CN1742184A - Metallic decorative sheet with sublimation-transferred pattern, heat-insulating panel and outer wall for refrigerator both employing the same, and processes for producing these - Google Patents
Metallic decorative sheet with sublimation-transferred pattern, heat-insulating panel and outer wall for refrigerator both employing the same, and processes for producing these Download PDFInfo
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- CN1742184A CN1742184A CN 200380103254 CN200380103254A CN1742184A CN 1742184 A CN1742184 A CN 1742184A CN 200380103254 CN200380103254 CN 200380103254 CN 200380103254 A CN200380103254 A CN 200380103254A CN 1742184 A CN1742184 A CN 1742184A
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- metal lagging
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
- F25D2400/00—General features of, or devices for refrigerators, cold rooms, ice-boxes, or for cooling or freezing apparatus not covered by any other subclass
- F25D2400/18—Aesthetic features
Abstract
A metallic decorative sheet bearing a sublimation-transferred pattern which comprises a metal sheet and a skin resin layer formed on a surface of the sheet through a skin adhesive layer. The skin resin layer comprises a light-transmitting resin. The glass transition temperature thereof is not lower than the temperatures at which a sublimable colorant sublimates again to blur the pattern and is lower than the temperatures at which the sublimable colorant is transferred. A colored pattern has been formed in at least either of the skin adhesive layer and the skin resin layer by infiltrating the sublimable colorant thereinto. When this metallic decorative sheet is used to produce a heat-insulating panel, the sublimable colorant does not sublimate again upon heating during resin foaming and hence the pattern does not blur.
Description
Technical field
The present invention relates to be suitable for the metal lagging of the band sublimation transfer pattern of the integrally formed thermal insulation board outside plate of foamed heat-insulating material, use its thermal insulation board, use the refrigerator outer wall of this thermal insulation board.The manufacture method that also relates to them.
Background technology
In recent years, enter the so-called individual character epoch, personal value is seen variation, and particularly to oneself liking the style of commodity, demand is very widely, and it also is high especially requiring.In addition, for can modify at an easy rate when making household electrical appliance such as refrigerators a large amount of, used can carry out back processing make the coated steel plate of one and laminated metallic plate with surface-treated layer and steel plate.In the operation of making this coated steel plate or laminated metallic plate, in case determined the style of surface-treated layer, just be difficult to change pattern continually, can only produce same pattern in a large number usually.Therefore,,, defer delivery the phase, generally can not carry out owing to can reduce production efficiency for diversified situation of wishing various patterns.
But,, make on laminated metallic plate or coated steel plate directly method of printing practicability recently because the subliming type colouring agent carries out the prosperity of Sublimation Transfer Printing Technology.Such as opening 2001-329 the spy, in No. 474 communiques, narrated and utilized vacuum attraction to make to be printed thing and transfer printing sheet to be in the state of being adjacent to carry out hot transfer printing, stamp the distinct method of patterning that does not have the color and luster inequality on the thing being printed.In the method, the coloured composition that contains the subliming type colouring agent with coatings such as ink-jet printers forms the transfer printing type printed sheet, it is overlapped be printed on the thing, puts between hot press and the sheet rubber.By the gap between hot press and the sheet rubber being vacuumized, make the transfer printing type printed sheet and be printed thing to be adjacent to then with vavuum pump.The heat energy that applies by hot press again is transferred to subliming type colouring agent heat from printed sheet most preferably and is printed on the thing.
In the method,, also can form the printed article that does not have the color and luster inequality being printed pressurization equably on the whole surface of thing even using large stretch of coated steel plate as being printed under the situation of thing.
When on metallic plates such as steel plate, printing, be necessary on the top layer, to form in advance the transparent or semitransparent resin coating film of dyeability excellence with such method.
The steel plate that utilizes such as patent the 2nd, 957, is narrated in No. 864 communiques to some extent.This steel plate is a metal lagging, has the semi-transparent resin layer on the plain color basic material of metallic plate.On this semi-transparent resin layer, have stacked multi-layer transparent resin bed, add the subliming type colouring agent, form colored pattern in the inside of each layer.
On this metal lagging, sticking in advance on the laminated metallic plate of hyaline membrane by direct sublimation transfer formation pattern.For this reason, under the situation of the patterned metal lagging of a small amount of manufacturing, shortened the time.Can on pattern plane, have the texture or the degree of depth, even see that closely the roughness of pattern is also not too noticeable by multiple-layer laminated processing.Can on all faces of metal lagging, colored pattern be set.
But, on the laminate that multilayer forms, generally when using vinyl chloride film or polyethylene film or polyester film,, the track of colored pattern is thickened owing to be multilayer.And this has just seriously reduced hear resistance or weatherability.Particularly when being heated to more than 50 ℃, cause the resublimed phenomenon of subliming type colouring agent in multiple-layer laminated layer, the pattern of initial stage processing is along with being easy to destruction time lapse.
Under the situation about in the thermal insulation board that refrigerator doors etc. is made of the polyurethane integral foaming, using, when polyurethane foam, be heated, in the middle of operation, the color and luster inequality can take place.And when reality is used, when on refrigerator doors, sticking note and using paper, also can produce the color and luster skew.
As the sublimation transfer band pattern metal lagging that has excellent weather resistance, opening narration to some extent in the 2002-59078 communique such as the spy.According to this communique, film the band pattern metal lagging that obtains having excellent weather resistance by on the specific thermosetting polyester resin of molecular weight, vitrifying transition temperature (Tg), content of melamine, forming.
In other words, this metal lagging is that mean molecule quantity is 1000～10000, Tg is 20～60 ℃, and with respect to the solid resin content of 100 mass parts, the ratio of melamine is that the thermosetting polyester resin of 20～150 mass parts is the clear dope formation of main component.This metal lagging, by soaking into the subliming type colouring agent, directly or by priming coat, precoated shet etc., form on the underlying metal plate band colored pattern on film.
So, if the specific thermosetting polyester resin of molecular weight and vitrifying transition temperature is as the clear dope of main component, then the weatherability of laminated metallic plate and again sublimability just can improve.
