CN1787916A - Emboss-designed sheet and metal plate covered with emboss-designed sheet - Google Patents
Emboss-designed sheet and metal plate covered with emboss-designed sheet Download PDFInfo
- Publication number
- CN1787916A CN1787916A CNA2004800126004A CN200480012600A CN1787916A CN 1787916 A CN1787916 A CN 1787916A CN A2004800126004 A CNA2004800126004 A CN A2004800126004A CN 200480012600 A CN200480012600 A CN 200480012600A CN 1787916 A CN1787916 A CN 1787916A
- Authority
- CN
- China
- Prior art keywords
- layer
- embossing
- resin
- sheet material
- sheet
- 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.)
- Granted
Links
- 239000002184 metal Substances 0.000 title claims abstract description 41
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 41
- 238000004049 embossing Methods 0.000 claims abstract description 146
- 229920005989 resin Polymers 0.000 claims abstract description 110
- 239000011347 resin Substances 0.000 claims abstract description 110
- 229920001225 polyester resin Polymers 0.000 claims abstract description 47
- 239000000463 material Substances 0.000 claims description 121
- 238000003475 lamination Methods 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 30
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 16
- 229920002799 BoPET Polymers 0.000 claims description 13
- 239000005041 Mylar™ Substances 0.000 claims description 13
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- -1 polybutylene terephthalate Polymers 0.000 claims description 6
- 229920000728 polyester Polymers 0.000 abstract description 8
- 238000002844 melting Methods 0.000 abstract description 5
- 230000008018 melting Effects 0.000 abstract description 5
- 239000010410 layer Substances 0.000 description 287
- 230000000052 comparative effect Effects 0.000 description 60
- 238000010438 heat treatment Methods 0.000 description 34
- 239000000049 pigment Substances 0.000 description 24
- 238000010023 transfer printing Methods 0.000 description 23
- 239000004800 polyvinyl chloride Substances 0.000 description 17
- 229920000915 polyvinyl chloride Polymers 0.000 description 17
- 230000004927 fusion Effects 0.000 description 12
- 239000000654 additive Substances 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 11
- 239000007767 bonding agent Substances 0.000 description 11
- 238000005755 formation reaction Methods 0.000 description 11
- 238000007639 printing Methods 0.000 description 11
- 238000005266 casting Methods 0.000 description 10
- 238000002425 crystallisation Methods 0.000 description 10
- 230000008025 crystallization Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000007796 conventional method Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 229920006038 crystalline resin Polymers 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000004645 polyester resin Substances 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 239000010953 base metal Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 229920005672 polyolefin resin Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 3
- 239000006057 Non-nutritive feed additive Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000000113 differential scanning calorimetry Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 229910001335 Galvanized steel Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000003490 calendering Methods 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000008397 galvanized steel Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 238000012800 visualization Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NMYFVWYGKGVPIW-UHFFFAOYSA-N 3,7-dioxabicyclo[7.2.2]trideca-1(11),9,12-triene-2,8-dione Chemical compound O=C1OCCCOC(=O)C2=CC=C1C=C2 NMYFVWYGKGVPIW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 241000220324 Pyrus Species 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 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
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000004166 bioassay Methods 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000002124 endocrine Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 235000021017 pears Nutrition 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002023 wood Substances 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
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- 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
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
- B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
- B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
Landscapes
- Laminated Bodies (AREA)
- Finishing Walls (AREA)
- Shaping Of Tube Ends By Bending Or Straightening (AREA)
Abstract
A laminated sheet excellent in the suitability for embossing, which comprises a non-oriented resin layer (A layer)(1) comprising a crystalline polyester based resin as a primary component and having a melting point in the range of 210 to 240 DEG C and, laminated on one side thereof, a non-oriented resin layer (B layer)(2) comprising a substantially amorphous polyester as a primary component, has a total thickness of 65 to 300 mum and a tensile strength at 180 DEG C of 5 MPa or higher; an emboss-designed sheet; and a metal plate covered with the emboss-designed sheet.
Description
Technical field
The present invention relates to be used for that household appliances goods such as AV equipment, air conditioner housing are adorned outward, in the laminate system furniture, steel furniture, building the embossing adaptability excellence of the coated material of dress etc. laminated sheet, and it has been implemented to compose the embossed pattern sheet material that embossing handles and the resin-coated metal sheet of lining embossed pattern sheet material.
Background technology
In the past, household appliances goods such as AV equipment, air conditioner housing are adorned outward, the coated material of dress etc. in the laminate system furniture, steel furniture, building, have used the flexible vinyl chloride-based resin sheet (hereinafter referred to as the flexible PVC sheet material) of having given embossed pattern well.
As the feature of flexible PVC sheet material, can enumerate following or the like some:
1. owing to compose embossing adaptability excellence, therefore can obtain being rich in ornamental coated material.
2. usually, better as the equilibrium ratio of the processability of reciprocal key element and surface damage.
From with the compatibility excellence of various additives, and additive in long-term, improve the situation of the investigation of rerum natura, raising weatherability, particularly light fastness stability are easy.
Though be flexible PVC sheet material with such advantageous feature, but since in recent years vinyl chloride-based resin result from stabilizing agent heavy metal compound problem, result from plasticizer or stabilizing agent VOC problem, endocrine disturbance effect problem, when burning, produce the problem of chlorine-containing gas such as hydrogen chloride gas etc., vinyl chloride-based resin is restricted gradually for its use.Therefore, vinyl chloride-based resin is not used in user's strong request of these goods.
So, substitute flexible vinyl chloride-based resin, using with polyolefin-based resins such as polypropylene as main body, cooperated the rerum natura of the soft composition of polystyrene or copolyalkenamer system etc. to approach flexible vinyl chloride-based resin.
Polyolefin-based resins sheet materials such as polypropylene, the temperature range that can give embossing is narrower than flexible PVC sheet material, temperature control accurately is necessary, but flexible PVC sheet material in the past has such advantage: can roughly directly adapt to the embossing of giving embossing continuously and give machine.
, about processability and machining damage, polyolefin-based resins such as polypropylene are in the bad problem of processability that has aspect the characteristic of its resin after being laminated on the steel plate.When increasing the cooperation ratio of soft composition in order to satisfy processability, the bad influence of the albefaction that adds the Ministry of worker, surperficial anti-wound property reduction etc. is arranged, have to become the design of sacrificing a certain side, there is this problem.
In addition, polyolefin-based resins is the resin of cementability difference basically, for the bonding force of guaranteeing the lamination interface for a long time or with the bonding force of metallic plate, need research especially.
In order to address these problems, carried out following work etc.: as so-called PETG is that the non-crystalline polyester of representative is the resin, lubricant or processing aid etc. is studied, make it to have calendering system film adaptability, the sheet material that comprises the polyester based resin of the anti-wound property excellence of processability and surface uses (for example opening the 2002-29000 communique referring to the spy) as the resin-coated metal sheet that embossed pattern is arranged.
Summary of the invention
For the sheet material that comprises polyester based resin, with the flexible PVC in past be that sheet material or polyolefin sheet material similarly use embossing to give the occasion that machine is given embossing, though can give embossing, the embossing hear resistance has problem.
The hear resistance of so-called embossing is to suffer highly when hot under user mode at embossed pattern sheet material or embossed pattern sheet material coated metal plate, and the answer of expression embossing is greatly or little index, and replying little situation is the embossing good heat resistance.
That is, give embossing can be regarded as give strain to the viscoelastic body that is heated after, the operation that strain is freezed by cooling.Owing to have residual stress in the frozen strain, in the time of therefore near being heated to the temperature of giving strain again, cause the reply phenomenon of strain.Therefore, for improving the embossing hear resistance necessity that improves the temperature of giving strain is arranged.; for improving the embossing hear resistance; and to improve strain give temperature (temperature by sheet material and the decision of the temperature of embossing plate roller) time; the fusion tension force of sheet material self reduces significantly; cause the result of the shrinkage in width that produces sheet material, wrinkling and then sheet material fracture etc., can not give the embossing hear resistance of the satisfaction that is comparable to flexible PVC sheet material in the past.
Its result, even under environment for use, skin-material as desk etc. uses, the occasion of spilling the occasion of the hot water of high temperature, using as the framework of the bigger home appliance of internal calorific power etc., embossing hear resistance deficiency causes easily also that embossing partly shoals or the bad order of disappearance etc.
In addition, when being laminated on the metallic plate in order to make the resin-coated metal sheet use, also have owing to toast the heat of the metallic plate of bonding agent, the problem that makes embossing shoal or disappear can not be widely used on the resin-coated metal sheet purposes.
On the other hand, as the method for the sheet material that comprises polyester based resin being given embossed pattern, the method that adopts the film extrusion legal system to make the polyester based resin sheet material is arranged.At this moment, not as common mirror roller, but as the embossing plate roller, give embossing with casting roller to the resin of the molten condition that flows out from the T die head.The method has and is easy to get than higher embossing hear resistance, no matter polyester based resin has or not the advantage that crystallinity can both transfer printing embossing style., dark embossing or complexly patterned embossing because problem such as sneaking into of release property or air is arranged, therefore can not be given, and produce above-mentioned or the like the problem that restricts the embossing style.
