CN1103283C - Metallic sheet covered with highly clear resin and having work adhesiveness - Google Patents
Metallic sheet covered with highly clear resin and having work adhesiveness Download PDFInfo
- Publication number
- CN1103283C CN1103283C CN97194566A CN97194566A CN1103283C CN 1103283 C CN1103283 C CN 1103283C CN 97194566 A CN97194566 A CN 97194566A CN 97194566 A CN97194566 A CN 97194566A CN 1103283 C CN1103283 C CN 1103283C
- Authority
- CN
- China
- Prior art keywords
- resin
- metallic plate
- coating
- layer
- pigment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 154
- 239000011347 resin Substances 0.000 title claims abstract description 154
- 239000010410 layer Substances 0.000 claims abstract description 122
- 230000003746 surface roughness Effects 0.000 claims abstract description 17
- 239000000758 substrate Substances 0.000 claims abstract description 11
- 239000011248 coating agent Substances 0.000 claims description 137
- 238000000576 coating method Methods 0.000 claims description 137
- 239000000049 pigment Substances 0.000 claims description 39
- 239000000843 powder Substances 0.000 claims description 23
- 239000011247 coating layer Substances 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 229920002799 BoPET Polymers 0.000 claims description 15
- 239000005041 Mylar™ Substances 0.000 claims description 15
- 238000007639 printing Methods 0.000 claims description 13
- 229920000178 Acrylic resin Polymers 0.000 claims description 10
- 239000004925 Acrylic resin Substances 0.000 claims description 10
- 238000009500 colour coating Methods 0.000 claims description 10
- 239000004411 aluminium Substances 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 229920005749 polyurethane resin Polymers 0.000 claims description 8
- 239000010445 mica Substances 0.000 claims description 7
- 229910052618 mica group Inorganic materials 0.000 claims description 7
- 239000003822 epoxy resin Substances 0.000 claims description 6
- 229920000647 polyepoxide Polymers 0.000 claims description 6
- 239000004800 polyvinyl chloride Substances 0.000 claims description 6
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 6
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 claims description 3
- 210000004276 hyalin Anatomy 0.000 claims description 3
- 239000004014 plasticizer Substances 0.000 claims description 3
- 229920001747 Cellulose diacetate Polymers 0.000 claims description 2
- 229920002284 Cellulose triacetate Polymers 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 claims description 2
- 150000008064 anhydrides Chemical group 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 claims description 2
- 239000000806 elastomer Substances 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 229920005668 polycarbonate resin Polymers 0.000 claims description 2
- 239000004431 polycarbonate resin Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920000306 polymethylpentene Polymers 0.000 claims description 2
- 239000011116 polymethylpentene Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 230000003014 reinforcing effect Effects 0.000 claims description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 2
- 229920005672 polyolefin resin Polymers 0.000 claims 1
- 239000003973 paint Substances 0.000 abstract description 15
- 239000012790 adhesive layer Substances 0.000 abstract 1
- 238000004040 coloring Methods 0.000 abstract 1
- 238000012545 processing Methods 0.000 description 24
- 238000002310 reflectometry Methods 0.000 description 22
- 238000000034 method Methods 0.000 description 15
- 229920000728 polyester Polymers 0.000 description 15
- 239000000853 adhesive Substances 0.000 description 14
- 230000001070 adhesive effect Effects 0.000 description 14
- 239000002245 particle Substances 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 239000007787 solid Substances 0.000 description 11
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 10
- 229910001335 Galvanized steel Inorganic materials 0.000 description 10
- 229910052804 chromium Inorganic materials 0.000 description 10
- 239000011651 chromium Substances 0.000 description 10
- 239000008397 galvanized steel Substances 0.000 description 10
- 238000010030 laminating Methods 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 238000005498 polishing Methods 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229920001225 polyester resin Polymers 0.000 description 6
- 239000004645 polyester resin Substances 0.000 description 6
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 101000856236 Clostridium acetobutylicum (strain ATCC 824 / DSM 792 / JCM 1419 / LMG 5710 / VKM B-1787) Butyrate-acetoacetate CoA-transferase subunit B Proteins 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 229920006026 co-polymeric resin Polymers 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000007731 hot pressing Methods 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- 235000014692 zinc oxide Nutrition 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 3
- 239000004922 lacquer Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000001058 brown pigment Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000001054 red pigment Substances 0.000 description 2
- 238000013517 stratification Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229920006352 transparent thermoplastic Polymers 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- IKZBVTPSNGOVRJ-UHFFFAOYSA-K chromium(iii) phosphate Chemical compound [Cr+3].[O-]P([O-])([O-])=O IKZBVTPSNGOVRJ-UHFFFAOYSA-K 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000002335 surface treatment layer Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 230000037303 wrinkles Effects 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
- Laminated Bodies (AREA)
Abstract
A highly clear metallic sheet, in which a soft resin layer smoothes out irregularities on metallic sheet surfaces and printed layers, and which is excellent in work adhesiveness and clearness. Thus the metallic sheet covered with a resin comprises a substrate, which is composed of a metallic sheet having a surface roughness represented by a center line average height (Ra) of above 0 Mum but at most 10 Mum, and at least on one side of which a coloring paint layer, soft resin layer, adhesive layer and transparent resin film are successively laminated in this order from the substrate.
Description
Technical field
The present invention relates to the resin-coating metallic plate that a kind of processing caking property is excellent and have high reflectivity true to nature (vividreflectivity).
