and Japanese unexamined patent publication No. publication (disclosing) No.6-173037 (JP-A-6-173037) easily slides, thereby is accompanied by in the section bundling process because of reeling loose or the folding problem that causes the coiled material fragmentation of load.Improve pulling force in the coiled material rolling-in process for the measure of avoiding these problems to take is included at present, it is loose that increase bandage quantity prevents to pack the back coiled material.
First main purpose of the present invention is to have that controlled film is formed and the surface-treated metal plate and the manufacture method thereof of the coefficient of kinetic friction on controlled film surface and confficient of static friction and can be used for making the water-based organic/inorganic composite coating of described surface-treated metal plate by providing, guarantee excellent corrosion resistance, adhesive force and weldability performance and keep resistance to compression system scratch property, improve simultaneously in the section bundling process because of reeling loose or the folding problem that causes the coiled material fragmentation of load.
Second main purpose of the present invention provides to be had excellent corrosion resistance, adhesive force and weldability performance and has the water-based organic/inorganic composite coating that excellent resistance to compression system abrades the surface-treated metal plate and the manufacture method thereof of property and anti-continuous skimming wear and can be used for making described surface-treated metal plate.
The 3rd main purpose of the present invention provides a kind of surface-treated metal plate and manufacture method thereof, described surface-treated metal plate shows excellent performance such as corrosion resistance, adhesive force and solderability and maintenance resistance to compression system scratch property, improve simultaneously in the section bundling process because of reeling loose or the folding problem that causes the coiled material fragmentation of load, and be suppressed in the pressing process generation that breaks away from the adhering residue thing that film causes by lubricant.
Summary of the invention
For realizing above-mentioned first purpose, the inventor is through a lot of industrious researchs, finish the present invention based on following discovery: comprising molecular weight by coating on the overlay metallization plate is that the polyolefin-wax dispersion of 6000-15000 is with the water-based organic/inorganic composite coating and the drying of colloidal silica form the water-based organic/inorganic composite film in right amount, can obtain not only to show excellent performance such as corrosion resistance, adhesive force and solderability, and showing the excellent resistance to compression system scratch property and the surface-treated metal plate of anti-Texturized property, wherein said metal sheet surface has the coefficient of kinetic friction that is controlled at 0.07-0.15 and is controlled at 0.10 or higher confficient of static friction.
Therefore, according to its first aspect, main points of the present invention are as follows.
(1) surface-treated metal plate of a kind of resistance to compression system scratch property and anti-Texturized property excellence is characterised in that to have 0.3-5.0g/m
2Comprise polyolefin-wax dispersion that one of water soluble resin and silicate compound or both and molecular weight are 6000-15000 and by the water-based organic/inorganic composite membrane of the colloidal silica of solid content 5-35% weight.
(2) according to the surface-treated metal plate of the resistance to compression system of above (1) scratch property and anti-Texturized property excellence, be characterised in that described polyolefin-wax dispersion be selected from not polar functionalities, molecular weight be 6000-15000 and granularity be the polyolefin-wax dispersion of 0.1-5.0 μ m and molecular weight be 6000-15000, acid number be 40 or lower and granularity be at least a in the improved polyalkene wax dispenser of 0.1-5.0 μ m.
(3) according to the resistance to compression system scratch property of above (1) or (2) and the surface-treated metal plate of anti-Texturized property excellence, the coefficient of kinetic friction that is characterised in that described surface is 0.07-0.15, and confficient of static friction is 0.10 or higher.
(4) a kind of water-based organic/inorganic composite coating is characterised in that to comprise polyolefin-wax dispersion, the colloidal silica by solid content 5-35% weight, the He Shui that one of water soluble resin and silicate compound or both and molecular weight are 6000-15000.
(5) the water-based organic/inorganic composite coating of above (4), be characterised in that described polyolefin-wax dispersion be selected from not polar functionalities, molecular weight be 6000-15000 and granularity be the polyolefin-wax dispersion of 0.1-5.0 μ m and molecular weight be 6000-15000, acid number be 40 or lower and granularity be at least a in the improved polyalkene wax dispenser of 0.1-5.0 μ m.
(6) manufacture method of the surface-treated metal plate of a kind of resistance to compression system scratch property and anti-Texturized property excellence is characterised in that the coating of above (4) is pressed dry weight basis with 0.3-5.0g/m
2After being applied on the overlay metallization plate, baking forms water-based organic/inorganic composite membrane.
(7) manufacture method of the surface-treated metal plate of a kind of resistance to compression system scratch property and anti-Texturized property excellence is characterised in that the coating of above (5) is pressed dry weight basis with 0.3-5.0g/m
2After being applied on the overlay metallization plate, baking forms water-based organic/inorganic composite membrane.
For realizing above-mentioned second purpose, the inventor is through a lot of industrious researchs, finish the present invention based on following discovery: comprise polyolefin-wax dispersion that molecular weight is 6000-15000, polyolefin-wax dispersion that molecular weight is 1000-5000 and the water-based organic/inorganic composite coating and the dry water-based organic/inorganic composite film that forms of an amount of colloidal silica by coating on the overlay metallization plate, can obtain the surface-treated metal plate of resistance to compression system scratch property and anti-continuous skimming wear excellence.
Therefore, according to its second aspect, main points of the present invention are as follows.
(1) surface-treated metal plate of a kind of resistance to compression system scratch property and anti-continuous skimming wear excellence, be characterised in that to have and comprise one of water soluble resin and silicate compound or both and be the lubricant (A) formed of the polyolefin-wax dispersion of 6000-15000, be the lubricant (B) formed of the polyolefin-wax dispersion of 1000-5000 and by the water-based organic/inorganic composite membrane of the colloidal silica of solid content 5-35% weight with have 0.3-5.0g/m by molecular weight by molecular weight
2Described water-based organic/inorganic composite membrane.
(2) according to the resistance to compression system scratch property of above (1) and the surface-treated metal plate of anti-continuous skimming wear excellence, be characterised in that described lubricant (A) be selected from not polar functionalities, molecular weight be 6000-15000 and granularity be the polyolefin-wax dispersion of 0.1-5.0 μ m and molecular weight be 6000-15000, acid number be 40 or lower and granularity be at least a lubricant of the improved polyalkene wax dispenser of 0.1-5.0 μ m, lubricant (B) is that polar functionalities, molecular weight are not that 1000-5000 and granularity are the polyolefin-wax dispersion of 0.1-5.0 μ m.
(3) a kind of water-based organic/inorganic composite coating comprises one of water soluble resin and silicate compound or both and is the lubricant (A) formed of the polyolefin-wax dispersion of 6000-15000, is lubricant (B), the colloidal silica by solid content 5-35% weight, the He Shui that the polyolefin-wax dispersion of 1000-5000 is formed by molecular weight by molecular weight.
(4) according to the water-based organic/inorganic composite coating of above (3), be characterised in that described lubricant (A) be selected from not polar functionalities, molecular weight be 6000-15000 and granularity be the polyolefin-wax dispersion of 0.1-5.0 μ m and molecular weight be 6000-15000, acid number be 40 or lower and granularity be at least a lubricant in the improved polyalkene wax dispenser of 0.1-5.0 μ m, lubricant (B) is that polar functionalities, molecular weight are not that 1000-5000 and granularity are the polyolefin-wax dispersion of 0.1-5.0 μ m.
(5) manufacture method of the surface-treated metal plate of a kind of resistance to compression system scratch property and the moving abrasiveness excellence of antiskid is characterised in that the coating of above (3) is pressed dry weight basis with 0.3-5.0g/m
2After being applied on the overlay metallization plate, baking forms water-based organic/inorganic composite membrane.
(6) manufacture method of the surface-treated metal plate of a kind of resistance to compression system scratch property and anti-continuous skimming wear excellence is characterised in that the coating of above (4) is pressed dry weight basis with 0.3-5.0g/m
2After being applied on the overlay metallization plate, baking forms water-based organic/inorganic composite membrane.
For realizing above-mentioned the 3rd purpose, the inventor is through a lot of industrious researchs, finish the present invention based on following discovery: comprising by molecular weight by coating on the upper strata of overlay metallization plate is the lubricant (A) that the polyolefin-wax dispersion of 6000-15000 is formed, be the water-based organic/inorganic composite coating (E) of the lubricant (B) formed of the polyolefin-wax dispersion of 1000-5000 when needing by molecular weight, baking forms ground floor, coating comprises the water-based organic/inorganic composite coating (F) of an amount of colloidal silica then, and baking forms the second layer, can obtain a kind of surface-treated metal plate, wherein the coefficient of kinetic friction of described metal sheet surface can be controlled at 0.07-0.15 and confficient of static friction is controlled at 0.10 or higher, also prevent from pressing process to break away from the generation of the adhering residue thing that film causes simultaneously by lubricant.
Therefore, according to its third aspect, main points of the present invention are as follows.
(1) surface-treated metal plate of a kind of resistance to compression system scratch property and anti-Texturized property excellence is characterised in that to have 0.05-0.3g/m
2Dry weight comprise one of water soluble resin and silicate compound or both and by molecular weight be the water-based organic/inorganic composite membrane (C) of the lubricant (A) formed of the polyolefin-wax dispersion of 6000-15000 as ground floor, and 0.5-5.0g/m
2The water-based organic/inorganic composite membrane of forming by one of water soluble resin and silicate compound or both with by the colloidal silica of solid content 5-35% weight (D) of dry weight is as the second layer.
(2) according to the surface-treated metal plate of the resistance to compression system of above (1) scratch property and anti-Texturized property excellence, be characterised in that described lubricant (A) be selected from not polar functionalities, molecular weight be 6000-15000 and granularity be the polyolefin-wax dispersion of 0.1-5.0 μ m and molecular weight be 6000-15000, acid number be 40 or lower and granularity be at least a lubricant in the improved polyalkene wax dispenser of 0.1-5.0 μ m.
(3), be characterised in that described water-based organic/inorganic composite membrane (C) is that the compounded lubricant that the lubricant (B) of the lubricant (A) of polyolefin-wax dispersion of 6000-15000 and the polyolefin-wax dispersion that molecular weight is 1000-5000 is mixed with is formed by water soluble resin with by molecular weight according to the surface-treated metal plate of the resistance to compression system of above (1) or (2) scratch property and anti-Texturized property excellence.
(4) according to the resistance to compression system scratch property of above (3) and the surface-treated metal plate of anti-Texturized property excellence, be characterised in that described lubricant (A) be selected from not polar functionalities, molecular weight be 6000-15000 and granularity be the polyolefin-wax dispersion of 0.1-5.0 μ m and molecular weight be 6000-15000, acid number be 40 or lower and granularity be at least a lubricant in the improved polyalkene wax dispenser of 0.1-5.0 μ m, lubricant (B) is that polar functionalities, molecular weight are not that 1000-5000 and granularity are the polyolefin-wax dispersion of 0.1-3.0 μ m.
(5) according to above (1) to (4) each resistance to compression system scratch property and the surface-treated metal plate of anti-Texturized property excellence, the coefficient of kinetic friction that is characterised in that described surface is 0.07-0.15, confficient of static friction is 0.10 or higher.
(6) manufacture method of the surface-treated metal plate of a kind of resistance to compression system scratch property and anti-Texturized property excellence is characterised in that on overlay metallization plate coating is that the lubricant (A) of polyolefin-wax dispersion of 6000-15000 and the water-based organic/inorganic composite coating (E) that water is formed extremely reach 0.05-0.3g/m by dry weight basis by one of water soluble resin and silicate compound or both and molecular weight
2Afterwards, baking forms ground floor, be coated with then by one of water soluble resin and silicate compound or both and wherein colloidal silica content count the colloidal silica of 5-35% weight by solid content and water-based organic/inorganic composite coating (F) that water is formed extremely reaches 0.5-5.0g/m by dry weight basis
2, baking forms the second layer.
(7) according to the manufacture method of the surface-treated metal plate of the resistance to compression system of above (6) scratch property and anti-Texturized property excellence, be characterised in that described lubricant (A) be selected from not polar functionalities, molecular weight be 6000-15000 and granularity be the polyolefin-wax dispersion of 0.1-5.0 μ m and molecular weight be 6000-15000, acid number be 40 or lower and granularity be at least a lubricant in the improved polyalkene wax dispenser of 0.1-5.0 μ m.
(8), be characterised in that described water-based organic/inorganic composite coating (E) is that compounded lubricant and the water that the lubricant (B) of the lubricant (A) of polyolefin-wax dispersion of 6000-15000 and the polyolefin-wax dispersion that molecular weight is 1000-5000 is mixed with is formed by water soluble resin, by molecular weight according to the manufacture method of the surface-treated metal plate of the resistance to compression system of above (6) or (7) scratch property and anti-Texturized property excellence.
(9) according to above (6) to (8) each resistance to compression system scratch property and the manufacture method of the surface-treated metal plate of anti-Texturized property excellence, be characterised in that described lubricant (A) is to be selected from not polar functionalities, molecular weight is that 6000-15000 and granularity are the polyolefin-wax dispersion of 0.1-5.0 μ m, with molecular weight be 6000-15000, acid number be 40 or lower and granularity be at least a lubricant in the improved polyalkene wax dispenser of 0.1-5.0 μ m, lubricant (B) is a polar functionalities not, molecular weight is that 1000-5000 and granularity are the polyolefin-wax dispersion of 0.1-3.0 μ m.
The accompanying drawing summary
Fig. 1 is the diagram according to the surface-treated metal plate of first aspect present invention.
Fig. 2 is the diagram according to the surface-treated metal plate of second aspect present invention.
Fig. 3 is the diagram according to a kind of embodiment of the surface-treated metal plate of third aspect present invention.
Fig. 4 is the diagram according to the another embodiment of the surface-treated metal plate of third aspect present invention.
Preferred forms
Explain the present invention in more detail below.
The conventional method that is used for improving the resistance to compression system scratch property of water-based organic/inorganic compound coating steel plate is that the water-based organic/inorganic composite membrane on steel plate adds lubricant such as low-molecular-weight polyolefin wax.By in water-based organic/inorganic film, adding the not low-molecular-weight polyolefin wax of polar functionalities in this way, described wax is present in the film surface with particle form, thereby can reduce the affinity of metal sheet surface, described wax is also crushed in pressing operation simultaneously forms lubricating layer between steel plate and punch die.Thereby obtain excellent lubricating effect, thereby can reduce the scratch in the pressing process.
According to first aspect present invention, molecular weight is that the polyolefin-wax dispersion of 6000-15000 is used as lubricant with ormal weight in water-based organic/inorganic composite coating.Described composite coating transfers to the content of colloidal silica and counts 5-35% weight by solid content.
Fig. 1 illustrates a kind of embodiment of surface-treated metal plate of the present invention.Surface-treated metal plate of the present invention has such structure: water-based organic/inorganic composite membrane 2 is arranged on overlay metallization plate 3.Described water-based organic/inorganic composite membrane 2 is to be coated with on overlay metallization plate 3 by proper method to comprise one of water soluble resin and silicate compound or both and colloidal silica, water and form as the water-based organic/inorganic composite coating of the polyolefin-wax dispersion 1 of lubricant.As shown in fig. 1, described polyolefin-wax dispersion 1 is exposed from water-based organic/inorganic composite membrane 2 with particle form.
Therefore, in water-based organic/inorganic composite membrane, add the polyolefin-wax dispersion, and the molecular weight of described wax is transferred to appropriate value, thereby on the film surface, produce the wax of particle form and control the hardness of described wax and the affinity on film surface.Also regulate dioxide-containing silica, not only for the hardness of film but also for obtaining film properties such as corrosion resistance and adhesive force.Thereby the surface-treated metal plate that can obtain not only to have satisfied corrosion resistance and adhesive force but also have still undiscovered excellent anti compacting scratch property and anti-Texturized property in the prior art, it has the coefficient of kinetic friction that is controlled at 0.07-0.15 and is controlled at 0.10 or higher confficient of static friction.
Explained later abrades the manufacture method of the surface-treated metal plate of property and anti-Texturized property excellence according to the resistance to compression system of first aspect present invention.
Be applied on the basic overlay metallization plate and baking forms water-based organic/inorganic composite membrane and makes according to the surface-treated metal plate of the first aspect present invention water-based organic/inorganic composite coating by will regulation.Be applicable to that basic overlay metallization plate of the present invention comprises plating, the steel plate of hot-dip and evaporation zinc-base metal, aluminize or the metallic plate of aluminium alloy, the metallic plate of the metallic plate of lead plating or metal and zinc-plated or ashbury metal, as zinc-plated metallic plate, the metallic plate of zinc-plated-nickel, the metallic plate of zinc-plated-iron, the metallic plate of zinc-plated-chromium, the metallic plate of zinc-plated-aluminium, the metallic plate of zinc-plated-titanium, the metallic plate of zinc-plated-magnesium, the metallic plate of zinc-plated-manganese etc., and the little cobalt of containing is arranged, molybdenum, tungsten, nickel, titanium, chromium, aluminium, manganese, iron, magnesium, plumbous, antimony, tin, copper, cadmium, arsenic etc. are as this coating of independent metallic element or impurity and/or wherein be dispersed with inorganic matter such as silica, those of aluminium oxide or titanium oxide.The present invention also can be used for compound overlay metallization plate, wherein above-mentioned coating and other coating such as iron plating or iron-combinations such as phosphorus coating.
The coating coverage rate of every kind of overlay metallization plate is preferably every side 1g/m at least
2, because lower coverage rate causes corrosion resistance to reduce.