And usually the diameter knurling rolls of giving machine than embossing are big for casting roller, get all the casting roller with the style corresponding number ready, from equipment cost or change the man-hour aspect and regard as and be problem.
As other the embossing method of giving, resin melt extrusion on the oriented steel plate, before resin cooling with the roll-in of embossing style, thereby the method for transfer printing style, the heating metallic plate of resin sheet that has been covered again, method of usefulness embossing style roller transfer or the like.
These methods, owing to give embossing to the resin of molten condition, therefore no matter the difference of crystallinity polyester, amorphism polyester can both be given embossed pattern, but same with the situation of carry-over pinch rolls transfer printing style when extruding the system film, style is restricted, in addition, the embossing plate roller is arranged, the danger of damage version is arranged owing to contact with the warpage of metallic plate end etc., the necessary a plurality of spare rolls of stock, problems such as equipment cost increase.
For addressing the above problem, first scheme of the present invention relates to a kind of laminated sheet of embossing adaptability excellence, it is characterized in that, be lamination to have crystalline polyester based resin, fusing point is the resin bed (the present invention also is expressed as this layer " A layer ") of the non-orientation of 210 ℃ of-240 ℃ of scopes, with based on the resin bed (the present invention also is expressed as this layer " B layer ") of the non-orientation that is essentially non-crystalline polyester based resin and comprise 2 layers laminated sheet at least, in this laminated sheet, the gross thickness of sheet material is the scope of 65 μ m-300 μ m, and the tensile break strength under 180 ℃ is more than the 5MPa.
Alternative plan relates to a kind of laminated sheet of embossing adaptability excellence, it is characterized in that, be to have crystalline polyester based resin, fusing point is that printed layers (the present invention also is expressed as this printed layers " C layer ") is given on resin bed (A layer) surface of the non-orientation of 210 ℃ of-240 ℃ of scopes, again in the above lamination based on the transparent resin layer (the present invention also is expressed as this layer " D layer ") of the non-orientation that is essentially non-crystalline polyester based resin and comprise 3 layers laminated sheet at least, in this laminated sheet, the gross thickness of sheet material is the scope of 65 μ m-300 μ m, and the tensile break strength under 180 ℃ is more than the 5MPa.
Third party's case relates to a kind of laminated sheet of embossing adaptability excellence, it is characterized in that, be that lamination is to have crystalline polyester based resin, fusing point is the resin bed (A layer) of the non-orientation of 210 ℃ of-240 ℃ of scopes, with resin bed (the present invention also is expressed as this layer " E layer ") based on the non-orientation that is essentially non-crystalline polyester based resin, give printed layers (C layer) to the surface of E layer one side, again in the above lamination based on the transparent resin layer (D layer) of the non-orientation that is essentially non-crystalline polyester based resin and comprise 4 layers laminated sheet at least, in this laminated sheet, the gross thickness of sheet material is the scope of 65 μ m-300 μ m, and the tensile break strength under 180 ℃ is more than the 5MPa.
With above-mentioned laminated sheet (promptly be meant: at A layer superimposed layer the B layer comprise 2 layers laminated sheet (following also be expressed as " A+B ") at least, on the A layer in turn lamination C layer and D layer comprise 3 layers laminated sheet (following also be expressed as " A+C+D ") at least, perhaps on the A layer in turn lamination the E layer, at least 4 layers the laminated sheet (following also be expressed as " A+E+C+D ") of comprising of C layer and D layer is heated to more than 160 ℃, after the temperature below the fusing point of A layer (Tm)-10 ℃, give embossed pattern with the embossing plate roller to the surface of B layer side or the surface of D layer side, can make the embossed pattern sheet material.
Above-mentioned embossed pattern sheet material, laminated sheet (" A+B ", " A+C+D " or " A+E+C+D ") is heated to more than 160 ℃, after the temperature below the fusing point (Tm)-10 of A layer ℃, can makes thereby give embossed pattern with the embossing plate roller to the surface of the surface of B layer side or D layer side.
Above-mentioned embossed pattern sheet material as bonding plane, adopts the heat curing-type bond layer to be pressed on the metallic plate on the surface of A layer side, can make embossed pattern sheet material coated metal plate.
The scope that sheet material of the present invention is got 65 μ m-300 μ m owing to thickness, it is more accurate therefore to be designated as " film and sheet material ", but at this, for the material of the thickness range that is commonly referred to as film, for convenience's sake, has also used this address of sheet material.
In the present invention, " being main body " this expression, be the meaning of content more than 50 weight % of all resins composition, " non-orientation " this expression, be the orientation process of not carried out stretched operation etc. wittingly, rather than when extruding the system film even because of casting roller, draw the also non-existent meanings such as orientation that produce.In addition, so-called " being essentially non-crystalline polyester based resin ", except when heating up, not demonstrating the mylar at clear and definite watery fusion peak, though also comprise crystallinity arranged, but crystallization rate is slow, at film making process, and do not reach the mylar of the high state of crystallinity in the manufacturing procedure of giving machine transfer printing embossing style with embossing.
In addition, in claim 5, used with giving of D layer and A layer the face lamination of having given printed layers (C layer) of the face of printed layers (C layer) or D layer and E layer and integrated this statement, this may not be limited to whole ground and use printed layers (C layer), in the occasion of partly giving printed layers, produce D layer and A layer or D layer and E layer not with printed layers for being situated between the directly part of heat fused lamination.
The polyester based resin that below will form the A layer sometimes is called polyester based resin A (perhaps simply being called Resin A).In addition, the polyester based resin that will form the B layer sometimes is called polyester based resin B (perhaps simply being called resin B).Equally, sometimes, will form the D layer, and the polyester based resin of E layer be called polyester based resin D (perhaps simply being called resin D) and polyester based resin E (perhaps simply being called resin E).
The simple declaration of accompanying drawing
Fig. 1 is the schematic sectional view of the laminated sheet of the present invention's first scheme.
Fig. 2 is the schematic sectional view of the laminated sheet of alternative plan of the present invention.
Fig. 3 is the schematic sectional view of the laminated sheet of third party's case of the present invention.
Fig. 4 is the schematic sectional view of an example of the expression metallic plate that the laminated sheet of Fig. 3 is pressed in the lining embossed pattern on the metallic plate by heat cured bond layer.
Fig. 5 is that the skeleton diagram of an example of machine is given in the embossing that expression is given embossed pattern to the flexible PVC sheet material in past.
The preferred plan that carries out an invention
Below with a description of drawings embodiment of the present invention.
(forming the resin of A layer)
A layer 1, when laminated sheet is delivered to embossing and is given machine, as the adherent layer of heated metallic roll is brought into play function, in addition, also be provided with in order to give preventing to be heated to the function of the narrowed width of the laminated sheet of the same temperature of flexible PVC in the past, wrinkling, fusion fracture etc.Therefore, the tensile break strength of stipulating in the present invention 1-3 scheme under 180 ℃, mainly composition and the thickness according to A layer 1 is endowed.
A layer 1 has the 50 weight %s of crystalline polyester based resin content more than all resins composition so that crystalline polyester based resin to be arranged, and preferably contains more than the 55 weight %, more preferably contains more than the 70 weight %.The fusing point of Resin A is 210-240 ℃ a scope, in view of the above, can directly use the laminating apparatus that uses for the flexible vinyl chloride sheet material that rolls on the metallic plate upper strata.
When the fusing point of Resin A is lower than this value, on metallic plate, during lamination, produce danger to the adhesion of heating of metal roller, rare to the preferred tensile break strength as laminated sheet, its result might produce the fusion fracture.
When the fusing point of Resin A was higher than this value, generation made the metal sheet surface temperature be higher than necessity that laminating temperature condition is in the past come lamination, and it is insufficient that the heating condition of past equipment becomes sometimes.In addition, because it is relatively remarkable to produce the cooling of the problem of thermo-color thermal discoloration of CB coating or end, so the metal sheet surface temperature easily becomes inhomogeneous at width, and the problem of the adhesive strength deficiency etc. of end easily takes place in view of the above.
Polyester based resin as forming A layer 1 can use the various crystalline polyester based resins that have.
Wherein, polybutylene terephthalate (PBT) (PBT) resin and poly terephthalic acid trimethylene ester (PTT) resin, because crystallization rate is fast, casting roller temperature when extruding the system film by suitable setting, giving than higher crystallinity A layer 1, so preferably through extruding the moment that the system film obtains sheet material.The PBT resin is because glass transformation temperature is lower, and crystalline sheet material therefore is easy to get when extruding the system film.
