CN1551826A - Resin-coated metal plate and method for production thereof - Google Patents
Resin-coated metal plate and method for production thereof Download PDFInfo
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- CN1551826A CN1551826A CNA038009862A CN03800986A CN1551826A CN 1551826 A CN1551826 A CN 1551826A CN A038009862 A CNA038009862 A CN A038009862A CN 03800986 A CN03800986 A CN 03800986A CN 1551826 A CN1551826 A CN 1551826A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
Abstract
A resin-coated metal plate (11) having a metal plate (12) and, laminated in the following order on one side thereof via an adhesive layer (13), a base resin layer (14) containing a polyester based resin as a primary component, a printed layer (15), and a transparent stretched polyester layer (16), characterized in that a polyester based resin constituting the base resin layer (14) satisfies the requirement that, in the state of an integrated sheet (S) before its lamination on the metal plate (12), a crystallization peak temperature (Tc) and a crystal melting peak temperature (Tm) are clearly observed in the temperature rise step of the measurement with a differential scanning calorimeter (DSC), and the amount of heat of crystallization (DELTAHc, J/g) and the amount of heat of crystal melting (DELTAHm, J/g) satisfy the relationship: (DELTAHm - DELTAHc) < 30.
Description
Technical field
The present invention relates to employed resin-covered metal sheet and manufacture method thereof in household electrical appliance external ornaments such as AV equipment, air-conditioning hood, steel furniture, elevator interior trim, building interior trim etc.More particularly, relate to and both have good anti-wound property, processability, have the specular reflective and the good boiling water resistance of design excellence again simultaneously, and do not use resin-covered metal sheet and the manufacture method thereof that contains halide resin.
Background technology
In the past, as employed resin-covered metal sheet in the such use, with with the resin bed that adds pigment coloring as the substrate resin layer, printed layers, further stacked transparent resin film and incorporate thin slice (Sheet) are set thereon thereon, on steel plate, carry out lamination and make goods and use.
As the transparent resin film in this formation, for example ethylene-vinyl alcohol copolymer film that common used thickness is 10～50 μ m, acrylic acid esters co-polymer film, biaxial stretch-formed PET (to call biaxial stretch-formed PET in the following text) based resin film etc.Wherein, preferably use the good biaxial stretch-formed PET resin film of various rerum naturas.
Also have, generally use soft PVC resinoid layer as painted resin bed.This is because the soft PVC resinoid can add plasticizer, can at random set its flexibility.Also have, in the formation of stacked transparent biaxial stretch-formed PET based resin film, can not only obtain good workability, and according to for many years Study of Stabilizer, also have comparison favorable durability, chemical proofing, hear resistance and good hot water resistance, be preferred for the purposes of bathtub etc.And, at soft PVC resinoid superimposed layer in the resinoid formation of biaxial stretch-formed PET, can obtain very good specular reflective.That is, one of feature of resin-covered metal sheet is that the image distortion degree of mirroring is little, vividness is high.
Yet, in recent years, because the problem of the heavy metal compound that causes by the stabilizing agent in the polyvinyl chloride resin, when the problem of the VOC (VOC) that is caused by a part of plasticizer, stabilizing agent, the problem of endocrine disturbance effect, burning reasons such as hydrogen chloride gas and other chlorine-containing gas problems take place, the use of polyvinyl chloride resin is restricted.
Therefore, replacement is as the soft PVC resinoid of the pigmentary resin layer of described formation, by based on polyolefin resins such as polypropylene, and soft composition such as styrene class, copolyalkenamer class, obtain having the material of the rerum natura close and use with the soft PVC resinoid.During this constitutes, the formation of laminated biaxially-stretched PET based resin film, the resinoid situation of soft PVC is same with having used on painted resin bed, can obtain good specular reflective.
Yet, as pre-coating (Pre-coat) steel plate, to give under the occasion of its abundant processability, the anti-wound property ratio in surface has used the resinoid occasion of soft PVC also inferior.Also have,, then produce the problem that can not obtain satisfied processability again, can not be widely used if make the resinoid resin-covered metal sheet of anti-wound property and soft PVC the same.
On the one hand, polyolefin resin is the inferior material of cementability in itself, so giving the printing designability, carrying out under the stacked situation with biaxial stretch-formed PET resinoid, having produced need be than the problem of the more operation of soft PVC resinoid [for example, corona) handle, substrate coating surface treatment procedures such as (Primercoating)].Also have, its bonding interface and be used for and bonding agent that metallic plate is bonding between the long term stability problem at interface, problem is also arranged.
Therefore, as the material that addresses these problems, inquired into the pigmentary resin layer of polyester resin as described formation.The metal plate hight that the metallic plate of this resin-coating can make its anti-wound property and processability all coat than soft PVC resinoid can solve the problems that exist in the polyolefin resin covered metal plate.
Yet, use under the occasion do not have the crystalline polyester resin that rolls class as the pigmentary resin layer, because its glass transition temperature (Tg) is lower than 100 ℃, thereby can not satisfy the anti-boiling water immersion test that in the assessment item of building interior trim, generally includes with resin-covered metal sheet.Corresponding with it, use PET, polybutylene terephthalate etc. to have under the occasion of crystalline polyester resin as the pigmentary resin layer, because its fusing point height, thereby need to improve the metal sheet surface temperature, make its temperature be higher than polyvinyl chloride resin film in the past, the lamination of polyolefin resin film.Therefore, be necessary existing lamination line is transformed.
Also have, handle though sometimes application is carried out at the back side of described resin-covered metal sheet, in the past, this application also had the hear resistance problem.At this moment, coating must be changed into the high coating of hear resistance or will be in the past, simultaneously carry out before the lamination the steel plate heating and overleaf the technological transformation of the drying of the coating of coating become coating composition behind the lamination, carry out the technology of dry heat etc. once more.And, though in the stacked incorporate thin slice, the hear resistance of printed layers, no problem under the laminating temperature in the past, when improving laminating temperature, problems such as tangible thermo-color, heat fade may take place.In this occasion,, be necessary to improve the hear resistance of printed layers owing to the pigment type of printing-ink, the change of adhesive kind.Yet, improve these problems, can relate to the burden that increases steel plate lamination manufacturer, and then the problem of bringing cost to increase, so be out of favour.
Summary of the invention
The present invention finishes in view of described problem, and the present invention's the 1st purpose provides a kind of soft PVC resinoid that do not use, and can utilize the resin-covered metal sheet with good specular reflective of laminating apparatus manufacturing in the past; The present invention's the 2nd purpose provides a kind of except having good specular reflective, and processability and the also good resin-coating of boiling water resistance belong to plate; Three of the object of the invention provides its manufacture method.