Surface-treated metal plate of the present invention can be by improving adhesive force or the acquisition of corrosion proof basic handling to described overlay metallization plate before forming described water-based organic/inorganic composite membrane.Also can be by directly on without the overlay metallization plate of basic handling, forming described water-based organic/inorganic composite membrane acquisition.Described basic handling does not have particular restriction, as long as it can achieve the above object, but general preferred chromium hydrochlorate processing, because it can improve corrosion resistance or adhesive force.
As the method that forms chromate film, for example can mention contain chromic anhydride, chromate or bichromate as the aqueous solution of main agents in dipping (reactivity) chromate handle or electrolytic chromate is handled, or the coating chromating, wherein will comprise the treatment fluid coating of mixture of colloidal silica etc. and dry under the situation of not washing then in the described aqueous solution.
The chromate coverage rate is preferably about 5-100mg/m
2(based on Cr).If coverage rate is lower than 5mg/m
2(based on Cr), gained corrosion resistance deficiency then is and if be higher than 100mg/m
2, the interior poly-deficiency of chromate film itself then takes place, thereby reduces coating adhesion.
Can use acrylate-acrylic copolymer, epoxy-acrylic copolymer, olefin-acrylic copolymer, alkene ion-exchange polymer, styrene-propene acid copolymer, ammonia ester-acrylic copolymer, ammonia ester-epoxy resin, ethene-imines-acrylic resin etc. as water soluble resin.In order to obtain coating, preferably make described resin dispersion become to form emulsion in the solvent at water with these water soluble resins.When needing, also can add various crosslinking agents such as melamine resin or amino resins.Wherein, from performance and cost, especially preferably use acrylic based resin such as olefin-acrylic copolymer.Under the situation of the violent press forming of needs, the preferred ammonia ester-epoxy that demonstrates hardness and ductility that uses.
Being used for silicate compound of the present invention generally represents with following formula: M
2OnSiO
2(wherein M is one of alkali metal that is selected from sodium, potassium and lithium, and n is the value of any needs), it is one or more the mixture that is selected from sodium metasilicate, potassium silicate and the lithium metasilicate.As M
2O and SiO
2" n " value of mol ratio preferred in the scope of 1-10.Preferably " n " value is not less than 1, otherwise the gained film is tending towards moisture absorption and film adhesive force deficiency.Preferably be no more than 10, otherwise the gained film becomes fragile and formability descends.
Be applicable to that colloidal silica of the present invention can be spherical or thread silica, or the dendritic string of bonding pearl colloidal silica.Under the situation of preparing spherical SiO 2, granularity is preferably 5-50nm, under the situation of thread silica, diameter is preferably 5-50nm, it is 1-5 that described wire chemical is bonded to length/thickness rate, and under the situation of the dendritic string of pearl silica, the ratio of [particle mean size of the length of aggregation/pearl silica] is preferably at least 4, and one or more branch is arranged.
Described colloidal silica adds in the water-based organic/inorganic composite coating of the present invention with 5-35% weight by solid content.When being lower than 5% weight, can not obtain enough corrosion resistances and resistance to compression system scratch property, and during greater than 35% weight, coating adhesion and resistance to compression system scratch property are relatively poor.
The used water-based organic/inorganic composite coating of first aspect present invention is to be the polyolefin-wax dispersion combined preparation of 6000-15000 by one of above-mentioned water soluble resin and silicate compound or both and colloidal silica and water and molecular weight.More preferably in described water-based organic/inorganic composite coating, add be selected from be substantially free of polar group, molecular weight be 6000-15000 and granularity be the polyolefin-wax dispersion of 0.1-5.0 μ m and molecular weight be 6000-15000, acid number be 40 or lower and granularity be at least a in the improved polyalkene wax dispenser of 0.1-5.0 μ m.
As the polyolefin-wax dispersion, can use the Tissuemat E, polypropylene wax or the polybutene wax that are substantially free of polar group at water or contain concentration and be not more than 5% emulsifying agent, preferably do not contain dispersion in the aqueous solution of emulsifying agent.
As the improved polyalkene wax dispenser, can use the Tissuemat E, polypropylene wax or the polybutene wax that contain polar group at water or contain concentration and be not more than 5% emulsifying agent, preferably do not contain dispersion in the aqueous solution of emulsifying agent.Described polar group can be introduced (the polyene wax of oxidation) by with oxidant such as oxygen, ozone, nitric acid etc. polyolefin-wax is carried out oxidation processes in the presence of catalyst, also can by make ethylenic unsaturated carboxylic acid monomer such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid etc. and polyolefin-wax be dissolved in crude benzol etc., then nitrogen stream and polymerization initiator (peroxide, reductant-oxidant, heavy metal catalyst etc.) down the heating grafting introduce.
The average particle size of described polyolefin-wax dispersion and improved polyalkene wax dispenser is preferably 0.1-5.0 μ m, more preferably 1.0-4.0 μ m.Described average particle size preferably is not less than 0.1 μ m, otherwise is tending towards causing assembling and infringement stability.Described average particle size also preferably is not more than 5.0 μ m, otherwise the stability decreases of dispersion.The ratio of described average particle size and number average particle size preferably make average particle size/number average particle size less than 3 scope in.
The weight average molecular weight range of described polyolefin-wax dispersion and improved polyalkene wax dispenser is preferably 6000-15000.Preferred described weight average molecular weight is not less than 6000, otherwise causes anti-Texturized property poor.Preferred described weight average molecular weight is not more than 15000, otherwise infringement resistance to compression system scratch property.
The analytical method and the condition of the weight average molecular weight of described polyolefin-wax dispersion and improved polyalkene wax dispenser are described below, but described molecular weight analyse is not necessarily limited to the method.
Analytical method: high temperature GPC (gel permeation chromatography)
Post: PS (polystyrene) gel mixed type (2-4 post series connection)
Solvent: o-dichlorohenzene (ODCB), trichloro-benzenes (TCB) etc.
Measure temperature: 130-140 ℃
Detector: differential refractometer (RI) or infrared detector
Calibration curve: be purchased the molecular weight that monodispersity PS converts based on using
As JIS K 5902 defineds, the acid number of described improved polyalkene wax dispenser (KOH-mg/g) scope is preferably 40 or lower.If acid number surpasses 40, then described lubricant hardening and can not obtain enough lubricities.
Described polyolefin-wax dispersion and improved polyalkene wax dispenser also preferably have 950-1000kg/m
3Density (as JIS K 6760 defineds), 0.2mm or lower hardness (acupuncture hardness) (as JIS K 2207 defineds), 80% or bigger degree of crystallinity (measuring) and 110-150 ℃ fusing point by X-ray diffraction.
Being selected from least a in these polyolefin-wax dispersions and the improved polyalkene wax dispenser preferably is included in the described water-based organic/inorganic composite coating in 1-30 weight % (by solid content).During less than 1 weight %, can not obtain enough resistance to compression system scratch property, and during greater than 30 weight %, coating adhesion is poor.
The coverage rate scope of described water-based organic/inorganic composite membrane is 0.3-5.0g/m
2(pressing dry weight basis).More preferably 1.0-3.0g/m
2Preferred coverage rate is not less than 0.3g/m
2To realize target resistance to compression system scratch property, preferably be not more than 5.0g/m
2Be beneficial to solderability.
It can be spraying, curtain coating, flow coat, roller coat, blade coating, brushing, dip-coating, air knife blade coating etc. that coating forms described water-based organic/inorganic composite membrane method therefor.
Baking temperature is preferably 80-250 ℃.Even more preferably temperature be higher than fusing point with lubricator.When being lower than 80 ℃, corrosion resistance is descended, and when surpassing 250 ℃, film overvulcanization and formability is reduced because of the water in the coating can not evaporate fully.
Drying equipment is not had particular restriction, and method therefor can be the combination that hot-air sprays, uses heater indirect, infrared ray heating, inductance heating or these methods.
The coefficient of kinetic friction on surface-treated metal plate of the present invention surface is preferably 0.07-0.15, and confficient of static friction is preferably 0.10 or higher.The coefficient of kinetic friction is higher than at 0.15 o'clock, and resistance to compression system scratch property is poor, and the coefficient of kinetic friction be lower than 0.07 or confficient of static friction be lower than at 0.10 o'clock, anti-Texturized property is poor.
According to second aspect present invention, in water-based organic/inorganic composite coating, add the lubricant with different molecular weight (A) of ormal weight and (B) as lubricant.Here, molecular weight be the polyolefin-wax dispersion of 6000-15000 as lubricant (A), molecular weight is that the polyolefin-wax dispersion of 1000-5000 is as lubricant (B).Also transfer to by solid content and count 5-35% weight, can reach film hardness and film properties for example corrosion resistance and adhesive force by dioxide-containing silica with described water-based organic/inorganic composite membrane.
Fig. 2 illustrates a kind of embodiment of surface-treated metal plate of the present invention.Surface-treated metal plate of the present invention has such structure: water-based organic/inorganic composite membrane 13 is arranged on overlay metallization plate 14.Described water-based organic/inorganic composite membrane 13 is to be coated with on overlay metallization plate 14 by proper method to comprise one of water soluble resin and silicate compound or both and lubricant (A), lubricant (B), form by the colloidal silica of solid content 5-35% weight and the water-based organic/inorganic composite coating of water.As shown in Figure 2, lubricant (A) 11 and lubricant (B) 12 expose from water-based organic/inorganic composite membrane 13 with particle form.
Therefore, low-molecular-weight polyolefin wax dispenser and high molecular polyolefine wax dispenser commonly used are all added in the water-based organic/inorganic composite membrane, suppress the fragmentation of wax in pressing mold and the continuous sliding process with the wax that on the film surface, produces particle form simultaneously.Also regulate dioxide-containing silica, not only for the hardness of film but also for reaching film properties such as corrosion resistance and adhesive force.Thereby not only can obtain satisfied corrosion resistance and adhesive force, but also improve the duration of lubricating effect in resistance to compression system scratch property and the continuous sliding process.
Explained later is according to the resistance to compression system scratch property of second aspect present invention and the manufacture method of the surface-treated metal plate of anti-continuous skimming wear excellence.This manufacture method is basic identical with the manufacture method according to the surface-treated metal plate of first aspect present invention, but institute's use organic/inorganic composite coating difference.
Also the water-based organic/inorganic composite coating by will regulation is applied on the basic overlay metallization plate and baking forms water-based organic/inorganic composite membrane and makes according to the surface-treated metal plate of second aspect present invention.
Be applicable to basic overlay metallization plate of the present invention as the front at as described in the surface-treated metal plate of first aspect present invention.The coating coverage rate of every kind of overlay metallization plate is preferably every side 1g/m at least
2, because lower coverage rate causes corrosion resistance to reduce.Form described water-based organic/inorganic composite membrane after can be before forming described water-based organic/inorganic composite membrane described overlay metallization plate being improved adhesive force or corrosion proof basic handling, also can be directly on without the overlay metallization plate of basic handling the described water-based organic/inorganic composite membrane of formation.Described basic handling there is not particular restriction, as long as can achieve the above object, but general preferred chromium hydrochlorate processing, because it can improve corrosion resistance or adhesive force.Described chromate film build method and chromate coverage rate as the front at as described in the surface-treated metal plate of first aspect.
As water soluble resin, can use the front at mentioned those of the surface-treated metal plate of first aspect.For obtaining coating, equally preferably make described resin dispersion become to form emulsion in the solvent at water, when needing, also can add various crosslinking agents such as melamine resin or amino resins.From performance and cost, especially preferably use acrylic based resin such as olefin-acrylic copolymer.Under the situation of the violent press forming of needs, or under the situation of the bigger anti-continuous skimming wear of needs, the preferred ammonia ester-epoxy that demonstrates hardness and ductility that uses.
The silicate compound that is used for second aspect present invention and colloidal silica can described those be identical at the surface-treated metal plate of first aspect with the front.
Described colloidal silica adds in the described water-based organic/inorganic composite coating with 5-35% weight by solid content.When being lower than 5% weight, can not obtain enough corrosion resistances and resistance to compression system scratch property, and during greater than 35% weight, coating adhesion and resistance to compression system scratch property are relatively poor.
The used water-based organic/inorganic composite coating of second aspect present invention is by the lubricant with different molecular weight (A) of one of above-mentioned water soluble resin and silicate compound or both and colloidal silica and water and ormal weight and (B) combined preparation.Here, molecular weight be the polyolefin-wax dispersion of 6000-15000 as lubricant (A), molecular weight is that the polyolefin-wax dispersion of 1000-5000 is as lubricant (B).More preferably, with be selected from not polar functionalities, molecular weight be 6000-15000 and granularity be the polyolefin-wax dispersion of 0.1-5.0 μ m and molecular weight be 6000-15000, acid number be 40 or lower and granularity be at least a lubricant in the improved polyalkene wax dispenser of 0.1-5.0 μ m as lubricant (A), be that 1000-5000 and granularity are that the polyolefin-wax dispersion of 0.1-5.0 μ m is as lubricant (B) with not polar functionalities, molecular weight.
As the polyolefin-wax dispersion, can use the Tissuemat E, polypropylene wax or the polybutene wax that are substantially free of polar group at water or contain concentration and be not more than 5% emulsifying agent, preferably do not contain dispersion in the aqueous solution of emulsifying agent.
As the improved polyalkene wax dispenser, can use the Tissuemat E, polypropylene wax or the polybutene wax that contain polar group at water or contain concentration and be not more than 5% emulsifying agent, preferably do not contain dispersion in the aqueous solution of emulsifying agent.Described polar group can be introduced (the polyene wax of oxidation) by with oxidant such as oxygen, ozone, nitric acid etc. polyolefin-wax is carried out oxidation processes in the presence of catalyst, also can by make ethylenic unsaturated carboxylic acid monomer such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid etc. and polyolefin-wax be dissolved in crude benzol etc., then nitrogen stream and polymerization initiator (peroxide, reductant-oxidant, heavy metal catalyst etc.) down the heating grafting introduce.
The average particle size of described polyolefin-wax dispersion and improved polyalkene wax dispenser is preferably 0.1-5.0 μ m, more preferably 1.0-4.0 μ m.Described average particle size preferably is not less than 0.1 μ m, otherwise is tending towards causing assembling and infringement stability.Described average particle size also preferably is not more than 5.0 μ m, otherwise the stability decreases of dispersion.The ratio of described average particle size and number average particle size preferably make average particle size/number average particle size less than 3 scope in.
Be used for the polyolefin-wax dispersion of lubricant (A) and the weight average molecular weight range of improved polyalkene wax dispenser and be preferably 6000-15000.Preferred described weight average molecular weight is not less than 6000, otherwise described lubricant is too soft, hinders the raising of described anti-continuous skimming wear.Preferred described weight average molecular weight is not more than 15000, otherwise infringement resistance to compression system scratch property.
The weight average molecular weight range that is used for the polyolefin-wax dispersion of lubricant (B) is preferably 1000-5000.Preferred described weight average molecular weight is not less than 1000, otherwise described lubricant will be tending towards experiencing thermal decomposition and described therein surface is exposed in the convection drying heating furnace of nearly 1000 ℃ of high temperature, may total energy obtain enough greasy properties.Described weight average molecular weight preferably is not more than 5000, otherwise anti-continuous skimming wear decline.
Explain at the surface-treated metal plate of first aspect present invention the analytical method of the weight average molecular weight of described polyolefin-wax dispersion and improved polyalkene wax dispenser and condition front.
As JIS K 5902 defineds, acid number (KOH-mg/g) scope that is used for the improved polyalkene wax dispenser of lubricant (A) is preferably 40 or lower.If acid number surpasses 40, then described lubricant hardening and can not obtain enough lubricities.
The polyolefin-wax dispersion and the improved polyalkene wax dispenser that are used for lubricant (A) also preferably have 950-1000kg/m
3Density (as JIS K 6760 defineds), 0.2mm or lower hardness (acupuncture hardness) (as JIS K 2207 defineds), 80% or bigger degree of crystallinity (measuring) and 110-150 ℃ fusing point by X-ray diffraction.
Lubricant (A) and total content (B) are preferably the 1-30% weight of described water-based organic/inorganic composite coating by solid content.During less than 1% weight, can not obtain enough anti-continuous skimming wears, during greater than 30% weight, coating adhesion is poor.
The content of lubricant (A) with respect to lubricant (A) and total content (B) preferably in the scope of 10-90%.Less than 10% o'clock, can not improve the moving abrasiveness of antiskid.Greater than 90% o'clock, resistance to compression system scratch property was than only making with lubricator (B) time difference.
The coverage rate scope of described water-based organic/inorganic composite membrane is 0.3-5.0g/m
2(pressing dry weight basis).More preferably 1.0-3.0g/m
2Preferred coverage rate is not less than 0.3g/m
2To realize the resistance to compression system scratch property of target, preferably be not more than 5.0g/m
2Be beneficial to solderability.
Forming the water-based organic/inorganic composite membrane of second aspect present invention used coating process, baking temperature and drying equipment front explains at the formation of the water-based organic/inorganic composite membrane of first aspect present invention.
Then, according to third aspect present invention, on the upper strata of overlay metallization plate, form 0.05-0.3g/m
2Dry weight by one of water soluble resin and silicate compound or both and molecular weight be the water-based organic/inorganic composite membrane (C) formed of the lubricant (A) of the polyolefin-wax dispersion of 6000-15000 as ground floor, form 0.5-5.0g/m then
2The water-based organic/inorganic composite membrane of being made up of one of water soluble resin and silicate compound or both and colloidal silica (D) of dry weight is as the second layer, and the content of wherein said colloidal silica is counted 5-35% weight by solid content.