Moreover, having used terephthalic acid (TPA) or dimethyl terephthalate (DMT) single component, used 1 as the dicarboxylic acids composition as pure composition, the fusing point of the so-called equal PBT resin of 4-butanediol single component is about 225 ℃.
Beyond equal PBT resins, can also use with M-phthalic acid to replace the PBT resin that the copolymerization of the part etc. of sour composition is formed.
In addition, A layer 1 also can use with the PBT resin as main body and cooperated the resin of noncrystalline resin etc.This occasion, in order to obtain having during film in the system of extruding the crystalline A layer 1 of the degree on the metallic roll etc. of the heating of not adhering to, 55 weight % of all resins composition of preferred A layer 1 are above to be the PBT resin.As the noncrystalline resin that adds in the A layer 1, can enumerate as the main body of B layer 2 described later and the non-crystalline resin that uses.
As being not suitable for resin of the present invention, resin that PETG (PET) is etc. is arranged, this be because, crystallization rate is slow, can not obtain tensile break strength, in addition, make it the occasion of crystallization, because its fusing point height, therefore with the lamination of metallic plate 6 in can not obtain sufficient adhesion.
Be sent to embossing by A layer 1 under the high state of crystallinity and give machine, near the temperature of A layer 1 its fusing point do not demonstrate the adherence with metal.In addition,, have under 180 ℃ more than the fracture strength 5MPa, produce that width reduces, the possibility of wrinkling, fusion fracture etc. is few, sheet material is heated to high temperature, the embossing style of transferability embossing excellent heat resistance by being formed in as all formations of laminated sheet.Moreover 180 ℃ is to give the temperature of heating sheet material under the occasion of embossing or the high slightly temperature that compares to the flexible PVC sheet material.
Also can in A layer 1, add the pigment as required of the hidden effect of vision of giving pattern, guaranteeing base metal plate 6, the colour developing that improves printed layers 3 etc.
Moreover, add the occasion of pigment with formation shown in Figure 1, owing to also can in B layer 2, add pigment, so may not necessarily need add pigment in the A layer 1.
With the occasion that formation shown in Figure 2 is added pigment, the D layer 4 that is imparted on the printed layers 3 need have the transparency, in A layer 1, add pigment become essential.
Occasion so that formation shown in Figure 3 is added pigment though printed layers 3 is arranged, is disposing E layer 53 times in printed layers, so pigment can add among A layer 1 or E layer 5 wantonly 1 or in two-layer.
At this moment, the pigment of use can be the pigment that generally is used as coloring resin usefulness, also can be general amount of adding about its addition.As an example, during white system painted, be base-material with the high titanium oxide pigments of hidden effect, carry out the adjustment of tone with inorganic, the organic pigment of colour.About the hidden effect of the vision of base metal plate 6, according to the different importance degree differences of purposes.In the interior resin-coated metal sheet of building the material purposes, the covering power of measuring according to JIS K54007.2 " coating ordinary test method covering power " is preferably more than 0.98.When covering power was lower than this value, the tone of metallic plate 6 grounds such as substrate such as grade was reflected in the tone of laminated sheet, during these tone variations, from the surface observation of laminated sheet to tone also change, so not preferred.But in the not debatable especially purposes of the tone variations that causes because of this reason, covering power can not be more than 0.95 also.
In A layer 1,, perhaps, also can add the various additives of Sq in order further to improve the object of the invention rerum natura in addition in the scope of not damaging its character.As additive, can enumerate: phosphorus be phenol system etc. various antioxidants, heat stabilizer, ultra-violet absorber, light stabilizer, nuclear agent, modified impact agent, processing aid, matal deactivator, residual polymerization catalyst passivator, make nuclear agent, antibiotic. terminal carboxylic acid-terminated dose of the general additive that uses, carbodiimide system or epoxy system etc. or hydrolysis-resisting agent etc. uses and commercially available additive as mylar in the resins for universal use materials such as mould inhibitor, antistatic additive, lubricant, fire retardant, packing material.In addition, for the Abherent of the further A of raising layer 1, also can add surface lubrication imparting agent, releasing agent etc. with the metal that heats.The occasion of printed layers 3 is set on A layer 1 surface, need uses in the scope that printability does not reduce.
Keeping of fusion tension force when giving the machine heating with embossing has more than the resin that depends on A layer 1 and forms and crystallinity, also can add the processing aid with the effect that increases fusion tension force.
The thickness range of A layer 1, need be decided to be hot strength when being heated to 180 ℃ and in laminated sheet is all, can keep thickness more than the 5MPa, because this also can form according to the resin of A layer 1, additive is formed, and A layer 1 beyond the composition of layer (B layer 2 or B layer 2 and D layer 4, E layer 5 and D layer 4) change, therefore can not stipulate entirely, but be preferably more than the 25 μ m, more preferably more than the 30 μ m.When than thin the time, rare to necessary hot strength.
In addition, see and also be preferably more than the 25 μ m from extruding stable aspect, and formation as shown in Figure 2 is such, an A layer 1 adds pigment and is necessary to guarantee the occasion of abundant covering effect, preferably has the above thickness of 45 μ m.When thickness compare thin the time, in order to give sufficient substrate covering effect, need to add the pigment of volume, might cause reductions such as processability.Perhaps, need to add the special pigment of burning till pigment etc. of combined oxidation system, cause cost and rise.
The thickness of A layer 1 is preferably below the 200 μ m, further preferably below the 100 μ m, especially preferably below the 60 μ m.Even the thick above thickness of this value that reaches, the intensity during as the heating of A layer 1 keeps the function of layer also saturated, and when thickening the thickness of A layer 1, needs the thickness of attenuate B layer 2, and its result can not be to the dark embossing style of B layer 2 transfer printing.
The gross thickness of laminated sheet is preferably below the above 300 μ m of 65 μ m, more preferably below the above 300 μ m of 70 μ m, is preferably about 150 μ m especially.When thickness is worth when thin than this; protection effect to base metal plate 6 is insufficient; when being worth than this when thick, the form metal mould that uses in the shaping processing of bending etc. of metallic plate of flexible PVC resin of having used in the past the lining difficulty or the like that becomes, processability reduces.
(forming the resin of B layer)
B layer 2 is being essentially non-crystalline polyester based resin, when the laminated sheet of the formation of Fig. 1 is delivered to embossing and given machine, is heated softeningly, pushes the layer of transfer printing embossing style by the embossing plate roller.Therefore, B layer 2 can not have high crystallinity in the moment of pushing with the embossing plate roller, based on the mylar of amorphism or low-crystalline in fact.
The 2 usefulness embossing of B layer give machine be heated to its glass transformation temperature (Tg) above after, carry out embossing and give.The elastic modelling quantity of B layer 2 is necessary fully to be reduced to the degree that can give embossing when heating.Therefore laminated sheet of the present invention is because A layer 1 is kept fusion tension force, can not produce that width reduces, wrinkling, fusion fracture etc.
As the polyester based resin that forms B layer 2, can use the polyester based resin that is essentially amorphism or low-crystalline as main body, can use by differential scanning calorimetry (DSC) (DSC) and not show that when heating up clear and definite crystal melts the mylar at peak, though crystallinity is arranged, but crystallization rate is slow, at film making process, and do not reach the mylar of the high state of crystallinity in the manufacturing procedure of giving machine transfer printing embossing style with embossing.
Example as noncrystalline copolymer polyester resin, can enumerate: have more from the stable supplying of raw material or output and send out and can seek the so-called PET-G of cost degradation, preferably use " イ-ス -PET-G6763 " or the resin similar of イ-ス ト マ Application chemical company with it." イ-ス -PET-G6763 " resin, be to have with 1, the 4-cyclohexanedimethanol has replaced the resin of structure of about 30mol% of the ethylene glycol part of PETG, is not see the noncrystalline mylar of being essentially of crystallization behavior in DSC mensuration.
But, be not limited thereto, though show crystallinity under given conditions, but the イ that under usual conditions, can handle-ス ト マ Application chemical company " PCTG5445 " etc. or have with 1 as non-crystalline resin, the 4-cyclohexanedimethanol replaced in the mylar of composition of ethylene glycol part of PETG, and the resin that the about 70mol% of about 30mol%-of ethylene glycol part has been substituted also can use.
When 1, the amount of 4-cyclohexanedimethanol is about 30mol% when following, becomes significantly as the feature of crystalline resin, and crystallization is carried out when giving machine and heat with embossing, and giving of embossing might become difficult.When reaching about 70mol% when above, crystallinity becomes significantly, and is not preferred.
Beyond this, among the neopentyl glycol copolymerization PET, do not show the resin that crystalline resin or crystallinity are low, or in copolymerization in the pet resin of M-phthalic acid, the resins that crystallinity is low etc. also can be formed as the resin of B layer 2 and use.
In addition, also can blend PBT or PTT and the high mylar of other crystallinity in B layer 2.When their blend ratio was high, the crystallinity of B layer 2 became significantly because above-mentioned, embossing give the difficulty that becomes, therefore add 40 weight % following, preferably add that 30 weight % are following to get final product.