Background technology
Recently, superior along with household electrical appliance, stereo set, kitchen articles and interior material, people are just pursuing high-grade decoration design.High-grade decoration design can shape and the ornamental of the package material surface formed by stretching or packaging material that degree of depth drawing-off material forms embody, and especially embodies by the pattern that is imprinted on the highly reflective on the packaging material.Therefore, to having excellent bonding processability and high reflectivity true to nature and being suitable for forming and the requirement of the decorative steel plate of processing such as degree of depth drawing-off increases such as stretching.
At present, because the surface roughness of metallic plate influences the verisimilitude of reflection widely, so (Ra) the little recommended metallic matrix of polishing plate of the vertical section arithmetic mean of instantaneous value deviation of characterizing metal plate surface roughness (arithmetical meandeviation of profile) as this height reflexive decorative metal plate true to nature.Yet when polishing plate was calendering production, the little coefficient of friction that little roughness causes made it to be easy to slide.Therefore, the polishing plate production efficiency that this vertical section arithmetic mean of instantaneous value deviation (Ra) is little is low and material is too expensive.And when this polishing plate was used as metallic matrix, it did not have enough cementations to the coat that forms on its surface, so the bonding processability deficiency of coat.
In addition, in order to use a little little more cheap metallic plate of a kind of surface roughness to obtain high reflexive decorative metal plate true to nature as the parent metal plate, Japan Patent open (spy opens flat 6-23909 communique) proposes, a kind of transparent thermoplastic resin film that has tack coat or printed layers is covered on the parent plate, make a kind of high reflexive laminated metal sheet true to nature that has with the hot pressing of mirror finish roller then.
Yet when this laminated metal sheet during by roller hot pressing, owing to be heated, thermoplastic resin unavoidably can produce the top layer wrinkle, and therefore the metallic plate that obtains can not must arrive the reflectivity high true to nature of being satisfied with.Another problem is that this can not make laminated metal sheet have reflectivity enough true to nature owing to the surface of printed patterns and the uneven transparent thermoplastic resin's of the showing layer of background patterns.
The present invention's general introduction
At the problem that occurs in the prior art, the purpose of this invention is to provide a kind of excellent and high reflexive resin-coating metallic plate true to nature of caking property of processing.
Resin-coating metallic plate of the present invention comprises: surface roughness (Ra, JIS B 0601) metallic plate that is not more than 10 μ m greater than 0 μ m is made substrate, colored enamelled coating, soft resin bed, tack coat and transparent resin film, and wherein the one side of metallic plate covers by the order from the one side of metallic plate to transparent resin film successively with above-mentioned layer at least.
And, in resin-coating metallic plate of the present invention, above-mentioned soft resin bed comprises a transparent resin, and be a kind of layer that comprises a kind of soft resin, the resin of this softness be by be mixed with the cold coating that is unlikely because of the completely crued curing agent of back heating be coated in a kind of be mixed with because of on the resin of the curing agent of the completely crued some of back heating then heating make it to have little hardness and make, or a kind of Polyester resin lacquer layer, or a kind of film that contains vistanex.
And in resin-coating metallic plate of the present invention, above-mentioned tack coat contains pigment, and this pigment comprises metal powder especially for example aluminium powder or mica powder.
And then in the resin-coating metallic plate of the present invention, the two-sided vision mirror finish of above-mentioned transparent resin film is a kind of Biaxially oriented film of PETG.
Moreover in the resin-coating metallic plate of the present invention, pattern printed layers or pattern and overall printing layer are between tack coat and soft resin bed, and perhaps pattern printed layers or pattern and overall printing layer are between tack coat and transparent resin film.
Implement mode of the present invention
Height of the present invention reflexive resin-coating metallic plate true to nature has a flexible resin layer between color coating layer that metal sheet surface forms and the bright finished transparent resin film of outermost two-sided vision, and then resin bed changes to absorb because the coarse out-of-flatness that causes of metallic plate, with when metallic plate and the above-mentioned resin bed hot pressing, be subjected to the out-of-flatness of the color coating layer that the out-of-flatness of the coarse or printed patterns of metallic plate or background patterns influences.In addition, the flexible resin layer allows transparent resin film hot pressing under the situation that does not cause outermost layer high polishing surface distortion visually.As a result, even resin-coating metallic plate of the present invention has reflectivity very true to nature and so excellent bonding processability such as stretching or the strong processing of degree of depth drawing-off can not cause layering yet.
Explain the present invention in detail according to following embodiment.
The simple declaration of accompanying drawing
Fig. 1 when Fig. 3 has provided metallic plate and has had resinous coat, the formation of resin-coating metallic plate one side.
Fig. 1 has provided the one embodiment of the invention that require according in the claim 1, and wherein, A is a transparent resin film, and B is a tack coat, and C is the flexible resin layer, and D is that color coating layer and S are metallic plates.
Among Fig. 1, A is a transparent resin film, has formed the outermost layer of resin-coating metallic plate.Transparent resin film adopts extrusion molding, rolling process, casting method etc., or the method production of casting back single shaft or biaxial orientation.
In order to obtain height of the present invention reflexive resin-coating metallic plate true to nature, transparent resin film must be a Double sided mirror mirror polish visually, and it forms the maximum surface roughness Ra in back and is no more than 5 μ m.If the surface roughness increase makes maximum Ra surpass 5 μ m, since the reflection of the scattering of film surface, resin-coating metallic plate reflectivity variation true to nature.
The preferred 5-100 μ of the thickness of transparent resin film m, more preferably 12-80 μ m.When the thickness of transparent resin film during, except in the lamination operation, handling transparent resin film very the difficulty, the reflectivity variation true to nature of whole resin-coating metallic plate less than 5 μ m.In addition, the thickness when transparent resin film surpasses 100 μ m, the bonding processability variation of resin-coating metallic plate.