Fig. 3 illustrates first kind of embodiment according to the surface-treated metal plate of third aspect present invention, and Fig. 4 illustrates second kind of embodiment of surface-treated metal plate.
Among Fig. 3, has such structure according to first embodiment of the surface-treated metal plate of third aspect present invention: ground floor water-based organic/inorganic composite membrane (C) 22 and second layer water-based organic/inorganic composite membrane (D) 24 are arranged on overlay metallization plate 23.Ground floor water-based organic/inorganic composite membrane (C) the 22nd, coating of being made up of one of water soluble resin and silicate compound or both and lubricant (A) and water by proper method coating (E) and baking form, and second layer water-based organic/inorganic composite membrane (D) the 24th is coated with the water-based organic/inorganic composite coating (F) be made up of one of water soluble resin and silicate compound or both and colloidal silica and water by proper method and also toasts and form.
Among Fig. 4, has such structure: ground floor water-based organic/inorganic composite membrane (C ') 22 and second layer water-based organic/inorganic composite membrane (D) 24 are arranged on overlay metallization plate 23 according to second embodiment of the surface-treated metal plate of third aspect present invention.Ground floor water-based organic/inorganic composite membrane (C ') the 22nd, coating of being made up of one of water soluble resin and silicate compound or both and lubricant (A), lubricant (B) and water by the proper method coating (E) and baking form, and second layer water-based organic/inorganic composite membrane (D) the 24th is coated with the water-based organic/inorganic composite coating (F) be made up of one of water soluble resin and silicate compound or both and colloidal silica and water by proper method and also toasts and form.
Therefore, add polyolefin-wax dispersion that molecular weight transfers to appropriate value to form water-based organic/inorganic composite membrane (C) or (C '), on this film, form water-based organic/inorganic composite membrane (D) then as the upper strata, make described wax on the film surface of described water-based organic/inorganic composite membrane (D), protrude, control the hardness of wax and the affinity on film surface simultaneously with particle form.Also regulate the dioxide-containing silica of water-based organic/inorganic composite membrane (D), not only for the hardness of film but also for obtaining film properties such as corrosion resistance and adhesive force.Thereby can obtain not only to have satisfied corrosion resistance and adhesive force but also have the excellent resistance to compression system scratch property and the surface-treated metal plate of anti-Texturized property, the coefficient of kinetic friction is controlled at 0.07-0.15, confficient of static friction is controlled at 0.10 or higher, and prevents from pressing process to be broken away from by lubricant the generation of the adhering residue thing that film causes.
Explained later abrades the manufacture method of the surface-treated metal plate of property and anti-Texturized property excellence according to the resistance to compression system of third aspect present invention.This manufacture method is basic identical with the manufacture method according to the surface-treated metal plate of first aspect present invention, but institute's use organic/inorganic composite coating difference, and form two-layer water-based organic/inorganic composite membrane.
Be applicable to basic overlay metallization plate of the present invention as the front at as described in the surface-treated metal plate of first aspect.The coating coverage rate of every kind of overlay metallization plate is preferably every side 1g/m at least
2, because lower coverage rate causes corrosion resistance to reduce.Form described water-based organic/inorganic composite membrane after can be before forming described water-based organic/inorganic composite membrane described overlay metallization plate being improved adhesive force or corrosion proof basic handling, also can be directly on without the overlay metallization plate of basic handling the described water-based organic/inorganic composite membrane of formation.Described basic handling there is not particular restriction, as long as can achieve the above object, but general preferred chromium hydrochlorate processing, because it can improve corrosion resistance or adhesive force.Explain at the surface-treated metal plate of first aspect described chromate film build method and chromate coverage rate such as front.
As water soluble resin, can use the front at mentioned those of the surface-treated metal plate of first aspect.Be to obtain coating, described resin dispersion is become in the solvent to form emulsion at water, when needing, also can add various crosslinking agents such as melamine resin or amino resins.According to third aspect present invention, the water soluble resin that is used for ground floor more preferably is selected from the high-hydrophilic resin.As the resin that is used for the second layer, from performance and cost consideration, especially preferably use acrylic based resin such as olefin-acrylic copolymer, under the situation of the violent press forming of needs, the preferred ammonia ester-epoxy that demonstrates hardness and ductility that uses.
The silicate compound that is used for third aspect present invention and colloidal silica can described those be identical at the surface-treated metal plate of first aspect with the front.
Described colloidal silica adds in the described water-based organic/inorganic composite coating (F) with 5-35% weight by solid content.When being lower than 5% weight, can not obtain enough corrosion resistances and resistance to compression system scratch property, and during greater than 35% weight, coating adhesion and resistance to compression system scratch property are relatively poor.
According to third aspect present invention, in described water-based organic/inorganic composite coating (E), lubricant of ormal weight (A) or lubricant (A) and (B) and one of above-mentioned water soluble resin and silicate compound or both and colloidal silica and water be used in combination.Here, molecular weight be the polyolefin-wax dispersion of 6000-15000 as lubricant (A), molecular weight is that the polyolefin-wax dispersion of 1000-5000 is as lubricant (B).More preferably, with be selected from not polar functionalities, molecular weight be 6000-15000 and granularity be the polyolefin-wax dispersion of 0.1-5.0 μ m and molecular weight be 6000-15000, acid number be 40 or lower and granularity be at least a lubricant in the improved polyalkene wax dispenser of 0.1-5.0 μ m as lubricant (A), be that 1000-5000 and granularity are that the polyolefin-wax dispersion of 0.1-3.0 μ m is as lubricant (B) with not polar functionalities, molecular weight.
As the polyolefin-wax dispersion, can use the Tissuemat E, polypropylene wax or the polybutene wax that are substantially free of polar group at water or contain concentration and be not more than 5% emulsifying agent, preferably do not contain dispersion in the aqueous solution of emulsifying agent.
As the improved polyalkene wax dispenser, can use the Tissuemat E, polypropylene wax or the polybutene wax that contain polar group at water or contain concentration and be not more than 5% emulsifying agent, preferably do not contain dispersion in the aqueous solution of emulsifying agent.Described polar group can be introduced (the polyene wax of oxidation) by with oxidant such as oxygen, ozone, nitric acid etc. polyolefin-wax is carried out oxidation processes in the presence of catalyst, also can by make ethylenic unsaturated carboxylic acid monomer such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid etc. and polyolefin-wax be dissolved in the crude benzol etc., then nitrogen stream and polymerization initiator (peroxide, reductant-oxidant, heavy metal catalyst etc.) down the heating grafting introduce.
The average particle size that is used for the polyolefin-wax dispersion of lubricant (A) and improved polyalkene wax dispenser is preferably 0.1-5.0 μ m, more preferably 1.0-4.0 μ m.Select the thickness of the granularity of lubricant (A) greater than the water-based organic/inorganic composite membrane (D) that forms as the upper strata.The average particle size of lubricant (A) preferably is not less than 0.1 μ m, otherwise is tending towards causing assembling and infringement stability.The average particle size of lubricant (A) also preferably is not less than the water-based organic/inorganic composite membrane (D) that forms as the upper strata, otherwise infringement resistance to compression system scratch property.In addition, described average particle size also preferably is not more than 5.0 μ m, otherwise the stability decreases of dispersion.The ratio of described average particle size and number average particle size preferably make average particle size/number average particle size less than 3 scope in.
The polyolefin-wax dispersion of lubricant (B) and the average particle size of improved polyalkene wax dispenser are preferably 0.1-3.0 μ m.Also select the thickness of the granularity of lubricant (B) greater than the water-based organic/inorganic composite membrane (D) that forms as the upper strata.Described average particle size preferably is not less than 0.1 μ m, otherwise is tending towards causing assembling and infringement stability.The average particle size of lubricant (B) also preferably is not more than 3.0 μ m or greater than the thickness of water-based organic/inorganic composite membrane (D), otherwise damages anti-Texturized property.
Be used for the polyolefin-wax dispersion of lubricant (A) and the weight average molecular weight of improved polyalkene wax dispenser and be preferably 6000-15000.Preferred described weight average molecular weight is not less than 6000, otherwise damages anti-Texturized property.Also preferred described weight average molecular weight is not more than 15000, otherwise infringement resistance to compression system scratch property.
The weight average molecular weight range that is used for the polyolefin-wax dispersion of lubricant (B) is preferably 1000-5000.Preferred described weight average molecular weight is not less than 1000, otherwise described lubricant will be tending towards experiencing thermal decomposition and described therein surface is exposed in the convection drying heating furnace of nearly 1000 ℃ of high temperature, may total energy obtain enough greasy properties.Described weight average molecular weight also preferably is not more than 5000, otherwise can not reach by adding the effect that lubricant (B) further improves resistance to compression system scratch property.
Explain at the surface-treated metal plate of first aspect present invention the analytical method of the weight average molecular weight of described polyolefin-wax dispersion and improved polyalkene wax dispenser and condition front.As JIS K 5902 defineds, acid number (KOH-mg/g) scope that is used for the improved polyalkene wax dispenser of lubricant (A) is preferably 40 or lower.If acid number surpasses 40, then described lubricant becomes too hard and can not obtain enough lubricities.
The polyolefin-wax dispersion and the improved polyalkene wax dispenser that are used for lubricant (A) also preferably have 950-1000kg/m
3Density (as JIS K 6760 defineds), 0.2mm or lower hardness (acupuncture hardness) (as JIS K 2207 defineds), 80% or bigger degree of crystallinity (measuring) and 110-150 ℃ fusing point by X-ray diffraction.
The content of lubricant (A) or lubricant (A) and total content (B) are preferably the 2-60% weight of described water-based organic/inorganic composite coating by solid content.During less than 2% weight, can not obtain enough resistance to compression system scratch property, and during greater than 60% weight, coating adhesion is poor.
The coverage rate scope of described water-based organic/inorganic composite membrane (C) is 0.05-0.3g/m
2(pressing dry weight basis).More preferably 0.05-0.2g/m
2Preferred coverage rate is not less than 0.05g/m
2To realize the resistance to compression system scratch property of target, preferably be not more than 0.3g/m
2The formation that hinders upper layer film to prevent to reduce wetability.The coverage rate scope of described water-based organic/inorganic composite membrane (D) is 0.5-5.0g/m
2(pressing dry weight basis).More preferably 1.0-3.0g/m
2Preferred coverage rate is not less than 0.5g/m
2To realize target resistance to compression system scratch property, preferably be not more than 5.0g/m
2Be beneficial to solderability.
Forming the water-based organic/inorganic composite membrane of third aspect present invention used coating process, baking temperature and drying equipment front explains at the formation of the water-based organic/inorganic composite membrane of first aspect present invention.
The coefficient of kinetic friction according to the surface-treated metal plate surface of third aspect present invention is preferably 0.07-0.15, and confficient of static friction is preferably 0.10 or higher.The coefficient of kinetic friction is higher than at 0.15 o'clock, and resistance to compression system scratch property is poor, and the coefficient of kinetic friction be lower than 0.07 or confficient of static friction be lower than at 0.10 o'clock, anti-Texturized property is poor.
Embodiment
Explain the present invention in more detail below by embodiment and Comparative Examples, should understand the present invention and limited by these embodiment.
At first, explanation is according to the embodiment of first aspect present invention.
(1) types of agents
The tabulation of agents useful for same is shown in Table 1.All polyolefin-wax dispersions except that D1 and D8 all have 950-1000kg/m
3Density (as JIS K 6760 defineds), 0.2mm or lower hardness (acupuncture hardness) (as JIS K 2207 defineds), 80% or bigger degree of crystallinity (measuring) and 110-150 ℃ fusing point by X-ray diffraction.
The tabulation of table 1 reagent
| Reagent | Number | Name of product |
| Organic resin | A1 | Acrylic resin (AP-1508 (12), Toa Gosei Co., Ltd.) |
| A2 | Polyolefin-based water soluble resin (AR-2300, Toho Chemical Indus try Co., Ltd.) | |
| A3 | The polyurethane-base water soluble resin (RA-85, Nippon-NSC) | |
| A4 | Epoxy radicals water soluble resin (DICFINE EM-60, Dainippon Ink and Chemicals Inc.) | |
| Silicate compound | B1 | Lithium metasilicate |
| B2 | Sodium metasilicate | |
| B3 | Potassium silicate | |
| Colloidal silica | C1 | Moisture colloidal silica (SNOWTEX N, Nissan Chemical Industries, Ltd.) |
| C2 | Moisture colloidal silica (SNOWTEX UP, Nissan Chemical Industries, Ltd.) | |
| The polyolefin-wax dispersion | D1 | Polyethylene (molecular weight: 1000, acid number: 0, granularity: 3.0 μ m) |
| D2 | Polyethylene (molecular weight: 6000, acid number: 0, granularity: 3.0 μ m) | |
| D3 | Polyethylene (molecular weight: 8000, acid number: 0, granularity: 3.0 μ m) | |
| D4 | Polyethylene (molecular weight: 15000, acid number: 0, granularity: 3.0 μ m) | |
| D5 | Polyethylene (molecular weight: 20000, acid number: 0, granularity: 3.0 μ m) | |
| D6 | Polyethylene (molecular weight: 6000, acid number: 0, granularity: 0.1 μ m) | |
| D7 | Polyethylene (molecular weight: 6000, acid number: 0, granularity: 5.0 μ m) | |
| D8 | Modified poly ethylene (molecular weight: 1000, acid number: 20, granularity: 1.0 μ m) | |
| D9 | Modified poly ethylene (molecular weight: 6000, acid number: 20, granularity: 1.0 μ m) | |
| D10 | Modified poly ethylene (molecular weight: 8000, acid number: 20, granularity: 1.0 μ m | |
| D11 | Modified poly ethylene (molecular weight: 15000, acid number: 20, granularity: 1.0 μ m) | |
| D12 | Modified poly ethylene (molecular weight: 20000, acid number: 20, granularity: 1.0 μ m) | |
| D13 | Modified poly ethylene (molecular weight: 6000, acid number: 20, granularity: 0.1 μ m | |
| D14 | Modified poly ethylene (molecular weight: 6000, acid number: 20, granularity: 5.0 μ m) | |
| D15 | Modified poly ethylene (molecular weight: 6000, acid number: 40, granularity: 1.0 μ m) | |
| D16 | Modified poly ethylene (molecular weight: 6000, acid number: 100, granularity: 1.0 μ m |
(2) type of metallic plate
Used metallic plate is shown in Table 2.
The type of table 2 metallic plate and coating coverage rate (thickness of slab: 0.8mm)
| Abbreviation | The type of metallic plate |
| EG | The steel plate of electrogalvanizing (coating coverage rate: 20g/m 2) |
| ZN | The steel plate of electrogalvanizing-nickel (coating coverage rate: 20g/m 2, nickel content: 12 weight %) |
| GI | The steel plate of galvanizing by dipping (coating coverage rate: 60g/m 2) |
(3) chromate is handled
By in the bath that contains 50g/l chromic acid and 0.3g/l sulfuric acid with 10A/dm
2Current density conduction regulation electric weight make EG in the table 2 and ZN stand electrolytic chromate to handle, after the washing, dry under 80 ℃ peak value metal temperature with hot-air drying stove.
With the SiO that goes back ortho-chromic acid and silica that contains 40% reduction
2/ CrO
3Than being GI in 3 the chromate treatment fluid coating table 2, dry under the situation of not washing then.
Determine chromate film coverage rate (by Cr) by fluorescent X-ray analysis.
(4) preparation of water-based organic/inorganic composite coating
Make one of the water soluble resin shown in the table 1 and silicate compound or both, colloidal silica and polyolefin-wax dispersion be mixed with water-based organic/inorganic composite coating in table 4 to ratio shown in 6.
(5) coating of water-based organic/inorganic composite coating and drying
The water-based organic/inorganic composite coating for preparing in above (4) is applied to reaching of obtaining in above (3) shows listed dry weight among the 4-6 on the overlay metallization plate that perchromate is handled, baking and dry under 140 ℃ peak value metal temperature is made sample and is used for estimating.Calculate the coverage rate of organic hybrid films according to the measurement of liquid film weight in the coating process.
(6) performance evaluation
A. the corrosion resistance of plate
By preparation in salt spraytest described in the JIS Z 2371 test above (5) respectively estimate sample, wherein on the steel plate sample after under 35 ℃ the atmosphere temperature 5%NaCl aqueous solution being sprayed onto coating, the generation of measuring white rust after 72 hours.◎ and zero opinion rating are judged to be satisfaction in the following evaluation criteria.
◎: no white rust
Zero: white rust less than 10%
△: 〉=10% and＜50% white rust
*: 〉=50% white rust
B. the corrosion resistance behind the Sven-Gan Eriksson cut (Erichsen drawing)
What make preparation in above (5) respectively estimates the Sven-Gan Eriksson cut that sample stands 6mm, then on the steel plate sample after under 35 ℃ the atmosphere temperature 5%NaCl aqueous solution being sprayed onto coating, and the generation of measuring white rust in the described scored area after 48 hours.◎ and zero opinion rating are judged to be satisfaction in the following evaluation criteria.
◎: no white rust
Zero: white rust less than 5%
△: 〉=5% and＜20% white rust
*: 〉=20% white rust
C. coating adhesion
(Amilack#1000, Kansai Paint Co. Ltd.) to the dried film thickness of 25 μ m, toast described dry film 20 minutes under 130 ℃ furnace temperature to be coated with melamine-phthalic resin coating on the sample with respectively estimating of preparing in above (5) of scraping strip coating machine.After the standing over night, the Sven-Gan Eriksson cut that makes in the boiling water sample that soaks 30 minutes and another unsoaked sample all stand 7mm is attached to adhesive tape (ProductName: Cellotape, Nichiban Co., the product of Ltd.) in the Sven-Gan Eriksson cut district of each sample.Tear described adhesive tape 45 ° diagonal fast, the outward appearance in the described Sven-Gan Eriksson cut of visual assessment district.◎ and zero opinion rating are judged to be satisfaction in the following evaluation criteria.