In order to reach described the 1st purpose, the described the present invention of claim 1 is in the resin-covered metal sheet that the following stated constitutes, promptly, substrate resin layer, printed layers, the clear stretch polyester resin layer that will be Main Ingredients and Appearance with the polyester resin carry out the laminated shim that laminated integratedization forms successively, face with described substrate resin layer side passes through bond layer as bonding plane, in the resin-covered metal sheet that on metallic plate, carries out lamination and form, constitute the polyester resin of described substrate resin layer, satisfy following necessary condition, that is:
Under the laminated shim state before carrying out lamination on the metallic plate, based on the intensification of the mensuration of differential scanning calorimetry (DSC) time, can observe clear and definite crystallization peak temperature (Tc) and watery fusion peak temperature (Tm).When crystallization heat was Δ Hm (J/g) as Δ Hc (J/g), watery fusion hotwork, set up (Δ Hm-Δ Hc)＜30.
Here, " with polyester resin as Main Ingredients and Appearance " means to be also included within and is added with an amount of additive in the polyester resin.As additive, for example, can use widely used additive in resin material usually.
In this invention, be lower than 30 by the value that makes (Δ Hm-Δ Hc), the crystallinity of substrate resin layer is restricted, and has shown crystallization melting hump temperature (Tm), but in fact from more just having meltbility during low temperature than Tm temperature.Therefore,, pressurize with laminating roll when becoming molten condition, can eliminate surface irregularity, obtain high specular reflective from substrate resin layer, metallic plate etc. even under surface temperature, carry out lamination less than described Tm+30 ℃ metallic plate.Also have, can obtain high specularity under the temperature when the resinoid lamination of soft PVC in the past, can effectively utilize existing equipment manufacturing.And printing-ink, bonding agent etc. also can be used in the polyvinyl chloride resin employed, can reduce product cost.
For reaching the 2nd purpose, invention according to claim 2, in the described invention of claim 1, described substrate resin layer contains the polybutylene terephthalate resinoid as the crystalline polyester resin composition, and under state behind the lamination on the metallic plate, the hot Δ Hm of described crystallization heat Δ Hc and described watery fusion satisfies at least one relational expression among 15＜Δ Hm and 5＜(the Δ Hm-Δ Hc).This invention not only makes specular reflective good, and makes processability and boiling water resistance also good.
Invention according to claim 3, in the described invention of claim 1, described substrate resin layer contains polytrimethylene-terephthalate's resinoid as the crystalline polyester resin composition, and under state behind the lamination on the metallic plate, the hot Δ Hm of described crystallization heat Δ Hc and described watery fusion satisfies at least one relational expression among 15＜Δ Hm and 5＜(the Δ Hm-Δ Hc).This present invention not only makes specular reflective good, and makes processability and boiling water resistance also good.
Invention according to claim 4, in any described invention, described clear stretch polyester resin layer is to be formed by biaxial stretch-formed polyethylene terephthalate resin film in claim 1～claim 3.Therefore, can guarantee the transparency, the anti-wound property of flatness and surface etc. in this invention easily.Simultaneously, also carry out so-called shop fixtures printing (Back Print) easily and form printed layers.
In any described invention, there is bond layer in invention according to claim 5 between described substrate resin layer and described printed layers in claim 1～claim 4.Cementability in this invention between substrate resin layer and the printed layers is good.
Invention according to claim 6, in any described invention, described substrate resin layer is made of the pigmented polyester resinoid in claim 1～claim 5.This invention can realize giving and the color emissivity improvement of printed layers etc. the covering of underlying metal plate, designability.
Invention according to claim 7, in claim 1～claim 6 in the manufacture method of any described resin-covered metal sheet, to be the substrate resin layer of Main Ingredients and Appearance with the polyester resin, printed layers, clear stretch polyester resin layer carries out the laminated shim that laminated integratedization forms successively, face with described substrate resin layer side passes through bond layer as bonding plane, when on metallic plate, carrying out lamination, described metal sheet surface temperature T s (℃) and constitute the polyester resin of described substrate resin layer watery fusion peak temperature Tm (℃) between set up under the state of (Tm+30)＞Ts relation and carry out lamination.
This invention can utilize laminating apparatus in the past easily to make described resin-covered metal sheet, and thermo-color, the heat that can suppress printed layers and metallic plate back coating are faded etc.
Description of drawings
Fig. 1 (a) is the ideograph of expression variation for the ideograph of the basic comprising of expression resin-covered metal sheet of the present invention, Fig. 1 (b).
Symbol description:
11-resin-covered metal sheet, 12-metallic plate, 13 and 17-bond layer, 14-substrate resin layer, 15-printed layers, 16-clear stretch polyester resin layer, S-as the laminated integratedization thin slice of laminated shim.
The specific embodiment
Below, the specific embodiment of the present invention is described.
Shown in Fig. 1 (a), resin-covered metal sheet 11 is at the single face of metallic plate 12, and by bond layer 13, being laminated with the polyester resin is the substrate resin layer 14 of Main Ingredients and Appearance, on substrate resin layer 14, be laminated with printed layers 15, and be laminated with clear stretch polyester resin layer 16 on it again.Promptly, resin-covered metal sheet 11 constitutes following structure: substrate resin layer 14, printed layers 15, the clear stretch polyester resin layer 16 that will be Main Ingredients and Appearance with the polyester resin stack gradually and the integrated laminated integratedization thin slice S as laminated shim that forms, with the face of substrate resin layer 14 side as bonding plane, by bond layer 13, lamination on metallic plate 12.Also have, except formation, between substrate resin layer 14 and printed layers 15, also be provided with bond layer 17 with Fig. 1 (a) at the resin-covered metal sheet 11 shown in Fig. 1 (b).
