CN1084673C - Method of mfg. vinyl chloride steel plates having film of high hardness - Google Patents
Method of mfg. vinyl chloride steel plates having film of high hardness Download PDFInfo
- Publication number
- CN1084673C CN1084673C CN96199735A CN96199735A CN1084673C CN 1084673 C CN1084673 C CN 1084673C CN 96199735 A CN96199735 A CN 96199735A CN 96199735 A CN96199735 A CN 96199735A CN 1084673 C CN1084673 C CN 1084673C
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- weight
- plastisol
- weight portions
- polyvinyl chloride
- particle diameter
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 49
- 239000010959 steel Substances 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 37
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229920001944 Plastisol Polymers 0.000 claims abstract description 80
- 239000004999 plastisol Substances 0.000 claims abstract description 80
- 239000002245 particle Substances 0.000 claims abstract description 57
- 239000004014 plasticizer Substances 0.000 claims abstract description 46
- 239000004800 polyvinyl chloride Substances 0.000 claims abstract description 44
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 44
- 229920005989 resin Polymers 0.000 claims abstract description 38
- 239000011347 resin Substances 0.000 claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- -1 phthalic acid ester Chemical class 0.000 claims description 70
- 229910052799 carbon Inorganic materials 0.000 claims description 63
- 239000000843 powder Substances 0.000 claims description 50
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 34
- 230000002902 bimodal effect Effects 0.000 claims description 15
- 239000000049 pigment Substances 0.000 claims description 14
- 239000003381 stabilizer Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 238000009826 distribution Methods 0.000 abstract description 31
- 238000013329 compounding Methods 0.000 abstract description 3
- 239000007767 bonding agent Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 61
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 59
- 239000011248 coating agent Substances 0.000 description 53
- 238000000576 coating method Methods 0.000 description 53
- 238000006116 polymerization reaction Methods 0.000 description 26
- 238000012216 screening Methods 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 17
- 239000006229 carbon black Substances 0.000 description 16
- 238000004049 embossing Methods 0.000 description 8
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- 238000007747 plating Methods 0.000 description 6
- 102100035474 DNA polymerase kappa Human genes 0.000 description 5
- 101710108091 DNA polymerase kappa Proteins 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- 238000001879 gelation Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 235000013980 iron oxide Nutrition 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 241001649081 Dina Species 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 229940031769 diisobutyl adipate Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- 239000005041 Mylar™ Substances 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- ARCGXLSVLAOJQL-UHFFFAOYSA-N anhydrous trimellitic acid Natural products OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920005678 polyethylene based resin Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000012800 visualization Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
Abstract
Provided is a method of manufacturing by a plastisol method vinyl chloride steel plates having excellent properties, for example a film hardness, a impression resistance and a bleed resistance. To obtain such a vinyl chloride steel plate, plastisol using a small amount of plasticizer and having a low viscosity which is produced by compounding a special plasticizer with a polyvinyl chloride resin having special particle diameter distribution is applied to the surface of a steel plate via a layer of a bonding agent.
Description
The present invention relates to high rigidity, resistance to pressure, anti-leachability (plasticizer) are superior, and the manufacture method of processability, vinyl chloride steel plates that design is superior.
Vinyl chloride steel plates is superior on characteristics such as processability, corrosion resistance, weatherability and design, is applicable to extensive fields such as building materials, electrical equipment, vehicle, furniture.
The manufacture method of vinyl chloride steel plates can roughly be divided into plastisol method and thin layer platen press.The plastisol method is after the plastisol that will be made of Corvic, plasticizer, stabilizing agent, pigment etc. is coated on the steel plate by adhesive layer thickness in accordance with regulations, with after the coating gelation, carries out film embossing processing by heating.
But, soft with the general coating matter of vinyl chloride steel plates of plastisol manufactured, to compare with the vinyl chloride steel plates of thin layer platen press manufacturing, characteristics such as the hardness of coating, resistance to pressure, anti-leachability are poor.About the plastisol method,, the plastisol with formations such as Corvic, plasticizer, stabilizing agent, pigment, diluents needs plastisol viscosity on the steel plate within the limits prescribed because of being coated to methods such as roller coat.So, use the plastisol that cooperates 40-60 weight portion plasticizer for 100 weight portion polyvinyl chloride usually, to compare with the thin layer platen press, it is many that the plasticizer in the coating becomes, then coating deliquescing.Its result, when goods suffer big pressure on coating surface, the resistance to pressure problem that exists the embossing decorative pattern to be easy to crush, and exist the plasticizer in the coating to be easy to transfer to surperficial anti-losing issue.
As the method for improving these plastisol method shortcomings, have the plastisol that can apply viscosity from selecting Corvic or aspects such as plasticizer and use diluent to study, but the improvement of characteristic is limited with low plasticiser.
So, suggestion cooperates liquid polymerism plasticizer in plastisol, the method of heat hardening during by gelation, the perhaps method (special public clear 44-31818, special public clear 50-22580, special public clear 57-9593 etc.) that with the ultraviolet ray irradiation coating is hardened again after the sclerosis.In addition, but suggestion in plastisol, cooperate the method for propylene-based copolymer powder and cooperate propylene-based copolymer powder and heat hardening or UV cured monomer, the method (special fair 5-31467, special fair 4-76747 etc.) of oligomer.But these methods are all used the compounding ingredient than the high several times of Corvic price, have big economic problems.
As mentioned above, the coating with the vinyl chloride steel plates of plastisol manufactured generally has the soft various shortcomings of matter.In addition, the method for advising as the method that addresses these problems, any one method all is to use the method for the compounding ingredient higher than Corvic price, economically existing problems.The present invention will solve exactly with the above-mentioned shortcoming of plastisol manufactured vinyl chloride steel plates, and excellents such as coating hardness, resistance to pressure, anti-leachability are provided, and the superior vinyl chloride steel plates manufacture method of economy.In addition, the present invention seeks to make with low plasticising dosage the lowering viscousity of plastisol.