In other words, any sublimation transfer pattern print process in laminated metallic plate and the coated steel plate by soak into the pattern of describing with the subliming type colouring agent in the clear dope of crust, also can freely demonstrate pattern.Thus, on coated steel plate or pre-coated steel plate, can freely form style in the operation afterwards, just can corresponding diversified demand.
But, in the metal lagging of above-mentioned existing band sublimation transfer pattern, aspect long-term reliability not enough.Even on the coated steel plate of having covered with paint, lacquer, colour wash, etc. thermosetting polyester resin, carry out the band pattern metal lagging of sublimation transfer, also do not solve the problem of transfer printing more fully.Owing to using thermosetting resin, make the situation that is coated with film rupture in the time of in the processing of back, can occurring in compression or bending.
Particularly, have under the situation about using on the refrigerator doors of thermal insulation,, resublimed phenomenon can take place, making that the sublimation transfer dim pattern is unclear owing to when making integral polyurethane foaming heat insulation plate, will stand the temperature more than 60 ℃.And be used under the situation of refrigerator doors, when sticking message paper with magnetic, can colouring agent take place owing to distilling again and move.
Therefore, exposing to the open air in the commodity of use in indoor and outdoor for a long time, on processing steel plate up to now, also be difficult to keep stable color and pattern.
Summary of the invention
The metal lagging that has the sublimation transfer pattern of the present invention is provided with the crust resin bed across the crust adhesive linkage on the metallic plate face.The crust resin bed is made of translucent resin, and its vitrifying transition temperature is higher than the distillation colouring agent and distils and make the temperature of dim pattern, is lower than the temperature that makes the transfer printing of distillation colouring agent.And on any at least one deck in crust adhesive linkage and crust resin bed, soak into the subliming type colouring agent and form colored pattern.Above-mentioned metal lagging is suitable for as the thermal insulation board that uses resin foamed material, and this thermal insulation board is suitable for using on the outer wall of refrigerator.Manufacture method according to metal lagging of the present invention comprises: A) will stick the laminated metallic plate of above-mentioned crust resin bed by above-mentioned crust adhesive linkage on first, overlapping with transfer printing type printed sheet with the face of being granted colored pattern by the subliming type colouring agent, so that the step that the crust resin bed contacts with the colored pattern face; B), make the temperature of crust resin bed be higher than the step of vitrifying transition temperature with the heating of overlapping crust resin bed and colored pattern face and compress.At least the subliming type colouring agent is soaked in the inside of one deck in such crust resin bed and crust adhesive linkage.In thermal insulation board, use under the situation of above-mentioned metal lagging, in the crust resin bed, used its vitrifying transition temperature to be higher than the material that in the expanded material foamed process, reaches temperature.
Description of drawings
Fig. 1 is the sectional view of metal lagging of the band sublimation transfer pattern of embodiment of the present invention 1;
Fig. 2 is the sectional view of the laminated metallic plate that uses in the metal lagging of Fig. 1;
Fig. 3 is illustrated in the embodiments of the present invention 1, in the sublimation transfer operation with the sectional view of laminated metallic plate and transfer printing type printed sheet overlap condition;
Fig. 4 is the process chart of the manufacture method of the metal lagging of expression embodiment of the present invention 1 and the thermal insulation board that uses it;
Fig. 5 is in the sublimation transfer device that uses when being illustrated in the metal lagging of making embodiments of the present invention 1, with the sectional view of transfer printing type printed sheet and laminated metallic plate stationary state;
Fig. 6 is the lowering or hoisting gear action that expression makes the sublimation transfer device among Fig. 5, makes drive chamber be pressed in the sectional view of the following surface state of chamber;
Fig. 7 is the vavuum pump work that expression makes the sublimation transfer device among Fig. 5, makes the sectional view of transfer printing type printed sheet and laminated metallic plate impaction state by decompression;
Fig. 8 is that expression will have been carried out the metal lagging and the combination of interior face component of bending machining in the embodiment of the present invention 1, constitutes the assembling stereogram of the state of thermal insulation board;
Fig. 9 is the sectional view of the polyurethane foam operation of the thermal insulation board in the expression embodiment of the present invention 1;
Figure 10 is in the sublimation transfer operation that is illustrated in the embodiment of the present invention 2, makes laminated metallic plate and the overlapping state sectional view of transfer printing type printed sheet by holding components;
Figure 11 is in the sublimation transfer operation that is illustrated in the embodiment of the present invention 3, makes the sectional view of the overlapping state of laminated metallic plate and transfer printing type printed sheet;
Figure 12 is the rough cross-sectional view of the later heat treatment step of the sublimation transfer in the expression embodiment of the present invention 4;
Figure 13 is the rough cross-sectional view of the later heat treatment step of the sublimation transfer in the expression embodiment of the present invention 5.
The specific embodiment
The metal lagging that has a sublimation transfer pattern of the present invention is described with reference to the accompanying drawings, uses the thermal insulation board of this decorative panel and the embodiment of the refrigerator doors that constitutes of thermal insulation board thus.In each embodiment, the structure identical with previous embodiment given same symbol, and its detailed description is omitted.
(embodiment 1)
Fig. 1 is the sectional view according to the metal lagging that has the sublimation transfer pattern of embodiment of the present invention 1; Fig. 2 is the sectional view of the laminated metallic plate that uses in this metal lagging; Fig. 3 is the sectional view that is illustrated in the sublimation transfer operation laminated metallic plate and transfer printing type printed sheet overlap condition.In the metal lagging that has the sublimation transfer pattern of present embodiment (below be called decorative panel) 1, the colored pattern on the transfer printing type printed sheet (below be called sheet) 2 (below be called pattern) 15A by sublimation transfer to laminated metallic plate (below be called plate) 3.
On metallic plate 8, on the two sides of the metal base material that constitutes by steel plate (below, be called basic material) 4, form composite plating zinc coat 5,5A.At coating 5 with above the 5A, form chemical treatment layer 6 by phosphoric acid, 6A forms the antirusting paint layer 7 that obtains with epoxy resin on chemical treatment layer 6A.On first chemical treatment layer 6, by second adhesive layer, 9 laminated opaque second resin beds 10 of film shape that constitute by vinyl chloride resin of going up.