In B layer 2, disguise or pattern in order to improve base metal also can add coloring pigment.Under this occasion, as described above, can add pigment in the B layer 2, perhaps can add among both at A layer 1 and B layer 2.The occasion of spendable pigment and A layer 1 is same, can use the painted pigment that generally is used for polyester based resin.
Also can similarly suit to add the various additives of necessity for B layer 2 with A layer 1.
The preferred thickness of B layer 2 is scopes of 45 μ m-250 μ m, further the scope of preferred 50 μ m-200 μ m.When thickness is worth when thin than this, the kind of the embossing style that can give is restricted significantly.On the contrary when being worth than this when thick, need the thickness of attenuate A layer 1, so the anti-breaking property when seldom arriving the laminate heated sheet material is not preferred.In addition, if B layer 2 has the thickness about 105 μ m, then can use over the major part of the embossing plate roller that uses when giving embossing to the flexible PVC sheet material.
(forming the resin of D layer)
Therefore, about forming the polyester based resin of D layer, also can use the resin identical with B layer 2.In addition, about additive or preferred thickness, also same with B layer 2.
Therefore but D layer 4 is layers of lamination on printed layers 3 (C layer), needs to have an X-rayed the transparency of degree of the style of printed layers 3.
(forming the resin of E layer)
In the formation of Fig. 2, the occasion of the deep embossing style of transfer printing, need set the thickness of D layer 4 thickly.This occasion though D layer 4 is layers that the transparency is arranged, be the layer of non-orientation, so the increase of haze is inevitable, and about the visibility of printing style, reduction is unavoidable.In addition, because polyester based resin is the resin that relatively is vulnerable to the light xanthochromia, therefore when the thickness that makes D layer 4 was blocked up, the xanthochromia of process became showy in time.
So also for giving the layer that is out of shape through pushing of embossing plate roller, the thickness of attenuate B layer 2 makes the visibility of printing style good under printed layers 3 (C layer), the purpose of the dark embossing style of transferability and what give is E layer 5 simultaneously.
Therefore, about forming the polyester based resin of E layer 5, can use the resin identical with B layer 2 or D layer 4.In addition, too about additive.The thickness of giving layer in embossing is the occasion of the superficial embossing style that also can give below the 120 μ m, and also can E layer 5 is not set especially and make the thickness of D layer 4 be 70 μ m-120 μ m.The aggregate thickness of laminated sheet needs occasion above about 150 μ m etc., the thickness of D layer 4 is decided to be below the 100 μ m, be preferably about 70 μ m, thereby the perspectivity that prevents printed layers 3 reduces, the E layer 5 that to set suitable depth simultaneously merges with it, makes more than aggregate thickness reaches about 150 μ m.
In addition, is that main body is relative with A layer 1 with the crystalline polyester resin that is essentially non-orientation, E layer 5 is to be essentially non-crystalline mylar, therefore also think better about the heat fused adaptability than A layer 1, make A layer 1 and E layer 5 integratedly by coextrusion system film, segment bounds printing printed layers 3 also can obtain firm heat fused between E layer 5 and D layer 4 again, can alleviate the possibility of peeling off of each interlayer, this also can be used as the effect of giving E layer 5 and enumerates.
(printed layers (C layer))
Printed layers 3 is implemented by the printing of photogravure, hectographic printing, serigraphy, other known method.The composition of printed layers 3 is patterns arbitrarily such as bag accent, wood grain accent or geometric pattern, abstract pattern.Can implement printing back and D layer 4 lamination to the surface of a side of the lamination of A layer 1 or E layer 5, also can implement printing back and A layer 1 or E layer 5 lamination the surface of D layer 4.Usually, with give printed layers 3 ratios to noncrystalline D layer 4 surface by back up, to surface or to give the operability of a side on track of printed layers 3 with the surface of the E layer 5 after A layer 1 and E layer 5 laminated integratedization good with crystalline A layer 1.
With arbitrary layer of A layer 1 and B layer 2, D layer 4, E layer 5 or E layer 5 and D layer 4 are used the occasion of laminated integratedization of bonding agent, the kind of the resin binder of printed layers 3 is restriction especially not, but by the resin binder that makes printed layers 3 resin binder with heat fused of the polyester system etc. of non-crosslinked or low cross-linking, when giving the sheet material that machine adds thermal polymerization with embossing, printed layers 3 is also as the bond layer of heat fused and act on.Perhaps, by on track, giving coating simultaneously, do not give bond layer separately and can present heat fused yet with heat fused.In addition, on this, be part printing or the thick printing in site by making printed layers 3, A layer 1 becomes with the non-printing of D layer 4 with D layer 4 or E layer 5 with B layer 2 or A layer 1 and directly contacts, and can obtain more firm heat fused.This is to be amorphous or low crystalline state because A layer 1 has before delivering to embossing to give machine, demonstrates the feature of fusion character when giving the machine heating with embossing.
(laminated sheet (A+B) or (A+C+D), the manufacture method of (A+E+C+D))
Film-forming method as laminated sheet of the present invention, various known method be can adopt, The tape casting or inflation method etc. extruded, in addition, about the B layer 2 that constitutes based on non-crystalline mylar, D layer 4, and E layer 5, also can be suitable for calendering system embrane method, be not particularly limited.
In formation shown in Figure 1, can be by coextrusion system film from originally with regard to laminated integratedization, in formation shown in Figure 3, can be by coextrusion system film from originally just with A layer 1 and E layer 5 laminated integratedization.About D layer 4,, therefore need make film separately owing to need give printed layers 3 (C layer) back lamination to A layer 1 or E layer 5.
Make printed layers 3 have the occasion of heat fused as described above,, preferably adopting embossing to give in the sheet material heating process of machine printed layers 3 sides of heat fused lamination A layer 1 and printed layers 3 sides and the D layer 4 of D layer 4 or E layer 5 from cutting down aspect consideration in man-hour.
(giving embossing) to laminated sheet
Fig. 5 is presented as and gives embossed pattern and a example that machine is given in the general embossing of using to the flexible PVC sheet material in past.
Laminated sheet of the present invention can adopt embossing to give machine and similarly give embossed pattern with flexible PVC sheet material in the past.Because the fusing point (Tm) of A layer 1 is 210 ℃-240 ℃ a scope, A layer 1 is the state of crystallization, even therefore embossing is given that laminated sheet heating-up temperature on the machine is set in more than 160 ℃, below the fusing point (Tm)-10 ℃, be below 200-230 ℃, can not produce adhesion to the heating of metal roller yet, in addition, by the tensile break strength at 180 ℃ is more than the 5MPa, the width that can not produce laminated sheet reduces, wrinkling, fusion fracture etc., and obtains and give flexible PVC sheet material that machine given embossed pattern equal or embossing hear resistance more than it with embossing.
(metallic plate F)
As the metallic plate 6 that becomes object of the present invention, can use the various steel plates of hot rolled plate, cold-reduced sheet, hot-dip galvanized steel sheet, plated steel sheet, tin plate, corrosion resistant plate etc. or aluminium sheet, aluminum series alloy plate, also can implement common chemical conversion and handle the back and use.The thickness of metallic plate 6 is according to the purposes of resin-coated metal sheet etc. and different, but can select in the scope of 0.1mm-10mm.
(manufacture method of embossed pattern sheet material coated metal plate)
The manufacture method of embossed pattern sheet material coated metal plate of the present invention then is described.
The bonding agent that uses as will adopt the embossing applicator to give the laminated sheet of embossing style (A+B, A+C+D or A+E+C+D) to be laminated on the metallic plate 6 time can be enumerated epoxy and be bonding agent, ammonia ester and be bonding agent, polyester and be the heat curing-type bonding agent 7 that generally is used of bonding agent etc.
As the method that obtains resin-coated metal sheet, use リ バ one ス coating machine, kiss to be coated with the coating equipment that machine etc. generally is used and on the metal covering of the sheet material of laminated integratedization of having fitted on the metallic plate 6, be coated with heat curing-type bonding agent 7, make dried bonding agent thickness reach about 2 μ m-10 μ m.
Then, adopt infrared heater and/or hot-blast heater to carry out the dry and heating of coated face, on one side the surface temperature with metallic plate 6 remains on temperature arbitrarily, Yi Bian use the roll-in laminator to be covered, to cool off by the mode that A layer 1 side of laminated sheet becomes bonding plane immediately.In view of the above, obtain resin-coated metal sheet shown in Figure 4.According to the present invention, owing to be positioned at and the fusing point (Tm) of the Resin A of bonding plane one side of metallic plate 6 scope at 210-240 ℃, therefore equal by the surface temperature that makes metallic plate 6 with the situation of flexible PVC sheet material lamination coated metal plate in the past, can access firm bonding force.