For achieving the above object, feature of the present invention is the known binding agent of coating and toast by heating and to make base steel sheet on surface of steel plate, prepare again and a kind ofly contain a small amount of certain plasticizers but still have low viscous plastisol, and it is coated on the above-mentioned base steel sheet, wherein plastisol is by cooperating the plasticizer of 20-40 weight portion in the polyvinyl chloride resin powder end that 100 weight portion specified particle diameters distribute, and adds known pigment and stabilizing agent prepares.
According to a kind of manufacture method of the present invention with vinyl chloride steel plates of film of high hardness, it may further comprise the steps: prepare a kind of plastisol, and it is coated on the steel plate, it is characterized in that, described plastisol is preparation like this: the plasticizer that the bimodal pattern polyvinyl chloride resin powder end A of 100 weight portions is cooperated the 20-40 weight portion, in described polyvinyl chloride resin powder end A and plasticizer, add conventional pigment and stabilizing agent again, wherein the above particle diameter of 95 weight % of polyvinyl chloride resin powder end A is 0.5-40 μ m, and 15-40 weight % is 0.5-3 μ m, has peak value at 1-3 μ m, and 55-80 weight % is 3-40 μ m, has peak value at 8-15 μ m; Plasticizer is made of the phthalic acid ester of the alcohol that contains 7-9 carbon atom of 5-25 weight portion and the adipate ester that contains 8-10 carbon atom alcohol of 5-15 weight portion.
Another kind according to the present invention has the manufacture method of the vinyl chloride steel plates of film of high hardness, it may further comprise the steps: prepare a kind of plastisol, and it is coated on the steel plate, it is characterized in that, described plastisol is preparation like this: to the polyvinyl chloride powder A of 100 weight portions and the plasticizer of B cooperation 20-40 weight portion, in described polyvinyl chloride resin powder end A and B and plasticizer, add conventional pigment and stabilizing agent again, wherein bimodal pattern polyvinyl chloride resin powder end A accounts for the 60-95 weight portion in the polyvinyl chloride powder, polyvinyl chloride resin powder end B accounts for the 5-40 weight portion, the above particle diameter of 95 weight % of toner A is 0.5-40 μ m, and 15-40 weight % is 0.5-3 μ m, has peak value at 1-3 μ m, and 55-80 weight % is 3-40 μ m, has peak value in 8-15 μ m; The above particle diameter of 90 weight % of toner B is 10-60 μ m, and has peak value in 20-40 μ m.
Fig. 1 is the particle diameter distribution figure at former single peak type polyvinyl chloride resin powder end.
Fig. 2 is the example of particle diameter distribution figure of the bimodal pattern polyvinyl chloride resin powder end A of the inventive method.
Fig. 3 is the example of particle diameter distribution figure of the coarse grained polyvinyl chloride resin powder end B of the inventive method.
For the inventive method, as steel plate, can use cold-rolled steel sheet and zinc-plated on cold-rolled steel sheet, chromium plating, zinc-plated, nickel plating, aluminize, lead plating or the steel plate that plates the alloy of these metals and carry out the multilayer plating, perhaps carry out again the chemically treated steel plates such as chromate processing, phosphate treated on the upper strata of these clad steel sheets. In addition, also can select corrosion resistant plate, aluminium sheet according to its purpose.
According to the inventive method, for the bonding of steel plate and pvc coating, can use with the known binding agent as main component such as acrylic resin, mylar, polyurethane resin, epoxy resin or acrylic rubber. After surface of steel plate covers with thickness 3-10 μ m, toasted in 1 minute 160-250 ℃ of heating, then applied plastic colloidal sol.
The present invention is the result that composition and the character of the plastisol of coating and the characteristic of the vinyl chloride steel plates that obtains are tested in detail, and more known than the maximum reason of thin layer platen press difference with characteristics such as the hardness of the coating of the vinyl chloride steel plates of common plastisol method manufacturing, resistance to pressure, anti-leachabilities is the difference of the plasticising dosage in the coating. Generally with the manufacturing of calendering processing method, the amount of the plasticizer in the film can be arbitrarily ratio to the film that the thin layer platen press is used basically, cooperates the 25-40 weight portion according to the purposes of vinyl chloride steel plates for 100 weight portion Corvics. To this, the situation of plastisol method need to be with the thickness applied plastic colloidal sol on steel plate with regulation such as roll coater. The viscosity of plastisol must below setting, usually, cooperate 40-60 weight portion plasticizer for 100 weight portion Corvics. The difference of this plasticising dosage affects the characteristic of coating greatly.
Therefore, the present invention is for guaranteeing that preparing low viscous plastisol with the low plasticiser amount is conceived to the result that the selection of polyvinyl chloride resin powder end particle diameter distribution and plasticizer is studied repeatedly, and find the excellents such as coating hardness, resistance to pressure, anti-leachability, and the superior plastisol of economy.
The polyvinyl chloride resin powder end A that is used for plastisol of the present invention makes with emulsion polymerization or microsuspending method, and average degree of polymerization is 500-2500.In addition, can use by VCM and ethene, propylene, vinyl acetate, propionate, alkyl vinyl ether, vinylidene chloride, DEF or methyl acrylate copoly and close the polyethylene-based resin powder that constitutes.