◎: do not have and peel off
Zero: the area of peeling off less than 5%
△: 〉=5% and＜50% peel off area
*: 〉=50% peel off area
D. continuous welding
Make each sample of preparation in above (5) stand the series spot welding test under condition shown in the table 3, measuring and firmly forming nugget size is 3mm or bigger number of welds.
Table 3 welding condition
| Parameter | Condition |
| Welding current | 8500A |
| Charging interval | 10 cycles (50Hz) |
| Electrode diameter | 4.5mm |
| Electrode force | 200kgf |
◎ and zero opinion rating are judged to be satisfaction in the following evaluation criteria.
◎: solder joint: 〉=5000
Zero: solder joint: 〉=2500 and＜5000
△: solder joint: 〉=1000 and＜2500
*: solder joint:＜1000
E. resistance to compression system abrades property
Make each sample of preparation in above (5) stand the rectangular drawing test.The condition of described rectangular drawing test is that blank folding power is 6 tons, and (0.8 * 220 * 180mm) is molded into 65 * 115mm and high 50mm, visual assessment slidingsurface after the mold pressing with sample.◎ and zero opinion rating are judged to be satisfaction in the following evaluation criteria.
◎: less than defective due to scratch
Zero: because of defective due to scratch and the slip scratch on less than 50% sliding area area
△: because of the scratch and the slip scratch due to defective at least 50% sliding area area
*: expose following metal, scratch
F. abrasion resistance test
Make each sample of preparation in above (5) pass through the vinylite film at 10g/cm
2Load under stand per minute 360 times the ellipse swing in sliding area, produce wearing and tearing.Test after 10 minutes the visual assessment specimen surface.◎ and zero opinion rating are judged to be satisfaction in the following evaluation criteria.
◎: less than defective due to scratch
Zero: because of defective due to scratch and the slip scratch on less than 50% sliding area area
△: because of the scratch and the slip scratch due to defective at least 50% sliding area area
*: expose following metal
G. confficient of static friction
Make 25cm
2Each sample of preparation is installed on the testing tool of plane in above (5) of removing deburring of area, with Shinto Scientific Co., the 10D HEIDON confficient of static friction measurement mechanism that Ltd. provides is being measured confficient of static friction with 0.5 °/second between the sample of preparation under the condition of 200g load in above (5).
H. the coefficient of kinetic friction
With Shinto Scientific Co., the coefficient of kinetic friction of each sample of preparation in (5) more than the 14S HEIDON dynamic friction coefficient measuring device that Ltd. provides is measured under the condition of the slip of 10mm diameter stainless steel ball, 100g load and 150mm/ minute sliding speed.
I. anti-Texturized property
Make several have the internal diameter 508mm of different coefficients of friction, the 10t coiled materials of thickness of slab 1mm, after every volume usefulness crane lifting 3 times, measurement is checked the relation of the mobile degree and the coefficient of kinetic friction and confficient of static friction because of the mobile degree (distance) of coiled material coiling direction (vertically) tip of the loose generation of outmost turns.Found that between the coefficient of kinetic friction, confficient of static friction and the mobile degree (distance) interrelated well because of coiling direction (vertically) the coiled material end of the loose generation of reeling.The coefficient of kinetic friction less than 0.07 and confficient of static friction less than 0.10 o'clock, because of reel loose due to the coiled material tip displacement surpass 50mm, but the coefficient of kinetic friction be 0.07 or bigger and confficient of static friction be 0.10 or when bigger, because of reel loose due to the coiled material tip displacement successfully be limited in less than 30mm.Thereby, in this laboratory test, with above by " g " and " h " measurement confficient of static friction and the coefficient of kinetic friction as the indication of anti-Texturized property.Zero opinion rating is judged to be satisfaction in the following evaluation criteria.
Zero: the coefficient of kinetic friction: 〉=0.07, confficient of static friction: 〉=0.1
*: the coefficient of kinetic friction:＜0.07, confficient of static friction:＜0.1
Evaluation result is shown in table 7 in 9.These results clearly prove, technology of the present invention can be produced the performance with excellence and be comprised that corrosion resistance, adhesive force and solderability and excellent resistance to compression system abrade the surface-treated metal plate of property and anti-Texturized property, the coefficient of kinetic friction of wherein said metal sheet surface is controlled at 0.07-0.15, and confficient of static friction is controlled at 0.1 or higher.
Table 4
| Number | Metallic plate | Cr coverage rate (mg/m 2) | The organic/inorganic composite membrane | ||||||||||
| Water soluble resin/silicate compound 1) | Silica 2) | Wax 3) | Coverage rate (g/m 2) | ||||||||||
| Type | Amount | Type | Amount | Type | Amount | Type | Amount | Type | Amount | ||||
| 1 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D1 | 10 | - | - | 1.0 |
| 2 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D2 | 10 | - | - | 1.0 |
| 3 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D3 | 10 | - | - | 1.0 |
| 4 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D4 | 10 | - | - | 1.0 |
| 5 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D5 | 10 | - | - | 1.0 |
| 6 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D6 | 10 | - | - | 1.0 |
| 7 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D7 | 10 | - | - | 1.0 |
| 8 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D8 | 10 | - | - | 1.0 |
| 9 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D9 | 10 | - | - | 1.0 |
| 10 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D10 | 10 | - | - | 1.0 |
| 11 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D11 | 10 | - | - | 1.0 |
| 12 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D12 | 10 | - | - | 1.0 |
| 13 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D13 | 10 | - | - | 1.0 |
| 14 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D14 | 10 | - | - | 1.0 |
| 15 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D15 | 10 | - | - | 1.0 |
| 16 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D16 | 10 | - | - | 1.0 |
| 17 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D3 | 1 | - | - | 1.0 |
| 18 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D3 | 6 | - | - | 1.0 |
| 19 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D3 | 30 | - | - | 1.0 |
| 20 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D4 | 1 | - | - | 1.0 |
| 21 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D4 | 6 | - | - | 1.0 |
| 22 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D4 | 30 | - | - | 1.0 |
| 23 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D9 | 1 | - | - | 1.0 |
| 24 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D9 | 6 | - | - | 1.0 |
| 25 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D9 | 30 | - | - | 1.0 |
1) type and the ratio of the every kind of water soluble resin that is added based on the total amount (in solid weight meter) of 100 parts of water soluble resins and/or silicate compound.
2) type and the ratio of the silica that is added based on the total amount (in solid weight meter) of 100 parts of organic/inorganic composite membranes.
3) type and the ratio of the every kind of spherical wax dispenser that is added based on the total amount (in solid weight meter) of 100 parts of organic/inorganic composite membranes.
Table 5
| Number | Metallic plate | Cr coverage rate (mg/m 2) | The organic/inorganic composite membrane | ||||||||||
| Water soluble resin/silicate compound 1) | Silica 2) | Wax 3) | Coverage rate (g/m 2) | ||||||||||
| Type | Amount | Type | Amount | Type | Amount | Type | Amount | Type | Amount | ||||
| 26 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D2 | 5 | D4 | 5 | 1.0 |
| 27 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D2 | 5 | D9 | 5 | 1.0 |
| 28 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D3 | 10 | - | - | 0.1 |
| 29 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D3 | 10 | - | - | 0.3 |
| 30 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D3 | 10 | - | - | 2.0 |
| 31 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D3 | 10 | - | - | 5.0 |
| 32 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D3 | 10 | - | - | 10.0 |
| 33 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D4 | 10 | - | - | 0.1 |
| 34 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D4 | 10 | - | - | 0.3 |
| 35 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D4 | 10 | - | - | 2.0 |
| 36 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D4 | 10 | - | - | 5.0 |
| 37 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D4 | 10 | - | - | 10.0 |
| 38 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D9 | 10 | - | - | 0.1 |
| 39 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D9 | 10 | - | - | 0.3 |
| 40 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D9 | 10 | - | - | 2.0 |
| 41 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D9 | 10 | - | - | 5.0 |
| 42 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D9 | 10 | - | - | 10.0 |
| 43 | EG | 40 | A1 | 100 | - | - | C1 | 0 | D3 | 10 | - | - | 1.0 |
| 44 | EG | 40 | A1 | 100 | - | - | C1 | 5 | D3 | 10 | - | - | 1.0 |
| 45 | EG | 40 | A1 | 100 | - | - | C1 | 10 | D3 | 10 | - | - | 1.0 |
| 46 | EG | 40 | A1 | 100 | - | - | C1 | 35 | D3 | 10 | - | - | 1.0 |
| 47 | EG | 40 | A1 | 100 | - | - | C1 | 50 | D3 | 10 | - | - | 1.0 |
| 48 | EG | 40 | A1 | 100 | - | - | C2 | 0 | D4 | 10 | - | - | 1.0 |
| 49 | EG | 40 | A1 | 100 | - | - | C2 | 5 | D4 | 10 | - | - | 1.0 |
| 50 | EG | 40 | A1 | 100 | - | - | C2 | 10 | D4 | 10 | - | - | 1.0 |
1) type and the ratio of the every kind of water soluble resin that is added based on the total amount (in solid weight meter) of 100 parts of water soluble resins and/or silicate compound.
2) type and the ratio of the silica that is added based on the total amount (in solid weight meter) of 100 parts of organic/inorganic composite membranes.
3) type and the ratio of the every kind of spherical wax dispenser that is added based on the total amount (in solid weight meter) of 100 parts of organic/inorganic composite membranes.
Table 6
| Number | Metallic plate | Cr coverage rate (mg/m 2) | The organic/inorganic composite membrane | ||||||||||
| Water soluble resin/silicate compound 1) | Silica 2) | Wax 3) | Coverage rate (g/m 2) | ||||||||||
| Type | Amount | Type | Amount | Type | Amount | Type | Amount | Type | Amount | ||||
| 51 | EG | 40 | A1 | 100 | - | - | C2 | 35 | D4 | 10 | - | - | 1.0 |
| 52 | EG | 40 | A1 | 100 | - | - | C2 | 50 | D4 | 10 | - | - | 1.0 |
| 53 | EG | 40 | A2 | 90 | A4 | 10 | C1 | 15 | D3 | 10 | - | - | 1.0 |
| 54 | EG | 40 | A2 | 90 | A4 | 10 | C1 | 15 | D4 | 10 | - | - | 1.0 |
| 55 | EG | 40 | A2 | 90 | A4 | 10 | C1 | 15 | D9 | 10 | - | - | 1.0 |
| 56 | EG | 40 | A3 | 90 | A4 | 10 | C1 | 15 | D3 | 10 | - | - | 1.0 |
| 57 | EG | 40 | A3 | 90 | A4 | 10 | C1 | 15 | D4 | 10 | - | - | 1.0 |
| 58 | EG | 40 | A3 | 90 | A4 | 10 | C1 | 15 | D9 | 10 | - | - | 1.0 |
| 59 | EG | 40 | B1 | 100 | - | - | C1 | 15 | D3 | 10 | - | - | 1.0 |
| 60 | EG | 40 | B2 | 100 | - | - | C1 | 15 | D3 | 10 | - | - | 1.0 |
| 61 | EG | 40 | B3 | 100 | - | - | C1 | 15 | D3 | 10 | - | - | 1.0 |
| 62 | EG | 40 | B1 | 90 | A1 | 10 | C1 | 15 | D3 | 10 | - | - | 1.0 |
| 63 | EG | 40 | B1 | 90 | A4 | 10 | C1 | 15 | D3 | 10 | - | - | 1.0 |
| 64 | EG | - | A3 | 90 | A4 | 10 | C1 | 15 | D3 | 10 | - | - | 1.0 |
| 65 | EG | - | A3 | 90 | A4 | 10 | C1 | 15 | D4 | 10 | - | - | 1.0 |
| 66 | EG | - | A3 | 90 | A4 | 10 | C1 | 15 | D9 | 10 | - | - | 1.0 |
| 67 | ZN | 40 | A3 | 90 | A4 | 10 | C1 | 15 | D3 | 10 | - | - | 1.0 |
| 68 | GI | 40 | A3 | 90 | A4 | 10 | C1 | 15 | D3 | 10 | - | - | 1.0 |
1) type and the ratio of the every kind of water soluble resin that is added based on the total amount (in solid weight meter) of 100 parts of water soluble resins and/or silicate compound.
2) type and the ratio of the silica that is added based on the total amount (in solid weight meter) of 100 parts of organic/inorganic composite membranes.
3) type and the ratio of the every kind of spherical wax dispenser that is added based on the total amount (in solid weight meter) of 100 parts of organic/inorganic composite membranes.
Table 7
| Number | Performance | Note | |||||||||
| Dull and stereotyped corrosion resistance | Corrosion resistance behind the Sven-Gan Eriksson cut | Coating adhesion | Solderability | Resistance to compression system scratch property | Abrasion resistance | Anti-Texturized property | The coefficient of kinetic friction | Confficient of static friction | |||
| Do not soak | Soak | ||||||||||
| 1 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | × | 0.05 | 0.07 | Comparative Examples |
| 2 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | 0.07 | 0.15 | The present invention |
| 3 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | 0.10 | 0.20 | The present invention |
| 4 | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ◎ | ○ | 0.15 | 0.25 | The present invention |
| 5 | ◎ | ◎ | ◎ | ◎ | ◎ | △ | ○ | ○ | 0.20 | 0.30 | Comparative Examples |
| 6 | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ◎ | ○ | 0.08 | 0.15 | The present invention |
| 7 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | 0.07 | 0.12 | The present invention |
| 8 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | × | 0.06 | 0.10 | Comparative Examples |
| 9 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | 0.09 | 0.20 | The present invention |
| 10 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | 0.10 | 0.25 | The present invention |
| 11 | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ○ | ○ | 0.15 | 0.30 | The present invention |
| 12 | ◎ | ◎ | ◎ | ◎ | ◎ | × | △ | ○ | 0.20 | 0.35 | Comparative Examples |
| 13 | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ○ | ○ | 0.08 | 0.20 | The present invention |
| 14 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | 0.07 | 0.17 | The present invention |
| 15 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | 0.15 | 0.30 | The present invention |
| 16 | ◎ | ◎ | ◎ | ◎ | ◎ | × | × | ○ | 0.20 | 0.35 | The present invention |
| 17 | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ○ | ○ | 0.15 | 0.30 | The present invention |
| 18 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | 0.10 | 0.25 | The present invention |
| 19 | ○ | ○ | ○ | ○ | ◎ | ◎ | ◎ | ○ | 0.08 | 0.15 | The present invention |
| 20 | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ○ | ○ | 0.15 | 0.30 | The present invention |
| 21 | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ◎ | ○ | 0.15 | 0.30 | The present invention |
| 22 | ○ | ○ | ○ | ○ | ◎ | ◎ | ◎ | ○ | 0.08 | 0.15 | The present invention |
| 23 | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ○ | ○ | 0.15 | 0.30 | The present invention |
| 24 | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ◎ | ○ | 0.15 | 0.30 | The present invention |
| 25 | ○ | ○ | ○ | ○ | ◎ | ◎ | ◎ | ○ | 0.08 | 0.15 | The present invention |
Table 8
| Number | Performance | Note | |||||||||
| Dull and stereotyped corrosion resistance | Corrosion resistance behind the Sven-Gan Eriksson cut | Coating adhesion | Solderability | Resistance to compression system scratch property | Abrasion resistance | Anti-Texturized property | The coefficient of kinetic friction | Confficient of static friction | |||
| Do not soak | Soak | ||||||||||
| 26 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | 0.07 | 0.15 | The present invention |
| 27 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | 0.07 | 0.18 | The present invention |
| 28 | × | × | △ | △ | ◎ | × | × | ○ | 0.25 | 0.40 | Comparative Examples |
| 29 | ○ | ○ | ○ | ○ | ◎ | ○ | ○ | ○ | 0.15 | 0.30 | The present invention |
| 30 | ◎ | ◎ | ◎ | ◎ | ○ | ◎ | ◎ | ○ | 0.10 | 0.20 | The present invention |
| 31 | ◎ | ◎ | ◎ | ○ | ○ | ◎ | ◎ | ○ | 0.10 | 0.20 | The present invention |
| 32 | ◎ | ◎ | ◎ | ○ | × | ◎ | ◎ | ○ | 0.10 | 0.20 | Comparative Examples |
| 33 | × | × | △ | △ | ◎ | × | × | ○ | 0.25 | 0.45 | Comparative Examples |
| 34 | ○ | ○ | ○ | ○ | ◎ | ○ | ○ | ○ | 0.15 | 0.35 | The present invention |
| 35 | ◎ | ◎ | ◎ | ◎ | ○ | ◎ | ◎ | ○ | 0.15 | 0.25 | The present invention |
| 36 | ◎ | ◎ | ◎ | ○ | ○ | ◎ | ◎ | ○ | 0.10 | 0.20 | The present invention |
| 37 | ◎ | ◎ | ◎ | ○ | × | ◎ | ◎ | ○ | 0.10 | 0.20 | Comparative Examples |
| 38 | × | × | △ | △ | ◎ | × | × | ○ | 0.25 | 0.45 | Comparative Examples |
| 39 | ○ | ○ | ○ | ○ | ◎ | ○ | ○ | ○ | 0.15 | 0.35 | The present invention |
| 40 | ◎ | ◎ | ◎ | ◎ | ○ | ◎ | ◎ | ○ | 0.09 | 0.20 | The present invention |
| 41 | ◎ | ◎ | ◎ | ○ | ○ | ◎ | ◎ | ○ | 0.09 | 0.20 | The present invention |
| 42 | ◎ | ◎ | ◎ | ○ | × | ◎ | ◎ | ○ | 0.09 | 0.20 | Comparative Examples |
| 43 | △ | △ | ◎ | ○ | ◎ | △ | ○ | ○ | 0.10 | 0.20 | Comparative Examples |
| 44 | ○ | ○ | ◎ | ◎ | ◎ | ○ | ○ | ○ | 0.10 | 0.20 | The present invention |
| 45 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | 0.10 | 0.20 | The present invention |
| 46 | ◎ | ◎ | ◎ | ○ | ◎ | ◎ | ◎ | ○ | 0.10 | 0.20 | The present invention |
| 47 | ○ | ○ | ○ | △ | ○ | △ | ○ | ○ | 0.10 | 0.20 | Comparative Examples |
| 48 | △ | △ | ◎ | ○ | ◎ | △ | ○ | ○ | 0.15 | 0.25 | Comparative Examples |
| 49 | ○ | ○ | ◎ | ◎ | ◎ | ○ | ○ | ○ | 0.15 | 0.25 | The present invention |
| 50 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | 0.15 | 0.25 | The present invention |
Table 9
| Number | Performance | Note | |||||||||
| Dull and stereotyped corrosion resistance | Corrosion resistance behind the Sven-Gan Eriksson cut | Coating adhesion | Solderability | Resistance to compression system scratch property | Abrasion resistance | Anti-Texturized property | The coefficient of kinetic friction | Confficient of static friction | |||
| Do not soak | Soak | ||||||||||
| 51 | ◎ | ◎ | ◎ | ○ | ◎ | ◎ | ◎ | ○ | 0.15 | 0.25 | The present invention |
| 52 | ○ | ○ | ○ | △ | ○ | △ | ○ | ○ | 0.15 | 0.25 | Comparative Examples |
| 53 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | 0.10 | 0.15 | The present invention |
| 54 | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ◎ | ○ | 0.15 | 0.20 | The present invention |
| 55 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | 0.09 | 0.15 | The present invention |
| 56 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | 0.10 | 0.20 | The present invention |
| 57 | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ◎ | ○ | 0.15 | 0.25 | The present invention |
| 58 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | 0.09 | 0.20 | The present invention |
| 59 | ◎ | ○ | ○ | △ | ◎ | ◎ | ◎ | ○ | 0.10 | 0.25 | The present invention |
| 60 | ◎ | ○ | ○ | △ | ◎ | ◎ | ◎ | ○ | 0.10 | 0.25 | The present invention |
| 61 | ◎ | ○ | ○ | △ | ◎ | ◎ | ◎ | ○ | 0.10 | 0.25 | The present invention |
| 62 | ◎ | ◎ | ◎ | ○ | ◎ | ◎ | ◎ | ○ | 0.10 | 0.25 | The present invention |
| 63 | ◎ | ◎ | ◎ | ○ | ◎ | ◎ | ◎ | ○ | 0.10 | 0.25 | The present invention |
| 64 | △ | △ | ◎ | ○ | ◎ | ◎ | ◎ | ○ | 0.10 | 0.20 | The present invention |
| 65 | △ | △ | ◎ | ○ | ◎ | ○ | ◎ | ○ | 0.15 | 0.25 | The present invention |
| 66 | △ | △ | ◎ | ○ | ◎ | ◎ | ◎ | ○ | 0.09 | 0.20 | The present invention |
| 67 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | 0.10 | 0.20 | The present invention |
| 68 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | 0.10 | 0.20 | The present invention |
Explained later is according to the embodiment of second aspect present invention.