Transparent resin film A comprises the film that mylar, polycarbonate resin, polyvinyl alcohol resin, acrylic resin and non-plasticizing or plastized polyvinyl chloride resin, polymethylpentene resin, cellulose triacetate resin, cellulose diacetate resin etc. form, if necessary, wherein can add stabilizing agent and plasticizer to its amount and not cause that the degree that reflectivity true to nature reduces all can.And polyester film comprises the film that pet resin and its copolymer resin form.In a word, biaxial orientation polyethylene glycol terephthalate's resin molding in fact more is applicable to height of the present invention reflexive resin-coating metallic plate true to nature.
Making or its marresistance and slip resistance during the process resin metallic sheet in order to improve, the outermost transparent resin film of resin-coating metallic plate of the present invention preferably applies thermosetting varnish that a bed thickness is the preferred 0.3-30 μ of 0.1-50 μ m m or such as the finish paint of the ultraviolet radiation lacquer type organic coating of silicone paint, fluororesin lacquer, acrylic resin paint, melamine resin paint or polyurethane resin paint.When the thickness of finish paint during, can obviously see interference colours, and marresistance reduces less than 0.2 μ m.On the other hand, when finish paint thickness during greater than 50 μ m, except business efficiency reduced, processability also reduced.
Among Fig. 1, B is a tack coat, contains a kind of key component as adhesive in mylar, acrylic resin, polyurethane resin, epoxy resin and the melmac.And except above-mentioned resin, the adhesive auxiliary agent with bond effect for example silicone couplet also can be used as component.
Tack coat can be transparent, or for higher ornamental of the color coating layer that obtains internal layer and contain pigment.The pigment that tack coat contains can be organic substance or inorganic substances.Especially, when the tack coat that contains metallic luster presents a kind of so-called metallochrome timing, preferably using the pigment that contains metal powder, can be painted metal powder or achromatic metal powder of paint, especially such as aluminium powder or mica powder.
Pigment is preferably 1-30% weight with the solid matter ratio in the adhesive resin, more preferably 3-20% weight.When pigment in the adhesive compares less than 1% weight to solid matter, can not get the tone of pigment (metallic luster pigment), when pigment in the adhesive compares greater than 30% weight to solid matter, except acutely adding man-hour, outside the processing adhesion strength variation, tack coat becomes fragile.
The particle of above-mentioned pigment may be class glove-like or squamous.The preferred 0.1-90 μ of its mean particle size m, more preferably 1-80 μ m.When mean particle size during less than 0.1 μ m, the metallochrome modulation is poor, when mean particle size surpasses 100 μ m, and the reflectivity variation true to nature of resin-coating metallic plate.
The preferred 1-50 μ of the thickness of above-mentioned tack coat m, more preferably 3-30 μ m.When the thickness of tack coat during less than 1 μ m, the boiling water resistance of resin-coating metallic plate and processing caking property variation, and when having added pigment, pigment is difficult to be uniformly dispersed in coating.On the other hand, uneconomical when the thickness of tack coat during, and when adding pigment greater than 50 μ m, because the residual solvent in the adhesive makes the degraded appearance of resin-coating metallic plate when heated lamination.So reflectivity variation true to nature.
Among Fig. 1, C is the flexible resin layer, clearly is provided for producing the processing caking property of resin-coating metallic plate excellence of the present invention and high reflectivity true to nature.According to the present invention, when shaggy metallic plate during as substrate, or owing to the local inhomogeneous metallic plate that makes coating of the thickness that is coated in the colour-wash on metallic plate when coarse, even or have pattern or/and the overall printing layer transparent resin film of (for the roughness that forms naturally) be when covering on the metallic plate, flexible resin layer C can absorb this coarse.
That is to say coarse absorption that produces owing to the rough surface of metallic plate, coloured coating and printed layers and do not appear at the surface of transparent resin film A by flexible resin layer C.In addition, if the coarse surface that comes from transparent resin film A can cause scattered reflection, thereby the reflectivity true to nature of reduction resin-coating metallic plate.
When each was pressed layer by layer, flexible resin layer C changed by laminating roll pressure and prevents transparent resin film A because metallic plate, coloured coating or the coarse of printed layers are out of shape.
On the other hand, flexible resin layer C requires to have excellent processing caking property, even so that laminate stand such as stretch or degree of depth drawing-off add man-hour strongly, layering does not take place yet between flexible resin layer C and other layers.
For above-mentioned requirements, the flexible resin layer of resin-coating metallic plate of the present invention comprises, for example contains the non-resin that solidifies (under the condition of cure) fully of two kinds of liquid mixture curing types.That is to say that completely crued resin obtains owing to solidify flexible resin with being unlikely because of heating completely crued a certain amount of curing agent in back mixes when heating in the back by curing agent, this resin is suitable for doing flexible resin layer of the present invention.
Perhaps, the film that contains above-mentioned flexible resin is preferably used as and is flexible resin layer C.
Transparent resin layer can be hyaline layer or opaque layer or the semitransparent layer that contains pigment.Yet most preferred hyaline layer is to make surface treated layer decorative pattern of bottom clear.
C is formed by the resin of owing to solidify when the flexible resin layer, and this resin comprises a kind of in mylar, acrylic resin, carbamate resins, epoxy resin and the melmac as key component.In a word, preferred polyester resin is used as key component, because when using it as the flexible resin layer, can obtain the most excellent processing adhesion strength and reflectivity true to nature.When using mylar, polyurethane resin joins in the mylar as curing agent, and its ratio is counted the polyurethane resin that adds 0.5-15 weight % in the 100 weight % mylar.Like this mylar of Xing Chenging be coated in form on the metal substrate through surface treatment layer on, then 230-280 ℃ down heating came semi-solid preparation in 0.3-2 minute.When curing agent content less than 0.5% weight, to the processing adhesion strength deficiency of metallic plate.On the other hand, surpass 15% weight when curing agent content but be not more than 20% weight, processing caking property excellence but resin hardens, the flexible resin layer no longer can absorb the coarse of metal substrate and/or printed layers as a result.And when curing agent content surpasses 20% weight, it is hard especially that resin becomes, and the flexible resin layer becomes fragile as a result, processing caking property variation.