With the situation of general plastisol manufactured vinyl chloride steel plates, use the Corvic of the peak value particle diameter distribution of average particulate diameter 1-2 μ m shown in Figure 1.So, the result that the particle diameter that reaches low viscous polyvinyl chloride resin powder end with the low plasticiser amount is attentively studied shows, to obtain low viscous plastisol with the low plasticiser amount, need to improve the packed density of the Corvic in the plastisol, for this reason, show that be desirable at Fig. 2 as the bimodal pattern particle diameter distribution shown in the example.
The particle diameter of polyvinyl chloride resin powder of the present invention end A is that to have the above particle diameter of 95 weight % be 0.5-40 μ m, and 15-40 weight % is 0.5-3 μ m and has peak value at 1-3 μ m, and 55-80 weight % is 3-40 μ m and is desirable at the bimodal pattern particle diameter that 8-15 μ m has a peak value, surpass 5 weight % as the powder more than the particle diameter 40 μ m, the plastisol coated surfaces that obtains degenerates, and is unfavorable.Less than 15 weight %, the powder of particle diameter 3-40 μ m surpasses 80 weight % as the powder of particle diameter 0.5-3 μ m, and the gelatinization performance of plastisol reduces, and the intensity of coating reduces, and is unfavorable.In addition, more than weight %, the powder of particle diameter 3-40 μ m is less than 55 weight % as the powder 40 of particle diameter 0.5-3 μ m, and it is big that plastisol viscosity becomes, and screening characteristics degenerates, and is unfavorable.
In addition, be that the plastisol lowering viscousity of 20-40 weight portion carries out result of study again and shows that as cooperating as a coarse grained polyvinyl chloride resin powder end B that example is shown in Figure 3, viscosity reduces again to plasticising dosage, screening characteristics significantly improves.
The polyvinyl chloride resin powder end B that uses in plastisol of the present invention makes with suspension method, and average degree of polymerization is 500-2000.In addition, can use by VCM and ethene, propylene, vinyl acetate, propionate, alkyl vinyl ether, vinylidene chloride, DEF or methyl acrylate copoly and close the polyvinyl chloride toner that constitutes.
The particle diameter of polyvinyl chloride resin powder end B is 10-60 μ m, and has peak value for well in 20-40 μ m.In addition, better more than 70 weight % as particle diameter 15-40 μ m.Surpassing 10 weight % as particle diameter less than the powder of 10 μ m, reduce the effect loss of the viscosity of plastisol, is unfavorable.In addition, as surpassing 10 weight % more than the particle diameter 60 μ m, the plastisol coated surfaces of finishing degenerates, and is unfavorable.
Corvic A in the plastisol of the present invention and the ratio of B are under the occasion of 100 weight portions at Corvic A and B total amount, Corvic A 60-95 weight portion, and Corvic B 5-40 weight portion is desirable.Less than 60 weight portions, and the Corvic B ultrasonic is crossed 40 weight portions as Corvic A, and the strength of coating after the gelation reduces, and is unfavorable.In addition, more than Corvic A95 weight portion, and Corvic B cooperates the effect of Corvic B not reach less than 5 weight portions, is unfavorable.
Moreover, the result who the plasticizer that cooperates in the plastisol is studied by the inventive method as can be known, can use known phthalic acid ester, trimellitic acid ester, adipate ester etc., main plasticizer or less important plasticizer such as aliphatic (acid) ester or various phosphate also can use, press the characteristic aspects such as hardness, resistance to pressure, processability, anti-leachability of aging stability, gelatinization performance and the coating of plastisol viscosity, viscosity, comprise 7-9 carbon pure composition phthalic acid ester and comprise that the combination of adipate ester of the pure composition of 8-10 carbon is desirable.
About its cooperation ratio, for polyvinyl chloride resin powder end 100 weight portions, the phthalic acid ester 5-25 weight portion and the adipate ester 5-15 weight portion that comprises the pure composition of 8-10 carbon that cooperate the pure composition that contains 7-9 carbon as plasticizer, and total 20-40 weight portion is desirable.
As the phthalic acid ester of pure composition that comprises 7-9 carbon is less than 5 weight portions, and comprises that the adipate ester of the pure composition of 8-10 carbon is more than 25 weight portions, and the anti-leachability of coating reduces, and is unfavorable.In addition, as comprise that the phthalic acid ester of the pure composition of 7-9 carbon is more than 25 weight portions, and the adipate ester of pure composition that comprises 8-10 carbon being less than 5 weight portions, reducing in the impact processability of low temperature, is unfavorable.Moreover less than 20 weight portions, the viscosity of plastisol uprises as if the plasticizer total amount, and screening characteristics reduces, and is unfavorable.In addition, be more than 40 weight portions as the plasticizer total amount, the hardness of coating reduces, and resistance to pressure reduces, and is unfavorable.
Comprise phthalic acid ester less than the pure composition of 7 carbon atoms as plasticizer such as use, the viscosity aging stability of plastisol reduces and coating hardness diminishes, and is unfavorable.In addition, comprise the phthalic acid ester of 10 pure compositions more than the carbon as use, the viscosity of plastisol uprises, and screening characteristics reduces, and is unfavorable.
In addition, comprise that as plasticizer such as use the anti-leachability of coating reduces, and is unfavorable less than the adipate ester of the pure composition formation of 7 carbon.Also have, comprise the phthalic acid ester that 10 pure compositions more than the carbon constitute as use, the viscosity of plastisol uprises, and screening characteristics reduces, and is unfavorable.
In addition, according to the present invention, in plastisol, can cooperate known pigment, stabilizing agent, various additive and diluent.About diluent,, wish less than 10 weight portions for 100 weight portion Corvics.As the above coating generation of 10 weight portions pore, be undesirable.
In the present invention, the plastisol that will have an above-mentioned feature, 210 ℃ of heating of carrying out 1 minute, is processed the embossing of stipulating after this coating gelation and is made vinyl chloride steel plates after coating 30-500 μ m on the surface of steel plate is thick by binding agent.