According to the present invention, become the better resin-coated metal sheet of embossing hear resistance, but preferably by carrying out the answer that water cooling alleviates the heating embossing that sheet material caused when the lamination behind the lamination immediately.
[embodiment]
Below provide more specifically and explain embodiments of the invention.The present invention is not limited by these embodiment.
Moreover bioassay standard, the test method(s) of the rerum natura of sheet material shown in embodiment and the comparative example and resin-coated metal sheet are as follows.
(1) tensile break strength under 180 ℃
Use has universal testing machine 2010 types ((strain) イ Application テ ス コ system) of thermostat, and insulation is the tension test of carrying out L type test film (according to the test film shape of ASTMD-1822-L) under 180 ℃ the state in groove, obtains tensile break strength.Mensuration is carried out at the MD direction of each laminated sheet (film vertically).
(2) embossing adaptability: anti-adherence
When giving machine and give embossing, to usefulness " * " expression of heating drum 8 (warm-up mill) adhesion sheet material, the usefulness of inadhesion sheet material " zero " expression with embossing shown in Figure 5.
(3) embossing adaptability: stretch-proof, refractory melt breaking property
When giving machine and give embossing with embossing shown in Figure 5, adopt in the heater heating sheet material process, usefulness " * " expression of sheet material fusing is though be unlikely to fusing, but the remarkable stretching of sheet material or wrinkling etc. usefulness " △ " expression take place, usefulness " zero " expression that does not produce these problems.
(4) embossing adaptability: transfer printing
Visualization is given the sheet material that machine is given embossing with embossing shown in Figure 5, usefulness " zero " expression of embossing style in transfer printing gallantly, and more shallow slightly than transfer printing with it situation represents that with " △ " transfer printing is poor, be shallow embossing style, perhaps do not have the embossing style and only shaggy usefulness " * " expression.
(5) embossing hear resistance
With lamination give the sheet material that machine given embossing with embossing shown in Figure 5 metallic plate 6 be statically placed in 105 ℃ the heated air circulation type baking oven after 3 hours, visualization, with put into before the baking oven relatively, the almost indeclinable usefulness of the shape of embossing " zero " expression, with it than situation that embossing replys taking place a little with " △ " expression, embossing is replied significant situation or the complete obiteration of embossing style and only shaggy usefulness " * " expression.
(6) processability of resin-coated metal sheet
Resin-coated metal sheet impacted adhere to bend test, the surface state of the decoration sheet of visual judgement bending machining portion, what almost do not change is expressed as (zero), produces be expressed as (△) of a little crackle, and what crack is expressed as (*).Impact is adhered to bend test and is carried out as follows.Make the length direction of coated metal plate and the sample that width is respectively 50mm * 150mm, after 23 ℃ temperature keep more than 1 hour, use Apparatus for Bending at low-temp to implement the prebuckling of 180 ° (inner bend radius 2mm), this sample is fallen the cylindrical hammer of diameter 75mm, quality 5kg in the mode of destroying the prebuckling part from the 50cm eminence.
(making of the laminated sheet of embodiment 1-19 and comparative example 5-10)
Shown in table 1 or table 2, as resin composition, each layer thickness, combination A layer 1 and B layer 2,2 twin shaft mixing extruders of use Φ 65mm by the coextrusion of feed head mode, obtain 2 lamination synusia materials.The system film of sheet material adopts with the conventional method of casting roller traction from the resin of T die head outflow.
(making of the single sheet of comparative example 1-4)
Use the twin shaft mixing extruder of Φ 65mm,, use the resin shown in table 1 or the table 2 to form, made the sheet material of individual layer respectively by having used the system of the extruding embrane method of T die head.The system film of sheet material adopts with the conventional method of casting roller traction from the resin of T die head outflow.About form, thickness, be documented in the hurdle corresponding to the A layer 1 of table 1.
The composition and the thickness of the A layer of table 1 embodiment 1-19, comparative example 1-10
| The A layer | ||||||
| Resin is formed (weight %) | Pigment addition (weight portion) | Thickness (μ m) | ||||
| イ-ス- 6763 | PCTG 5445 | ノバデュラン 5020S | コルテラ PTT | |||
| Embodiment 1 | 20 | 0 | 80 | 0 | 0 | 45 |
| Embodiment 2 | 10 | 0 | 90 | 0 | 0 | 30 |
| Embodiment 3 | 0 | 0 | 100 | 0 | 0 | 45 |
| Embodiment 4 | 30 | 0 | 70 | 0 | 0 | 30 |
| Embodiment 5 | 30 | 0 | 70 | 0 | 0 | 60 |
| Embodiment 6 | 0 | 20 | 80 | 0 | 0 | 35 |
| Embodiment 7 | 0 | 0 | 0 | 100 | 0 | 45 |
| Embodiment 8 | 20 | 0 | 80 | 0 | 0 | 45 |
| Embodiment 9 | 20 | 0 | 80 | 0 | 0 | 45 |
| Embodiment 10 | 30 | 0 | 70 | 0 | 0 | 25 |
| Embodiment 11 | 40 | 0 | 60 | 0 | 0 | 45 |
| Embodiment 12 | 45 | 0 | 55 | 0 | 0 | 45 |
| Embodiment 13 | 20 | 0 | 80 | 0 | 0 | 45 |
| Embodiment 14 | 20 | 0 | 80 | 0 | 0 | 25 |
| Embodiment 15 | 20 | 0 | 80 | 0 | 0 | 50 |
| Embodiment 16 | 20 | 0 | 80 | 0 | 0 | 50 |
| Embodiment 17 | 0 | 0 | 100 | 0 | 0 | 45 |
| Embodiment 18 | 20 | 0 | 80 | 0 | 0 | 45 |
| Embodiment 19 | 20 | 0 | 80 | 0 | 0 | 45 |
| Comparative example 1 | 100 | 0 | 0 | 0 | 16 | 150 |
| Comparative example 2 | 80 | 0 | 20 | 0 | 16 | 150 |
| Comparative example 3 | 0 | 0 | 100 | 0 | 16 | 150 |
| Comparative example 4 | 20 | 0 | 80 | 0 | 16 | 150 |
| Comparative example 5 | 20 | 0 | 80 | 0 | 0 | 45 |
| Comparative example 6 | 20 | 0 | 80 | 0 | 0 | 15 |
| Comparative example 7 | 20 | 0 | 80 | 0 | 0 | 15 |
| Comparative example 8 | 0 | 55 | 45 | 0 | 0 | 45 |
| Comparative example 9 | 65 | 0 | 35 | 0 | 0 | 45 |
| Comparative example 10 | 20 | 0 | 80 | 0 | 30 | 45 |
The composition of the B layer of table 2 embodiment 1-19, comparative example 1-10 and thickness, hot strength
| The B layer | 180 ℃ of hot strengths (Mpa) of laminated sheet | Give sheet temperature before the embossing (℃) | ||||
| Resin is formed (weight %) | Pigment addition (weight portion) | Thickness (μ m) | ||||
| イ-ス- 6763 | ノバデュラン 5020S | |||||
| Embodiment 1 | 80 | 20 | 24 | 105 | 13.8 | 170 |
| Embodiment 2 | 80 | 20 | 20 | 120 | 11.7 | 170 |
| Embodiment 3 | 80 | 20 | 24 | 105 | 13.7 | 170 |
| Embodiment 4 | 80 | 20 | 20 | 120 | 7.9 | 170 |
| Embodiment 5 | 80 | 20 | 26 | 90 | 16.2 | 170 |
| Embodiment 6 | 80 | 20 | 21 | 115 | 11.4 | 170 |
| Embodiment 7 | 80 | 20 | 24 | 105 | 17.9 | 170 |
| Embodiment 8 | 70 | 30 | 24 | 105 | 13.1 | 170 |
| Embodiment 9 | 100 | 0 | 24 | 105 | 12.8 | 170 |
| Embodiment 10 | 100 | 0 | 20 | 125 | 5.4 | 170 |
| Embodiment 11 | 80 | 20 | 24 | 105 | 9.2 | 170 |
| Embodiment 12 | 80 | 20 | 24 | 105 | 6.8 | 170 |
| Embodiment 13 | 80 | 20 | 36 | 50 | 13.3 | 170 |
| Embodiment 14 | 80 | 20 | 36 | 45 | 7.1 | 170 |
| Embodiment 15 | 70 | 30 | 12 | 200 | 14.5 | 170 |
| Embodiment 16 | 70 | 30 | 10 | 250 | 14.2 | 170 |
| Embodiment 17 | 60 | 40 | 24 | 105 | 16.2 | 170 |
| Embodiment 18 | 80 | 20 | 24 | 105 | 13.8 | 200 |
| Embodiment 19 | 80 | 20 | 24 | 105 | 13.8 | 160 |
| Comparative example 1 | - | - | - | - | Can not measure | 170 |
| Comparative example 2 | - | - | - | - | Can not measure | 170 |
| Comparative example 3 | - | - | - | - | 41.9 | 170 |
| Comparative example 4 | - | - | - | - | 35.8 | 170 |
| Comparative example 5 | 50 | 50 | 24 | 105 | 23.7 | 170 |
| Comparative example 6 | 80 | 20 | 18 | 135 | 4.6 | 170 |
| Comparative example 7 | 80 | 20 | 18 | 135 | 4.6 | 140 |
| Comparative example 8 | 80 | 20 | 24 | 105 | Can not measure | 170 |
| Comparative example 9 | 80 | 20 | 24 | 105 | Can not measure | 170 |
| Comparative example 10 | 80 | 20 | 30 | 15 | 12.7 | 170 |
Can not measure then and be judged as below the 5MPa.