Resin molding as the flexible resin layer comprises, be mixed with the toughness reinforcing polyester resin film of elastomer, be selected from the improved polyalkene film that the functional group of carboxyl, hydroxyl, hydrolyzable base and anhydride group prepares by at least a group in the molecule, by adding the softening polyvinyl chloride resin film of making of a kind of known plasticizers.In a word, vistanex or Corvic are preferably as the flexible resin layer C of resin-coating metallic plate of the present invention.
The preferred 10-100 μ of the thickness m of above-mentioned flexible resin layer C, more preferably 20-70 μ m.When the thickness of flexible resin layer less than 10 μ m, because the flexible resin layer no longer can absorb the coarse of metallic plate and/or printed layers, the reflectivity variation true to nature of whole resin-coating metallic plate fully.On the other hand, the thickness when the flexible resin layer surpasses 100 μ m, the case hardness of whole resin-coating metallic plate and processing adhesion strength variation.
By way of parenthesis when flexible resin film as flexible resin layer C, might handle adhesion strength between the resin bed (film) that is used for improving lamination by the cementation of silane coupler on the top layer of flexible resin film or bottom (or simultaneously at top layer and bottom).
Among Fig. 1, D is a coloured coating.This coloured coating is to embody decorative pattern in order to form a color layer.To this coloured coating, be coated with coating resins and comprise a kind of in mylar, acrylic resin, polyurethane resin, epoxy resin and the melmac as key component.Especially, preferred polyester resin is as key component, because the processing adhesion strength is good especially.For the pigment in this coating, can use known organic and inorganic pigment.
Pigment is to the preferred 1-30% weight of the ratio of solid matter, more preferably 3-20% weight in the cold coating.When pigment to the ratio of solid matter less than 1% weight, the pigment tone can not embody.When pigment to the ratio of solid matter greater than 30% weight, coloured coating becomes fragile, when standing violent process operation, processing adhesion strength variation.Granules of pigments may be gloves type or squama type.Its average particle size particle size size preferred 0.1-100 μ m, more preferably 1-80 μ m.When average particle size particle size less than 0.1 μ m, deal with very difficult, when average particle size particle size greater than 100 μ m, paintability variation, and the reflectivity variation true to nature of resin-coating metallic plate.
The preferred 1-60 μ of the thickness m that comprises the coloured coating D of above-mentioned pigment, more preferably 3-30 μ m.When the thickness of coloured coating D less than 1 μ m, pigment cover variation.And when the thickness of coloured coating greater than 60 μ m, business efficiency reduces.
And coloured coating D comprises by layer two-layer or that multilayer is formed.That is to say that coloured coating D comprises that one has the laminated material that the composite bed for the priming paint that contains rust resisting pigment of the rust-preventing characteristic that improves metallic matrix forms.
Among Fig. 1, S is the metallic plate as substrate.This metallic plate comprises: steel plate, corrosion resistant plate, galvanized steel plain sheet, galvanized alloy steel plate, compound galvanized steel plain sheet, nickel-clad steel plate, further through the chemical transformation surface-treated steel plate such as known chromium is handled, phosphate chromium is handled and electrochemistry chromium is handled; Directly in its surface through surface treated steel plate such as the Wuxi processing; There are not ferrous metallic plate such as aluminium alloy plate and copper coin; And the steel plate of further handling through above-mentioned chemical transformation.
In addition, for resin-coating metallic plate of the present invention, it is necessary that the arithmetic mean of instantaneous value deviation (Ra) in vertical section is not more than 10 μ m greater than 0 μ m.When metallic plate has the high polishing surface that Ra is 0 μ m,, therefore process the adhesion strength deficiency to the cementation disappearance of coloured coating D.And, make that to have Ra be that the metallic plate of high polishing surface of 0 μ m is not efficient at all, it is expensive especially that this metallic plate becomes.
On the other hand, when the metallic plate that surpasses 10 μ m with Ra as substrate because coarse can not the absorption by flexible resin layer B fully that the surface roughness of metallic plate causes, reflectivity therefore true to nature reduces.The Ra of metallic plate is 0.1-2 μ m more preferably.
Fig. 2 is the invention of describing according in the claim 12, has a pattern and/or the overall printing layer between tack coat B and flexible resin layer C, has the composition similar to Fig. 1.
Fig. 3 is the invention of describing according in the claim 13, has between tack coat B and transparent resin film A a pattern and/or the overall printing layer, has the composition similar to Fig. 1.
Below, explain the manufacture method of resin-coating metallic plate of the present invention.
(1) formation of flexible resin layer
In the resin-coating metallic plate (being described in claim 1) of Fig. 1, the coating that contains pigment is coated with on the surface of metallic plate S with methods such as roller coat and forms coloured coating D once or twice.When coating layer thickness needs to increase, apply the number of times increase.Then, flexible resin layer C forms on coloured coating.C is formed by a kind of coating when the flexible resin layer, the resin of completely crued a kind of curing agent applies with the coating that contains another kind of resin when being added with the back heating, the amount of the curing agent that contains in the wherein another kind of resin is unlikely when the heating of back solidifies fully, then heating, drying.Another kind of situation, when flexible resin layer C formed by the film that contains a flexible resin, flexible resin covered on the dope layer by the film of extruding application formation.Also can, heat the above-mentioned metallic plate that has coloured coating D, the film contact that forms with flexible resin then, and pressurize lamination with a pair of laminating roll obtains flexible resin layer C like this.