The available scraper coating machine of the coating of plastisol, roll coating machine, rod are coated with any method of machine.
The rerum natura of plastisol of the present invention and the characteristic of vinyl chloride steel plates are with following method evaluation.
(1) viscosity of plastisol
With the BM type viscosimeter that Tokyo gauge (strain) is made, No.4 roller, be to measure under the condition of 6rpm at revolution.
(2) screening characteristics and appearance of coat evaluation
After being coated to plastisol on the steel plate with the scraper coating machine, the preceding coating surface of embossing processing that adds Thermogelling according to range estimation is estimated.
(metewand) zero: good (surface smoothing, defectives such as shape or striped are speckless)
△: general (defectives such as spottiness shape or striped a little)
*: bad (defectives such as spottiness shape or striped comprehensively).
(3) hardness of coating
With the hardometer (A type) that (strain) Shimadzu Seisakusho Ltd. makes, under 25 ℃ of temperature, measure.
(4) low-temperature impact processability
With Du Pont impact the processing experiment machine (punch diameter: 1/2 inch, load-carrying: 1kg, height of fall: 50cm), after 0 ℃ of humid test, estimate the generation of coating crack.
(5) resistance to pressure
The size of pressing 15cm * 15cm banks out several, to add 3kg/cm on it after vinyl chloride steel plates is cut off
2The state of loading was placed 10 at 40 ℃.Take out breadboard, the embossing state of visual coating surface thereafter.
(metewand) zero: good (embossing is not unusual)
△: general (embossing of crushing a little)
*: bad (embossing of comprehensively crushing)
(6) anti-leachability
After the size of pressing 15cm * 15cm is cut off vinyl chloride steel plates, between vinyl chloride steel plates and vinyl chloride steel plates, insert the polyester film of biaxial orientation, several are banked out, to add 10kg/cm on it
2The state of loading was placed 10 at 50 ℃.Take out breadboard, the polyester film face that visualization contacts with coat side thereafter.
(metewand) zero: good (not seeing loss fully)
△: good slightly (seeing) like aqueous material
*: bad (seeing aqueous material) comprehensively
Embodiment
With embodiment the present invention is described below.
Embodiment 1-8
Implementing plating amount 20g/m
2Chromic acid handle, on the galvanized sheet of thickness of slab 0.5mm behind the binding agent of the known acrylic epoxy resin of coating dry film thick 5 μ m, the plastisol that cooperates shown in the coating table 1-3 on the surface of toasting under 230 ℃ and cooling off in gas burner, then adding Thermogelling in gas burner under 210 ℃ makes vinyl chloride steel plates.
(table 1)
| Embodiment | The cooperation of plastisol is formed | |||
| Corvic | Plasticizer | Stabilizing agent | Pigment | |
| 1 | Corvic A 100 weight portion particle diameter distribution: the position at 0.5-3 μ m:15 weight % 3-40 μ m:85 weight % peak: 1.0 μ m, 15 μ m averages degree of polymerization: 1,600 | Two-ethylhexyl phthalic acid ester, 5 weight portions, (DOP: the carbon number 8 of pure composition) two-ethylhexyl adipate ester, 15 weight portions, (DOA: the carbon number 8 of pure composition) | Organotin 3 weight portions | Carbon black 1.5 weight portions |
| 2 | Corvic A 100 weight portion particle diameter distribution: the position at 0.5-3 μ m:20 weight % 3-40 μ m:80 weight % peak: 1.8 μ m, 12 μ m averages degree of polymerization: 1,600 | Diheptyl phthalic acid ester 5 weight portions (DHP: the carbon number 7 of pure composition) two-ethylhexyl phthalic acid ester, 10 weight portions (DOP: the carbon number 8 of pure composition) diisononyl phthalic acid ester 5 weight portions (DINP: the carbon of pure composition is individual to apply 9) diisononyl adipate ester 5 weight portions (DINA: the carbon number 9 of pure composition) | Ba-Zn is 2 weight portions | Carbon black 1.5 weight portions |
| 3 | Corvic A 100 weight portion particle diameter distribution: the position at 0.5-3 μ m:40 weight % 3-40 μ m:60 weight % peak: 2.5 μ m, 8 μ m averages degree of polymerization: 1,600 | Two-ethylhexyl phthalic acid ester, 10 weight portions (DOP: the carbon number 8 of pure composition) diisononyl phthalic acid ester 10 weight portions (DINP: the carbon number 9 of pure composition) two-ethylhexyl adipate ester, 15 weight portions (DOA: the carbon number 8 of pure composition) | Ba-Zn is 2 weight portions | Titanium oxide 14 weight portion iron oxide 0.3 weight portion |
(table 2)
| Embodiment | The cooperation of plastisol is formed | |||
| Corvic | Plasticizer | Stabilizing agent | Pigment | |
| 4 | Corvic A 100 weight portion particle diameter distribution: the position at 0.5-3 μ m:20 weight % 3-40 μ m:80 weight % peak: 1.8 μ m, 12 μ m averages degree of polymerization: 1,600 | Two-ethylhexyl phthalic acid ester, 5 weight portions (DOP: the carbon number 8 of pure composition) diisononyl phthalic acid ester 20 weight portions (DINP: the carbon number 9 of pure composition) diiso decyl adipate ester 15 weight portions (DIDA: the carbon number 4 of pure composition) | Pb is 3 weight portions | Titanium oxide 22 weight portion red iron oxides 0.1 weight portion carbon black 0.01 weight portion |