(1) types of agents
The tabulation of agents useful for same is shown in Table 10.All lubricants (A) except that D7 all have 950-1000kg/m
3Density (as JIS K 6760 defineds), 0.2mm or lower hardness (acupuncture hardness) (as JIS K 2207 defineds), 80% or bigger degree of crystallinity (measuring) and 110-150 ℃ fusing point by X-ray diffraction.
The tabulation of table 10 reagent
| Reagent | Number | Name of product |
| Organic resin | A1 | Acrylic resin (AP-1508 (12), Toa Gosei Co., Ltd.) |
| A2 | Polyolefin-based water soluble resin (AR-2300, Toho Chemical Industry Co., Ltd.) | |
| A3 | The polyurethane-base water soluble resin (RA-85, Nippon-NSC) | |
| A4 | Epoxy radicals water soluble resin (DICFINE EM-60, Dainippon Ink and Chemicals Inc.) | |
| Silicate compound | B1 | Lithium metasilicate |
| B2 | Sodium metasilicate | |
| B3 | Potassium silicate | |
| Colloidal silica | C1 | Moisture colloidal silica (SNOWTEX N, Nissan Chemical Industries, Ltd. |
| C2 | Moisture colloidal silica (SNOWTEX UP, Nissan Chemical Industries, Ltd. | |
| Lubricant A﹠ contrast | D1 | Polyethylene (molecular weight: 6000, acid number: 0, granularity: 3.0 μ m) |
| D2 | Polyethylene (molecular weight: 8000, acid number: 0, granularity: 3.0 μ m) | |
| D3 | Polyethylene (molecular weight: 15000, acid number: 0, granularity: 3.0 μ m) | |
| D4 | Polyethylene (molecular weight: 20000, acid number: 0, granularity: 3.0 μ m) | |
| D5 | Polyethylene (molecular weight: 6000, acid number: 0, granularity: 0.1 μ m) | |
| D6 | Polyethylene (molecular weight: 6000, acid number: 0, granularity: 5.0 μ m) | |
| D7 | Modified poly ethylene (molecular weight: 1000, acid number: 20, granularity: 1.0 μ m) | |
| D8 | Modified poly ethylene (molecular weight: 6000, acid number: 20, granularity: 1.0 μ m) | |
| D9 | Modified poly ethylene (molecular weight: 8000, acid number: 20, granularity: 1.0 μ m) | |
| D10 | Modified poly ethylene (molecular weight: 15000, acid number: 20, granularity: 1.0 μ m) | |
| D11 | Modified poly ethylene (molecular weight: 20000, acid number: 20, granularity: 1.0 μ m) | |
| D12 | Modified poly ethylene (molecular weight: 6000, acid number: 20, granularity: 0.1 μ m) | |
| D13 | Modified poly ethylene (molecular weight: 6000, acid number: 20, granularity: 5.0 μ m) | |
| D14 | Modified poly ethylene (molecular weight: 6000, acid number: 40, granularity: 1.0 μ m) | |
| D15 | Modified poly ethylene (molecular weight: 6000, acid number: 100, granularity: 1.0 μ m) | |
| Lubricant B﹠ contrast | E16 | Polyethylene (molecular weight: 500, acid number: 0, granularity: 3.0 μ m) |
| E17 | Polyethylene (molecular weight: 1000, acid number: 0, granularity: 3.0 μ m) | |
| E18 | Polyethylene (molecular weight: 5000, acid number: 0, granularity: 3.0 μ m) | |
| E19 | Polyethylene (molecular weight: 1000, acid number: 0, granularity: 5.0 μ m) | |
| E20 | Polyethylene (molecular weight: 1000, acid number: 0, granularity: 0.1 μ m) | |
| E21 | Polyethylene (molecular weight: 5500, acid number: 0, granularity: 3.0 μ m) |
(2) type of metallic plate
Used metallic plate is listed those in the table 2.
(3) chromate is handled
The carrying out of explaining at first aspect as the front.
(4) preparation of water-based organic/inorganic composite coating
Make from one of the water soluble resin of table 10 and silicate compound or both, colloidal silica and lubricant and be mixed with water-based organic/inorganic composite coating with table 11 to ratio shown in 13.
(5) coating of water-based organic/inorganic composite coating and drying
The water-based organic/inorganic composite coating of preparation in above (4) is applied on the overlay metallization plate that the chromate that obtains in above (3) handles reaches listed dry weight among the table 11-13, baking and dry in the heat-wind circulate drying stove under the peak value metal temperature of 500 ℃ atmosphere temperatures and 140 ℃ is made sample and is used for estimating.Calculate the coverage rate of organic hybrid films according to the measurement of liquid film weight in the coating process.
(6) performance evaluation
A. the corrosion resistance of plate
To estimate at the mode of being explained according to the embodiment of first aspect.
B. the corrosion resistance behind the Sven-Gan Eriksson cut
To estimate at the mode of being explained according to the embodiment of first aspect.
C. coating adhesion
To estimate at the mode of being explained according to the embodiment of first aspect.
D. continuous welding
To estimate at the mode of being explained according to the embodiment of first aspect.
E. resistance to compression system abrades property
To estimate at the mode of being explained according to the embodiment of first aspect.
F. abrasion resistance test
To estimate at the mode of being explained according to the embodiment of first aspect.
G. anti-continuous skimming wear
The plastic products (video cassette) that 10mm is stamped out are fixed in the end of 500g load in the rotary type sliding wear testing instrument, are placed on then on the specimen surface of having made disk.Change the observation specimen surface with 60 rev/mins of every rotations 50, estimate the revolution when scratch occurring in the coating.
H. the coefficient of kinetic friction
To estimate at the mode of being explained according to the embodiment of first aspect.
I. thermal decomposition stability
Each sample that makes preparation in above (5) is heat-treated under the peak value metal temperature of air ratio at 140 ℃ of 900 ℃ atmosphere temperature and 1.0-1.5 in the convection drying heating furnace, resistance to compression system scratch property and anti-continuous skimming wear reduction if the coefficient of kinetic friction is higher, then be evaluated as dissatisfied (*), be evaluated as satisfied (zero) if they are constant.
Zero: the coefficient of kinetic friction after the heat treatment, resistance to compression system scratch property and anti-continuous skimming wear are constant
*: the higher and resistance to compression system of the coefficient of kinetic friction after heat treatment scratch property and anti-continuous skimming wear reduction
Evaluation result is shown in table 14 in 16.These results prove that clearly technology of the present invention can be produced has the surface-treated metal plate that excellent performance comprises the resistance to compression system scratch property of corrosion resistance, adhesive force and solderability and excellence and resists continuous skimming wear.
Table 11
| Number | Metallic plate | Cr coverage rate (mg/m 2) | The organic/inorganic composite membrane | ||||||||||||
| Water soluble resin/silicate compound 1) | Silica 2) | Lubricant (A) 3) | Lubricant (B) 3) | Coverage rate (g/m 2) | |||||||||||
| Type | Amount | Type | Amount | Type | Amount | Type | Amount | Type | Amount | Type | Amount | ||||
| 1 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D1 | 5 | - | - | E17 | 5 | 1.0 |
| 2 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D2 | 5 | - | - | E17 | 5 | 1.0 |
| 3 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D3 | 5 | - | - | E17 | 5 | 1.0 |
| 4 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D4 | 5 | - | - | E17 | 5 | 1.0 |
| 5 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D5 | 5 | - | - | E17 | 5 | 1.0 |
| 6 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D6 | 5 | - | - | E17 | 5 | 1.0 |
| 7 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D7 | 5 | - | - | E17 | 5 | 1.0 |
| 8 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D8 | 5 | - | - | E17 | 5 | 1.0 |
| 9 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D9 | 5 | - | - | E17 | 5 | 1.0 |
| 10 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D10 | 5 | - | - | E17 | 5 | 1.0 |
| 11 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D11 | 5 | - | - | E17 | 5 | 1.0 |
| 12 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D12 | 5 | - | - | E17 | 5 | 1.0 |
| 13 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D13 | 5 | - | - | E17 | 5 | 1.0 |
| 14 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D14 | 5 | - | - | E17 | 5 | 1.0 |
| 15 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D15 | 5 | - | - | E17 | 5 | 1.0 |
| 16 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D2 | 5 | - | - | E16 | 5 | 1.0 |
| 17 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D2 | 5 | - | - | E18 | 5 | 1.0 |
| 18 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D2 | 5 | - | - | E19 | 5 | 1.0 |
| 19 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D2 | 5 | - | - | E20 | 5 | 1.0 |
| 20 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D2 | 5 | - | - | E21 | 5 | 1.0 |
| 21 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D3 | 5 | - | - | E16 | 5 | 1.0 |
| 22 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D3 | 5 | - | - | E18 | 5 | 1.0 |
| 23 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D3 | 5 | - | - | E19 | 5 | 1.0 |
| 24 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D3 | 5 | - | - | E20 | 5 | 1.0 |
| 25 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D3 | 5 | - | - | E21 | 5 | 1.0 |
| 26 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D9 | 5 | - | - | E16 | 5 | 1.0 |
| 27 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D9 | 5 | - | - | E18 | 5 | 1.0 |
| 28 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D9 | 5 | - | - | E19 | 5 | 1.0 |
| 29 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D9 | 5 | - | - | E20 | 5 | 1.0 |
| 30 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D9 | 5 | - | - | E21 | 5 | 1.0 |
1) type and the ratio of the every kind of water soluble resin that is added based on the total amount (in solid weight meter) of 100 parts of water soluble resins and/or silicate compound.
2) type and the ratio of the silica that is added based on the total amount (in solid weight meter) of 100 parts of organic/inorganic composite membranes.
3) type and the ratio of the every kind of spherical wax dispenser that is added based on the total amount (in solid weight meter) of 100 parts of organic/inorganic composite membranes.
Table 12
| Number | Metallic plate | Cr coverage rate (mg/m 2) | The organic/inorganic composite membrane | ||||||||||||
| Water soluble resin/silicate compound 1) | Silica 2) | Lubricant (A) 3) | Lubricant (B) 3) | Coverage rate (g/m 2) | |||||||||||
| Type | Amount | Type | Amount | Type | Amount | Type | Amount | Type | Amount | Type | Amount | ||||
| 31 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D2 | 1 | - | - | E17 | 9 | 1.0 |
| 32 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D2 | 9 | - | - | E17 | 1 | 1.0 |
| 33 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D3 | 1 | - | - | E17 | 9 | 1.0 |
| 34 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D3 | 9 | - | - | E17 | 1 | 1.0 |
| 35 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D2 | 2.5 | D8 | 2.5 | E17 | 5 | 1.0 |
| 36 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D3 | 2.5 | D8 | 2.5 | E17 | 5 | 1.0 |
| 37 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D2 | 0.5 | - | - | E17 | 0.5 | 1.0 |
| 38 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D2 | 3.0 | - | - | E17 | 3 | 1.0 |
| 39 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D2 | 15.0 | - | - | E17 | 15 | 1.0 |
| 40 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D3 | 0.5 | - | - | E17 | 0.5 | 1.0 |
| 41 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D3 | 3.0 | - | - | E17 | 3 | 1.0 |
| 42 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D3 | 15.0 | - | - | E17 | 15 | 1.0 |
| 43 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D2 | 5 | - | - | E17 | 5 | 0.1 |
| 44 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D2 | 5 | - | - | E17 | 5 | 0.3 |
| 45 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D2 | 5 | - | - | E17 | 5 | 2.0 |
| 46 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D2 | 5 | - | - | E17 | 5 | 5.0 |
| 47 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D2 | 5 | - | - | E17 | 5 | 10.0 |
| 48 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D3 | 5 | - | - | E17 | 5 | 0.1 |
| 49 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D3 | 5 | - | - | E17 | 5 | 0.3 |
| 50 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D3 | 5 | - | - | E17 | 5 | 2.0 |
| 51 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D3 | 5 | - | - | E17 | 5 | 5.0 |
| 52 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D3 | 5 | - | - | E17 | 5 | 10.0 |
| 53 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D9 | 5 | - | - | E17 | 5 | 0.1 |
| 54 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D9 | 5 | - | - | E17 | 5 | 0.3 |
| 55 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D9 | 5 | - | - | E17 | 5 | 2.0 |
| 56 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D9 | 5 | - | - | E17 | 5 | 5.0 |
| 57 | EG | 40 | A1 | 100 | - | - | C1 | 15 | D9 | 5 | - | - | E17 | 5 | 10.0 |
| 58 | EG | 40 | A1 | 100 | - | - | C1 | 0 | D2 | 5 | - | - | E17 | 5 | 1.0 |
| 59 | EG | 40 | A1 | 100 | - | - | C1 | 5 | D2 | 5 | - | - | E17 | 5 | 1.0 |
| 60 | EG | 40 | A1 | 100 | - | - | C1 | 10 | D2 | 5 | - | - | E17 | 5 | 1.0 |
1) type and the ratio of the every kind of water soluble resin that is added based on the total amount (in solid weight meter) of 100 parts of water soluble resins and/or silicate compound.
2) type and the ratio of the silica that is added based on the total amount (in solid weight meter) of 100 parts of organic/inorganic composite membranes.
3) type and the ratio of the every kind of spherical wax dispenser that is added based on the total amount (in solid weight meter) of 100 parts of organic/inorganic composite membranes.