(2) production of cold coating film
In the cold coating film of (describing in the claim 1) shown in Figure 1, be mixed with contain metal powder especially adhesive or the non-mixed adhesive of the pigment of aluminium powder or mica powder be coated on the transparent resin film A, dry then, obtain tack coat B like this.
In the cold coating film of (describing in the claim 12) shown in Figure 2, be mixed with and contain metal powder especially the adhesive or the non-mixed adhesive of the pigment of aluminium powder or mica powder are coated on the transparent resin film A, drying obtains tack coat B then, coat pattern printed layers P2 more then, or pattern printed layers P2 and overall printing layer P1.
In the cold coating film of (describing in the claim 13) shown in Figure 3, pattern printed layers P2 at first, or pattern printed layers P2 and overall printing layer P1 are coated in transparent resin film A and go up and form, then, as above-mentioned, be mixed with contain metal powder especially the adhesive or the non-mixed adhesive of the pigment of aluminium powder or mica powder be coated on the above-mentioned printed layers, drying obtains tack coat B then.
(3) cover
Heat the flexible resin metallic sheet of above-mentioned preparation, then with the contact of cold coating film, with a pair of laminating roll pressurization.Further heating and with a pair of mirror roller pressurization is cooled off then.
At this moment, the laminating roll pressure of Shi Heing is 1-80kg/cm
2, preferred 5-60kg/cm
2When roll-in less than 5kg/cm
2, on the whole width of metallic plate, coating resin film can not evenly pressurize, the apparent injustice of result (reflectivity true to nature).In addition, surpass 60kg/cm when roll-in
2, the friction of roller is serious, and the resultant layer pressure roller needs frequent the replacing, and production efficiency reduces.
(embodiment 1)
The formation of flexible resin layer
Thick for the zinc-plated amount of 0.5mm be 12g/m
2, 0.08g/dm
2Chromium layer (chromium plating amount), average surface roughness Ra are to apply the thick polyester copolymer coating that contains Chinese white of 12 μ m on the galvanized steel plain sheet of 0.55 μ m, and be dry then.And the transparent polyester resin of 100% weight portion and the polyurethane resin of 3% weight portion apply on it as the mixture of curing agent, and thickness is 10 μ m, and be dry then, and toast the metallic plate that obtained having the flexible resin layer in 1 minute down at 260 ℃.
The preparation of cold coating layer
Containing the pigment that mean particle size is the golden squamous aluminium powder of 3 μ m, and it is 25 μ m that pigment is coated in thick to solid matter in the resin binder than the polyester copolymer resin binder that is 15% weight, average surface roughness Ra is on the transparent biaxially oriented PETG film of 0.8 μ m, coating layer thickness is 10 μ m, applying thick subsequently is the acrylic resin finish paint of 3 μ m, and drying obtains the cold coating layer then.
Cover
The above-mentioned metallic plate that has the flexible resin layer is heated to 200 ℃, is 20kg/cm then with above-mentioned cold coating film contact, and in roll-in
2Following to a pair of laminating roll pressurization.Press at 200 ℃ of lower rolls with a pair of mirror roller then and state the metallic plate that has the flexible resin layer, cooling obtains the resin-coating metallic plate then.
Estimate
According to following standard the performance of the resin-coating metallic plate that obtains is estimated.
(i) reflectivity true to nature
With the portable image distinguishing gloss meter of PGD-4 type (making) by Japan Color ResearchInstitute but measure the reflectivity true to nature of the reflection image on the resin-coating metallic plate combination with decorative surfaces, but the i.e. reflectivity true to nature of common reflection image.The high more reflectivity true to nature of measured value is good more.
(ii) process adhesion strength
The processing adhesion strength is to integrate by following two kinds of method of testings and with the result to consider among the present invention.
(a) Erichsen method of testing
Downcut the grid tangent line that is deep to substrate with cutter on the resin coated surface of resin-coating metallic plate, the Erichsen tester is finished resin-coating metallic plate 8mm stretching at the back side of resin-coating metallic plate then.Continue heating resin-coating metallic plate 1 hour down at 100 ℃ then, and observe the layering that exists subsequently and estimate degeee of stratification.
(b) the dark drawing-off test of cup
With the Yamada method degree of depth drawing-off tester drawing-off of the resin-coating metallic plate degree of depth is become cup type, draw ratio r=2.2.The grid tangent line that downcuts dark and substrate on the resin surface of resin-coating metallic plate forms the column part of 5mm cup at interval.Continue down heating at 100 ℃ then and form the resin-coating metallic plate 1 hour of a cup, and observe the layering that exists subsequently and estimate degeee of stratification by degree of depth drawing-off.
The reflexive numerical value true to nature that shows the resin-coating metallic plate of above-mentioned preparation is 0.8, for well, processes adhesion strength in addition.
(Comparative Examples 1)
Contain identical polyester copolymer coating as the Chinese white of embodiment 1 and be coated on the galvanized steel plain sheet that embodiment 1 uses, thickness is 12 μ m, and is dry then.And coat the transparent polyester resin that contains 100% weight and the 17% weight mixture as the carbamate resins of curing agent thereon, thickness is 10 μ m, and is dry then, and 280 ℃ down baking prepared resin bed in 0.3 minute.With cold coating film identical among the embodiment 1 according to covering on this resin bed with embodiment 1 described identical condition, prepare the resin-coating metallic plate.The performance of the resin-coating metallic plate that obtains is like this estimated in use with embodiment 1 identical evaluation method.As a result, the processing adhesion strength is good, is 0.1 but embody reflexive numerical value true to nature, this point variation.