| 5 | Corvic A 100 weight portion particle diameter distribution: the position at 0.5-3 μ m:20 weight % 3-40 μ m:80 weight % peak: 1.8 μ m, 12 μ m averages degree of polymerization: 1,600 | Two-ethylhexyl phthalic acid ester, 20 weight portions, (DOP: the carbon number 8 of pure composition) diiso decyl adipate ester 10 weight portions, (DIDA: the carbon number 10 of pure composition) | Ba-Zn is 2 weight portions | Carbon black 1.5 weight portions |
| 6 | Corvic A 100 weight portion particle diameter distribution: the position at 0.5-3 μ m:20 % by weight 3-40 μ m:80 % by weight peak: 1.8 μ m; 12 μ m averages degree of polymerization: 1; 600 Corvic B, 40 weight portion particle diameter distribution: the position at 10-50 μ m:95 % by weight peak: 20 μ m averages degree of polymerization: 1,000 | Two-ethylhexyl phthalic acid ester, 5 weight portions (DOP: the carbon number 8 of pure composition) diisononyl phthalic acid ester 20 weight portions (DIDA: the carbon number 9 of pure composition) diiso decyl adipate ester 15 weight portions (DIDA: the carbon number 10 of pure composition) | Pb is 3 weight portions | Titanium oxide 22 weight portion red iron oxides 0.1 weight portion carbon black 0.01 weight portion |
(table 3)
| Embodiment | The cooperation of plastisol is formed | |||
| Corvic | Plasticizer | Stabilizing agent | Pigment | |
| 7 | Corvic A 80 weight portion particle diameter distribution: the position at 0.5-3 μ m:20 % by weight 3-40 μ m:80 % by weight peak: 1.8 μ m; 12 μ m averages degree of polymerization: 1; 600 Corvic B, 20 weight portion particle diameter distribution: the position at 15-50 μ m:95 % by weight peak: 36 μ m averages degree of polymerization: 1,000 | Two-ethylhexyl phthalic acid ester, 20 weight portions, (DOP: the carbon number 8 of pure composition) diiso decyl adipate ester 10 weight portions, (DOA: the carbon number 10 of pure composition) | Ba-Zn is 2 weight portions | Carbon black 1.5 weight portions |
| 8 | Corvic A 100 weight portion particle diameter distribution: the position at 0.5-3 μ m:40 % by weight 3-40 μ m:60 % by weight peak: 2.5 μ m; 8 μ m averages degree of polymerization: 1; 600 Corvic B, 5 weight portion particle diameter distribution: the position at 15-50 μ m:95 % by weight peak: 36 μ m averages degree of polymerization: 1,000 | Two-ethylhexyl phthalic acid ester, 10 weight portions (DHP: the carbon number 8 of pure composition) diisononyl phthalic acid ester 10 weight portions (DOP: the carbon number 9 of pure composition) two-ethylhexyl phthalic acid ester, 15 weight portions (DINP: the carbon number 8 of pure composition) | Ba-Zn is 2 weight portions | Titanium oxide 14 weight portion iron oxide 0.3 weight portion |
According to the vinyl chloride steel plates that embodiment of the invention 1-8 makes, as shown in table 4, the viscosity of plastisol is low, and screening characteristics is good, and the coating hardness height of acquisition and low-temperature impact processability, resistance to pressure and anti-leachability are superior.
(table 4)
| Embodiment | The viscosity of plastisol (cps) | Coating layer thickness (μ m) | The outward appearance of screening characteristics and coating | Coating characteristic | |||
| Coating hardness | The low-temperature impact processability | Resistance to pressure | Anti-leachability | ||||
| 1 | 8,500 | 80 | ○ | 96 | ○ | ○ | ○ |
| 2 | 7,000 | 100 | ○ | 95 | ○ | ○ | ○ |
| 3 | 6,500 | 150 | ○ | 93 | ○ | ○ | ○ |
| 4 | 6,500 | 200 | ○ | 93 | ○ | ○ | ○ |
| 5 | 6,000 | 150 | ○ | 95 | ○ | ○ | ○ |
| 6 | 4,300 | 200 | ○ | 93 | ○ | ○ | ○ |
| 7 | 4,300 | 150 | ○ | 95 | ○ | ○ | ○ |
| 8 | 5,800 | 150 | ○ | 93 | ○ | ○ | ○ |
Comparative example 1-11
Implementing plating amount 20g/m
2Chromate handle, on the galvanized steel plain sheet of thickness of slab 0.5mm behind the binding agent of known acrylic/epoxy resin of coating dry film thick 5 μ m, the plastisol that cooperates shown in the table of the coating from the teeth outwards 5-7 that toasts under 230 ℃ in gas burner and cool off then adds Thermogelling at 210 ℃ and makes vinyl chloride steel plates in gas burner.
The result of the test of ratio example 1-7 method is shown in table 8.
Comparative example 1 is to use the situation that the end of the single peak type polyvinyl chloride resin powder before 100 weight portions is cooperated 30 weight portion plasticizer, and the viscosity of the plastisol of acquisition is high significantly, the coating difficulty.
Comparative example 2 is to use the situation that the end of the single peak type polyvinyl chloride resin powder before 100 weight portions is cooperated 50 weight portion plasticising dosage, and the plastisol viscosity of acquisition is low, and screening characteristics is good, and coating hardness is low, and resistance to pressure, anti-leachability are poor.
Comparative example 3 is to use the situation at the too high bimodal pattern polyvinyl chloride resin powder end of the ratio of particle diameter 0.5-3 μ m, and cooperating plasticising dosage is 30 weight portions, the viscosity height of plastisol, and screening characteristics, resistance to pressure are poor.
It is the situation at 90% bimodal pattern polyvinyl chloride resin powder end that comparative example 4 is to use the ratio of particle diameter 3-40 μ m, and the viscosity of plastisol is low, and low-temperature impact processability, resistance to pressure are poor.