On second resin bed 10, by first adhesive layer 11 and ink lay 12 laminated last first resin beds 13.First adhesive layer 11 is that film constitutes by the hot melt of the saturated copolymer polyester resin of 114 ℃ of fusing points.First resin bed 13 is made of the transparent or semitransparent film as the PETG of the mylar of the degree of crystallinity 35% of 74 ℃ of vitrifying transition temperatures.First resin bed 13 has light transmission in other words.
In the present embodiment, on the two sides of metallic plate 8, be provided with electrodeposited coating 5 and 5A, chemical treatment layer 6 and 6A are set in the above again, antirusting paint layer 7 is set second side.This is in order to improve the rustless property of decorative panel 1, but and nonessential.
The following describes according to the manufacture method of the decorative panel 1 of present embodiment and thus decorative panel 1 make the method for metal finishing thermal insulation board (below be called thermal insulation board) 20.
Fig. 4 is the process chart that is used for illustrating the manufacture method of the decorative panel 1 of present embodiment and thermal insulation board 20.Fig. 5 represents in the present embodiment, sheet 2 and plate 3 is fixed on the sectional view of the state on the sublimation transfer device 17.Fig. 6 is illustrated in the same sublimation transfer device 17, is realized the sectional view of impaction state by press.Fig. 7 is the sectional view that is illustrated in decompression state in the same sublimation transfer device 17.Fig. 8 is illustrated in the metal lagging 1 of bending machining and the stereogram that 18 combinations of interior face component are in chimerism.Fig. 9 is the sectional view of the thermal insulation board 20 in polyurethane mould 19.
At first, in the antirust treatment process (operation A) of basic material 4, the chemical treatment layer 6 and the 6A that on the two sides, form the electrodeposited coating 5 of compound zinc-plated formation and 5A and form by phosphoric acid.In middle thermoplastic resin bonding process (process B), stick second resin bed 10 of opaque Corvic on first of metallic plate 8 then, it posts second adhesive layer 9 that is made of acrylic pressure-sensitive adhesive.
In crust resin bed bonding process (operation C), on second resin bed 10, stick first resin bed 13 with first adhesive layer 11 with ink lay 12, produce plate 3 as shown in Figure 2.This ink lay 12 is realized metallicity in advance.First adhesive layer 11 is that film constitutes by the saturated copolymer polyester resin hot melt of 114 ℃ of fusing points.First resin bed 13 is by 74 ℃ of vitrifying transition temperatures, and the mylar of degree of crystallinity 35% is that the transparent membrane of PETG constitutes.
In addition, in the pattern printing process (step D) of Fig. 4, use ink-jet printer,, produce printed sheet 2 by colouring agent 14 printing original edition plate pattern 15A on transfer paper 21.
As at Fig. 5～shown in Figure 7, in the hectographic printing device 17 when making decorative panel 1, be fixed with lowering or hoisting gear 23 on the basal disc 22 and by four sides directing pin 24 on chamber 25.In last chamber 25, be provided with the pressure-reducing chamber 27 of built-in heater 26 as heating source.To reduce pressure in the pressure-reducing chamber 27 by relief pipe 29 and decompression valve 30 by vavuum pump 28.
Connecting on lowering or hoisting gear 23 can be along the drive chamber 31 of directing pin 24 free liftings.In drive chamber 31, fixing extraction transfer groove 32.The clamping piece 33 that polytetrafluoroethylene (PTFE) or silicon rubber are made on whole inner covering of transfer groove 32.Periphery configuration polytetrafluoroethylene (PTFE) rubber or silicon rubber pad (packing) 34 in transfer groove 32.
Transfer groove 32 is drawn forward by bearing 36 along guiding it out of rail 35.Under the state that transfer groove 32 is drawn, on the clamping piece 33 in transfer groove 32 successively heat-resistant sheet below the fixed ventilation (below be called sheet) 37, sheet 2, plate 3 and above heat-resistant sheet (below be called sheet) 38.
On pressure-reducing chamber 27, be provided with and connecting vent 39 that leads to transfer groove 32 and the relief valve 40 that is communicated with outside atmosphere.
At this, on clamping piece 33, can use silicon rubber, fluorubber, butyl rubber, in chlorobutadiene, add sulphur or 2, the soft elastomers such as rubber of 3-dichloro 1,3-butadiene copolymerization.Owing to will under the temperature more than 150 ℃, carry out hot transfer printing discontinuously repeatedly, the silicon rubber or the fluorubber of preferred especially excellent heat resistance.
And using hectographic printing device 17, carrying out on the plate 3 under the situation of hectographic printing with the subliming type dyestuff, owing to plate 3 does not have gas permeability, can not remove and sheet 2 between air.And just remain between sheet 2 and the plate 3 easily from the steam of contained humidity in the sheet 2.Residual air and residual moisture become the reason that produces density unevenness on the pattern of giving on the plate 3 15.Therefore with sheet 37 with plate 3 in sheet 38 clampings and sheet 2 has just improved the state of closely bonding.
As sheet 37 and 38, can use cotton, mylar, the heat-resistant felt of aromatic polyamide fibre manufacturing, the silicone sponge pad or the fluorubber foam-rubber cushion of connection.For sheet 37,38, preferably has hear resistance and the easy material of restoring of shape after hot pressing is tight.
In the present embodiment, as by the sublimation transfer product, use the steel plate with prime treatment, but be not limited to steel plate, using stainless steel or aluminium sheet also is possible as basic material 4.
As first resin bed 13 of light transmission, be mylar, it is characterized in that pet resin is the easiest selected good grade.First resin bed 13 is being so long as by moving colouring agent 14 and passing through easily when carrying out sublimation transfer from sheet 2, and constitutes just passable at normal temperature or the resin that is not easy to pass through below 70 ℃.In other words, so long as the vitrifying transition temperature is between 70～120 ℃, perhaps the resin of crystallization degree between 20～50% just can.