(making of the laminated sheet of embodiment 20,21,25)
Use the twin shaft mixing extruder of Φ 65mm,, make A layer 1 and D layer 4 as the sheet material of individual layer individually respectively by having used the system of the extruding embrane method of T die head.The system film of sheet material adopts with the conventional method of casting roller traction from the resin of T die head outflow.Then, printed the pattern of abstract style by gravure processes on A layer 1 surface.About the combination of the composition degree of layer, in table 3 or table 4, express.These sheet materials are supplied with embossing shown in Figure 5 from 2 unwinding shafts give machine, integrated passing through the heat fused lamination with the contact portion of heating drum 8.
(making of the single sheet of comparative example 11)
Use the twin shaft mixing extruder of Φ 65mm, by having used the system of the extruding embrane method of T die head, made the sheet material of the individual layer that the resin that used shown in table 3 or the table 4 forms.The system film of sheet material adopts with the conventional method of casting roller traction from the resin of T die head outflow.Then, printed the pattern of abstract style by gravure processes on the surface of single sheet.For easy, about form, thickness, be documented in the hurdle corresponding to the A layer 1 of table 3.
(making of the laminated sheet of embodiment 22-24,26-28 and comparative example 12)
Shown in table 3 or table 4, as the resin of A layer 1 and E layer 5 form, each layer thickness and making up, use 2 twin shaft mixing extruders of Φ 65mm, by the coextrusion of feed head mode, obtain 2 lamination synusia materials.The resin of the D layer 4 of record is formed identical in the composition of E layer 5 and the table 4.
Therewith additionally, use the twin shaft mixing extruder of Φ 65mm,, made the D layer 4 of composition shown in the table 4 and thickness as single sheet by having used the system of the extruding film of T die head.The system film of these sheet materials adopts with the conventional method of casting roller traction from the resin of T die head outflow.Then, printed the pattern of abstract style by gravure processes on the surface of E layer 5.These sheet materials are supplied with embossing shown in Figure 5 from 2 unwinding shafts give machine, integrated passing through the heat fused lamination with the contact portion of heating drum 8.
The A layer composition of table 3 embodiment 20-28, comparative example 11,12 and thickness, have or not the E layer
| The A layer | The E layer | ||||||||
| Resin is formed (weight %) | Pigment addition (weight portion) | Thickness (μ m) | Have or not the E layer | Pigment addition (weight portion) | E layer thickness (μ m) | ||||
| イ-ス- 6763 | PCTG 5445 | ノバデュラン 5020S | コルテラ PTT | ||||||
| Embodiment 20 | 20 | 0 | 80 | 0 | 36 | 60 | Do not have | - | - |
| Embodiment 21 | 10 | 0 | 90 | 0 | 36 | 45 | Do not have | - | - |
| Embodiment 22 | 0 | 0 | 100 | 0 | 24 | 30 | Have | 24 | 70 |
| Embodiment 23 | 30 | 0 | 70 | 0 | 24 | 30 | Have | 24 | 70 |
| Embodiment 24 | 40 | 0 | 60 | 0 | 24 | 60 | Have | 24 | 70 |
| Embodiment 25 | 20 | 0 | 80 | 0 | 36 | 45 | Do not have | - | - |
| Embodiment 26 | 20 | 0 | 80 | 0 | 0 | 45 | Have | 30 | 80 |
| Embodiment 27 | 0 | 20 | 80 | 0 | 0 | 30 | Have | 34 | 70 |
| Embodiment 28 | 30 | 0 | 70 | 0 | 24 | 80 | Have | 24 | 120 |
| Comparative example 11 | 30 | 0 | 70 | 0 | 16 | 150 | Do not have | - | - |
| Comparative example 12 | 30 | 0 | 70 | 0 | 24 | 20 | Have | 24 | 80 |
The D layer composition of table 4 embodiment 20-28, comparative example 11,12 and thickness, hot strength
| The D layer | 180 ℃ of hot strengths (Mpa) of laminated sheet | ||||
| Resin is formed (weight %) | Pigment addition (weight portion) | Thickness (μ m) | |||
| イ-ス- 6763 | ノバデユラン 5020S | ||||
| Embodiment 20 | 80 | 20 | 0 | 90 | 16.3 |
| Embodiment 21 | 80 | 20 | 0 | 105 | 19.7 |
| Embodiment 22 | 80 | 20 | 0 | 50 | 14.9 |
| Embodiment 23 | 80 | 20 | 0 | 50 | 6.8 |
| Embodiment 24 | 80 | 20 | 0 | 50 | 13.4 |
| Embodiment 25 | 70 | 30 | 0 | 105 | 11.9 |
| Embodiment 26 | 60 | 40 | 0 | 50 | 13.6 |
| Embodiment 27 | 80 | 20 | 0 | 50 | 10.7 |
| Embodiment 28 | 80 | 20 | 0 | 50 | 19.3 |
| Comparative example 11 | - | - | - | - | 30.3 |
| Comparative example 12 | 80 | 20 | 0 | 50 | 4.3 |
Resin as these each layers is formed, and has specifically used following composition.
ノ バ デ ュ ラ Application 5020S: all PBT resin, Mitsubishi's engineering plastics corporate system, glass transition point: 45[℃], crystal melting peak temperature: 223[℃]
コ Le テ ラ CP509200: all PTT resin, シ エ Le corporate system, glass transition point: 49[℃], crystal melting peak temperature: 225[℃]
イ-ス -PET-G 6763: with 1, the 4-cyclohexanedimethanol has replaced the amorphous polyester resin, イ-ス ト マ Application chemical company system, glass transition point: 81[℃ of about 31mol% of the ethylene glycol part of PETG], the crystal melting peak temperature: do not observe [℃]
PCTG 5445: with 1, the 4-cyclohexanedimethanol has replaced that the polyester based resin that can be used as the amorphism operation in fact, イ-ス ト マ Application chemistry (strain) of about 70mol% of the ethylene glycol part of PETG made, glass transition point: 88[℃], the crystal melting peak temperature: do not observe [℃]
(sheet material to embodiment 1-28, comparative example 1-12 is given embossed pattern)
Employing also general embossing that use, continuity method in flexible vinyl chloride-based sheet material shown in Figure 5 is given machine and has been carried out giving of embossed pattern.About the printed sheet material of a part, carry out the heat fused lamination at the heating drum 8 part places that machine is given in this embossing as described above.Roughly situation as the embossing applicator of continuity method, at first by having used contact-type heating the carrying out preheating of sheet material of METAL HEATING PROCESS roller, then, by the non-contact type heating of having used infrared heater 9 sheet material is heated to temperature arbitrarily, by knurling rolls 10 transfer printing embossed pattern.Heating drum 8 is set at 100 ℃, then, adopts heater to heat and makes that contacting preceding sheet material with embossing style roller reaches the preference temperature shown in each table.In addition, the temperature of embossing style roller is 80 ℃, is the pears roller of surface average roughness Ra=10 μ m.Among Fig. 5 11 represents carry-over pinch rolls, 12 expression niprolls, 13 expression chill rolls.
(making of resin-coated metal sheet)
Then, the polyester that is generally used as polyvinyl chloride coated metal plate usefulness in the metal covering coating is a heat curing-type bonding agent 7, make dried bonding agent thickness reach about 2 μ m-4 μ m, then, adopt hot-blast heater and infrared heater 9 to carry out the dry and heating of coated face, (metallic plate 6: surface temperature thickness 0.45mm) is set in 235 ℃ with galvanized steel plain sheet, use roll-in laminator lining polyester based resin sheet material immediately, by the water-cooled cooling, made embossed pattern sheet material coated metal plate.
(evaluation of embossed pattern sheet material and embossed pattern sheet material coated metal plate)
Above-mentioned projects have been estimated.Table 5 or table 6 are expressed the result.In table 5 or the table 6, produce adhesion, do not carry out later evaluation, give the significant occasion of the stretching of sheet material in the machine or sheet material fusion fracture, do not carry out later evaluation for embossing for the heating drum 8 of embossing being given machine.