It is that the position at the peak of 20 weight % is the situation at the polyvinyl chloride resin powder end of 0.8 μ m that comparative example 5 is to use the ratio of particle diameter 0.5-3 μ m, the viscosity height of plastisol, and screening characteristics, resistance to pressure are poor.
It is that the position at the peak of 80 weight % is the situation at the bimodal pattern polyvinyl chloride resin powder end of 18 μ m that comparative example 6 is to use the ratio of particle diameter 3-40 μ m, and the viscosity of plastisol is low, and screening characteristics is good, the low-temperature impact poor in processability.
It is that the position at the peak of 80 weight % is the situation at the bimodal pattern polyvinyl chloride resin powder end of 5 μ m (peak is little) that comparative example 7 is to use the ratio of particle diameter 3-40 μ m, the viscosity height of plastisol, and screening characteristics, resistance to pressure are poor.
Comparative example 8 be for bimodal pattern polyvinyl chloride resin powder of the present invention end A cooperate total amount 30 weight portions pure composition carbon number each be 4 Plasticizer DBP (diisobutyl phthalate) and the situation of DIBA (diisobutyl adipate ester), the viscosity of plastisol is low, screening characteristics is superior, and coating hardness is low, resistance to pressure, anti-leachability are poor.
Comparative example 9 is that to cooperate the carbon number of the pure composition of total amount 30 weight portions for bimodal pattern polyvinyl chloride resin powder of the present invention end A be 10 plasticizer DIDP (diiso decyl phthalic acid ester) and the situation of DIDA (diiso decyl adipate ester), the viscosity height of plastisol, screening characteristics is bad, and resistance to pressure is poor.
Comparative example 10 is the polyvinyl chloride resin powder end A50 weight portion of bimodal pattern of the present invention and the situation that polyvinyl chloride resin powder of the present invention end B50 weight portion cooperates, and the viscosity of the plastisol of acquisition is low, and screening characteristics is bad, and low-temperature impact processability, resistance to pressure are poor.
Comparative example 11 is that to cooperate particle diameter 80-120 μ m for bimodal pattern polyvinyl chloride resin powder of the present invention end A be that the position at the peak of 90 weight % is the situation at the coarse granule polyvinyl chloride resin powder end of 100 μ m, the viscosity of the plastisol that obtains is low, screening characteristics is bad, and low-temperature impact processability, resistance to pressure are poor.
(table 5)
| Comparative example | The cooperation of plastisol is formed | |||
| Corvic | Plasticizer | Stabilizing agent | Pigment | |
| 1 | Corvic A 100 weight portion particle diameter distribution: the position at 0.5-6 μ m:95 weight % peak: 1.8 μ m averages degree of polymerization: 1,600 | Two-ethylhexyl phthalic acid ester, 20 weight portions, (DOP: the carbon number 8 of pure composition) diiso decyl adipate ester 10 weight portions, (DIDA: the carbon number 10 of pure composition) | Ba-Zn is 2 weight portions | Carbon black 1.5 weight portions |
| 2 | Corvic A 100 weight portion particle diameter distribution: the position at 0.5-6 μ m:95 weight % peak: 1.8 μ m averages degree of polymerization: 1,600 | Two-ethylhexyl phthalic acid ester, 40 weight portions, (DOP: the carbon number 8 of pure composition) diiso decyl adipate ester 10 weight portions, (DIDA: the carbon number 10 of pure composition) | Ba-Zn is 2 weight portions | Carbon black 1.5 weight portions |
| 3 | Corvic 100 weight portion particle diameter distribution: the position at 0.5-3 μ m:70 weight % 3-40 μ m:30 weight % peak: 1.5 μ m, 13 μ m averages degree of polymerization: 1,600 | Two-ethylhexyl phthalic acid ester, 20 weight portions, (DOP: the carbon number 8 of pure composition) diiso decyl adipate ester 10 weight portions, (DIDA: the carbon number 10 of pure composition) | Ba-Zn is 2 weight portions | Carbon black 1.5 weight portions |
| 4 | Corvic A 100 weight portion particle diameter distribution: the position at 0.5-3 μ m:10 weight % 3-40 μ m:90 weight % peak: 1.5 μ m, 13 μ m averages degree of polymerization: 1,600 | Two-ethylhexyl phthalic acid ester, 20 weight portions, (DOP: the carbon number 8 of pure composition) diiso decyl adipate ester 10 weight portions, (DIDA: the carbon number 10 of pure composition) | Ba-Zn is 2 weight portions | Carbon black 1.5 weight portions |
(table 6)
| Comparative example | The cooperation of plastisol is formed | |||
| Corvic | Plasticizer | Stabilizing agent | Pigment | |
| 5 | Corvic 100 weight portion particle diameter distribution: the position at 0.5-3 μ m:20 weight % 3-40 μ m:80 weight % peak: 0.8 μ m, 13 μ m averages degree of polymerization: 1,600 | Two-ethylhexyl phthalic acid ester, 20 weight portions, (DOP: the carbon number 8 of pure composition) diiso decyl adipate ester 10 weight portions, (DIDA: the carbon number 10 of pure composition) | Ba-Zn is 2 weight portions | Carbon black 1.5 weight portions |
| 6 | Corvic 100 weight portion particle diameter distribution: the position at 0.5-3 μ m:20 weight % part 3-40 μ m:80 weight % peak: 1.5 μ m, 18 μ m averages degree of polymerization: 1,600 | Two-ethylhexyl phthalic acid ester, 20 weight portions, (DOP: the carbon number 8 of pure composition) diiso decyl adipate ester 10 weight portions, (DIDA: the carbon number 10 of pure composition) | Ba-Zn is 2 weight portions | Carbon black 1.5 weight portions |