For first resin bed 13, preferably significantly not softening under 150～200 ℃ of the heating-up temperatures when transfer printing.As the PETG monomer of mylar, its fusing point does not then become big problem about 250 ℃.And when using the melt blending resin of PEN, hear resistance and vitrifying transition temperature are just higher.When forming first resin bed 13 with such material, when hot transfer printing, give printed patterns after, just suppressed plate 3 lustrous surfaces and reduced.
As sheet 2, use sheet material by printing coating colouring agents 14 such as intaglio printing, hectographic printing, serigraphys.Use need not the xerography, electrostatic recording, ink-jet printing process, thermographic transfer method of the computer graphics of plate-making process etc. sublimable dye printing coating also is fine when small lot is printed.Sublimable dye is the dyestuff that can shift by distillation, volatilization etc. in when heating.Being fit to use such as Kui phthalein ketone derivatives, anthraquinone derivative, azo is dispersion dyestuffs such as pigment.Be not specially limited the conventional dyes of in the middle of heat of sublimation transfer printing, sublimation transfer stamp etc., using.
And as the material of first adhesive layer 11, under 170 ℃ of high temperature in the sublimation transfer operation reliably constraint by the colouring agent 14 of first resin bed 13, the adhesive of the acrylic resin that preferably has excellent weather resistance.And the saturated copolymer polyester resin of 100～180 ℃ of fusing points is only to the restrictive excellence of colouring agent 14.Not only can use the thermosol of the saturated copolymer polyester resin of conduct of 114 ℃ of fusing points is film, also can use the resin of 140 ℃ of fusing points.
Below with Fig. 5～7 explanation sublimation transfer operations (operation E).Draw transfer groove 32, superimposed sheets 37, sheet 2, plate 3 and sheet 38 successively on clamping piece 33 are fixed in the drive chamber 31 that drives transfer groove 32.
Start lowering or hoisting gear 23 then, drive chamber 31 risen as shown in Figure 6, up to pad 34 be pressed on chamber 25 below.
Start vavuum pump 28 then, open decompression valve 30.Relief pipe 29 and vent 39 are communicated with, rise, make by last chamber 25 and clamping piece 33 to constitute decompression in the transfer groove 32 that becomes air-tight state by drive chamber 31.When decompression reaches about 0.05MPa, clamping piece 33 attracted to chamber 25 below.At this moment as shown in Figure 7, the power by clamping piece 33 makes overlapping sheet 37, sheet 2, plate 3 and sheet 38 compacted.
When sheet 2 and plate 3 are in compacted state, will be heated to 150～200 ℃ in the transfer groove 32 by heater 26, the colouring agent 14 that is printed on the pattern 15A on the sheet 2 is distilled.
As shown in FIG. 7, when sheet 2 and plate 3 heated under contact condition, the colouring agent 14 of distillation soaked into first resin bed 13 of plate 3 on thickness direction.By soaking into of colouring agent 14, not only transfer printing is on first resin bed 13 for pattern 15, and transfer printing is on the ink lay 12 and first adhesive layer 11.
In about 6 minutes sublimation transfer operation (operation E) afterwards, at the pressure of keeping indoor 0.02MPa in one minute of beginning, 5 minutes thereafter, control by decompression valve 30 and to make pressure be elevated to 0.08MPa.Make first adhesive layer 11 or second resin bed 10 finish when above and be close to not reaching softening point thus.When being warmed up to the humidity province of carrying out sublimation transfer, need not apply the pressure that is higher than necessity then, just advance sublimation transfer.For this reason, keep the flatness on surface.By temperature, time, be colored the transferring rate and the distinctiveness of the distance decision sublimation transfer phenomenon of thing and colouring agent 14, the influence that not too is stressed.
Compress operation by once compressing under the situation that operation and secondary compression operation constitute in heating, preferably heat less than the condition that once compresses operation and compress with the pressure of secondary compression operation.Also do not have the time point that softens owing to heating at first adhesive layer 11 and second resin bed 10 in other words, just the face with first resin bed 13 and pattern 15A is adjacent to securely.Subsequently, raise along with temperature and reduce pressure.Sheet 2 and holding components just do not have the vestige of quality as long as so.
In operation E,, prevent the end face part of clamping piece 33 direct contact plates 3 preferably in the laying on every side of plate 3 and the roughly the same stainless steel space bar (not shown) of thickness of plate 3.This space bar is pressed in the end face part of plate 3 on the clamping piece 33, prevents from that the resin that softens owing to being heated from overflowing from end face part to diminish outward appearance.
In the present embodiment, first resin bed 13 is made of the resin of 73 ℃ of vitrifying transition temperatures, becomes the zone of caoutchouc elasticity under 170 ℃.Under this temperature, macromolecular structure becomes noncrystalline and is in a lot of state in gap, and first resin bed 13 passes through the colouring agent 14 that becomes molecular state by heating easily.But, owing on first adhesive layer 11, used the saturated copolymer polyester resin of 114 ℃ of fusing points, make and can not pass through, and its constraint is lived as low molecule and the colouring agent 14 that is in the molecular structure of molten condition.
Then, when operation E finishes, close decompression valve 30, open relief valve 40, the air pressure in the transfer groove 32 is returned to atmospheric pressure, start lowering or hoisting gear 23 drive chamber 31 is descended.Set cool time as required, from transfer groove 32, take out the decorative panel 1 that plate 3 is colored.
Just entered glassy state when first resin bed 13 being cooled to the vitrifying transition temperature below 73 ℃ the time, crystallization proceeds to the degree of degree of crystallinity 35%.When becoming such state, because macromolecular chain becomes fine and close state, colouring agent 14 can not pass through.And owing to first adhesive layer 11 of 114 ℃ of fusing points also solidifies, just colouring agent 14 is completely fixed.