As the polyester resin that constitutes substrate resin layer 14, can use from containing ethylene glycol, propane diols, butanediol, cyclohexanedimethanol etc. as pure composition and containing the monomer or the admixture of optional resin the copolymer of terephthalic acid (TPA), M-phthalic acid etc. as the dicarboxylic acids composition.But, under the state of the laminated shim on metallic plate 12 before the lamination, based on the intensification in the mensuration of differential scanning calorimeter (DSC) time, observe tangible crystallization peak temperature (Tc), watery fusion peak temperature (Tm), if when making crystallization heat be Δ Hc (J/g), the hot Δ Hm of watery fusion (J/g), following formula is set up:
ΔHm-ΔHc＜30…(1)
If the value of (Δ Hm-Δ Hc) is higher than 30, then show the crystallinity height of this polyester resin.Therefore, the surface temperature of metallic plate 12 during lamination, usually, if be not higher than substrate resin layer 14 fusing point Tm (℃) more than 30 ℃, will cause the fusion of substrate resin layer 14 insufficient, can not eliminate concavo-convex from substrate resin layer 14 surface, also have, because also residual surface from metallic plate 12 is uneven, can not get high specularity.The watery fusion peak temperature of substrate resin layer 14 is equivalent to its fusing point.It is in order to prevent that following phenomenon from producing that the surface temperature of metallic plate 12 must be higher than more than substrate resin layer 14 fusing point Tm30 ℃: lamination moment produces heat transmission from heated metal board 12 to laminated integratedization thin slice, and the mean temperature of instantaneous resin-covered metal sheet 11 integral body descends; Heat is consumed in the watery fusion of substrate resin layer 14; During the spreading of the laminating roll that utilization is lower with respect to metallic plate 12 temperature, taken away heat etc. by laminating roll.
Yet, at this moment, usually, the surface temperature of the metallic plate 12 during lamination must be more much higher as the occasion of substrate resin layer 14 than use soft PVC resinoid in the past, and is more obvious in the variety of issue described in " problem that the present invention need solve ".
Yet, being lower than 30 by the value that makes (Δ Hm-Δ Hc), substrate resin layer 14 crystallinity are restricted, though show crystalline melting temperature peak (Tm), in fact, begin just to have meltbility in the temperature lower than Tm.Therefore,,, eliminate, obtain high specular reflective because that above-mentioned a variety of causes causes is uneven by when becoming molten condition, pressurizeing with laminating roll even carry out lamination not satisfying under described Tm+30 ℃ the surface temperature of metallic plate 12.
More have, when substrate resin layer 14 contains polybutylene terephthalate (PBT) resinoid or polytrimethylene-terephthalate (PTT) resinoid as the crystalline polyester resin composition, and during the necessary condition below satisfying, can obtain the good resin-covered metal sheet of boiling water resistance 11.Under the state behind the lamination on the metallic plate 12, during based on the intensification of the mensuration of DSC, can observe watery fusion peak temperature (Tm), when crystallization heat is Δ Hm (J/g) as Δ Hc (J/g), watery fusion hotwork, satisfy in following formula (2), (3) at least.
15＜ΔHm…(2)
5＜(ΔHm-ΔHc)…(3)
If these values are lower than setting, then the crystallinity of substrate resin layer 14 is low, and complete amorphous polyester resin is the same as the situation of substrate resin layer 14 with using, and can't pass boiling water test, and is restricted as the interior purposes of building material.
If formula (2), at least one relational expression in (3) is set up, and can obtain the good resin-covered metal sheet of boiling water resistance 11 is owing to following reason.If the Δ Hm of the substrate resin layer 14 of regulation is higher than 15 in the formula (2), then show the PBT resinoid that uses as the crystalline resin composition or the resinoid crystalline rate of PTT is very fast and, the ratio height that the crystalline resin composition accounts in the admixture of substrate resin layer 14 is formed.Therefore, even almost be noncrystalline state behind lamination, when the boiling water impregnation state, at once crystallization takes place, its result can obtain bearing the crystallinity of boiling water test.
Relative with it, if under the situation that does not satisfy formula (2), show that then the ratio that the crystalline resin composition accounts in the admixture of substrate resin layer 14 is formed is low.Therefore, the crystalline rate of admixture system is slack-off, if the crystallization more than the time point behind the lamination does not take place necessarily just can not bear boiling water test.
If will obtain satisfying described formula (1), (2) or formula (1), the resin of substrate resin layer 14 (3) is formed, and then respectively uses all polybutylene terephthalate (PBT) resins single composition, so-called or equal polytrimethylene-terephthalate (PTT) resin to use as the crystalline resin composition sour composition and pure composition.And, when carrying out fusion, adjust easily and wish the rerum natura that obtains, so preferred with the copolyesters resinoid of amorphism or low-crystalline.
As noncrystalline resin, consider " イ one ス 1 " that preferably use cheaply, イ one ス ト マ Application chemical company produces or similar resin from the stable supplying and the high-throughput angle of raw material.But do not have special restriction, can use under special cooling condition yet and show fusing point, but can be used as " PGTG5445 " that イ one ス ト マ Application chemical company that non-crystalline resin uses produces etc. usually.
As crystalline resin, even under the occasion of the fast resin of use crystalline rate as equal PBT and equal PTT, by with crystallinity low resin or the fusion with it of noncrystalline resin, the crystalline rate of admixture system integral body is descended, also can be met the laminated integratedization thin slice S of formula (1).Also have, when using these crystalline resins, can obtain the good resin-covered metal sheet of processability easily, so preferred.
In substrate resin layer 14,, can attach pigment in order to cover underlying metal plate 12, give designability and to improve color emissivity of printed layers 15 etc.Employed pigment can use general in the past use, coloring resin pigment, and its addition also can add by general addition according to described purpose.
In substrate resin layer 14 and clear stretch polyester resin layer 16,, also can attach an amount of additive not damaging on the object of the invention degree.As having of additive, for example, various antioxidants, heat stabilizer, ultra-violet absorber, lubricant, matal deactivator, residual polymerization catalyst passivator, nucleator, antibacterial mildew inhibitor, antistatic additive, fire retardant and the packing material etc. of Phosphorus, phenol etc. widely used additive in resin material usually.Also have, can enumerate terminal carboxylic acid sealing agent, hydrolysis-resisting agents such as Carbodiimides, the additive that ester exchange inhibitor etc. are developed for specific resin etc.
Between substrate resin layer 14 and printed layers 15, or also can there be bond layer 17 in printed layers 15 and 16 on clear stretch polyester resin layer.As the spendable material of bonding agent that constitutes this bond layer 17 being, for example, is host with polyester resin, polyethers resin etc., makes it to harden with isocyanates crosslinking agent etc., generally is referred to as the dry lamination bonding agent.Consider from the angle that reduces this bonding agent, preferably use the bonding agent of aliphatic category because of the problem of ultraviolet flavescence.
Also have, especially added the situation etc. of the pigment etc. of light fastness stability difference at substrate resin layer 14, when controlling the ultraviolet transit dose to substrate resin layer 14 if necessary, on the degree of not damaging its character, also can be at bond layer 17 suitably with addition of the additive as ultra-violet absorber.