Table 13
| Number | Metallic plate | Cr coverage rate (mg/m 2) | The organic/inorganic composite membrane | ||||||||||||
| Water soluble resin/silicate compound 1) | Silica 2) | Lubricant (A) 3) | Lubricant (B) 3) | Coverage rate (g/m 2) | |||||||||||
| Type | Amount | Type | Amount | Type | Amount | Type | Amount | Type | Amount | Type | Amount | ||||
| 61 | EG | 40 | A1 | 100 | - | - | C1 | 35 | D2 | 5 | - | - | E17 | 5 | 1.0 |
| 62 | EG | 40 | A1 | 100 | - | - | C1 | 50 | D2 | 5 | - | - | E17 | 5 | 1.0 |
| 63 | EG | 40 | A1 | 100 | - | - | C2 | 0 | D2 | 5 | - | - | E17 | 5 | 1.0 |
| 64 | EG | 40 | A1 | 100 | - | - | C2 | 5 | D2 | 5 | - | - | E17 | 5 | 1.0 |
| 65 | EG | 40 | A1 | 100 | - | - | C2 | 10 | D2 | 5 | - | - | E17 | 5 | 1.0 |
| 66 | EG | 40 | A1 | 100 | - | - | C2 | 35 | D2 | 5 | - | - | E17 | 5 | 1.0 |
| 67 | EG | 40 | A1 | 100 | - | - | C2 | 50 | D2 | 5 | - | - | E17 | 5 | 1.0 |
| 68 | EG | 40 | A2 | 90 | A4 | 10 | C1 | 15 | D2 | 5 | - | - | E17 | 5 | 1.0 |
| 69 | EG | 40 | A2 | 90 | A4 | 10 | C1 | 15 | D3 | 5 | - | - | E17 | 5 | 1.0 |
| 70 | EG | 40 | A2 | 90 | A4 | 10 | C1 | 15 | D9 | 5 | - | - | E17 | 5 | 1.0 |
| 71 | EG | 40 | A3 | 90 | A4 | 10 | C1 | 15 | D2 | 5 | - | - | E17 | 5 | 1.0 |
| 72 | EG | 40 | A3 | 90 | A4 | 10 | C1 | 15 | D3 | 5 | - | - | E17 | 5 | 1.0 |
| 73 | EG | 40 | A3 | 90 | A4 | 10 | C1 | 15 | D9 | 5 | - | - | E17 | 5 | 1.0 |
| 74 | EG | 40 | B1 | 100 | - | - | C1 | 15 | D2 | 5 | - | - | E17 | 5 | 1.0 |
| 75 | EG | 40 | B2 | 100 | - | - | C1 | 15 | D2 | 5 | - | - | E17 | 5 | 1.0 |
| 76 | EG | 40 | B3 | 100 | - | - | C1 | 15 | D2 | 5 | - | - | E17 | 5 | 1.0 |
| 77 | EG | 40 | B1 | 90 | A1 | 10 | C1 | 15 | D2 | 5 | - | - | E17 | 5 | 1.0 |
| 78 | EG | 40 | B1 | 90 | A4 | 10 | C1 | 15 | D2 | 5 | - | - | E17 | 5 | 1.0 |
| 79 | EG | - | A3 | 90 | A4 | 10 | C1 | 15 | D2 | 5 | - | - | E17 | 5 | 1.0 |
| 80 | EG | - | A3 | 90 | A4 | 10 | C1 | 15 | D3 | 5 | - | - | E17 | 5 | 1.0 |
| 81 | EG | - | A3 | 90 | A4 | 10 | C1 | 15 | D9 | 5 | - | - | E17 | 5 | 1.0 |
| 82 | ZN | 40 | A3 | 90 | A4 | 10 | C1 | 15 | D2 | 5 | - | - | E17 | 5 | 1.0 |
| 83 | GI | 40 | A3 | 90 | A4 | 10 | C1 | 15 | D2 | 5 | - | - | E17 | 5 | 1.0 |
1) type and the ratio of the every kind of water soluble resin that is added based on the total amount (in solid weight meter) of 100 parts of water soluble resins and/or silicate compound.
2) type and the ratio of the silica that is added based on the total amount (in solid weight meter) of 100 parts of organic/inorganic composite membranes.
3) type and the ratio of the every kind of spherical wax dispenser that is added based on the total amount (in solid weight meter) of 100 parts of organic/inorganic composite membranes.
Table 14
| Number | Performance | Note | |||||||||
| Dull and stereotyped corrosion resistance | Corrosion resistance behind the Sven-Gan Eriksson cut | Coating adhesion | Solderability | Resistance to compression system scratch property | Abrasion resistance | Anti-Texturized property | The coefficient of kinetic friction | Thermal decomposition stability | |||
| Do not soak | Soak | ||||||||||
| 1 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | 800 | 0.05 | ○ | The present invention |
| 2 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | 1000 | 0.05 | ○ | The present invention |
| 3 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | 1000 | 0.05 | ○ | The present invention |
| 4 | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ◎ | 400 | 0.07 | ○ | Comparative Examples |
| 5 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | 500 | 0.05 | ○ | The present invention |
| 6 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | 800 | 0.05 | ○ | The present invention |
| 7 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | 400 | 0.05 | ○ | Comparative Examples |
| 8 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | 500 | 0.05 | ○ | The present invention |
| 9 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | 1000 | 0.05 | ○ | The present invention |
| 10 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | 900 | 0.06 | ○ | The present invention |
| 11 | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ◎ | 450 | 0.07 | ○ | Comparative Examples |
| 12 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | 500 | 0.05 | ○ | The present invention |
| 13 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | 600 | 0.05 | ○ | The present invention |
| 14 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | 600 | 0.06 | ○ | The present invention |
| 15 | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ◎ | 400 | 0.08 | ○ | The present invention |
| 16 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | 800 | 0.05 | × | Comparative Examples |
| 17 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | 1200 | 0.06 | ○ | The present invention |
| 18 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | 1100 | 0.05 | ○ | The present invention |
| 19 | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ◎ | 700 | 0.06 | ○ | The present invention |
| 20 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | 450 | 0.10 | ○ | Comparative Examples |
| 21 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | 800 | 0.05 | × | Comparative Examples |
| 22 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | 1200 | 0.07 | ○ | The present invention |
| 23 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | 1100 | 0.06 | ○ | The present invention |
| 24 | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ◎ | 700 | 0.07 | ○ | The present invention |
| 25 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | 450 | 0.15 | ○ | Comparative Examples |
| 26 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | 800 | 0.05 | × | Comparative Examples |
| 27 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | 1200 | 0.07 | ○ | The present invention |
| 28 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | 1100 | 0.06 | ○ | The present invention |
| 29 | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ◎ | 700 | 0.07 | ○ | The present invention |
| 30 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | 450 | 0.10 | ○ | Comparative Examples |
Table 15
| Number | Performance | Note | |||||||||
| Dull and stereotyped corrosion resistance | Corrosion resistance behind the Sven-Gan Eriksson cut | Coating adhesion | Solderability | Resistance to compression system scratch property | Abrasion resistance | Continuous slip pass | The coefficient of kinetic friction | Thermal decomposition stability | |||
| Do not soak | Soak | ||||||||||
| 31 | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ◎ | 800 | 0.05 | ○ | The present invention |
| 32 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | 1000 | 0.06 | ○ | The present invention |
| 33 | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ◎ | 900 | 0.05 | ○ | The present invention |
| 34 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | 1200 | 0.06 | ○ | The present invention |
| 35 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | 1000 | 0.05 | ○ | The present invention |
| 36 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | 1200 | 0.06 | ○ | The present invention |
| 37 | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ○ | 800 | 0.06 | ○ | The present invention |
| 38 | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ◎ | 1100 | 0.05 | ○ | The present invention |
| 39 | ○ | ○ | ◎ | ○ | ◎ | ◎ | ◎ | 1500 | 0.05 | ○ | The present invention |
| 40 | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ○ | 800 | 0.06 | ○ | The present invention |
| 41 | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ◎ | 1100 | 0.05 | ○ | The present invention |
| 42 | ○ | ○ | ◎ | ○ | ◎ | ◎ | ◎ | 1500 | 0.05 | ○ | The present invention |
| 43 | × | × | △ | △ | ◎ | × | × | 100 | 0.08 | ○ | Comparative Examples |
| 44 | ○ | ○ | ○ | ○ | ◎ | ○ | ○ | 500 | 0.06 | ○ | The present invention |
| 45 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | 1000 | 0.05 | ○ | The present invention |
| 46 | ◎ | ◎ | ◎ | ○ | ○ | ◎ | ◎ | 1500 | 0.05 | ○ | The present invention |
| 47 | ◎ | ◎ | ◎ | ○ | × | ◎ | ◎ | 1800 | 0.06 | ○ | Comparative Examples |
| 48 | × | × | △ | △ | ◎ | × | × | 100 | 0.08 | ○ | Comparative Examples |
| 49 | ○ | ○ | ○ | ○ | ◎ | ○ | ○ | 500 | 0.06 | ○ | The present invention |
| 50 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | 1000 | 0.05 | ○ | The present invention |
| 51 | ◎ | ◎ | ◎ | ○ | ○ | ◎ | ◎ | 1500 | 0.05 | ○ | The present invention |
| 52 | ◎ | ◎ | ◎ | ○ | × | ◎ | ◎ | 1800 | 0.06 | ○ | Comparative Examples |
| 53 | × | × | △ | △ | ◎ | × | × | 100 | 0.08 | ○ | Comparative Examples |
| 54 | ○ | ○ | ○ | ○ | ◎ | ○ | ○ | 500 | 0.06 | ○ | The present invention |
| 55 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | 1000 | 0.05 | ○ | The present invention |
| 56 | ◎ | ◎ | ◎ | ○ | ○ | ◎ | ◎ | 1500 | 0.05 | ○ | The present invention |
| 57 | ◎ | ◎ | ◎ | ○ | × | ◎ | ◎ | 1800 | 0.06 | ○ | Comparative Examples |
| 58 | △ | △ | ◎ | ○ | ◎ | △ | ○ | 800 | 0.10 | ○ | Comparative Examples |
| 59 | ○ | ○ | ◎ | ◎ | ◎ | ○ | ○ | 1000 | 0.10 | ○ | The present invention |
| 60 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | 1000 | 0.10 | ○ | The present invention |
Table 16
| Number | Performance | Note | |||||||||
| Dull and stereotyped corrosion resistance | Corrosion resistance behind the Sven-Gan Eriksson cut | Coating adhesion | Solderability | Resistance to compression system scratch property | Abrasion resistance | Continuous slip pass | The coefficient of kinetic friction | Thermal decomposition stability | |||
| Do not soak | Soak | ||||||||||
| 61 | ◎ | ◎ | ◎ | ○ | ◎ | ◎ | ◎ | 1000 | 0.10 | ○ | The present invention |
| 62 | ○ | ○ | ○ | △ | ○ | △ | ○ | 1000 | 0.10 | ○ | Comparative Examples |
| 63 | △ | △ | ◎ | ○ | ◎ | △ | ○ | 800 | 0.10 | ○ | Comparative Examples |
| 64 | ○ | ○ | ◎ | ◎ | ◎ | ○ | ○ | 1000 | 0.10 | ○ | The present invention |
| 65 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | 1000 | 0.10 | ○ | The present invention |
| 66 | ◎ | ◎ | ◎ | ○ | ◎ | ◎ | ◎ | 1000 | 0.10 | ○ | The present invention |
| 67 | ○ | ○ | ○ | △ | ○ | △ | ○ | 1000 | 0.10 | ○ | Comparative Examples |
| 68 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | 1000 | 0.05 | ○ | The present invention |
| 69 | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ◎ | 1000 | 0.07 | ○ | The present invention |
| 70 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | 1000 | 0.05 | ○ | The present invention |
| 71 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | 1000 | 0.05 | ○ | The present invention |
| 72 | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ◎ | 1000 | 0.07 | ○ | The present invention |
| 73 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | 1000 | 0.05 | ○ | The present invention |
| 74 | ◎ | ○ | ○ | △ | ◎ | ◎ | ◎ | 2000 | 0.06 | ○ | The present invention |
| 75 | ◎ | ○ | ○ | △ | ◎ | ◎ | ◎ | 2000 | 0.06 | ○ | The present invention |
| 76 | ◎ | ○ | ○ | △ | ◎ | ◎ | ◎ | 2000 | 0.06 | ○ | The present invention |
| 77 | ◎ | ◎ | ◎ | ○ | ◎ | ◎ | ◎ | 1800 | 0.06 | ○ | The present invention |
| 78 | ◎ | ◎ | ◎ | ○ | ◎ | ◎ | ◎ | 1800 | 0.06 | ○ | The present invention |
| 79 | △ | △ | ◎ | ○ | ◎ | ◎ | ◎ | 1000 | 0.05 | ○ | The present invention |
| 80 | △ | △ | ◎ | ○ | ◎ | ○ | ◎ | 1000 | 0.05 | ○ | The present invention |
| 81 | △ | △ | ◎ | ○ | ◎ | ◎ | ◎ | 1000 | 0.05 | ○ | The present invention |
| 82 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | 1500 | 0.05 | ○ | The present invention |
| 83 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | 2000 | 0.05 | ○ | The present invention |
Explained later is according to the embodiment of third aspect present invention.
(1) types of agents
The tabulation of agents useful for same is shown in Table 17.All lubricants (A) except that D7 all have 950-1000kg/m
3Density (as JIS K 6760 defineds), 0.2mm or lower hardness (acupuncture hardness) (as JIS K 2207 defineds), 80% or bigger degree of crystallinity (measuring) and 110-150 ℃ fusing point by X-ray diffraction.
The tabulation of table 17 reagent
| Reagent | Number | Name of product |
| Organic resin | A1 | Acrylic resin (AP-1508 (12), Toa Gosei Co., Ltd.) |
| A2 | Polyolefin-based water soluble resin (AR-2300, Toho Chemical Industry Co., Ltd. | |
| A3 | The polyurethane-base water soluble resin (RA-85, Nippon-NSC) | |
| A4 | Epoxy radicals water soluble resin (DICFINE EM-60, Dainippon Ink and Chemicals Inc.) | |
| Silicate compound | B1 | Lithium metasilicate |
| B2 | Sodium metasilicate | |
| B3 | Potassium silicate | |
| Cabosil | C1 | Moisture cabosil (SNOWTEX N, Nissan Chemical Industries, Ltd.) |
| C2 | Moisture cabosil (SNOWTEX UP, Nissan Chemical Industries, Ltd.) | |
| Lubricant A﹠ contrast | D1 | Polyethylene (molecular weight: 6000, acid number: 0, granularity: 3.0 μ m) |
| D2 | Polyethylene (molecular weight: 8000, acid number: 0, granularity: 3.0 μ m) | |
| D3 | Polyethylene (molecular weight: 15000, acid number: 0, granularity: 3.0 μ m) | |
| D4 | Polyethylene (molecular weight: 20000, acid number: 0, granularity: 3.0 μ m) | |
| D5 | Polyethylene (molecular weight: 6000, acid number: 0, granularity: 0.1 μ m) | |
| D6 | Polyethylene (molecular weight: 6000, acid number: 0, granularity: 5.0 μ m) | |
| D7 | Modified poly ethylene (molecular weight: 1000, acid number: 20, granularity: 3.0 μ m) | |
| D8 | Modified poly ethylene (molecular weight: 6000, acid number: 20, granularity: 3.0 μ m) | |
| D9 | Modified poly ethylene (molecular weight: 8000, acid number: 20, granularity: 3.0 μ m) | |
| D10 | Modified poly ethylene (molecular weight: 15000, acid number: 20, granularity: 3.0 μ m) | |
| D11 | Modified poly ethylene (molecular weight: 20000, acid number: 20, granularity: 3.0 μ m) | |
| D12 | Modified poly ethylene (molecular weight: 6000, acid number: 20, granularity: 0.1 μ m) | |
| D13 | Modified poly ethylene (molecular weight: 6000, acid number: 20, granularity: 5.0 μ m) | |
| D14 | Modified poly ethylene (molecular weight: 6000, acid number: 40, granularity: 3.0 μ m) | |
| D15 | Modified poly ethylene (molecular weight: 6000, acid number: 100, granularity: 3.0 μ m) | |
| Lubricant B﹠ contrast | E16 | Polyethylene (molecular weight: 1000, acid number: 0, granularity: 0.6 μ m) |
| E17 | Polyethylene (molecular weight: 5000, acid number: 0, granularity: 0.6 μ m) | |
| E18 | Polyethylene (molecular weight: 1000, acid number: 0, granularity: 3.0 μ m) | |
| E19 | Polyethylene (molecular weight: 1000, acid number: 0, granularity: 0.1 μ m) |
(2) type of metallic plate
Used metallic plate is listed those in the table 2.
(3) chromate is handled
The carrying out of explaining at first aspect as the front.
(4) preparation of water-based organic/inorganic composite coating
Make from one of the water soluble resin of table 17 and silicate compound or two, cabosil and lubricant be mixed with water-based organic/inorganic composite coating with table 18 to ratio shown in 20.
(5) coating of water-based organic/inorganic composite coating and drying
The water-based organic/inorganic composite coating of preparation in above (4) is applied on the overlay metallization plate that the chromate that obtains in above (3) handles reaches listed dry weight among the table 18-20, baking and drying are made sample and are used for evaluation under 140 ℃ peak value metal temperature.Calculate the coverage rate of organic hybrid films according to the measurement of liquid film weight in the coating process.
(6) performance evaluation
A. the corrosion resistance of plate
To estimate at the mode of being explained according to the embodiment of first aspect.
B. the corrosion resistance behind the Sven-Gan Eriksson cut
To estimate at the mode of being explained according to the embodiment of first aspect.
C. coating adhesion
To estimate at the mode of being explained according to the embodiment of first aspect.
D. continuous welding
To estimate at the mode of being explained according to the embodiment of first aspect.
E. resistance to compression system abrades property
To estimate at the mode of being explained according to the embodiment of first aspect.