And when using the material of vitrifying transition temperature more than 70 ℃, in less than the limit more than 70 ℃, be difficult to cause distillation again as first resin bed 13.And when using first adhesive layer 11 of fusing point more than 100 ℃, in the temperature range of life, can not take place to distil again.But fusing point is difficult to carry out the stickup of film more than 180 ℃ the time, and the constraint to colouring agent 14 is also not enough when sublimation transfer.For first adhesive layer 11, preferably use its fusing point to distil again and cause the temperature of dim pattern above colouring agent 14, and the material in the close-burning temperature range of first adhesive layer, 11 performances.The degree of crystallinity of first resin bed 13 is low more, and transparency is just high more, when degree of crystallinity 20% when following, near 70 ℃, can see the phenomenon that distils again, when degree of crystallinity 50% when above, owing to transparency extremely reduces, just be difficult to see the distillation pattern.
According to such present embodiment, owing to can give necessary pattern where necessary easily,, also can freely on plate 3, give style even in mass-produced family electrical article, become also durable steel plate.
In operation F, the bight of the decorative panel 1 finished is cut off then, in operation G, carry out bending machining again.
In step H, as shown in FIG. 8, by face component 18 in side plate cap 41,42 and the door backboard etc. is chimeric, the face that forms first resin bed 13 that makes decorative panel 1 is the space 45 of outside then.In operation J, as shown in FIG. 9, in polyurethane mould 19, be configured in parts chimeric in the step H then, in space 45, inject polyurethane resin, just obtain the thermal insulation board 20 that constitutes with decorative panel 1 and interior face component 18 integral foams.
At this, in the operation of carrying out polyurethane foam, temperature is reached more than 60 ℃ by the heat that foams.But, do not have the situation that distillation again causes dim pattern because first resin bed 13 is made of at resin molding more than 70 ℃ the vitrifying transition temperature.Owing to use the resin of high-crystallinity, colouring agent 14 be difficult to by, will irregular colour can not take place.
The decorative panel 1 of present embodiment by by first adhesive layer 11, forms plate 3 formations of light transmission first resin bed 13 on the face of metallic plate 8 as mentioned above.Constitute the resin of first resin bed 13, thereby its vitrifying transition temperature takes place more than the fuzzy temperature of distillation pattern 15 and less than the temperature of transfer printing colouring agent 14 at colouring agent 14 again.Make colouring agent 14 soak at least one inside of first resin bed 13 and first adhesive layer 11, form pattern 15.Because as first resin bed 13, constitute by the material of its vitrifying transition temperature less than colouring agent 14 transfer printing temperature, superimposed sheets 2 on plate 3, make colouring agent 14 distillations, can be on first resin bed 13 or first adhesive layer 11 pattern transferring 15.
In general, because the temperature that is reached in polyurethane foam operation or the living environment is less than 70 ℃, as long as the vitrifying transition temperature of first resin bed 13 is more than 70 ℃, colouring agent 14 just can not distil again.The vitrifying transition temperature of such first resin bed 13 is higher than colouring agent 14 and distils and make the fuzzy temperature of pattern 15, so kept long-term weatherability and hear resistance.And because to make the temperature of colouring agent 14 transfer printings be 150～200 ℃, the vitrifying transition temperature of first resin bed 13 is preferably below 120 ℃ in the case.
In first resin bed 13, can also sneak into ultra-violet absorber.In first resin bed 13, sneak under the situation of ultra-violet absorber, can improve the weatherability of more weak sublimation transfer printing ink (pattern 15 that forms by colouring agent 14) by ultra-violet absorber.
The decorative panel 1 of present embodiment has used polyester resin film on first resin bed 13.Owing to utilized to have the suitable vitrifying transition temperature scope and the characteristic of crystalline mylar, improved sublimation transfer, suppressed distillation again.And, used the ethylene glycol terephthalate resin as polyester resin film.By such structure, set 80～120 ℃ vitrifying transition temperature scope easily, also just select suitable degree of crystallinity easily.As the ethylene glycol terephthalate resin, the resin of use is in the serviceability temperature that is higher than decorative panel 1, less than colouring agent 14 distil again the temperature that makes dim pattern, degree of crystallinity is at the resin below 50% more than 20%.Under such structure, the degree of crystallinity height, the molecular structure densification has suppressed the distillation again behind the sublimation transfer.
In first resin bed 13, also can use fusion to sneak into the film of inferior light (mat-toned) pet resin of fine silicon dioxide.Because such structure makes that the bad orders such as impression that produce are not remarkable when sublimation transfer.The decorative panel 1 of the enough sublimation transfers of energy produces veined matt wall at an easy rate.
As polyester resin film, also can use the resin of PETG and PEN melt blending.In the case, by the mixing ratio of the about 121 ℃ pet resin of the about 75 ℃ PEN resin of vitrifying transition temperature and vitrifying transition temperature, just be easy to control the vitrifying transition temperature of first resin bed 13.Because the hear resistance of PEN resin is higher than pet resin, this has just improved the hear resistance of first resin bed 13.Suppress the reduction of sublimation transfer operation rear surface gloss thus, kept the good surface appearance state.
In first adhesive layer 11, also can sneak into the pearl material.Be applicable to the decorative panel 1 of this structure, very attractive in appearance, increased freedom of appearance design, can be suitable for the platen of whole kitchen or the similar product of wall surface material.
The decorative panel 1 of present embodiment has used the saturated copolymer polyester resin of 100～180 ℃ of fusing points in first adhesive layer 11.First adhesive layer 11 so can not peeled off in temperature in polyurethane foam operation (operation J) or the common life temperature scope.And in sublimation transfer operation (operation E), when heating, have the softening viscosity of crystallization fusion, and make colouring agent 14 not by the ground constraint, suppressed distillation again.
The decorative panel 1 of present embodiment is provided with second resin bed 10 between first of metallic plate 8 and first adhesive layer 11.Owing to given second resin bed 10 with flexibility, make decorative panel 1 carry out bending machining or pressure processing easily, can carry out back processing.
The decorative panel 1 of present embodiment has used vinyl chloride resin film or polypropylene resin film as second resin bed 10.When in second resin bed 10, using vinyl chloride resin film with flexibility or polypropylene resin film, the uneven of metallic plate 8 relaxed, improved the pressure machining characteristics and the bending machining performance of decorative panel 1 significantly.