Photogravure, hectographic printing, serigraphy and other known printing process printing printed layers 15.The pattern style of printed layers 15 can be bag style, wood grain style or arbitrary graphic patterns such as geometry pattern, abstract design, can local printing, also can overall printing.After the local printing, also can further carry out overall printing.Usually use and carry out so-called shop fixtures method of printing, but also can carry out surface printing substrate resin layer 14 in the stromatolith side of the good clear stretch polyester resin layer 16 of flatness.
As clear stretch polyester resin layer 16 used in the present invention; can use in soft PVC resinoid covered metal plate, polyolefin resin covered metal plate with same purpose promptly with, the clear stretch polyester resin layer that protection printed layers, the design of giving the degree of depth, the various rerum naturas of improved surface are used as purpose.
Especially consider from aspects such as the transparency and flatness, the anti-wound property in surface, use biaxial stretch-formed PET based resin film proper.The clear stretch polyester resin layer 16 of this embodiment is made of transparent biaxially stretched polyester based resin film (transparent biaxial stretch-formed PET resin film).Can use as film, thickness is the film about 220 ℃～240 ℃, that in the past generally used as described purpose of the heat fixation temperature after 15 μ m～75 mu m ranges and the stretch processing.
Metallic plate as object of the present invention can use, and various steel plates, aluminium sheets such as hot rolled steel plate, cold-rolled steel sheet, hot-dip galvanized steel sheet, plated steel sheet, tin plate, stainless-steel sheet carry out common chemical treatment and use also passable afterwards.The thickness of metallic plate 12 according to the purposes of resin-covered metal sheet 11 and difference, but can be selected in the scope of 0.1mm～10mm.
Secondly, the manufacture method with regard to laminated integratedization thin slice S and resin-covered metal sheet 11 describes.Film-forming method as laminated integratedization thin slice S of the present invention can adopt known method, for example, that uses T shape mould extrudes casting method, blown film method (inflation) etc., though there is not special restriction, but consider from aspects such as the system film of thin slice and steady production, preferably use the casting method of extruding of T shape mould.
The thickness of laminated integratedization thin slice S is generally 50～500 μ m.If the thickness less than 50 μ m of thin slice, then under the situation as the resin-covered metal sheet use, its performance as the protective layer of metallic plate 12 is inferior.And because underlying metal plate screening capacity is low, the printing style is subjected to the influence of underlying metal plate color, so not preferred; On the other hand, if thickness surpasses 500 μ m, then the secondary operations adaptability such as perforation processing as resin-covered metal sheet 11 are often inferior.
Also have, as the crystalline method of control substrate resin layer 14 of the present invention, the method for the cast temperature when also having control to extrude casting.
By carrying out lamination at metallic plate 12, obtain resin-covered metal sheet 11 of the present invention by the laminated integratedization thin slice S that described method is carried out laminated integratedization.Bonding agent as bond layer 13 usefulness that are used for lamination can use, epoxies bonding agent, carbamates bonding agent and polyesters bonding agent etc.
To metallic plate 12, use reverse roll coating machine, roll-type kiss to be coated with the general coating equipments that use such as machine (kiss roll coater), the described bonding agent of coating makes dried adhesive film thickness about 2～10 μ m on the metal covering of laminated integratedization thin slice S of will fitting.Then, utilize at least one side of infrared heater and hot-blast heater, carry out the dry and heating of coated face, when the surface temperature with metallic plate 12 remains on to fixed temperature, cover laminated integratedization thin slice S, also cooling with the roll-type laminating machine at once, obtain resin-covered metal sheet 11.
If the watery fusion peak temperature that makes substrate resin layer 14 as Tm (℃) time, the surface temperature Ts of metallic plate 12 during lamination (℃) though be lower than (Tm+30) (℃), also can obtain high specularity outward appearance.But, if the surface temperature Ts of metallic plate 12 (℃) be not higher than (Tm-10) (℃), then can not get high specularity outward appearance.
Though this is because substrate resin layer 14 has the meltbility feature below watery fusion peak temperature Tm, than melting temperature low when too many, can not obtain sufficient smoothing sclerosis.Therefore, when using equal PBT, because the watery fusion peak temperature Tm of this resin is near 225 ℃, so the metal sheet surface temperature during lamination will be controlled at more than 215 ℃, below 255 ℃ as the crystalline resin composition of substrate resin layer 14.
Resin-covered metal sheet 11 with the laminating roll lamination is imported in the refrigerating work procedure continuously.Refrigerating work procedure will be guaranteed long distance, can use natural air cooling or forced air-cooling, but consider speed of production, generally adopts water cooling.In the case, the PET resinoid admixture slow with using crystalline rate formed comparing of the method that forms substrate resin layer 14, PBT resinoid and the resinoid admixture of PTT are formed the method that forms substrate resin layer 14 faster to use crystalline rate, satisfying described formula (2) under the cooling condition more rapidly, (3), so preferred.
Embodiment
Below, be described in more detail with embodiment and Comparative Examples, but the invention is not restricted to these examples.
[making of laminate film]
Use resin as shown in table 1 to form [cooperation ratio (weight %)] twin shaft mixing extruder, making thickness is the pigmented polyester resinoid thin slice (substrate resin layer 14) of 80 μ m.The addition of pigment is that titanium white and titan yellow are 24 weight portions (the gross weights of resin composition as 100 parts), and this addition is identical in all embodiment and Comparative Examples.Then, as clear stretch polyester resin layer 16, thickness is on transparent biaxial stretch-formed PET resin film (the Mitsubishi Chemical polyester company product) single face of 25 μ m, with the heliogravure rubbing method, carry out the part printing of abstract design, forms printed layers 15.Then, coated heat curable polyester class bonding agent on this printing surface forms bond layer 17, and substrate resin layer 14 makes it by between the pair of rolls after superimposed, thereby integrated, make laminated integratedization thin slice S.The kind of the kind of transparent biaxial stretch-formed PET resin film, printing-ink and Thermocurable polyesters bonding agent and specified criteria etc. are all identical in all embodiment and Comparative Examples.
Cut out substrate resin layer 14, carry out DSC mensuration from laminated integratedization thin slice S with slicer, obtain lamination preceding (Δ Hm-Δ Hc).This measurement result is as shown in table 2.Equally, relevant fusing point also is a measured value at this point described in table 2.
Form as the resin shown in the table 1, be specially:
PBT: ノ バ デ ユ ラ Application 5020S (engineering plastics company of Mitsubishi product).
PTT: コ Le テ ラ CP509200 (シ エ Le company product).