F. anti-superficial layer lubricant fissility test
Make each sample of preparation in above (5) stand above-mentioned rectangular drawing test 100 times continuously.After drawing continuously, visual assessment adheres to the situation of peeling off of the superficial layer lubricant of mould.Zero opinion rating is judged to be satisfaction in the following evaluation criteria.
Zero: do not adhere to the lubricant substance accumulation
*: adhere to the lubricant substance accumulation
G. abrasion resistance test
To estimate at the mode of being explained according to the embodiment of first aspect.
H. confficient of static friction
To estimate at the mode of being explained according to the embodiment of first aspect.
I. the coefficient of kinetic friction
To estimate at the mode of being explained according to the embodiment of first aspect.
J. anti-Texturized property
To estimate at the mode of being explained according to the embodiment of first aspect.
Evaluation result is shown in table 21 in 23.These results clearly prove, technology of the present invention can be produced has the surface-treated metal plate that fabulous performance comprises corrosion resistance, adhesive force and solderability and fabulous resistance to compression system scratch property and operating characteristics, also is suppressed in the pressing process generation that is broken away from the adhering residue that film causes by lubricant simultaneously.
Table 18
1) type and the ratio of the every kind of water soluble resin that is added based on the total amount (in solid weight meter) of 100 parts of water soluble resins and/or silicate compound.
2) type and the ratio of the silica that is added based on the total amount (in solid weight meter) of 100 parts of organic/inorganic composite membranes.
3) type and the ratio of the every kind of spherical wax dispenser that is added based on the total amount (in solid weight meter) of 100 parts of organic/inorganic composite membranes.
Table 19
| Number | Metallic plate | Cr coverage rate (mg/m 2) | Organic/inorganic composite membrane (C) | Organic/inorganic composite membrane (D) | ||||||||||||||||
| Water soluble resin/silicate compound 1) | Lubricant (A) 3) | Lubricant (B) 3) | Coverage rate (g/m 2) | Water soluble resin/silicate compound 1) | Silica 2) | Coverage rate (g/m 2) | ||||||||||||||
| Type | Amount | Type | Amount | Type | Amount | Type | Amount | Type | Amount | Type | Amount | Type | Amount | Type | Amount | |||||
| 31 | EG | 40 | A1 | 100 | - | - | D3 | 10 | D8 | 10 | E16 | 20 | 0.2 | A1 | 100 | - | - | C1 | 15 | 1.0 |
| 32 | EG | 40 | A1 | 100 | - | - | D2 | 1.0 | - | - | E16 | 1.0 | 0.2 | A1 | 100 | - | - | C1 | 15 | 1.0 |
| 33 | EG | 40 | A1 | 100 | - | - | D2 | 10 | - | - | E16 | 10 | 0.2 | A1 | 100 | - | - | C1 | 15 | 1.0 |
| 34 | EG | 40 | A1 | 100 | - | - | D2 | 20 | - | - | E16 | 20 | 0.2 | A1 | 100 | - | - | C1 | 15 | 1.0 |
| 35 | EG | 40 | A1 | 100 | - | - | D2 | 30 | - | - | E16 | 30 | 0.2 | A1 | 100 | - | - | C1 | 15 | 1.0 |
| 36 | EG | 40 | A1 | 100 | - | - | D3 | 1.0 | - | - | E16 | 1.0 | 0.2 | A1 | 100 | - | - | C1 | 15 | 1.0 |
| 37 | EG | 40 | A1 | 100 | - | - | D3 | 10 | - | - | E16 | 10 | 0.2 | A1 | 100 | - | - | C1 | 15 | 1.0 |
| 38 | EG | 40 | A1 | 100 | - | - | D3 | 20 | - | - | E16 | 20 | 0.2 | A1 | 100 | - | - | C1 | 15 | 1.0 |
| 39 | EG | 40 | A1 | 100 | - | - | D3 | 30 | - | - | E16 | 30 | 0.2 | A1 | 100 | - | - | C1 | 15 | 1.0 |
| 40 | EG | 40 | A1 | 100 | - | - | D2 | 40 | - | - | - | - | 0.2 | A1 | 100 | - | - | C1 | 15 | 0.1 |
| 41 | EG | 40 | A1 | 100 | - | - | D2 | 40 | - | - | - | - | 0.2 | A1 | 100 | - | - | C1 | 15 | 0.5 |
| 42 | EG | 40 | A1 | 100 | - | - | D2 | 40 | - | - | - | - | 0.2 | A1 | 100 | - | - | C1 | 15 | 2.0 |
| 43 | EG | 40 | A1 | 100 | - | - | 06 | 40 | - | - | - | - | 0.2 | A1 | 100 | - | - | C1 | 15 | 5.0 |
| 44 | EG | 40 | A1 | 100 | - | - | D6 | 40 | - | - | - | - | 0.2 | A1 | 100 | - | - | C1 | 15 | 10.0 |
| 45 | EG | 40 | A1 | 100 | - | - | 09 | 40 | - | - | - | - | 0.2 | A1 | 100 | - | - | C1 | 15 | 0.1 |
| 46 | EG | 40 | A1 | 100 | - | - | D9 | 40 | - | - | - | - | 0.2 | A1 | 100 | - | - | C1 | 15 | 0.5 |
| 47 | EG | 40 | A1 | 100 | - | - | D9 | 40 | - | - | - | - | 0.2 | A1 | 100 | - | - | C1 | 15 | 2.0 |
| 48 | EG | 40 | A1 | 100 | - | - | D13 | 40 | - | - | - | - | 0.2 | A1 | 100 | - | - | C1 | 15 | 5.0 |
| 49 | EG | 40 | A1 | 100 | - | - | D13 | 40 | - | - | - | - | 0.2 | A1 | 100 | - | - | C1 | 15 | 10.0 |
| 50 | EG | 40 | A1 | 100 | - | - | D2 | 40 | - | - | - | - | 0.01 | A1 | 100 | - | - | C1 | 15 | 1.0 |
| 51 | EG | 40 | A1 | 100 | - | - | D2 | 40 | - | - | - | - | 0.05 | A1 | 100 | - | - | C1 | 15 | 1.0 |
| 52 | EG | 40 | A1 | 100 | - | - | D2 | 40 | - | - | - | - | 0.3 | A1 | 100 | - | - | C1 | 15 | 1.0 |
| 53 | EG | 40 | A1 | 100 | - | - | D9 | 40 | - | - | - | - | 0.01 | A1 | 100 | - | - | C1 | 15 | 1.0 |
| 54 | EG | 40 | A1 | 100 | - | - | D9 | 40 | - | - | - | - | 0.05 | A1 | 100 | - | - | C1 | 15 | 1.0 |
| 55 | EG | 40 | A1 | 100 | - | - | D9 | 40 | - | - | - | - | 0.3 | A1 | 100 | - | - | C1 | 15 | 1.0 |
| 56 | EG | 40 | A1 | 100 | - | - | D2 | 40 | - | - | - | - | 0.2 | A1 | 100 | - | - | C1 | 0 | 1.0 |
| 57 | EG | 40 | A1 | 100 | - | - | D2 | 40 | - | - | - | - | 0.2 | A1 | 100 | - | - | C1 | 5 | 1.0 |
| 58 | EG | 40 | A1 | 100 | - | - | D2 | 40 | - | - | - | - | 0.2 | A1 | 100 | - | - | C1 | 10 | 1.0 |
1) type and the ratio of the every kind of water soluble resin that is added based on the total amount (in solid weight meter) of 100 parts of water soluble resins and/or silicate compound.
2) type and the ratio of the silica that is added based on the total amount (in solid weight meter) of 100 parts of organic/inorganic composite membranes.
3) type and the ratio of the every kind of spherical wax dispenser that is added based on the total amount (in solid weight meter) of 100 parts of organic/inorganic composite membranes.
Table 20
| Number | Metallic plate | Cr coverage rate (mg/m 2) | Organic/inorganic composite membrane (C) | Organic/inorganic composite membrane (D) | ||||||||||||||||
| Water soluble resin/silicate compound 1) | Lubricant (A) 3) | Lubricant (B) 3) | Coverage rate (g/m 2) | Water soluble resin/silicate compound 1) | Silica 2) | Coverage rate (g/m 2) | ||||||||||||||
| Type | Amount | Type | Amount | Type | Amount | Type | Amount | Type | Amount | Type | Amount | Type | Amount | Type | Amount | |||||
| 59 | EG | 40 | A1 | 100 | - | - | D2 | 40 | - | - | - | - | 0.2 | A1 | 100 | - | - | C1 | 35 | 1.0 |
| 60 | EG | 40 | A1 | 100 | - | - | D2 | 40 | - | - | - | - | 0.2 | A1 | 100 | - | - | C1 | 50 | 1.0 |
| 61 | EG | 40 | A1 | 100 | - | - | D2 | 40 | - | - | - | - | 0.2 | A1 | 100 | - | - | C2 | 0 | 1.0 |
| 62 | EG | 40 | A1 | 100 | - | - | D2 | 40 | - | - | - | - | 0.2 | A1 | 100 | - | - | C2 | 5 | 1.0 |
| 63 | EG | 40 | A1 | 100 | - | - | D2 | 40 | - | - | - | - | 0.2 | A1 | 100 | - | - | C2 | 10 | 1.0 |
| 64 | EG | 40 | A1 | 100 | - | - | D2 | 40 | - | - | - | - | 0.2 | A1 | 100 | - | - | C2 | 35 | 1.0 |
| 65 | EG | 40 | A1 | 100 | - | - | D2 | 40 | - | - | - | - | 0.2 | A1 | 100 | - | - | C2 | 50 | 1.0 |
| 66 | EG | 40 | A2 | 90 | A4 | 10 | D2 | 40 | - | - | - | - | 0.2 | A2 | 90 | A4 | 10 | C1 | 15 | 1.0 |
| 67 | EG | 40 | A2 | 90 | A4 | 10 | D3 | 40 | - | - | - | - | 0.2 | A2 | 90 | A4 | 10 | C1 | 15 | 1.0 |
| 68 | EG | 40 | A2 | 90 | A4 | 10 | D9 | 40 | - | - | - | - | 0.2 | A2 | 90 | A4 | 10 | C1 | 15 | 1.0 |
| 69 | EG | 40 | A3 | 90 | A4 | 10 | D2 | 40 | - | - | - | - | 0.2 | A3 | 90 | A4 | 10 | C1 | 15 | 1.0 |
| 70 | EG | 40 | A3 | 90 | A4 | 10 | D3 | 40 | - | - | - | - | 0.2 | A3 | 90 | A4 | 10 | C1 | 15 | 1.0 |
| 71 | EG | 40 | A3 | 90 | A4 | 10 | D9 | 40 | - | - | - | - | 0.2 | A3 | 90 | A4 | 10 | C1 | 15 | 1.0 |
| 72 | EG | 40 | B1 | 100 | - | - | D2 | 40 | - | - | - | - | 0.2 | B1 | 100 | - | - | C1 | 15 | 1.0 |
| 73 | EG | 40 | B2 | 100 | - | - | D2 | 40 | - | - | - | - | 0.2 | B2 | 100 | - | - | C1 | 15 | 1.0 |
| 74 | EG | 40 | B3 | 100 | - | - | D2 | 40 | - | - | - | - | 0.2 | B3 | 100 | - | - | C1 | 15 | 1.0 |
| 75 | EG | 40 | B1 | 90 | A1 | 10 | D2 | 40 | - | - | - | - | 0.2 | B1 | 90 | A1 | 10 | C1 | 15 | 1.0 |
| 76 | EG | 40 | B1 | 90 | A4 | 10 | D2 | 40 | - | - | - | - | 0.2 | B1 | 90 | A4 | 10 | C1 | 15 | 1.0 |
| 77 | EG | - | A3 | 90 | A4 | 10 | D2 | 40 | - | - | - | - | 0.2 | A3 | 90 | A4 | 10 | C1 | 15 | 1.0 |
| 78 | EG | - | A3 | 90 | A4 | 10 | D3 | 40 | - | - | - | - | 0.2 | A3 | 90 | A4 | 10 | C1 | 15 | 1.0 |
| 79 | EG | - | A3 | 90 | A4 | 10 | D9 | 40 | - | - | - | - | 0.2 | A3 | 90 | A4 | 10 | C1 | 15 | 1.0 |
| 80 | ZN | 40 | A3 | 90 | A4 | 10 | D2 | 40 | - | - | - | - | 0.2 | A3 | 90 | A4 | 10 | C1 | 15 | 1.0 |
| 81 | GI | 40 | A3 | 90 | A4 | 10 | D2 | 40 | - | - | - | - | 0.2 | A3 | 90 | A4 | 10 | C1 | 15 | 10 |
1) type and the ratio of the every kind of water soluble resin that is added based on the total amount (in solid weight meter) of 100 parts of water soluble resins and/or silicate compound.
2) type and the ratio of the silica that is added based on the total amount (in solid weight meter) of 100 parts of organic/inorganic composite membranes.
3) type and the ratio of the every kind of spherical wax dispenser that is added based on the total amount (in solid weight meter) of 100 parts of organic/inorganic composite membranes.