The evaluation result of table 5 embodiment 1-19 and comparative example 1-10
| The embossing adaptability | The embossing hear resistance | The processability of resin-coated metal sheet | |||
| Anti-adherence | The stretch-proof refractory melts breaking property | The style transfer printing | |||
| Embodiment 1 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 2 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 3 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 4 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 5 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 6 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 7 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 8 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 9 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 10 | ○ | △ | ○ | ○ | ○ |
| Embodiment 11 | ○ | △ | ○ | ○ | ○ |
| Embodiment 12 | △ | △ | ○ | ○ | ○ |
| Embodiment 13 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 14 | ○ | △ | △ | ○ | ○ |
| Embodiment 15 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 16 | ○ | ○ | ○ | ○ | △ |
| Embodiment 17 | ○ | ○ | Δ | ○ | ○ |
| Embodiment 18 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 19 | ○ | ○ | ○ | ○ | ○ |
| Comparative example 1 | × | - | - | - | - |
| Comparative example 2 | × | - | - | - | - |
| Comparative example 3 | ○ | ○ | × | - | ○ |
| Comparative example 4 | ○ | ○ | × | - | ○ |
| Comparative example 5 | ○ | ○ | × | - | ○ |
| Comparative example 6 | ○ | × | - | - | - |
| Comparative example 7 | ○ | ○ | ○ | × | ○ |
| Comparative example 8 | △ | × | - | - | - |
| Comparative example 9 | × | - | - | - | - |
| Comparative example 10 | ○ | △ | × | - | - |
The evaluation result of table 6 embodiment 20-28 and comparative example 11,12
| The embossing adaptability | The embossing hear resistance | The processability of resin-coated metal sheet | |||
| Anti-adherence | The stretch-proof refractory melts breaking property | The style transfer printing | |||
| Embodiment 20 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 21 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 22 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 23 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 24 | ○ | △ | ○ | ○ | ○ |
| Embodiment 25 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 26 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 27 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 28 | ○ | ○ | ○ | ○ | ○ |
| Comparative example 11 | × | - | - | - | ○ |
| Comparative example 12 | ○ | × | - | - | ○ |
Comparative example 1 and 2 is the sheet materials based on the individual layer of amorphous polyester resin, and 180 ℃ tensile break strength is low, and produces the adhesion of giving the heating drum 8 of machine to embossing, and it is difficult that later operation becomes.
Comparative example 3 and 4 is the sheet materials based on the individual layer of crystalline polyester resin, by using the fast equal PBT resin of crystallization rate as crystalline resin, become the high state of crystallinity in the moment of extruding the system film, can not produce adhesion to heating drum 8, even but sheet material is heated to 170 ℃, also because of crystallinity keeps high elastic modelling quantity, transferability embossing style not.
Though the composition of comparative example 5 A layers 1 is consistent with scope of the present invention, the composition of B layer 2 is not an amorphism polyester main body, gives adding in the machine in embossing and pines for crystallization and carry out, not transferability embossing style.
Though the composition of comparative example 6 A layer 1B layers 2 is all consistent with scope of the present invention, but because the thin thickness of A layer 1, thereby the tensile break strength under 180 ℃ is outside the scope of the invention, its result, when sheet material is heated, generation wrinkling or width significantly reduces, and can not carry out the transfer printing of gratifying embossing style.
The sheet material that comparative example 7 is to use the composition identical with comparative example 6 to constitute, and will be limited in 140 ℃ situation in the sheet material heating-up temperature that embossing is given in the machine, and the problem such as wrinkling of sheet material does not take place, obtain the transfer printing of good embossing style, but the hear resistance of embossing is low, and being judged as can not be durable.
Though the composition of comparative example 8 and 9 B layers 2 is consistent with scope of the present invention, but the composition of A layer 1 is not that crystalline polyester based resin main body is arranged, tensile break strength under 180 ℃ is low, and produces the adhesion of giving the heating drum 8 of machine to embossing, and it is difficult that later operation becomes.
Though the composition of comparative example 10 A layer 1B layers 2 is all consistent with scope of the present invention,, thereby can not carry out the transfer printing of gratifying embossing style because gross thickness is thin.
With respect to these comparative examples, embodiments of the invention 1-19, the sheet material fracture when not producing the adhesion of heating drum 8 or heater heating obtains good embossing style transfer printing.The hear resistance of the embossing style of being given in addition, and the processability of resin-coated metal sheet are also good.
Comparative example 11 is that printing has been implemented on the surface of single sheet, composition of sheet material self and comparative example 3 and 4 constitute based on the PBT resin equally, therefore the tensile break strength under 180 ℃ demonstrates high value, do not produce the adhesion of heating drum 8 or the stretching of sheet material, but transferability embossing style not.
Though the composition of comparative example 12 A layers 1, E layer 5 and D layer 4 conforms with scope of the present invention, but because the thin thickness of A layer 1, thereby at the tensile break strength under 180 ℃ outside scope of the present invention, its result, when sheet material is heated, generation wrinkling or width significantly reduces, and can not carry out the transfer printing of gratifying embossing style.
With respect to this, the embodiment 20-28 that the formation of printed layers 3 is arranged of the present invention, the sheet material fracture when not producing the adhesion of heating drum 8 or heater heating obtains good embossing style transfer printing.The hear resistance of the embossing style of being given in addition, and the processability of resin-coated metal sheet are also good.
In addition, the embodiment 21 that the thickness of D layer 4 is thick, the perspectivity of printed layers 3 is poor slightly as a result, but gives E layer 5 and reduced among the embodiment 22 and embodiment 23 of thickness of D layer 4, the perspectivity of printed layers 3 is good, does not also have difference with embodiment 20 about the transfer printing of embossing.
Claims (11)
1. the laminated sheet of an embossing adaptability excellence, it is characterized in that, be lamination to have resin bed (A layer) that crystalline polyester based resin, fusing point are the non-orientation of 210 ℃ of-240 ℃ of scopes and based on the resin bed (B layer) of the non-orientation that is essentially non-crystalline polyester based resin and comprise 2 layers laminated sheet at least, in this laminated sheet, the gross thickness of sheet material is the scope of 65 μ m-300 μ m, and the tensile break strength under 180 ℃ is more than the 5MPa.
2. the laminated sheet of an embossing adaptability excellence, it is characterized in that, be to being that printed layers (C layer) is given on resin bed (A layer) surface of the non-orientation of 210 ℃ of-240 ℃ of scopes to have crystalline polyester based resin, fusing point, again in the above lamination based on the transparent resin layer (D layer) of the non-orientation that is essentially non-crystalline polyester based resin and comprise 3 layers laminated sheet at least, in this laminated sheet, the gross thickness of sheet material is the scope of 65 μ m-300 μ m, and the tensile break strength under 180 ℃ is more than the 5MPa.
3. the laminated sheet of an embossing adaptability excellence, it is characterized in that, be that lamination is to have crystalline polyester based resin, fusing point is the resin bed (A layer) of the non-orientation of 210 ℃ of-240 ℃ of scopes, with resin bed (E layer) based on the non-orientation that is essentially non-crystalline polyester based resin, give printed layers (C layer) to the surface of E layer side, again in the above lamination based on the transparent resin layer (D layer) of the non-orientation that is essentially non-crystalline polyester based resin and comprise 4 layers laminated sheet at least, in this laminated sheet, the gross thickness of sheet material is the scope of 65 μ m-300 μ m, and the tensile break strength under 180 ℃ is more than the 5MPa.
4. according to the laminated sheet of claim 1 or 3 described embossing adaptability excellences, it is characterized in that, the A layer, with laminated integratedization of B layer or E layer be to finish by lamination in the mould of coetrusion.
5. according to the laminated sheet of claim 2 or 3 described embossing adaptability excellences, it is characterized in that, laminated integratedization of the face of having given printed layers (C layer) of D layer and A layer or the face of having given printed layers (C layer) of D layer and E layer finished by the heat fused lamination.
6. according to the laminated sheet of wantonly 1 described embossing adaptability excellence of claim 1-3, it is characterized in that, B layer, D layer, and the E layer be essentially non-crystalline mylar, be with 1, the 4-cyclohexanedimethanol has replaced the 30-70mol% of ethylene glycol part of PETG and the resin that obtains.
7. according to the laminated sheet of wantonly 1 described embossing adaptability excellence of claim 1-3, it is characterized in that, is polybutylene terephthalate (PBT) (PBT) resin more than the 55 weight % of all resins composition of A layer.
8. embossed pattern sheet material, it is characterized in that, the sheet material of wantonly 1 described laminated integratedization of claim 1-3 is heated to more than 160 ℃, after the temperature below the fusing point (Tm)-10 of A layer ℃, gives embossed pattern with the embossing plate roller to the surface of B layer side or the surface of D layer side.
9. the manufacture method of an embossed pattern sheet material, it is characterized in that, the sheet material of wantonly 1 described laminated integratedization of claim 1-3 is heated to more than 160 ℃, after the temperature below the fusing point (Tm)-10 of A layer ℃, gives embossed pattern with the embossing plate roller to the surface of B layer side or the surface of D layer side.