| 7 | Corvic 100 weight portion particle diameter distribution: the position at 0.5-3 μ m:20 weight % 3-40 μ m:80 weight % peak: 1.5 μ m, 5 μ m averages degree of polymerization: 1,600 | Two-ethylhexyl phthalic acid ester, 20 weight portions, (DOP: the carbon number 8 of pure composition) diiso decyl adipate ester 10 weight portions, (DIDA: the carbon number 10 of pure composition) | Ba-Zn is 2 weight portions | Carbon black 1.5 weight portions |
| 8 | Corvic A 100 weight portion particle diameter distribution: the position at 0.5-3 μ m:20 weight % 3-40 μ m:80 weight % peak: 1.5 μ m, 13 μ m averages degree of polymerization: 1,600 | DI-ISOBUTYL PHTHALATE 20 weight portions, (DBP: the carbon number 4 of pure composition) diisobutyl adipate ester 10 weight portions, (DIBA: the carbon number 4 of pure composition) | Ba-Zn is 2 weight portions | Carbon black 1.5 weight portions |
(table 7)
| Comparative example | The cooperation of plastisol is formed | |||
| Corvic | Plasticizer | Stabilizing agent | Pigment | |
| 9 | Corvic A 100 weight portion particle diameter distribution: the position at 0.5-3 μ m:20 weight % 3-40 μ m:80 weight % peak: 1.5 μ m, 13 μ m averages degree of polymerization: 1,600 | Diiso decyl phthalic acid ester 20 weight portions, (DIDP: the carbon number 10 of pure composition) diiso decyl adipate ester 10 weight portions, (DIDA: the carbon number 10 of pure composition) | Ba-Zn is 2 weight portions | Carbon black 1.5 weight portions |
| 10 | Corvic A 50 weight portion particle diameter distribution: the position at 0.5-3 μ m:40 % by weight 3-40 μ m:60 % by weight peak: 1.5 μ m; 13 μ m averages degree of polymerization: 1; 600 Corvic B, 50 weight portion particle diameter distribution: the position at 15-50 μ m:95 % by weight peak: 36 μ m averages degree of polymerization: 1,000 | Two-ethylhexyl phthalic acid ester, 20 weight portions, (DOP: the carbon number 8 of pure composition) diisononyl adipate ester 10 weight portions, (DINA: the carbon number 10 of pure composition) | Ba-Zn is 2 weight portions | Carbon black 1.5 weight portions |
| 11 | Corvic A 80 weight portion particle diameter distribution: the position at 0.5-3 μ m:20 % by weight 3-40 μ m:80 % by weight peak: 1.5 μ m; 13 μ m averages degree of polymerization: 1,600 Corvic, 20 weight portion particle diameter distribution: the position at 80-120 μ m:90 % by weight peak: 100 μ m averages degree of polymerization: 800 | Diheptyl phthalic acid ester 5 weight portions (DHP: the carbon number 7 of pure composition) two-ethylhexyl phthalic acid ester, 5 weight portions (DOP: the carbon number 8 of pure composition) diisononyl phthalic acid ester 5 weight portions (DINP: the carbon number 9 of pure composition) diisononyl adipate ester 5 weight portions (DINA: the carbon number 9 of pure composition) | Organotin 2 weight portions | Titanium oxide 10 weight portion acidifying iron 0.8 weight portion |
(table 8)
| Comparative example | The viscosity of plastisol (cps) | Coating layer thickness (μ m) | The outward appearance of screening characteristics and coating | Coating characteristic | |||
| Coating hardness | The low-temperature impact processability | Resistance to pressure | Anti-leachability | ||||
| 1 | More than 100,000 | - | * can not apply | - | - | - | - |
| 2 | 8,000 | 200 | ○ | 80 | ○ | × | × |
| 3 | 37,000 | 150 | △ | 94 | ○ | △ | ○ |
| 4 | 5,200 | 150 | ○ | 94 | × | △ | ○ |
| 5 | 48,000 | 150 | × | 94 | ○ | × | ○ |
| 6 | 4,600 | 150 | ○ | 94 | × | ○ | ○ |
| 7 | 43,000 | 150 | △ | 94 | ○ | △ | ○ |
(table 9)
| Comparative example | The viscosity of plastisol (cps) | Coating layer thickness (μ m) | The outward appearance of screening characteristics and coating | Coating characteristic | |||
| Coating hardness | The low-temperature impact processability | Resistance to pressure | Anti-leachability | ||||
| 8 | 4,600 | 150 | ○ | 88 | ○ | △ | × |
| 9 | 20,000 | 200 | △ | 94 | ○ | △ | ○ |
| 10 | 3,600 | 150 | × | 94 | × | △ | ○ |
| 11 | 3,000 | 200 | × | 94 | × | × | ○ |
Can efficiently make the vinyl chloride steel plates of coating hardness height and excellents such as low-temperature impact processability, resistance to pressure and anti-leachability at an easy rate according to the present invention.
Claims (2)
1. the manufacture method that has the vinyl chloride steel plates of film of high hardness, it may further comprise the steps: prepare a kind of plastisol, and it is coated on the steel plate, it is characterized in that, described plastisol is preparation like this: the plasticizer that the bimodal pattern polyvinyl chloride resin powder end A of 100 weight portions is cooperated the 20-40 weight portion, in described polyvinyl chloride resin powder end A and plasticizer, add conventional pigment and stabilizing agent again, wherein the above particle diameter of 95 weight % of polyvinyl chloride resin powder end A is 0.5-40 μ m, and 15-40 weight % is 0.5-3 μ m, has peak value at 1-3 μ m, and 55-80 weight % is 3-40 μ m, has peak value at 8-15 μ m; Plasticizer is made of the phthalic acid ester of the alcohol that contains 7-9 carbon atom of 5-25 weight portion and the adipate ester that contains 8-10 carbon atom alcohol of 5-15 weight portion.