Table 21
| Number | Performance | Note | ||||||||||
| Dull and stereotyped corrosion resistance | Corrosion resistance behind the Sven-Gan Eriksson cut | Coating adhesion | Solderability | Resistance to compression system scratch property | Abrasion resistance | Stripper-resistance | Anti-Texturized property | The coefficient of kinetic friction | Confficient of static friction | |||
| Do not soak | Soak | |||||||||||
| 1 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ○ | 0.07 | 0.15 | The present invention |
| 2 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ○ | 0.10 | 0.20 | The present invention |
| 3 | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ◎ | ○ | ○ | 0.15 | 0.25 | The present invention |
| 4 | ◎ | ◎ | ◎ | ◎ | ◎ | △ | ○ | ○ | ○ | 0.20 | 0.30 | Comparative Examples |
| 5 | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ◎ | ○ | ○ | 0.08 | 0.15 | The present invention |
| 6 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ○ | 0.07 | 0.12 | The present invention |
| 7 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | × | 0.06 | 0.10 | Comparative Examples |
| 8 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ○ | 0.09 | 0.20 | The present invention |
| 9 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ○ | 0.10 | 0.25 | The present invention |
| 10 | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ○ | ○ | ○ | 0.15 | 0.30 | The present invention |
| 11 | ◎ | ◎ | ◎ | ◎ | ◎ | × | △ | ○ | ○ | 0.20 | 0.35 | Comparative Examples |
| 12 | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ○ | ○ | ○ | 0.08 | 0.20 | The present invention |
| 13 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ○ | 0.07 | 0.17 | The present invention |
| 14 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ○ | 0.15 | 0.30 | The present invention |
| 15 | ◎ | ◎ | ◎ | ◎ | ◎ | × | × | ○ | ○ | 0.20 | 0.35 | Comparative Examples |
| 16 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ○ | 0.10 | 0.20 | The present invention |
| 17 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ○ | 0.10 | 0.20 | The present invention |
| 18 | ◎ | ◎ | ◎ | ◎ | ○ | ◎ | ◎ | ○ | ○ | 0.10 | 0.20 | The present invention |
| 19 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ○ | 0.10 | 0.20 | The present invention |
| 20 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ○ | 0.10 | 0.20 | The present invention |
| 21 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ○ | 0.10 | 0.25 | The present invention |
| 22 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ○ | 0.10 | 0.25 | The present invention |
| 23 | ◎ | ◎ | ◎ | ◎ | ○ | ◎ | ◎ | ○ | ○ | 0.10 | 0.25 | The present invention |
| 24 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ○ | 0.10 | 0.25 | The present invention |
| 25 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ○ | 0.10 | 0.25 | The present invention |
| 26 | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ◎ | ○ | ○ | 0.12 | 0.25 | The present invention |
| 27 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ○ | 0.10 | 0.20 | The present invention |
| 28 | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ◎ | ○ | ○ | 0.20 | 0.35 | The present invention |
| 29 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ○ | 0.15 | 0.30 | The present invention |
| 30 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ○ | 0.10 | 0.20 | The present invention |
Table 22
| Number | Performance | Note | ||||||||||
| Dull and stereotyped corrosion resistance | Corrosion resistance behind the Sven-Gan Eriksson cut | Coating adhesion | Solderability | Resistance to compression system scratch property | Abrasion resistance | Stripper-resistance | Anti-Texturized property | The coefficient of kinetic friction | Confficient of static friction | |||
| Do not soak | Soak | |||||||||||
| 31 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ○ | 0.15 | 0.30 | The present invention |
| 32 | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ○ | ○ | ○ | 0.15 | 0.30 | The present invention |
| 33 | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ◎ | ○ | ○ | 0.12 | 0.25 | The present invention |
| 34 | ○ | ○ | ◎ | ○ | ◎ | ◎ | ◎ | ○ | ○ | 0.10 | 0.20 | The present invention |
| 35 | △ | △ | ○ | △ | ◎ | ◎ | ◎ | ○ | ○ | 0.10 | 0.20 | The present invention |
| 36 | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ○ | ○ | ○ | 0.20 | 0.35 | The present invention |
| 37 | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ◎ | ○ | ○ | 0.18 | 0.30 | The present invention |
| 38 | ○ | ○ | ◎ | ○ | ◎ | ◎ | ◎ | ○ | ○ | 0.15 | 0.30 | The present invention |
| 39 | △ | △ | ○ | △ | ◎ | ◎ | ◎ | ○ | ○ | 0.15 | 0.30 | The present invention |
| 40 | × | × | △ | △ | ◎ | × | × | × | ○ | 0.08 | 0.15 | Comparative Examples |
| 41 | ○ | ○ | ○ | ○ | ◎ | ○ | ○ | ○ | ○ | 0.08 | 0.15 | The present invention |
| 42 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ○ | 0.10 | 0.20 | The present invention |
| 43 | ◎ | ◎ | ◎ | ○ | ○ | ◎ | ◎ | ○ | ○ | 0.10 | 0.30 | The present invention |
| 44 | ◎ | ◎ | ◎ | ○ | × | ◎ | ◎ | ○ | ○ | 0.25 | 0.35 | Comparative Examples |
| 45 | × | × | △ | △ | ◎ | × | × | × | ○ | 0.08 | 0.15 | Comparative Examples |
| 46 | ○ | ○ | ○ | ○ | ◎ | ○ | ○ | ○ | ○ | 0.08 | 0.20 | The present invention |
| 47 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ○ | 0.10 | 0.25 | The present invention |
| 48 | ◎ | ◎ | ◎ | ○ | ○ | ◎ | ◎ | ○ | ○ | 0.10 | 0.25 | The present invention |
| 49 | ◎ | ◎ | ◎ | ○ | × | ◎ | ◎ | ○ | ○ | 0.25 | 0.35 | Comparative Examples |
| 50 | ◎ | ◎ | ◎ | ◎ | ◎ | × | × | ○ | ○ | 0.2 | 0.30 | Comparative Examples |
| 51 | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ○ | ○ | ○ | 0.15 | 0.25 | The present invention |
| 52 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ○ | 0.1 | 0.20 | The present invention |
| 53 | ◎ | ◎ | ◎ | ◎ | ◎ | × | × | ○ | ○ | 0.20 | 0.30 | Comparative Examples |
| 54 | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ○ | ○ | ○ | 0.15 | 0.30 | The present invention |
| 55 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ○ | 0.10 | 0.25 | The present invention |
| 56 | △ | △ | ◎ | ○ | ◎ | △ | ○ | ○ | ○ | 0.10 | 0.20 | Comparative Examples |
| 57 | ○ | ○ | ◎ | ◎ | ◎ | ○ | ○ | ○ | ○ | 0.10 | 0.20 | The present invention |
| 58 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ○ | 0.10 | 0.20 | The present invention |
Table 23
| Number | Performance | Note | ||||||||||
| Dull and stereotyped corrosion resistance | Corrosion resistance behind the Sven-Gan Eriksson cut | Coating adhesion | Solderability | Resistance to compression system scratch property | Abrasion resistance | Stripper-resistance | Anti-Texturized property | The coefficient of kinetic friction | Confficient of static friction | |||
| Do not soak | Soak | |||||||||||
| 59 | ◎ | ◎ | ◎ | ○ | ◎ | ◎ | ◎ | ○ | ○ | 0.10 | 0.20 | The present invention |
| 60 | ○ | ○ | ○ | △ | ○ | △ | ○ | ○ | ○ | 0.10 | 0.20 | Comparative Examples |
| 61 | △ | △ | ◎ | ○ | ◎ | △ | ○ | ○ | ○ | 0.10 | 0.20 | Comparative Examples |
| 62 | ○ | ○ | ◎ | ◎ | ◎ | ○ | ○ | ○ | ○ | 0.10 | 0.20 | The present invention |
| 63 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ○ | 0.10 | 0.20 | The present invention |
| 64 | ◎ | ◎ | ◎ | ○ | ◎ | ◎ | ◎ | ○ | ○ | 1.00 | 0.20 | The present invention |
| 65 | ○ | ○ | ○ | △ | ○ | △ | ○ | ○ | ○ | 0.10 | 0.20 | Comparative Examples |
| 66 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ○ | 0.10 | 0.20 | The present invention |
| 67 | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ◎ | ○ | ○ | 0.15 | 0.25 | The present invention |
| 68 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ○ | 0.10 | 0.20 | The present invention |
| 69 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ○ | 0.10 | 0.20 | The present invention |
| 70 | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ◎ | ○ | ○ | 0.15 | 0.25 | The present invention |
| 71 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ○ | 0.10 | 0.20 | The present invention |
| 72 | ◎ | ○ | ○ | △ | ◎ | ◎ | ◎ | ○ | ○ | 0.10 | 0.25 | The present invention |
| 73 | ◎ | ○ | ○ | △ | ◎ | ◎ | ◎ | ○ | ○ | 0.15 | 0.30 | The present invention |
| 74 | ◎ | ○ | ○ | △ | ◎ | ◎ | ◎ | ○ | ○ | 0.10 | 0.25 | The present invention |
| 75 | ◎ | ◎ | ◎ | ○ | ◎ | ◎ | ◎ | ○ | ○ | 0.10 | 0.25 | The present invention |
| 76 | ◎ | ◎ | ◎ | ○ | ◎ | ◎ | ◎ | ○ | ○ | 0.10 | 0.25 | The present invention |
| 77 | △ | △ | ◎ | ○ | ◎ | ◎ | ◎ | ○ | ○ | 0.10 | 0.20 | The present invention |
| 78 | △ | △ | ◎ | ○ | ◎ | ○ | ◎ | ○ | ○ | 0.15 | 0.25 | The present invention |
| 79 | △ | △ | ◎ | ○ | ◎ | ◎ | ◎ | ○ | ○ | 0.10 | 0.20 | The present invention |
| 80 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ○ | 0.10 | 0.20 | The present invention |
| 81 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | ○ | 0.10 | 0.20 | The present invention |
Industrial applicibility
Surface-treated metal plate according to first aspect present invention shows the performance of excellent corrosion resistance, adhesive force and solderability and keeps resistance to compression system scratch property, also improve simultaneously in the section bundling process because reeling loose or the folding problem that causes the coiled material fragmentation of load, thereby be suitable as the material in household electrical appliance, construction material and the automotive field. Water-based organic/inorganic composite coating and manufacture method according to first aspect present invention provide satisfied resistance to compression system scratch property and anti-Texturized property for commercially available surface-treated metal plate.
Surface-treated metal plate according to second aspect present invention shows the performance of excellent corrosion resistance, adhesive force and solderability and keeps resistance to compression system scratch property and anti-continuous skimming wear, thereby is suitable as the material in household electrical appliance, construction material and the automotive field. Water-based organic/inorganic composite coating and manufacture method according to second aspect present invention provide satisfied resistance to compression system scratch property and anti-continuous skimming wear for commercially available surface-treated metal plate.
Surface-treated metal plate according to third aspect present invention shows the performance of excellent corrosion resistance, adhesive force and solderability and keeps resistance to compression system scratch property, also improve simultaneously in the section bundling process and to cause the problem of coiled material fragmentation because the loose or load of reeling is folding and to be suppressed in the pressing process generation that is broken away from the adhering residue thing that film causes by lubricant, thereby be suitable as the material in household electrical appliance, construction material and the automotive field. Water-based organic/inorganic composite coating and manufacture method according to third aspect present invention provide satisfied resistance to compression system scratch property and anti-Texturized property for commercially available surface-treated metal plate.
Claims (15)
1. the surface-treated metal plate of a resistance to compression system scratch property and anti-continuous skimming wear excellence is characterised in that to have 0.3-5.0g/m
2Comprise one of water soluble resin and silicate compound or both and be the lubricant A that forms of the polyolefin-wax dispersion of 6000-15000, be the lubricant B that forms of the polyolefin-wax dispersion of 1000-5000 and by the water-based organic/inorganic composite membrane of the colloidal silica of solid content 5-35% weight by molecular weight by molecular weight, wherein the total content of lubricant A and B is counted 1-30 weight % by solid content, the content of lubricant A with respect to the total content of lubricant A and B in the scope of 10-90%.
2. the resistance to compression system of claim 1 abrades the surface-treated metal plate of property and anti-continuous skimming wear excellence, be characterised in that described lubricant A be selected from not polar functionalities, molecular weight be 6000-15000 and granularity be the polyolefin-wax dispersion of 0.1-5.0 μ m and molecular weight be 6000-15000, acid number be 40 or lower and granularity be at least a lubricant in the improved polyalkene wax dispenser of 0.1-5.0 μ m, lubricant B be do not conform to polar group, molecular weight is that 1000-5000 and granularity are the polyolefin-wax dispersion of 0.1-5.0 μ m.
3. water-based organic/inorganic composite coating, comprise one of water soluble resin and silicate compound or both and by molecular weight be the lubricant A that forms of the polyolefin-wax dispersion of 6000-15000, by molecular weight be the lubricant B that forms of the polyolefin-wax dispersion of 1000-5000, by the colloidal silica and the water of solid content 5-35% weight, wherein the total content of lubricant A and B is counted the 1-30 weight % of described water-based organic/inorganic composite coating by solid content, the content of lubricant A with respect to the total content of lubricant A and B in the scope of 10-90%.
4. the water-based organic/inorganic composite coating of claim 3, be characterised in that described lubricant A be selected from not polar functionalities, molecular weight be 6000-15000 and granularity be the polyolefin-wax dispersion of 0.1-5.0 μ m and molecular weight be 6000-15000, acid number be 40 or lower and granularity be at least a lubricant in the improved polyalkene wax dispenser of 0.1-5.0 μ m, lubricant B is that polar functionalities, molecular weight are not that 1000-5000 and granularity are the polyolefin-wax dispersion of 0.1-5.0 μ m.
5. the manufacture method of the surface-treated metal plate of resistance to compression system scratch property and the moving abrasiveness excellence of antiskid, be characterised in that water-based organic/inorganic composite coating with claim 3 by dry weight basis with 0.3-5.0g/m
2After being applied on the overlay metallization plate, baking forms water-based organic/inorganic composite membrane.
6. the manufacture method of the surface-treated metal plate of resistance to compression system scratch property and anti-continuous skimming wear excellence, be characterised in that water-based organic/inorganic composite coating with claim 4 by dry weight basis with 0.3-5.0g/m
2After being applied on the overlay metallization plate, baking forms water-based organic/inorganic composite membrane.
7. the surface-treated metal plate of a resistance to compression system scratch property and anti-Texturized property excellence is characterised in that to have 0.05-0.3g/m
2Dry weight comprise one of water soluble resin and silicate compound or both and by molecular weight be the water-based organic/inorganic composite membrane C of the lubricant A that forms of the polyolefin-wax dispersion of 6000-15000 as ground floor, and 0.5-5.0g/m
2The water-based organic/inorganic composite membrane D that forms by one of water soluble resin and silicate compound or both with by the colloidal silica of solid content 5-35% weight of dry weight is as the second layer, and wherein the content of lubricant A is counted 2-60% weight by solid content.
8. the surface-treated metal plate of the resistance to compression system of claim 7 scratch property and anti-Texturized property excellence, be characterised in that described lubricant A be selected from not polar functionalities, molecular weight be 6000-15000 and granularity be the polyolefin-wax dispersion of 0.1-5.0 μ m and molecular weight be 6000-15000, acid number be 40 or lower and granularity be at least a lubricant in the improved polyalkene wax dispenser of 0.1-5.0 μ m.
9. the surface-treated metal plate of claim 7 or 8 resistance to compression system scratch property and anti-Texturized property excellence is characterised in that described water-based organic/inorganic composite membrane C is that the compounded lubricant that the lubricant B of the lubricant A of polyolefin-wax dispersion of 6000-15000 and the polyolefin-wax dispersion that molecular weight is 1000-5000 is mixed with is formed by water soluble resin and by molecular weight.
10. the resistance to compression system of claim 9 abrades the surface-treated metal plate of property and anti-Texturized property excellence, be characterised in that described lubricant A be selected from not polar functionalities, molecular weight be 6000-15000 and granularity be the polyolefin-wax dispersion of 0.1-5.0 μ m and molecular weight be 6000-15000, acid number be 40 or lower and granularity be at least a lubricant in the improved polyalkene wax dispenser of 0.1-5.0 μ m, lubricant B is that polar functionalities, molecular weight are not that 1000-5000 and granularity are the polyolefin-wax dispersion of 0.1-3.0 μ m.
11. the surface-treated metal plate of the resistance to compression system of claim 7 scratch property and anti-Texturized property excellence, the coefficient of kinetic friction that is characterised in that described surface is 0.07-0.15, and confficient of static friction is 0.10 or higher.
12. the manufacture method of the surface-treated metal plate of resistance to compression system scratch property and anti-Texturized property excellence is characterised in that on overlay metallization plate coating is that the lubricant A of polyolefin-wax dispersion of 6000-15000 and the water-based organic/inorganic composite coating E that water is formed extremely reach 0.05-0.3g/m by dry weight basis by one of water soluble resin and silicate compound or both and molecular weight
2Afterwards, baking forms ground floor, and wherein the content of lubricant A is counted the 2-60 weight % of described water-based organic/inorganic composite coating by solid content; Be coated with then by one of water soluble resin and silicate compound or both and wherein colloidal silica content count the colloidal silica of 5-35% weight and water-based organic/inorganic composite coating F that water is formed to reaching 0.5-5.0g/m by solid content by dry weight basis
2, baking forms the second layer.
13. the manufacture method of the surface-treated metal plate of the resistance to compression system of claim 12 scratch property and anti-Texturized property excellence, be characterised in that described lubricant A be selected from not polar functionalities, molecular weight be 6000-15000 and granularity be the polyolefin-wax dispersion of 0.1-5.0 μ m and molecular weight be 6000-15000, acid number be 40 or lower and granularity be at least a lubricant in the improved polyalkene wax dispenser of 0.1-5.0 μ m.
14. the manufacture method of the surface-treated metal plate of resistance to compression system scratch property and anti-Texturized property excellence is characterised in that on overlay metallization plate coating is that the water-based organic/inorganic composite coating E that the compounded lubricant that is mixed with of the lubricant B of the lubricant A of polyolefin-wax dispersion of 6000-15000 and the polyolefin-wax dispersion that molecular weight is 1000-5000 and water are formed extremely reaches 0.05-0.3g/m by dry weight basis by water soluble resin, by molecular weight
2Afterwards, baking forms ground floor, and wherein the total content of lubricant A and B is counted the 2-60 weight % of described water-based organic/inorganic composite coating by solid content; Be coated with then by one of water soluble resin and silicate compound or both and wherein colloidal silica content count the colloidal silica of 5-35% weight and water-based organic/inorganic composite coating F that water is formed to reaching 0.5-5.0g/m by solid content by dry weight basis
2, baking forms the second layer.
15. the manufacture method of the surface-treated metal plate of the resistance to compression system of claim 14 scratch property and anti-Texturized property excellence, be characterised in that described lubricant A be selected from not polar functionalities, molecular weight be 6000-15000 and granularity be the polyolefin-wax dispersion of 0.1-5.0 μ m and molecular weight be 6000-15000, acid number be 40 or lower and granularity be at least a lubricant in the improved polyalkene wax dispenser of 0.1-5.0 μ m, lubricant B be do not conform to polar group, molecular weight is that 1000-5000 and granularity are the polyolefin-wax dispersion of 0.1-3.0 μ m.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12321/2001 | 2001-01-19 | ||
| JP2001012319A JP2002212754A (en) | 2001-01-19 | 2001-01-19 | Surface treated metallic sheet having excellent press galling resistance and coil deformation resistance, and method for manufacturing the same |
| JP12319/2001 | 2001-01-19 | ||
| JP12347/2001 | 2001-01-19 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02803860 Division CN1276995C (en) | 2001-01-19 | 2002-01-18 | Surface-treated metal sheets excellent in press dragging resistance and coil deformation resistance and process for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1727078A CN1727078A (en) | 2006-02-01 |
| CN100368098C true CN100368098C (en) | 2008-02-13 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100906977A Expired - Lifetime CN100368098C (en) | 2001-01-19 | 2002-01-18 | Surface-treated metal sheets excellent in press dragging resistance and coil deformation resistance and process for producing the same |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2002212754A (en) |
| CN (1) | CN100368098C (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4380120B2 (en) * | 2002-08-01 | 2009-12-09 | Ｊｆｅスチール株式会社 | Electrical steel sheet with insulation film |
| JP4360667B2 (en) * | 2002-08-01 | 2009-11-11 | Ｊｆｅスチール株式会社 | Electrical steel sheet with insulation film |
| JP6107458B2 (en) * | 2013-06-18 | 2017-04-05 | コニカミノルタ株式会社 | Electrostatic latent image developing toner and electrophotographic image forming method |
| CN106042866A (en) * | 2016-08-12 | 2016-10-26 | 安徽省地坤汽车天窗科技有限公司 | Skylight frame assembly with front beam |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09267073A (en) * | 1996-04-01 | 1997-10-14 | Nippon Steel Corp | Production of surface treated steel sheet having excellent press workability |
| CN1266872A (en) * | 1999-03-16 | 2000-09-20 | 日本巴卡莱近估股份有限公司 | Water surface treatment agent for metal material and furface treated metal plate |
| WO2000055260A1 (en) * | 1999-03-18 | 2000-09-21 | International Coatings Ltd. | Coating composition for metal substrates |
-
2001
- 2001-01-19 JP JP2001012319A patent/JP2002212754A/en active Pending
-
2002
- 2002-01-18 CN CNB2005100906977A patent/CN100368098C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09267073A (en) * | 1996-04-01 | 1997-10-14 | Nippon Steel Corp | Production of surface treated steel sheet having excellent press workability |
| CN1266872A (en) * | 1999-03-16 | 2000-09-20 | 日本巴卡莱近估股份有限公司 | Water surface treatment agent for metal material and furface treated metal plate |
| WO2000055260A1 (en) * | 1999-03-18 | 2000-09-21 | International Coatings Ltd. | Coating composition for metal substrates |
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| Publication number | Publication date |
|---|---|
| JP2002212754A (en) | 2002-07-31 |
| CN1727078A (en) | 2006-02-01 |
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