10. an embossed pattern sheet material coated metal plate is characterized in that, is bonding plane with the described embossed pattern sheet material of claim 8 with the surface of A layer side, adopts the heat curing-type bond layer to be pressed on the metallic plate.
11. used dress material in the building of door material, bathroom, unit wall material, bathroom, unit ceiling material, dividing plate material, panel material etc. of the described embossed pattern sheet material of claim 10 coated metal plate.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP132182/2003 | 2003-05-09 | ||
| JP2003132182 | 2003-05-09 | ||
| PCT/JP2004/006575 WO2004098883A1 (en) | 2003-05-09 | 2004-05-10 | Emboss-designed sheet and metal plate covered with emboss-designed sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1787916A true CN1787916A (en) | 2006-06-14 |
| CN1787916B CN1787916B (en) | 2010-05-12 |
Family
ID=33432157
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2004800126004A Expired - Fee Related CN1787916B (en) | 2003-05-09 | 2004-05-10 | Emboss-designed sheet and metal plate covered with emboss-designed sheet |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP4898220B2 (en) |
| KR (1) | KR100741240B1 (en) |
| CN (1) | CN1787916B (en) |
| TW (1) | TW200524731A (en) |
| WO (1) | WO2004098883A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102514310A (en) * | 2011-12-07 | 2012-06-27 | 常熟市东涛金属复合材料有限公司 | Clad metal sheet |
| CN105960329A (en) * | 2014-01-31 | 2016-09-21 | 日铁住金建材株式会社 | Resin film for decorative boards, method for producing decorative board, and decorative board |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4791864B2 (en) * | 2005-03-23 | 2011-10-12 | リケンテクノス株式会社 | Laminated decorative sheet |
| JP4654084B2 (en) * | 2005-07-21 | 2011-03-16 | 三菱樹脂株式会社 | Laminated sheet for covering a metal plate, and laminated sheet-coated metal plate |
| JP5064593B2 (en) * | 2006-01-12 | 2012-10-31 | シーアイ化成株式会社 | Plastic mirror laminate |
| JP4843507B2 (en) * | 2006-01-12 | 2011-12-21 | シーアイ化成株式会社 | Plastic mirror laminate |
| JP5116241B2 (en) * | 2006-03-08 | 2013-01-09 | 三菱樹脂株式会社 | Laminated sheet, embossed design sheet and embossed design sheet coated metal plate |
| KR100728662B1 (en) * | 2006-06-26 | 2007-06-14 | 도레이새한 주식회사 | Environment-friendly interior sheet |
| KR100908008B1 (en) * | 2008-04-25 | 2009-07-16 | 주식회사 폴리쉘 | Method for producing foamed sheets |
| JP5121665B2 (en) * | 2008-10-16 | 2013-01-16 | 三菱樹脂株式会社 | Laminated sheet for resin-coated metal sheet, method for producing the laminated sheet, and designed laminated sheet-coated metal sheet, unit bath member, building interior material, and steel furniture member |
| EP2534702A1 (en) * | 2010-02-10 | 2012-12-19 | Tata Steel Nederland Technology BV | Layered system for producing a solar cell on a metal substrate, method for producing said layered system |
| JP6252491B2 (en) * | 2013-11-18 | 2017-12-27 | 東レ株式会社 | Molded body and method for producing the same |
| US10603878B2 (en) * | 2015-12-28 | 2020-03-31 | Zeon Corporation | Optical laminate, method for producing same, polarizing plate, and display device |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03218830A (en) * | 1989-11-29 | 1991-09-26 | Sekisui Chem Co Ltd | Composite packaging material and packaging container using the same |
| JP3137450B2 (en) * | 1992-08-11 | 2001-02-19 | ポリプラスチックス株式会社 | Laminated polyester film |
| TWI225820B (en) * | 1998-11-17 | 2005-01-01 | Toyo Kohan Co Ltd | Polyester resin film for metal sheet lamination and decorative metal sheet laminated with the same |
| JP3782919B2 (en) * | 2000-03-28 | 2006-06-07 | 三菱樹脂株式会社 | Polyester sheet for building materials |
| JP2002210905A (en) * | 2001-01-17 | 2002-07-31 | Mitsubishi Plastics Ind Ltd | Polyester resin sheet for heat seal packaging and package using the same |
| JP3911127B2 (en) * | 2001-01-17 | 2007-05-09 | 三菱樹脂株式会社 | POLYESTER RESIN SHEET FOR HEAT WELDING PACKAGING AND PACKAGE USING THE SAME |
| JP4507449B2 (en) * | 2001-05-14 | 2010-07-21 | 凸版印刷株式会社 | Decorative sheet |
| JP4329277B2 (en) * | 2001-05-14 | 2009-09-09 | 凸版印刷株式会社 | Decorative sheet |
| JP4209847B2 (en) * | 2002-12-26 | 2009-01-14 | 三菱樹脂株式会社 | Resin-coated metal plate, laminated sheet for resin-coated metal plate, and method for producing resin-coated metal plate |
| JP4654084B2 (en) * | 2005-07-21 | 2011-03-16 | 三菱樹脂株式会社 | Laminated sheet for covering a metal plate, and laminated sheet-coated metal plate |
-
2004
- 2004-05-10 WO PCT/JP2004/006575 patent/WO2004098883A1/en active Application Filing
- 2004-05-10 JP JP2005506054A patent/JP4898220B2/en not_active Expired - Lifetime
- 2004-05-10 KR KR1020057021244A patent/KR100741240B1/en not_active IP Right Cessation
- 2004-05-10 CN CN2004800126004A patent/CN1787916B/en not_active Expired - Fee Related
- 2004-05-10 TW TW093113080A patent/TW200524731A/en not_active IP Right Cessation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102514310A (en) * | 2011-12-07 | 2012-06-27 | 常熟市东涛金属复合材料有限公司 | Clad metal sheet |
| CN105960329A (en) * | 2014-01-31 | 2016-09-21 | 日铁住金建材株式会社 | Resin film for decorative boards, method for producing decorative board, and decorative board |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2004098883A1 (en) | 2006-07-13 |
| KR100741240B1 (en) | 2007-07-19 |
| WO2004098883A1 (en) | 2004-11-18 |
| KR20060013650A (en) | 2006-02-13 |
| CN1787916B (en) | 2010-05-12 |
| TWI337938B (en) | 2011-03-01 |
| JP4898220B2 (en) | 2012-03-14 |
| TW200524731A (en) | 2005-08-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI438087B (en) | Molding resin sheet and molded article | |
| CN1787916A (en) | Emboss-designed sheet and metal plate covered with emboss-designed sheet | |
| JP4742123B2 (en) | Resin-coated metal plate and design sheet for resin-coated metal plate | |
| CN1638965A (en) | Multilayered polyester film and process for producing the same | |
| JP4846777B2 (en) | Laminated resin sheet, embossed sheet and coated substrate | |
| TWI396625B (en) | Multilayer articles and methods for making multilayer articles | |
| CN1732228A (en) | Polylactic acid polymer composition for thermoforming, polylactic acid polymer sheet for thermoforming, and thermoformed object obtained therefrom | |
| CN1052631A (en) | The deep-draw thin pot is with resin-coated steel sheet and deep-draw thin pot | |
| JP4654084B2 (en) | Laminated sheet for covering a metal plate, and laminated sheet-coated metal plate | |
| JP2008188970A (en) | Laminate sheet and laminate sheet-coated metal plate | |
| JP4907102B2 (en) | Laminated sheet for design coating and laminated sheet coated metal sheet | |
| JP5198128B2 (en) | Laminated sheet for coating a metal plate, and a metal plate coated with the laminated sheet | |
| CN1028163C (en) | Receiver sheet | |
| JP4227429B2 (en) | Laminated sheet and resin-coated metal plate using the same | |
| TW201139130A (en) | Resin sheet-coated metal laminate and process of producing the same | |
| CN1294202C (en) | Polyester-based resin sheet-like material and resin-covered metal plate using the resin sheet-like material | |
| JP5586177B2 (en) | Laminated sheet and metal plate coated with laminated sheet | |
| JP5116241B2 (en) | Laminated sheet, embossed design sheet and embossed design sheet coated metal plate | |
| TWI305515B (en) | ||
| JP2008254348A (en) | Laminated sheet for coating metal sheet and laminated sheet-coated metal sheet | |
| JP4776905B2 (en) | Laminated sheet, embossed design sheet and embossed design sheet coated metal plate | |
| CN1692015A (en) | Resin-covered metal sheet, pattern sheet for resin -covered metal sheet, and process for the production of resin-covered metal sheet | |
| JP3544648B2 (en) | Polyester resin coated metal plate | |
| JP2006341403A (en) | Laminated sheet for design coating and laminated sheet coated metal panel | |
| JP2004106411A (en) | Decorative sheet for ornamentation |
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 | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100512 Termination date: 20130510 |