Also can use the pet resin film as second resin bed 10.Because the hear resistance of pet resin film is better, the stability of decorative panel 1 outward appearance that is improved is improved pressure machining characteristics and bending machining performance and caking property.
The decorative panel 1 of present embodiment is provided with painted ink lay 12 between first adhesive layer 11 and first resin bed 13.Ink lay 12 when changing basic tone, can make the pattern variation of sublimation transfer in ink lay 12 when covering the first very poor adhesive layer 11 of outward appearance, have depth perception and novel designs.
The thermal insulation board 20 of present embodiment has decorative panel 1, is configured in inner surface parts 18 and polyurethane foam heat-barrier material on second of metallic plate 8.The polyurethane foam heat-barrier material is filled in the space 45 that is formed by decorative panel 1 and interior face component 18 and foams.In thermal insulation board 20, use the vitrifying transition temperature at the material below 120 ℃ more than 70 ℃, as first resin bed 13 that on first of metallic plate 8, is provided with by first adhesive layer 11.In other words in the polyurethane foam operation, first resin bed, 13 heated temperature are lower than the vitrifying transition temperature of the resin that constitutes first resin bed 13.Therefore, even the temperature in operation J rises near 60 ℃, the sublimation transfer pattern is not transfer printing more also, and it is uneven or shift to the look of polyurethane mould inwall that color and luster can not take place.
The refrigerator doors of present embodiment has thermal insulation board 20, constitutes the front of refrigerator by decorative panel 1, and interior face component 18 constitutes the part of the indoor storeroom of the refrigerator that is cooled by freeze cycle.So the refrigerator doors of structure can be given diversified various style as required.Even when sticking note from the teeth outwards and using paper, can not produce the color and luster skew yet, in common living environment, can suppress variable color significantly and fade.
Use polyurethane as foamed heat-insulating material in the present embodiment, but also can use the foaming body of resins such as phenol formaldehyde foam, styrenic foams.In the case, owing to the temperature that has changed in foamed process, in first resin bed, use to have the material of corresponding vitrifying transition temperature therewith.
Decorative panel in the present embodiment is suitable on the refrigerator doors, but under the situation that is provided with the slidingtype vegetables box, also is suitable in the outer wall of front panel etc.
(embodiment 2)
Figure 10 is illustrated in the sublimation transfer operation of embodiment of the present invention 2, makes laminated metallic plate and the overlapping state sectional view of transfer printing type printed sheet by holding components.
In the manufacture method of the metal lagging of present embodiment, the pattern 15A face of transfer printing type printed sheet 2 is overlapped heat on the crust resin bed (first resin bed) 13 of laminated metallic plate 3 by holding components 50 to compress.On the surface of holding components 50, be provided with concavo-convex or candy strip.On plate 3, give thus and have relief extinction type pattern 15, obtain the outward appearance of half bright and new (semi-glossy) type, perhaps form the third dimension of longitudinal stripe travers etc. easily.By obtaining such metal lagging that has the sublimation transfer pattern, has the free degree of design when making the metal lagging of the sheet material of making imitative whole kitchen or wall material.
(embodiment 3)
Figure 11 is illustrated in the sublimation transfer operation of embodiment of the present invention 3, makes the sectional view of the overlapping state of laminated metallic plate and transfer printing type printed sheet.
In metal finishing board fabrication method, used the transfer printing type printed sheet 51 that has concavo-convex or candy strip from the teeth outwards according to present embodiment.Crust resin bed (first resin bed) 13 of laminated metallic plate 3 and the pattern 15A face of sheet 51 are contacted, carry out overlapping heating and compress.Give plate 3 thus to have relief extinction type colored pattern.In other words, transfer printing type printed sheet 51 has the function of the holding components 50 in embodiment 2.Thus, except the effect of embodiment 2, can also stablize and obtain at an easy rate half bright and new (semi-glossy) type or in length and breadth striped etc. have the metal lagging of relief band sublimation transfer pattern.
(embodiment 4)
Figure 12 is illustrated in the embodiments of the present invention 4, in the rough cross-sectional view of the later heat treatment step of sublimation transfer.
On crust resin bed (first resin bed) 13, use the decorative panel 1 of high bright-coloured gloss film, will have facing up of colored pattern 15 (first resin bed 13) by first, second conveyer belt 52,53 and carry.In the process of carrying, at first by with the heater that preheats groove 54 of conveyer belt 52 relative configurations, first resin bed 13 of laminated metallic plate 3 is preheated.Then, make to be configured in warm-up mill 55 between conveyer belt 52 and the conveyer belt 53, that outer peripheral face is made of level and smooth metal covering, first resin bed, 13 heating to plate 3 under about 200 ℃ temperature compress about 1 minute.Then, by with the cooling jet 56A of the cooling device 56 of conveyer belt 53 relative configurations in the gas that blows out, make first resin bed, 13 coolings of plate 3.
In manufacture method according to the metal lagging of present embodiment, on first resin bed 13, used the film of high bright-coloured gloss, the overlapping contiguously and heating of the pattern 15A face of first resin bed 13 and transfer printing type printed sheet 2 is compressed, thereby on plate 3, give pattern 15.After this sublimation transfer operation, under subliming type colouring agent (colouring agent) the 14 resublimed temperature and time conditions of in not making plate 3, soaking into, first resin bed 13 is heat-treated.By this heat treatment step, make the high bright-coloured glossiness of first resin bed 13 turn back to the preceding state of sublimation transfer operation.
In the time will being compressed with sheet 2 overlapping heating by first resin bed 13 that the bright-coloured gloss film of height constitutes, the high bright-coloured glossiness of first resin bed 13 can reduce.At this, by can not resublimed temperature at the colouring agent 14 that soaks into plate 3, first resin bed 13 is heat-treated under the time conditions, can make the state before the high bright-coloured glossiness of first resin bed 13 turns back to the sublimation transfer operation.Obtain having the decorative panel 1 of high bright-coloured glossiness thus, when the metal lagging 1 of the sheet material of making imitative whole kitchen or wall material, can enlarge the free degree of design.