7% of the sour composition of co-PET:BK-2180 (Mitsubishi Chemical polyester company product) is the copolymerization PET of M-phthalic acid.
PETG: イ one ス 1 (Eastman chemical company product) is that with 1, the 4-cyclohexanedimethanol replaces amorphism (amorphism) polyester resin of the ethylene glycol part (about 30～60 moles of %) of PET.
PCTG:PCTG5445 (Eastman chemical company product).
[making of resin-covered metal sheet]
Then, the polyesters bonding agent with being generally used in the polyvinyl chloride resin covered metal plate is coated with on metal covering, and making dried adhesive film thickness is about 2～4 μ m, forms bond layer 13.Then, utilize hot-blast heater and infrared heater that coated face is carried out drying and heating, press the surface temperature Ts that each temperature described in the table 1 sets galvanized steel plain sheet (thickness 0.45mm) (℃), cover laminated integratedization thin slice S with the roll-type laminating machine at once, spray water and cool off or the natural air cooling, obtain resin-covered metal sheet 11 thereby make.The kind of bonding agent, coating condition are all identical in all embodiment and Comparative Examples.And metal sheet surface temperature and cooling means during lamination are documented in the table 1.
Also have, resin-covered metal sheet 11 is placed in the watery hydrochloric acid floods, after separating metal plate 12 and the laminated integratedization thin slice S, cut out substrate resin layer 14, carry out Δ Hm and (Δ Hm-Δ Hc) after DSC measures, obtains lamination with slicer.The result collects in table 2.
Each resin-covered metal sheet 11 is done the evaluation of the following order, and its result is as shown in table 3.Mensuration specification, test method to the resin-covered metal sheet rerum natura shown in embodiment and the Comparative Examples are as follows.[the hot Δ Hm of watery fusion peak temperature Tm and watery fusion]:
With パ one キ Application エ Le マ one system DSC-7, by JIS-K7121 (the transition temperature measuring method-fusion temperature of plastics ask calculation method) preparation 10mg sample, measure, try to achieve with 10 ℃/minute firing rate.Watery fusion peak peak temperature when heating up for the 1st time is as Tm.Simultaneously, according to this peak area, ask and calculate crystallization heat of fusion Δ Hm.
[crystallization peak temperature Tc and crystallization heat Δ Hc]:
With パ one キ Application エ Le マ one system DSC-7, by JIS-K7121 (the transition temperature measuring method-fusion temperature of plastics ask calculation method) preparation 10mg sample, measure, try to achieve with 10 ℃/minute firing rate.Crystallization peak peak temperature when heating up for 1 time is as Tc.Simultaneously, according to this peak area, ask and calculate crystallization heat Δ Hc.
[vividness gloss value (Gd value)]:
With the exploitation of juridical person Japan color research institute＜PGD portable vividness Grossmeters PGDIV, according to the assay method of same juristic person regulation, measure the specular reflective of each resin-covered metal sheet of embodiment and Comparative Examples, as the judgment standard of high specularity.5 points in same sample are measured, its mean value as vividness gloss value (Gd value).The Gd value be 0.9 when above with (zero) expression, 0.8 or more and be lower than at 0.9 o'clock, be lower than at 0.8 o'clock and represent with (*) with (△) expression.
[boiling water resistance test]:
On the resin-covered metal sheet of 60mm * 60mm, with cupping (Erichsen Test) experimental rig of JIS-K7121 regulation, make resin cover overhanging protrusions of side 6mm after, dipping is 3 hours in boiling water, the surface state of this resin flake of range estimation judgement.And the usefulness (zero) that does not have fully to change represents that usefulness (△) expression that a little Chap splits appears in the surface, and resin bed has produced usefulness (*) expression of distortion such as remarkable expansion.
[processability]:
Resin-covered metal sheet impacted be close to bend test, the thin slice (laminated integratedization thin slice S) of bending machining portion is estimated its surface state of judgement, and usefulness (△) expression of a little crackle, usefulness (*) expression of breaking are represented, taken place to the usefulness (zero) that does not almost have to change.Moreover impact is close to bend test and is performed as follows.The sample for preparing 50mm * 150mm respectively from the length direction and the width of resin-covered metal sheet, after 23 ℃ keep more than 1 hour, carry out 180 degree crooked (inner bend radius is 2mm) with Apparatus for Bending at low-temp, to this sample, falling diameter from the height of 50cm is that 75mm, quality are the cylindrical hammer of 5kg.
Table 1
| Resin forms 1 | Cooperation ratio (wt%) | Resin forms 2 | Cooperation ratio (wt%) | Laminating temperature (℃) | Cooling method behind the lamination | ||
| Embodiment | ??1 | ????PBT | ????30 | ??PETG | ????70 | ????245 | Air cooling |
| ??2 | ????PBT | ????40 | ??PETG | ????60 | ????225 | Water-cooled | |
| ??3 | ????PBT | ????40 | ??PETG | ????60 | ????245 | Water-cooled | |
| ??4 | ????PBT | ????40 | ??PETG | ????60 | ????245 | Water-cooled | |
| ??5 | ????PBT | ????50 | ??PETG | ????50 | ????245 | Water-cooled | |
| ??6 | ????PBT | ????60 | ??PETG | ????40 | ????245 | Water-cooled | |
| ??7 | ????PBT | ????40 | ??PETG | ????60 | ????245 | Water-cooled | |
| ??8 | ????PTT | ????40 | ??PETG | ????60 | ????245 | Water-cooled | |
| ??9 | ????PTT | ????50 | ??PETG | ????50 | ????245 | Water-cooled | |
| Comparative example | ??1 | ????PBT | ????0 | ??PETG | ????100 | ????245 | Water-cooled |
| ??2 | ????PBT | ????10 | ??PETG | ????90 | ????245 | Water-cooled | |
| ??3 | ????PBT | ????20 | ??PETG | ????80 | ????245 | Water-cooled | |
| ??4 | ????PBT | ????30 | ??PETG | ????70 | ????245 | Water-cooled | |
| ??5 | ????PBT | ????40 | ??PETG | ????60 | ????260 | Water-cooled | |
| ??6 | ????PBT | ????70 | ??PETG | ????30 | ????245 | Water-cooled | |
| ??7 | ????PBT | ????100 | ??PETG | ????0 | ????245 | Water-cooled | |
| ??8 | ????co-PET | ????30 | ??PETG | ????70 | ????245 | Water-cooled | |