(embodiment 2)
The preparation of flexible resin layer
Thick for the zinc-plated amount of 0.5mm be 14g/m
2, 0.07g/dm
2Chromium layer (chromium plating amount), average surface roughness Ra are to apply the thick polyester copolymer coating that contains Chinese white of 5 μ m on the galvanized steel plain sheet of 8.5 μ m, and be dry then.The metallic plate of this coating is heated to 200 ℃, with thick be the maleic acid modification transparent polyethylene membrance contact of 100 μ m, at 20kg/cm
2With a pair of laminating roll pressurization, cooling obtains having the metallic plate of flexible resin layer to pressure then down.
The preparation of cold coating film
Comprise that containing mean particle size is the pigment of the squamous aluminium powder of 3 μ m, and it is 20 μ m that pigment is coated in thick to solid matter in the resin binder than the polyester copolymer adhesive that is 20% weight, average surface roughness Ra is on the transparent biaxially oriented PETG film of 0.8 μ m, coating layer thickness is 12 μ m, applying thick subsequently is the fluororesin finish paint of 1 μ m, and drying obtains the cold coating layer then.
Cover
The above-mentioned metallic plate that has the flexible resin layer is heated to 200 ℃, is 20kg/cm then with above-mentioned cold coating resin molding contact, and in roll-in
2Following to the pressurization of a pair of laminating roll, and with a pair of mirror roller 200 ℃ of following roll-ins, cool off then and obtain the resin-coating metallic plate.
According to the performance of estimating the resin-coating metallic plate that obtains like this with identical evaluation method described in the embodiment 1.As a result, the reflexive numerical value true to nature that embodies the resin-coating metallic plate is 1.0, and for well, and the processing adhesion strength might as well.
(Comparative Examples 2)
The identical polyester copolymer coating that contains the Chinese white of embodiment 2 is coated on the galvanized steel plain sheet that uses as embodiment 2, and thickness is 5 μ m, and is dry then.The metallic plate of this coating is heated to 200 ℃, with thick be the polyethylene film contact of 100 μ m, at 20kg/cm
2With a pair of laminating roll pressurization, cooling obtains a transparent resin metallic sheet to pressure then down.With cold coating film identical among the embodiment 1 according to covering on this transparent resin metallic sheet with embodiment 1 described identical condition, prepare the resin-coating metallic plate.The performance of the resin-coating metallic plate that obtains is like this estimated in use with embodiment 1 identical evaluation method.As a result, embodying reflexive numerical value true to nature is 0.9, and for well, but the processing adhesion strength is bad.
(embodiment 3)
The preparation of flexible resin layer
Thick for the zinc-plated amount of 0.5mm be 15g/m
2, 0.06g/dm
2Apply the thick polyester copolymer coating that contains red pigment of 10 μ m on the galvanized steel plain sheet that chromium layer (chromium plating amount) and average surface roughness Ra are 0.1 μ m, dry then.The metallic plate of this coating is heated to 200 ℃, with thick be the transparent polyvinyl chloride film contact of 50 μ m, at 20kg/cm
2With a pair of laminating roll pressurization, cooling obtains having the metallic plate of flexible resin layer to pressure then down.
The preparation of cold coating film
Comprise that containing mean particle size is the pigment of the squamous mica powder of 2 μ m, and it is 25 μ m that pigment is coated in thick to solid matter in the resin binder than the polyester copolymer resin binder that is 20% weight, average surface roughness Ra is on the transparent biaxially oriented PETG film of 0.8 μ m, coating layer thickness is 10 μ m, applying thick subsequently is the melmac finish paint of 4 μ m, and drying obtains the cold coating layer then.
The metallic plate that has above-mentioned flexible resin layer is heated to 200 ℃, is 20kg/cm then with above-mentioned cold coating film contact, and in roll-in
2Following to the pressurization of a pair of laminating roll, and with a pair of mirror roller 200 ℃ of following roll-ins, cool off then and obtain the resin-coating metallic plate.
According to the performance of estimating the resin-coating metallic plate that obtains like this with identical evaluation method described in the embodiment 1.As a result, the reflexive numerical value true to nature that embodies the resin-coating metallic plate is 0.9, and for well, and the processing adhesion strength might as well.
(Comparative Examples 3)
Thick for the zinc-plated amount of 0.5mm be 15g/m
2, 0.06g/dm
2Chromium layer (chromium plating amount), and average surface roughness Ra applies the thick polyester copolymer coating that contains red pigment of 10 μ m on 11.5 the galvanized steel plain sheet, dry then.With transparent polyvinyl chloride film identical among the embodiment 3 according to further covering on the metallic plate of this coating with embodiment 3 identical conditions, prepare the resin-coating metallic plate.With cold coating film identical among the embodiment 3 according to covering on this resin-coating metallic plate with embodiment 3 identical conditions, prepare the resin-coating metallic plate.The performance of the resin-coating metallic plate that obtains is like this estimated in use with embodiment 1 described identical evaluation method.As a result, the processing adhesion strength is good, is 0.1 and embody reflexive numerical value true to nature, and this point is bad.