2. the manufacture method that has the vinyl chloride steel plates of film of high hardness, it may further comprise the steps: prepare a kind of plastisol, and it is coated on the steel plate, it is characterized in that, described plastisol is preparation like this: to the polyvinyl chloride powder A of 100 weight portions and the plasticizer of B cooperation 20-40 weight portion, in described polyvinyl chloride resin powder end A and B and plasticizer, add conventional pigment and stabilizing agent again, wherein bimodal pattern polyvinyl chloride resin powder end A accounts for the 60-95 weight portion in the polyvinyl chloride powder, polyvinyl chloride resin powder end B accounts for the 5-40 weight portion, the above particle diameter of 95 weight % of toner A is 0.5-40 μ m, and 15-40 weight % is 0.5-3 μ m, has peak value at 1-3 μ m, and 55-80 weight % is 3-40 μ m, has peak value in 8-15 μ m; The above particle diameter of 90 weight % of toner B is 10-60 μ m, and has peak value in 20-40 μ m.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP349446/95 | 1995-12-22 | ||
| JP7349446A JP2971382B2 (en) | 1995-12-22 | 1995-12-22 | Method for producing PVC steel sheet having high hardness coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1207704A CN1207704A (en) | 1999-02-10 |
| CN1084673C true CN1084673C (en) | 2002-05-15 |
Family
ID=18403811
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96199735A Expired - Fee Related CN1084673C (en) | 1995-12-22 | 1996-12-20 | Method of mfg. vinyl chloride steel plates having film of high hardness |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JP2971382B2 (en) |
| KR (1) | KR100404158B1 (en) |
| CN (1) | CN1084673C (en) |
| AU (1) | AU1172497A (en) |
| TW (1) | TW322448B (en) |
| WO (1) | WO1997023349A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR0010322A (en) | 1999-05-06 | 2002-04-09 | Univ Wake Forest | Expression vector, vaccine and its method of use to elicit an immune response directed against an antigen in a mammal |
| GB2411657A (en) * | 2004-03-01 | 2005-09-07 | Basf Coatings Ag | PVC plastisol coatings |
| KR101431490B1 (en) * | 2013-12-13 | 2014-08-21 | 삼화페인트 공업주식회사 | Pvc plastisol coating composition and color steel sheet using the same |
| JP6445790B2 (en) * | 2014-06-10 | 2018-12-26 | 東洋鋼鈑株式会社 | Polyvinyl chloride laminated substrate and waterproof panel substrate |
| CN104962142A (en) * | 2015-07-03 | 2015-10-07 | 河南锂动电源有限公司 | Automobile battery box body protective coating material and protection method thereof |
| CN112409712A (en) * | 2019-08-20 | 2021-02-26 | 贝内克-长顺汽车内饰材料（张家港）有限公司 | Composition comprising polyvinyl chloride, use thereof and artificial leather obtained therefrom |
| CN112452692A (en) * | 2020-10-16 | 2021-03-09 | 广东中晨电子科技有限公司 | Preparation method of high-performance composite base plate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5050029A (en) * | 1973-09-03 | 1975-05-06 | ||
| JPS565450A (en) * | 1979-06-12 | 1981-01-20 | Bayer Ag | Manufacture of 3*33dimethyllcyclopropanee 1*1*22tricarboxylic acid derivative* novel intermediate alphaahalogennnitrile for said manufacture and its manufacture |
| JPH104923A (en) * | 1996-06-26 | 1998-01-13 | Kikkoman Corp | Stabilization of color tone of edible meat |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0550029A (en) * | 1991-08-09 | 1993-03-02 | Aisin Chem Co Ltd | Coating method for automobile having chipping resistant coating film |
| JPH0565450A (en) * | 1991-09-06 | 1993-03-19 | Honda Motor Co Ltd | Vinyl chloride plastisol composition |
| JPH07304923A (en) * | 1994-05-13 | 1995-11-21 | Sekisui Chem Co Ltd | Plastisol composition |
-
1995
- 1995-12-22 JP JP7349446A patent/JP2971382B2/en not_active Expired - Fee Related
-
1996
- 1996-12-20 WO PCT/JP1996/003741 patent/WO1997023349A1/en active IP Right Grant
- 1996-12-20 KR KR10-1998-0704715A patent/KR100404158B1/en not_active IP Right Cessation
- 1996-12-20 CN CN96199735A patent/CN1084673C/en not_active Expired - Fee Related
- 1996-12-20 AU AU11724/97A patent/AU1172497A/en not_active Abandoned
-
1997
- 1997-01-06 TW TW086100124A patent/TW322448B/zh active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5050029A (en) * | 1973-09-03 | 1975-05-06 | ||
| JPS565450A (en) * | 1979-06-12 | 1981-01-20 | Bayer Ag | Manufacture of 3*33dimethyllcyclopropanee 1*1*22tricarboxylic acid derivative* novel intermediate alphaahalogennnitrile for said manufacture and its manufacture |
| JPH104923A (en) * | 1996-06-26 | 1998-01-13 | Kikkoman Corp | Stabilization of color tone of edible meat |
Also Published As
| Publication number | Publication date |
|---|---|
| TW322448B (en) | 1997-12-11 |
| KR19990076613A (en) | 1999-10-15 |
| KR100404158B1 (en) | 2004-07-05 |
| AU1172497A (en) | 1997-07-17 |
| JP2971382B2 (en) | 1999-11-02 |
| CN1207704A (en) | 1999-02-10 |
| JPH09174757A (en) | 1997-07-08 |
| WO1997023349A1 (en) | 1997-07-03 |
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