| ??9 | ????co-PET | ????50 | ??PETG | ????50 | ????245 | Water-cooled | |
| ??10 | ????co-PET | ????50 | ??PETG | ????50 | ????245 | Air cooling | |
Table 2
| Fusing point (℃) | Before the lamination | Behind the lamination | |||
| ????ΔH-ΔHc | ????ΔHm | ????ΔHm-ΔHm | |||
| Embodiment | ??1 | ????224 | ????1.7 | ????14.6 | ????10.1 |
| ??2 | ????224 | ????4.3 | ????25.6 | ????12.1 | |
| ??3 | ????224 | ????4.3 | ????25.6 | ????11.4 | |
| ??4 | ????224 | ????4.3 | ????28.1 | ????24.2 | |
| ??5 | ????224 | ????6.8 | ????29.3 | ????23.6 | |
| ??6 | ????224 | ????26.8 | ????33.5 | ????30.7 | |
| ??7 | ????224 | ????9.4 | ????27.7 | ????16.4 | |
| ??8 | ????225 | ????5.3 | ????27.3 | ????10.2 | |
| ??9 | ????225 | ????5.5 | ????32.8 | ????18.6 | |
| Comparative example | ??1 | ????- | ????- | ????- | ????- |
| ??2 | ????224 | ????0 | ????3.2 | ????0 | |
| ??3 | ????224 | ????0 | ????10.5 | ????0 | |
| ??4 | ????224 | ????1.7 | ????14.1 | ????3.8 | |
| ??5 | ????224 | ????4.3 | ????25.1 | ????13.5 | |
| ??6 | ????224 | ????34.6 | ????37.5 | ????35.2 | |
| ??7 | ????224 | ????45.9 | ????45.6 | ????45.6 | |
| ??8 | ????247 | ????1.7 | ????10.9 | ????0 | |
| ??9 | ????247 | ????5.7 | ????22.7 | ????3.1 | |
| ??10 | ????247 | ????5.7 | ????23.3 | ????10.6 | |
Table 3
| High specularity | Boiling water resistance | Processability | Remarks | ||
| Embodiment | ??1 | ??○ | ????○ | ??○ | |
| ??2 | ??△ | ????○ | ??○ | ||
| ??3 | ??○ | ????○ | ??○ | ||
| ??4 | ??○ | ????○ | ??○ | ||
| ??5 | ??○ | ????○ | ??○ | ||
| ??6 | ??○ | ????○ | ??○ | ||
| ??7 | ??○ | ????○ | ??○ | ||
| ??8 | ??○ | ????○ | ??○ | ||
| ??9 | ??○ | ????○ | ??○ | ||
| Comparative example | ??1 | ??○ | ????× | ??○ | |
| ??2 | ??○ | ????× | ??○ | ||
| ??3 | ??○ | ????× | ??○ | ||
| ??4 | ??○ | ????△ | ??○ | ||
| ??5 | ??○ | ????○ | ??○ | ???* | |
| ??6 | ??× | ????○ | ??○ | ||
| ??7 | ??× | ????○ | ??○ | ||
| ??8 | ??○ | ????× | ??○ | ||
| ??9 | ??○ | ????× | ??○ | ||
| ??10 | ??○ | ????△ | ??× | ||
*: the variable color of printed layers CB coating
Can obviously find out from table 3,, can obtain high specularity, boiling water resistance and 3 all good evaluation results of processability at the resin-covered metal sheet 11 of the embodiment of the scope of the invention 1～embodiment 9.
On the other hand, only use Comparative Examples 1 He of amorphism polyester as the resin composition of substrate resin layer 14, high Comparative Examples 2 and the Comparative Examples 3 of resin composition amorphism polyester ratio as substrate resin layer 14, though can obtain good evaluation result aspect high specularity and the processability, its boiling water resistance is inferior.
Also have, Comparative Examples 4, compare with embodiment 1 behind lamination cooling condition different, other condition all together, but both all can not satisfy necessary condition of the present invention for the Δ Hm behind lamination and (Δ Hm-Δ Hc), though high specularity and processability aspect can obtain good evaluation result, its boiling water resistance is inferior.
Comparative Examples 5, use the 4 same substrate resin layers of forming 14 with embodiment 2～embodiment, owing under than the higher temperature of the laminating temperature of in the past soft PVC resinoid thin slice, carried out lamination, so its specularity, boiling water resistance and processability are good, but the thermal discoloration of printing-ink (particularly pink group printing ink) is obvious, simultaneously, the application at metallic plate 12 back sides also produces thermo-color.
Only used the Comparative Examples 7 of the equal PET of crystallinity polyester as the resin composition of substrate resin layer 14, the value of (Δ Hm-Δ Hc) before the lamination is bigger than necessary condition of the present invention, near the laminating temperature of in the past soft PVC resinoid thin slice, and the temperature below this melting point resin (Tm)+30 ℃ can not obtain high specularity.
In the Comparative Examples 6, as the resin composition of substrate resin layer 14, use with the same crystalline resin of Comparative Examples 7 and with the amorphism polyester and carry out fusion and form the resin composition, but, the value of (Δ Hm-Δ Hc) is bigger than necessary condition of the present invention before the lamination, still can not obtain high specularity.
In Comparative Examples 8 and the Comparative Examples 9, used copolymerization PET rather than all PBT or all PTT as the resin composition of substrate resin layer 14, laminating temperature though can obtain high specularity, can not satisfy the boiling water resistance requirement below melting point resin simultaneously.Promptly, the hot Δ Hm of crystallization heat Δ Hc and watery fusion, even satisfy at least one relational expression among 15＜Δ Hm and 5＜(the Δ Hm-Δ Hc), as the crystallinity polyester resin composition that constitutes substrate resin layer 14, do not contain under fast PBT resinoid of crystalline rate or the resinoid situation of PTT, be difficult to improve boiling water resistance.In Comparative Examples 10, except the cooling method behind the lamination from water-cooled changes air cooling this point difference into, with the same condition of Comparative Examples 9 under make and obtain resin-covered metal sheet 11, cooling method promotes crystallization by adopting stably, boiling water resistance has been compared with Comparative Examples 9 slightly and has been improved, but processability worsens.
This embodiment has following effect.
(1) resin-covered metal sheet 11, and is stacked with the substrate resin layer 14 of polyester resin as Main Ingredients and Appearance by bond layer 13 on the single face of metallic plate 12, and stacked thereon printed layers 15, then stacked thereon clear stretch polyester resin layer 16.Constitute under the laminated shim state of polyester resin before being laminated to metallic plate 12 of substrate resin layer 14, based on the intensification of the mensuration of differential scanning calorimetry the time, be observed clear and definite crystallization peak temperature (Tc) and watery fusion peak temperature (Tm).When crystallization heat was (J/g) Δ Hm (J/g) as Δ Hc, watery fusion hotwork, set up (Δ Hm-Δ Hc)＜30.