(embodiment 4)
The same embodiment 1 identical polyester copolymer coating that contains brown pigments is coated on the galvanized steel plain sheet of embodiment 1 use, and thickness is 5 μ m, and is dry then.And, in above-mentioned coating metallic plate on form the transparent flexible resin bed that one deck contains the identical polyester that uses with embodiment 1, thickness is 10 μ m.Next step, it is 25 μ m that silane coupler is coated in thick, and surface roughness Ra is the one side of 0.8 transparent biaxially oriented PETG film, and coating layer thickness is 0.3 μ m, and applying thick at its another side subsequently is the silicones finish paint of 2 μ m, dry then.Coating thick then on it is transparent polyester copolymer resin adhesive and the drying of 30 μ m, and more then, coating thick with mylar printing ink thereon is the wood grain printing pattern formation cold coating layer of 1 μ m.The metallic plate that has above-mentioned flexible resin layer further obtains the resin-coating metallic plate with the cold coating film covering for preparing like this under with embodiment 1 described identical condition.The performance of the resin-coating metallic plate that obtains is like this estimated in use with embodiment 1 described identical evaluation method.As a result, embodying reflexive numerical value true to nature is 0.8, for well, processes adhesion strength.
(embodiment 5)
The same embodiment 1 identical polyester copolymer coating that contains brown pigments is coated on the galvanized steel plain sheet of embodiment 1 use, and thickness is 5 μ m, and is dry then.And on above-mentioned metallic plate, according to forming the transparent flexible resin bed that one deck contains the identical polyester that uses with embodiment 1 with embodiment 1 identical method, thickness is 10 μ m.Next step, use mylar printing ink to form pattern printed layers in one side with the identical transparent biaxially oriented PETG film of embodiment 4, subsequently at its another side according to coating finish paint with embodiment 4 identical methods, form solid printed layers (gross thickness is 7 μ m) then thereon.Then according to coating the identical silane coupler of embodiment 4 with embodiment 4 identical methods, next step coats thick thereon is the identical transparent polyester copolymer resin adhesive of 30 μ m and dry.The metallic plate that has above-mentioned flexible resin layer covers with the cold coating film of preparation like this under the condition identical with embodiment 1 and obtains the resin-coating metallic plate.The performance of the resin-coating metallic plate that obtains is like this estimated in use with embodiment 1 described identical evaluation method.As a result, embodying reflexive numerical value true to nature is 0.8, for well, processes adhesion strength.
(invention effect)
Resin-coating metallic plate of the present invention is between color coating layer and tack coat or at colour-wash Between layer and the printed layers flexible resin layer is arranged, so the flexible resin layer can absorb because the table of metallic plate Face coarse or color coating layer and printed layers coarse and produce coarse so that the resin-coating metallic plate Be added with excellent reflectivity true to nature.
In addition, except tack coat and printed layers have the excellent adhesion strength with transparent resin layer, The flexible resin layer also has excellent adhesion strength to color coating layer, printed layers and tack coat, therefore Even under the strong processing conditions such as stretch formation and degree of depth drawing-off resin-coating metallic plate, upper State and do not produce layering between the layer at all. Like this, resin-coating metallic plate of the present invention has excellent The processing adhesion strength.
(brief description of drawings)
Fig. 1 is the cross sectional representation that shows that resin-coating metallic plate of the present invention constitutes; Fig. 2 is the cross sectional representation that shows this another formation of resin-coating metallic plate; Fig. 3 is the cross sectional representation that shows the another formation of this resin-coating metallic plate.
(quoting the explanation of letter)
A: transparent resin film
B: tack coat
C: flexible resin layer
D: color coating layer
P1: overall printing layer
P2: pattern printed layers
S: metallic plate
Claims (11)
1 one kinds of resin-coating metallic plates comprise: surface roughness be not more than greater than 0 μ m 10 μ m the metallic plate of making substrate, contain the color coating layer of 1-30wt% pigment, comprise a kind of in mylar, acrylic resin, polyurethane resin, epoxy resin and the melmac; The flexible resin layer, comprise contain mylar, acrylic resin, carbamate resins, epoxy resin or melmac as key component owe cured resin or contain make its toughness reinforcing flexible resin, modified polyolefin resin film with elastomer blended mylar or by adding the softening polyvinyl chloride resin film of making of a kind of known plasticizers; Tack coat, comprise a kind of in mylar, acrylic resin, polyurethane resin, epoxy resin and the melmac as its main component and transparent resin layer, comprise mylar, polycarbonate resin, polyvinyl alcohol resin, acrylic resin, non-plasticizing or plastized polyvinyl chloride resin, polymethylpentene resin, cellulose triacetate resin, cellulose diacetate resin, wherein the one side of metallic plate covers by the order from the one side of metallic plate to transparent resin film successively with color coating layer, flexible resin layer, tack coat and transparent resin layer at least.
The resin-coating metallic plate of 2 claims 1, wherein said flexible resin layer is a hyaline layer.
The resin-coating metallic plate of 3 claims 1, wherein said vistanex have at least one functional group that is selected from carboxyl, hydroxyl, hydrolyzable base and anhydride group.
The resin-coating metallic plate of 4 claims 1, wherein said tack coat contains pigment.
The resin-coating metallic plate of 5 claims 4, wherein said pigment is metal powder.
The resin-coating metallic plate of 6 claims 5, wherein said pigment is aluminium powder.
The resin-coating metallic plate of 7 claims 5, wherein said pigment is mica powder.
The resin-coating metallic plate of 8 claims 1, wherein said transparent resin film is the two sides mirror finish.
The resin-coating metallic plate of 9 claims 1, wherein said transparent resin film are biaxial orientation polyethylene glycol terephthalate's films.
The resin-coating metallic plate of 10 claims 1 wherein is formed with a pattern printed layers or a pattern printed layers and overall printing layer between said tack coat and flexible resin layer.