According to the heat treatment step of present embodiment, undertaken by first resin bed 13 with the level and smooth metal covering pressure strip 3 that heats.Level and smooth metal covering by can sublimation transfer with colouring agent 14 compresses first resin bed 13, has suppressed to obtain the high bright-coloured outward appearance that can not fade as the colouring agent 14 that is transferred thing distillation again from first resin bed 13.
In heat treatment step according to present embodiment, make outer peripheral face relative with first resin bed 13 by the heated warm-up mill 55 that level and smooth metal covering constitutes, carry out roll-in with 55 pairs of plates of warm-up mill 3.Owing to do not use flat board, but pressurize with roller, just can be cheap and recover the high bright-coloured glossiness of first resin bed 13 of plate 3 effectively.
(embodiment 5)
Figure 13 is the rough cross-sectional view of the heat treatment step behind the sublimation transfer in the expression embodiment of the present invention 5.
On crust resin bed (first resin bed) 13, use the metal lagging that has the sublimation transfer pattern 1 of high bright-coloured gloss film, will have facing up of colored pattern 15 (first resin bed 13), carry by resin system conveyer belt 57.In the process of carrying, at first transport the electromagnetic induction heating of the electromagnetic induction heater 58 of upstream one side by being configured in conveyer belt 57 inside, first resin bed 13 of laminated metallic plate 3 is heated.At this moment,, be difficult to be cooled off, heat effectively by electromagnetic induction heater 58 by ambient air at plate 3 owing on plate 3, be covered with insulation cover 59.
Then, the cold air that blows out of the cooling jet 56A by cooling device 56 makes 13 coolings of first resin bed.
In heat treatment step, plate 3 is heated by electromagnetic induction according to present embodiment.Constitute, be bonded in first first resin bed 13 of metallic plate 8 by thermoplastic resin, can be heated effectively, therefore just can recover the high bright-coloured glossiness of first resin bed 13 at short notice effectively with shorter time.
To the manufacturing process of the metal lagging of embodiment 5, the predetermined buyer's designated whole kitchen of reference in its entirety refrigerator for kitchen use sheet material sample just can produce outward appearance and the closely similar metal lagging of above-mentioned whole kitchen sheet material at embodiment 1.The kind of refrigerator is not limited to the refrigerator of whole kitchen special use thus, can provide the whole kitchen of coordinating very much with whole kitchen refrigerator according to order.
The possibility of utilizing on the industry
Metal lagging with the sublimation transfer pattern of the present invention is because the polyurethane foam worker In the scope of the heat of order and living environment temperature, the pattern that is sublimated hectographic printing can not rise again China has kept weatherability and heat resistance, goes for by metal lagging and inner surface portion The filled polyurethane foamed heat-insulating material consists of the usefulness such as refrigerator doors of refrigerator front in the space that part forms In the way.
Claims (29)
1. the metal lagging with the sublimation transfer pattern is characterized in that, has:
Metallic plate;
First adhesive layer that on first of described metallic plate, forms;
Light transmission first resin bed that on first of described metallic plate, forms by described first adhesive layer,
The inside of the one deck at least in described first resin bed and described first adhesive layer is soaked into the subliming type colouring agent and is formed colored pattern,
The vitrifying transition temperature of first resin bed distils more than the temperature that makes dim pattern and less than the temperature of the described subliming type colouring agent of transfer printing at described subliming type colouring agent again.
2. metal lagging as claimed in claim 1, it is characterized in that, described first resin bed is more than the serviceability temperature of described metal lagging, and not enough described subliming type colouring agent distils when causing the temperature of dim pattern again, and its degree of crystallinity is more than 20% below 50%.
3. metal lagging as claimed in claim 1 is characterized in that, the vitrifying transition temperature of described first resin bed is more than 70 ℃ below 120 ℃.
4. metal lagging as claimed in claim 1 is characterized in that, described first resin bed contains ultra-violet absorber.
5. metal lagging as claimed in claim 1 is characterized in that, described first resin bed is made of polyester resin film.
6. metal lagging as claimed in claim 5 is characterized in that described polyester resin film is made of pet resin.
7. metal lagging as claimed in claim 5 is characterized in that the pet resin that described polyester resin film is sneaked into the inferior light of fine silicon dioxide by fusion constitutes.
8. metal lagging as claimed in claim 5 is characterized in that, described polyester resin film is made of the melt blending resin of pet resin and PEN resin.
9. metal lagging as claimed in claim 5 is characterized in that, the vitrifying transition temperature of described polyester resin film is more than 70 ℃ below 120 ℃, in the degree of crystallinity of the described polyester resin film below 120 ℃ more than 70 ℃ more than 20% below 50%.
10. metal lagging as claimed in claim 1 is characterized in that, described first adhesive layer contains the pearl material.
11. metal lagging as claimed in claim 1 is characterized in that, the fusing point of described first adhesive layer distils above described subliming type colouring agent again and makes the temperature of dim pattern, can bring into play in the close-burning temperature range at described first adhesive layer.
12. metal lagging as claimed in claim 11 is characterized in that, described first adhesive layer is made of at the saturated copolymer polyester resin below 180 ℃ more than 100 ℃ fusing point.
13. metal lagging as claimed in claim 1 is characterized in that, between described metallic plate and described first adhesive layer, also has second resin bed.
14. metal lagging as claimed in claim 13 is characterized in that, described second resin bed is made of in vinyl chloride resin film and the polypropylene resin film any.
15. metal lagging as claimed in claim 13 is characterized in that, described second resin bed is made of the pet resin film.
16. metal lagging as claimed in claim 1 is characterized in that, has painted ink lay between described first adhesive layer and described first resin bed.
17. a thermal insulation board is characterized in that having:
The metal lagging of band sublimation transfer pattern as claimed in claim 1;
With first of described metallic plate second relative interior face component that goes up configuration;
By described metal lagging and described in fill in the space that forms of face component and the foamed heat-insulating material of foaming.
18. a refrigerator outer wall is characterized in that,
It is made of the described thermal insulation board of claim 14, constitutes the front of described refrigerator by described metal lagging, described in face component constitute the part of the storeroom in the described refrigerator case.