Therefore, the crystallinity of substrate resin layer 14 is restricted, and shows watery fusion peak temperature (Tm), but in fact, from carrying out lamination even lower temperature just begins to have meltbility being lower than under Tm+30 ℃ metallic plate 12 surface temperatures, also can obtain high specular reflective than (Tm).Simultaneously, can under the laminating temperature of soft PVC based resin film in the past, obtain high specularity, can effectively utilize existing equipment and make.And printing-ink, bonding agent etc. also can be used the material that polyvinyl chloride resin is used, and can reduce product cost.
(2) the substrate resin layer 14, contain the PBT resinoid and on metallic plate 12, satisfy the occasion of a relational expression among 15＜Δ Hm and 5＜(the Δ Hm-Δ Hc) under the state behind the lamination at least as crystallinity polyester resin composition, not only specular reflective is good, and processability and boiling water resistance are also good.Therefore, can be suitable as the bathtub unit etc. in bathroom.
(3) the substrate resin layer 14, contain the PTT resinoid and on metallic plate 12, satisfy the occasion of a relational expression among 15＜Δ Hm and 5＜(the Δ Hm-Δ Hc) under the state behind the lamination at least as crystallinity polyester resin composition, not only specular reflective is good, and processability and boiling water resistance are also good.Therefore, can be fit to bathtub unit of acting as in the bathroom etc.
(4) owing on substrate resin layer 14, carry out the lamination of clear stretch polyester resin layer 16, can give easily the degree of depth design, improved surface rerum natura, prevent that the pigment that adds in the polyester resin etc. from attaching the ejection of agent etc.
(5) clear stretch polyester resin layer 16 is to form with biaxial stretch-formed PET resin film.Therefore, can guarantee the transparency, the anti-wound property of flatness and surface etc. easily.Simultaneously, also carry out so-called shop fixtures printing easily, form printed layers.
(6) owing to have bond layer 17 between substrate resin layer 14 and printed layers 15, the cementability that substrate resin layer 14 and printed layers are 15 is good.
(7) since substrate resin layer 14 constitute by the pigmented polyester resinoid, so can realize giving and the color emissivity improvement of printed layers 15 etc. to the covering of underlying metal plate 12, designability.
(8) with laminated integratedization thin slice S with the face of substrate resin layer 14 side as bonding plane, by bond layer 13 when metallic plate 12 carries out lamination, the surface temperature Ts of metallic plate 12 (℃) and constitute the polyester resin of substrate resin layer 14 watery fusion peak temperature Tm (℃) between, (Tm+30)＞relation of Ts sets up.Therefore, when can utilize in the past laminating apparatus easily to make resin-covered metal sheet 11, thermo-color, the heat that can suppress printed layers 15 and metallic plate back coating are faded.
(9) constitute the polyester resin that not only has the also good substrate resin layer 14 of good specular reflective but also processability and boiling water resistance, comprise PBT resinoid or PTT resinoid as the crystalline polyester resin composition.Therefore, can obtain easily in order to obtain good and processability of specular reflective and the also good resin-covered metal sheet 11 of boiling water resistance and satisfy the polyester resin of necessary condition.
(10) because the thickness of laminated integratedization film S is 50～500 μ m, so can suppress deterioration as the secondary workabilities such as perforation processing of the performance degradation of the protective layer of metallic plate 12 and resin-covered metal sheet 11.Simultaneously, the printed patterns of printed layers 15 is not subject to the color influence of underlying metal plate 12 yet.
(11) owing to the polyester resin that constitutes substrate resin layer 14 is, crystallinity polyester resin and amorphism polyester resin carry out that fusion forms, so obtain the polyester resin that watery fusion peak temperature Tm, crystallization heat Δ Hc, the hot Δ Hm of watery fusion etc. satisfy necessary condition easily.
The surface temperature Ts of the metallic plate 12 when (12) laminated integratedization thin slice S being carried out lamination on metallic plate 12 (℃), be set in watery fusion peak temperature Tm than the polyester resin that constitutes substrate resin layer 14 (℃) high temperature.Therefore, produce the good resin-covered metal sheet of boiling water resistance and processability 11 easily.
Embodiment is not limited only to described content, for example, also can specialize as described below.
Zero constitutes the polyester resin of substrate resin layer 14, be not limited only to crystallinity polyester resin and amorphism polyester resin and carry out fusion and form, also can use the ratio of adjusting each multiple glycol composition and dicarboxylic acids composition and the polyester resin that makes it to satisfy described necessary condition.
Zero substrate resin layer 14 may not be colored, and also can use uncoloured.
Zero clear stretch polyester resin layer 16 can confirm that from clear stretch polyester resin layer 16 sidelong glance survey printed layers 15 is just passable in resin-covered metal sheet 11, also can be translucent.
The invention that from described embodiment, fully understands (technological thought), following record:
(1) in the described invention of claim 4, described printed layers forms by carry out shop fixtures printing (back print) on described biaxial stretch-formed polyethylene terephthalate resin film.
(2) in any described invention in claim 1～claim 6 and the described technological thought, the polyester resin that constitutes described substrate resin layer is, undertaken by crystallinity polyester resin and amorphism polyester resin that fusion forms.
(3) in any described invention of claim 1～6, the thickness of described laminated integratedization thin slice is 50～500 μ m.
(4) in the described invention of claim 7, with the surface temperature Ts of the metallic plate 12 of laminated integratedization thin slice S when metallic plate carries out lamination (℃) be set at watery fusion peak temperature Tm than the polyester resin that constitutes the substrate resin layer (℃) higher temperature.
The effect of invention
According to the described invention of the claim 1～6 of above detailed description, do not use the soft PVC resinoid and can utilize laminating apparatus in the past to produce the resin-covered metal sheet with good specular reflective. Simultaneously, reach according to claim 2 invention claimed in claim 3, not only specular reflective is good, and processability and boiling water resistance are also good. Also have, invention according to claim 7 can utilize laminating apparatus in the past easily to make described resin-covered metal sheet.