The resin-coating metallic plate of 11 claims 1 wherein is formed with a pattern printed layers or a pattern printed layers and overall printing layer between said tack coat and transparent resin layer.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP142378/96 | 1996-05-14 | ||
| JP142378/1996 | 1996-05-14 | ||
| JP14237896 | 1996-05-14 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1222881A CN1222881A (en) | 1999-07-14 |
| CN1103283C true CN1103283C (en) | 2003-03-19 |
Family
ID=15313989
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97194566A Expired - Lifetime CN1103283C (en) | 1996-05-14 | 1997-05-14 | Metallic sheet covered with highly clear resin and having work adhesiveness |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JP3090956B2 (en) |
| KR (1) | KR100366984B1 (en) |
| CN (1) | CN1103283C (en) |
| AU (1) | AU2788597A (en) |
| ID (1) | ID17403A (en) |
| MY (1) | MY121257A (en) |
| TW (1) | TW434145B (en) |
| WO (1) | WO1997043119A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005011977A1 (en) * | 2003-07-30 | 2005-02-10 | Dainippon Ink And Chemicals, Inc. | Laminated sheet for forming article |
| JP5498035B2 (en) * | 2009-03-05 | 2014-05-21 | 北海製罐株式会社 | Printed polyester film for coating can body material, method for producing the same, and can body using the same |
| KR101058352B1 (en) | 2009-09-08 | 2011-08-22 | 정영철 | Coating composition for ultraviolet mirror coating |
| US8409678B2 (en) | 2010-04-06 | 2013-04-02 | Pao Yi Technology Co., Ltd. | Thin metal casing with plastic part and manufacturing method thereof |
| CN103553437B (en) * | 2013-10-26 | 2015-01-07 | 桂林理工大学 | Preparation method of high-flame-retardant quartz stone plate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0255126A (en) * | 1988-08-22 | 1990-02-23 | Toyo Kohan Co Ltd | Preparation of resin coated metal plate having high sharpness |
| JPH04238026A (en) * | 1991-01-22 | 1992-08-26 | Dainippon Printing Co Ltd | Laminated metal plate with highly bright color and decorative sheet used therein |
| CN1171758A (en) * | 1994-12-29 | 1998-01-28 | 东洋钢钣株式会社 | High-image-sharpness resin-coated metal sheet excellent in adhesion after work |
-
1997
- 1997-05-13 MY MYPI97002096A patent/MY121257A/en unknown
- 1997-05-13 TW TW086106332A patent/TW434145B/en not_active IP Right Cessation
- 1997-05-14 JP JP09540740A patent/JP3090956B2/en not_active Expired - Fee Related
- 1997-05-14 WO PCT/JP1997/001623 patent/WO1997043119A1/en active IP Right Grant
- 1997-05-14 AU AU27885/97A patent/AU2788597A/en not_active Abandoned
- 1997-05-14 KR KR10-1998-0709034A patent/KR100366984B1/en active IP Right Grant
- 1997-05-14 CN CN97194566A patent/CN1103283C/en not_active Expired - Lifetime
- 1997-05-14 ID IDP971610A patent/ID17403A/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0255126A (en) * | 1988-08-22 | 1990-02-23 | Toyo Kohan Co Ltd | Preparation of resin coated metal plate having high sharpness |
| JPH04238026A (en) * | 1991-01-22 | 1992-08-26 | Dainippon Printing Co Ltd | Laminated metal plate with highly bright color and decorative sheet used therein |
| CN1171758A (en) * | 1994-12-29 | 1998-01-28 | 东洋钢钣株式会社 | High-image-sharpness resin-coated metal sheet excellent in adhesion after work |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100366984B1 (en) | 2003-09-19 |
| JP3090956B2 (en) | 2000-09-25 |
| TW434145B (en) | 2001-05-16 |
| MY121257A (en) | 2006-01-28 |
| AU2788597A (en) | 1997-12-05 |
| KR20000010887A (en) | 2000-02-25 |
| ID17403A (en) | 1997-12-24 |
| WO1997043119A1 (en) | 1997-11-20 |
| CN1222881A (en) | 1999-07-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1208185C (en) | Adhesive tape for coating decoration | |
| CN105992694B (en) | Decoration sheet and use its decorative element | |
| CA2628183C (en) | Decorative paint film laminate | |
| EP1800859B1 (en) | Dressed lumber | |
| CN1087686C (en) | High-image-sharpness resin-coated metal sheet excellent in adhesion after work | |
| CN1243894C (en) | Decoration surface of board for building | |
| EP1669193A1 (en) | Decorating material | |
| CN1209094A (en) | Synthetic laminated structure and method for mfg. same | |
| CN1103283C (en) | Metallic sheet covered with highly clear resin and having work adhesiveness | |
| CN1061670C (en) | Namometre automotive metal finish | |
| CN1849210A (en) | Pearl-like decorative paper having suitability for postforming and thermosetting resin decorative sheet | |
| CN1506169A (en) | Coating method for plastic parts | |
| KR20080014269A (en) | High glossy sheet having aluminum foil | |
| JP5016577B2 (en) | Manufacturing method of decorative metal plate | |
| JP5028932B2 (en) | Decorative sheet | |
| JPS63280627A (en) | Highly bright laminated metal plate and its manufacture | |
| CN114102782A (en) | Production process of metal paint solid wood composite floor and floor thereof | |
| JP7294560B1 (en) | decorative material | |
| JP2020056184A (en) | Float-tone wood decorative material | |
| CA2209137C (en) | A resin-coated metal sheet with higher vivid reflectivity having the excellent workable adhesion strength | |
| JP4319714B2 (en) | Wood grain decorative sheet | |
| JPH09277449A (en) | Thermosetting resin decorative material and its production | |
| US20240124725A1 (en) | Decorative material | |
| CN1887598A (en) | Metal plate forming process and structure for electronic device casing | |
| CN117124680A (en) | Semi-hard polypropylene floor and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20030319 |