19. the manufacture method of a metal lagging is characterized in that, has following step:
A) will be by first adhesive layer, the sticking glass transition temperature is higher than the subliming type colouring agent and distils and make the temperature of dim pattern on first, be lower than laminated metallic plate with light transmission first resin bed of described subliming type colouring agent transfer printing temperature, with have that to form the transfer printing type printed sheet of face of colored pattern by described subliming type colouring agent overlapping, the step that described first resin bed is contacted with described colored pattern face;
B) temperature at described first resin bed is higher than under the temperature of described vitrifying transition temperature, will heat the step that compresses by overlapping described first resin bed and described colored pattern face in described steps A,
Wherein, described subliming type colouring agent is soaked in the inside of the one deck at least in described first resin bed and described first adhesive layer.
20. the manufacture method of metal lagging as claimed in claim 19 is characterized in that,
In described steps A, by being provided with in the concavo-convex and candy strip any holding components from the teeth outwards, described colored pattern face is overlapped on described first resin bed,
In described step B, described colored pattern face is pressed on described first resin bed by described holding components.
21. the manufacture method of metal lagging as claimed in claim 19 is characterized in that, in relief pattern and the candy strip any is set on the surface of described transfer printing type printed sheet.
22. the manufacture method of metal lagging as claimed in claim 19 is characterized in that, this manufacture method also has:
C) soaking under the not resublimed condition of described subliming type colouring agent of described laminated metallic plate, to the described first resin bed step of heat treatment,
Wherein, described first resin bed comprises high bright-coloured glossy film.
23. the manufacture method of metal lagging as claimed in claim 22 is characterized in that, in described step C, heated level and smooth metal covering is pressed on described first resin bed.
24. the manufacture method of metal lagging as claimed in claim 22, it is characterized in that, in described step C, make outer peripheral face relative with described first resin bed by the heated roller that level and smooth metal covering constitutes, use described roller that described laminated metallic plate is carried out roll-in.
25. the manufacture method of metal lagging as claimed in claim 22 is characterized in that, in described step C, by electromagnetic induction described laminated metallic plate is heated.
26. the manufacture method of a thermal insulation board is characterized in that, has:
The manufacturing process of metal lagging as claimed in claim 19;
D) with described first relative second of the described laminated metallic plate of band colored pattern on the step of face component in the configuration;
E) by described laminated metallic plate and described in inject the step of Foamex in the space that forms of face component; And
F) in described space, make described Foamex foaming and form foamed heat-insulating material, make described laminated metallic plate and the incorporate step of described foamed heat-insulating material,
Described thermal insulation board satisfies following arbitrary condition:
1) the vitrifying transition temperature of the resin of described first resin bed of formation is higher than in the heated temperature of first resin bed described in the described step F, is lower than in the heated temperature of first resin bed described in the described step B;
2) be lower than the vitrifying transition temperature of described first resin bed in the heated temperature of first resin bed described in the described step F.
27. the manufacture method of thermal insulation board as claimed in claim 26 is characterized in that, described first adhesive layer comprises resin, this resin can not peeled off under the temperature of described step F, softening when heating compresses in described step B, have viscosity, retrain described subliming type colouring agent.
28. the refrigerator manufacture method of outer wall is characterized in that having:
The manufacturing process of metal lagging as claimed in claim 19;
G) will be processed into the step of refrigerator with the described laminated metallic plate of colored pattern with the shape of outer wall;
H) with described outer wall in described first relative second of described laminated metallic plate on the step of face component in the configuration;
J) by described outer wall and described in inject the step of Foamex in the space that forms of face component; And
K) in described space, make described Foamex foaming form foamed heat-insulating material, make described outer panels and the incorporate step of described foamed heat-insulating material,
Described refrigerator satisfies following arbitrary condition with outer wall:
1) the vitrifying transition temperature of the resin of described first resin bed of formation is higher than in the heated temperature of first resin bed described in the described step K, and is lower than in the heated temperature of first resin bed described in the described step B,
2), be lower than the vitrifying transition temperature of described first resin bed in the heated temperature of first resin bed described in the described step K.
29. the refrigerator as claimed in claim 28 manufacture method of outer wall, this method is the manufacture method of whole kitchen with the outer wall of refrigerator, it is characterized in that, in the manufacturing process of the described metal lagging of claim 16 as described, with reference to the sample of described whole kitchen sheet material, make outward appearance and the very approximate metal lagging of described sample.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP330552/2002 | 2002-11-14 | ||
| JP2002330552 | 2002-11-14 | ||
| JP360230/2003 | 2003-10-21 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1742184A true CN1742184A (en) | 2006-03-01 |
| CN100351080C CN100351080C (en) | 2007-11-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003801032546A Expired - Fee Related CN100351080C (en) | 2002-11-14 | 2003-11-12 | Metallic decorative sheet with sublimation-transferred pattern, heat-insulating panel and outer wall for refrigerator both employing the same, and processes for producing these |
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| Country | Link |
|---|---|
| CN (1) | CN100351080C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109489325A (en) * | 2017-09-11 | 2019-03-19 | 松下电器产业株式会社 | Refrigerator |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2957864B2 (en) * | 1993-10-07 | 1999-10-06 | 三菱電機株式会社 | Metal decorative plate and manufacturing method thereof |
| JP4085502B2 (en) * | 1999-02-10 | 2008-05-14 | 三菱電機株式会社 | Coated steel sheet, refrigerator |
| KR100749308B1 (en) * | 2000-08-22 | 2007-08-14 | 닛신 세이코 가부시키가이샤 | A painted metal sheet printed with a sublimation dye |
-
2003
- 2003-11-12 CN CNB2003801032546A patent/CN100351080C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109489325A (en) * | 2017-09-11 | 2019-03-19 | 松下电器产业株式会社 | Refrigerator |
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| Publication number | Publication date |
|---|---|
| CN100351080C (en) | 2007-11-28 |
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Owner name: PANASONIC ELECTRIC EQUIPMENT INDUSTRIAL CO.,LTD. Free format text: FORMER OWNER: MATSUSHITA REFRIGERATION CO. Effective date: 20090417 |
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