Claims (7)
1, a kind of resin-covered metal sheet, substrate resin layer, printed layers, the clear stretch polyester resin layer that will be Main Ingredients and Appearance with the polyester resin stack gradually the integrated laminated shim that forms, on metallic plate carrying out lamination as bonding plane by bond layer with the face of described substrate resin layer side forms, it is characterized in that: constitute the polyester resin of described substrate resin layer, satisfy following necessary condition:
Under the laminated integratedization thin slice state on metallic plate before the lamination, during based on the intensification of the mensuration of differential scanning calorimetry (DSC), can observe clear and definite crystallization peak temperature (Tc) and watery fusion peak temperature (Tm), when crystallization heat was Δ Hm (J/g) as Δ Hc (J/g), watery fusion hotwork, set up (Δ Hm-Δ Hc)＜30.
2, resin-covered metal sheet according to claim 1 is characterized in that:
Described substrate resin layer, contain the polybutylene terephthalate resinoid as crystallinity polyester resin composition, and under the state after carrying out lamination on the metallic plate, the hot Δ Hm of described crystallization heat Δ Hc and described watery fusion satisfies at least one relational expression among 15＜Δ Hm and 5＜(the Δ Hm-Δ Hc).
3, resin-covered metal sheet according to claim 1 is characterized in that:
Described substrate resin layer, contain the polytrimethylene-terephthalate as crystallinity polyester resin composition, and under the state after carrying out lamination on the metallic plate, the hot Δ Hm of described crystallization heat Δ Hc and described watery fusion satisfies at least one relational expression among 15＜Δ Hm and 5＜(the Δ Hm-Δ Hc).
4, according to any described resin-covered metal sheet in claim 1～claim 3, it is characterized in that: described clear stretch polyester resin layer is formed by biaxial stretch-formed polyethylene terephthalate resin film.
5, according to any described resin-covered metal sheet in claim 1～claim 4, it is characterized in that: between described substrate resin layer and described printed layers, have bond layer.
6, according to any described resin-covered metal sheet in claim 1～claim 5, it is characterized in that: described substrate resin layer is made of the pigmented polyester resinoid.
7, manufacture method according to any described resin-covered metal sheet in claim 1～claim 6, it is characterized in that: will be the substrate resin layer of Main Ingredients and Appearance with the polyester resin, printed layers, clear stretch polyester resin layer stacks gradually the integrated laminated shim that forms, when on metallic plate, carrying out lamination by bond layer as bonding plane with the face of described substrate resin layer side, described metal sheet surface temperature T s (℃) and constitute the polyester resin of described substrate resin layer watery fusion peak temperature Tm (℃) between set up under the state of (Tm+30)＞Ts relation and carry out lamination.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002037720 | 2002-02-15 | ||
| JP37720/2002 | 2002-02-15 |
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| Publication Number | Publication Date |
|---|---|
| CN1551826A true CN1551826A (en) | 2004-12-01 |
| CN100382954C CN100382954C (en) | 2008-04-23 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB038009862A Expired - Fee Related CN100382954C (en) | 2002-02-15 | 2003-02-06 | Resin-coated metal plate and method for production thereof |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP4194950B2 (en) |
| KR (1) | KR100969445B1 (en) |
| CN (1) | CN100382954C (en) |
| TW (1) | TW200303261A (en) |
| WO (1) | WO2003068498A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101180179B (en) * | 2005-05-25 | 2011-08-03 | 三菱树脂株式会社 | Laminate for name plate preparation which can prevent fluctuation in reflected light |
| CN107822295A (en) * | 2017-06-26 | 2018-03-23 | 东莞市晶鑫真空科技有限公司 | A kind of antistatic health-care comb |
| CN109312167A (en) * | 2016-06-15 | 2019-02-05 | 住友化学株式会社 | Resin combination and its application |
| CN111164781A (en) * | 2017-10-11 | 2020-05-15 | 大日本印刷株式会社 | Polybutylene terephthalate film, battery packaging material, method for producing battery packaging material, and battery |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4631583B2 (en) * | 2005-07-29 | 2011-02-16 | 東レ株式会社 | Laminated polyester film for lamination and polyester resin laminated metal sheet |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0576682B1 (en) * | 1992-01-16 | 1998-09-02 | Teijin Limited | Polyester film for metal sheet lamination and use thereof |
| JP3366205B2 (en) * | 1997-01-06 | 2003-01-14 | ユニチカ株式会社 | Polyester film for lamination of metal plate for can body and method for producing laminated metal plate for can body using the film |
| JP2000246832A (en) * | 1999-02-26 | 2000-09-12 | Toyo Kohan Co Ltd | Printed resin film to be laminated to highly sharp decorative panel, and highly sharp decorative panel whereto the resin film is laminated |
| CN1205030C (en) * | 2000-05-30 | 2005-06-08 | 尤尼吉可株式会社 | Polyester film for metal sheet laminating, metal sheet laminated with this film, and metal vessel formed from this metal sheet |
-
2003
- 2003-02-06 JP JP2003567655A patent/JP4194950B2/en not_active Expired - Fee Related
- 2003-02-06 CN CNB038009862A patent/CN100382954C/en not_active Expired - Fee Related
- 2003-02-06 KR KR1020047012283A patent/KR100969445B1/en not_active IP Right Cessation
- 2003-02-06 WO PCT/JP2003/001278 patent/WO2003068498A1/en active Application Filing
- 2003-02-14 TW TW092103116A patent/TW200303261A/en not_active IP Right Cessation
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101180179B (en) * | 2005-05-25 | 2011-08-03 | 三菱树脂株式会社 | Laminate for name plate preparation which can prevent fluctuation in reflected light |
| CN109312167A (en) * | 2016-06-15 | 2019-02-05 | 住友化学株式会社 | Resin combination and its application |
| US10920034B2 (en) | 2016-06-15 | 2021-02-16 | Sumitomo Chemical Company, Limited | Resin composition and use thereof |
| CN107822295A (en) * | 2017-06-26 | 2018-03-23 | 东莞市晶鑫真空科技有限公司 | A kind of antistatic health-care comb |
| CN107822295B (en) * | 2017-06-26 | 2020-08-28 | 东莞市晶鑫真空科技有限公司 | Anti-static health-care comb |
| CN111164781A (en) * | 2017-10-11 | 2020-05-15 | 大日本印刷株式会社 | Polybutylene terephthalate film, battery packaging material, method for producing battery packaging material, and battery |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2003068498A1 (en) | 2003-08-21 |
| JP4194950B2 (en) | 2008-12-10 |
| CN100382954C (en) | 2008-04-23 |
| TWI305515B (en) | 2009-01-21 |
| TW200303261A (en) | 2003-09-01 |
| KR20040081192A (en) | 2004-09-20 |
| KR100969445B1 (en) | 2010-07-14 |
| JPWO2003068498A1 (en) | 2005-06-02 |
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