CN1340416A - Coated metal plate for excellent-light resistance sublimable dye transfer printing and printing of coated metal plate - Google Patents
Coated metal plate for excellent-light resistance sublimable dye transfer printing and printing of coated metal plate Download PDFInfo
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- CN1340416A CN1340416A CN01130706A CN01130706A CN1340416A CN 1340416 A CN1340416 A CN 1340416A CN 01130706 A CN01130706 A CN 01130706A CN 01130706 A CN01130706 A CN 01130706A CN 1340416 A CN1340416 A CN 1340416A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2202/00—Metallic substrate
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Abstract
The coated metal sheet for sublimable dye transfer printing excellent in light fastness is constituted by providing the topcoating film 4 based on the thermosetting polyester resin, which has a number average mol.wt. of 1,000-10,000 and a glass transition temperature (Tg) of 20-60 deg.C, and contains 20-150 pts.mass of melamine per 100 pts.mass of a resin solid, on a substrate metal sheet directly or through a base coat layer 2, a primer layer 3 or the like. When thermal transfer is performed using a sublimable dye, a sublimable dye deposited layer 5 is formed on the topcoating film 4 and a color pattern excellent in light fastness is imparted.
Description
Technical field
The present invention relates to by adopting hot transfer printing dying the sublimable dye hectographic printing metallic sheet of the additional various printed patterns of sublimable dye, and additional various printed patterns, iridescent advertisement Graphic Panel, decorate with interior finish material, decorate, decorate with showing employed printing of coated metal plates such as package material, elevator door material, household electrical appliance external application plate, article external application plate with flooring material.
Background technology
When using sublimable dye to make the printing of coated metal plate, printing processes such as adopting hectograph print through, silk screening, gravure, transfer printing sublimable dye is printed on metallic sheet on the hyaline layer after, by heat treated, sublimable dye is soaked in the transparent coating.
Adopt the pattern of sublimable dye to be printed with: the method (the open communique of No. 24313/1976 application for a patent for invention of Japan) that the coat film of hardening synthetic resin layer contacts with transfer plate and heats, hectographic printing by adopting sublimable dye is after forming printed layers on the metallic sheet, on forming, the surface films, then soak into the method (the open communique of No. 104907/1979 application for a patent for invention of Japan) of sublimable dye from the internal layer of filming by heat treatment, surface of steel plate form bottom coating and coloured on soak into heat sublimation printing ink on the filming of the precoated metal sheet of filming method (the open communique of No. 31931/1995 application for a patent for invention of Japan), the method for sublimability colouring agent (the open communique of No. 102733/1995 application for a patent for invention of Japan) etc. is soaked in the inside of the opaque resin floor that is provided with in the metallic plate substrate.
No matter any pattern print process all presents pattern by soak into sublimable dye in last filming.But general sublimable dye is little disperse dyes of polarity or oiliness dyestuff, causes rotten by plasticizer and organic chemical etc. easily.Also be take place to be decomposed by light such as ultraviolet rays easily and variable color or the dyestuff that fades.Therefore, in outdoor environment for use, be difficult to keep stable color and pattern in long term exposure.Illumination is penetrated the variable color that causes and is faded, and can prevent by mixing ultra-violet absorber with the ratio of 0.5～3 weight % in coating for non-volatile part with respect to coating.
But, the sintering condition of filming that prints employed pre-coated steel plate reaches as high as 200～240 ℃ of plate temperature, retention time is 1～2 minute, the transfer printing condition that sublimable dye is immersed in filming is 160～190 ℃ * 1～4 minute, that is to say that ultra-violet absorber finishes will to have at least until the manufacturing of printing of coated metal plate and is exposed in the high-temperature atmosphere for twice.Therefore, be in the ultra-violet absorber at benzophenone system or BTA commonly used, hear resistance and anti-sublimability are poor, and the contained ultra-violet absorber of filming reduces because of distillation.The minimizing of ultra-violet absorber is not only to the variable color of ultra-violet absorber with fade adverse effect is arranged, and the distillation of ultra-violet absorber also causes coated surface to form shaddock skin shape and flavescence.Flavescence phenomenon thick more coating raw sheet under the condition of sintering condition and the strictness of transfer printing condition of filming is remarkable more.
In this respect, in the open communique of No. 206678/1997 application for a patent for invention of Japan, be that the ratio interpolation heat endurance of 6～18 weight % and the BTA system or the triazine of favorable solubility are ultra-violet absorber with respect to non-volatile part of coating.Adding BTA system or triazine is ultra-violet absorber, is effectively to multiple sublimable dye, still, for the part sublimable dye of light resistance difference particularly, can't suppress variable color and fades, and makes it can be used for outdoor application.Also can consider to change the more good sublimable dye of light resistance, still, consider the adaptability of the employed printing machine kind of printout and the restriction of color etc., change sublimable dye and also be difficult for.That is, in basic four color inks (cyanine (cyanic), peony, Huang, indigo plant) that use, even there is a kind of light resistance difference of color all can not be in outdoor application.
Summary of the invention
The present invention is in order to address the above problem, provide by adopting the good resin of light resistance to form finishing coat and filmed, the variable color of the sublimable dye that the face that is suppressed at greatly soaks in filming and fading, provide the sublimable dye hectographic printing metallic sheet that adds various printed patterns by hot transfer printing sublimable dye, and the printing of coated metal plate with various printed patterns.
In order to achieve the above object, sublimable dye hectographic printing of the present invention is characterised in that with metallic sheet: the face that is provided with on metal sheet surface is filmed, this face film by with number-average molecular weight be 1000～10000, glass transition temperature (Tg) is 20～60 ℃, be that the thermal hardening type polyester resin of 20～150 weight portions is that the transparent or translucent coating of Main Ingredients and Appearance is made with respect to resin solid part 100 weight portion melamine resins.And the printing of coated metal plate adds multicolour pattern by soaking into sublimable dye on filming at face.
As thermal hardening type polyester resin, it is 1 of monomer that the part of preferred molecular structure contains from dicarboxylic acids, 2-benzene-dicarbonyl structure and/or be 2 of monomer from glycol, the resin of 2-dimethyl trimethylene structure.On face was filmed, preferably can add with respect to non-volatile part 100 weight portions of coating was that the triazine of 3～22 weight portions is that ultra-violet absorber and BTA are ultra-violet absorber independent or compoundly.
Description of drawings
Fig. 1 represents dying the cross section of the printing of coated metal plate of filming by the face of priming coat setting.
Fig. 2 represents dying the cross section of the printing of coated metal plate of filming by the face of bottom and priming coat setting.
Fig. 3 represents dying the cross section of the printing of coated metal plate of the transparent coating that directly is provided with on end steel plate.
The specific embodiment
Sublimable dye hectographic printing of the present invention with metallic sheet with electroplating steel plate, Stainless-steel sheet, aluminium sheet etc. are provided with priming coat 2 as required as substrate metal plate 1 With bottom 3, form a transparent or translucent coating on the top layer and film 4. As long as There is face to film 4 on the top layer, films at substrate metal plate 1 and face and establish between 4 The printing of coated metal plate (Fig. 1) of bottom set coating 2, the printing that bottom 3 further is set is coated with Cover metallic plate (Fig. 2), film 4 printing of the face that on substrate metal plate 1, directly arranges Metallic sheet (Fig. 3) all can. In this manual, comprising the implication of transparent coating Lower, use " face is filmed ", and, in order to present the outward appearance of delustring style, Can apply aggregates such as adding silica in the coating at face. Priming coat 2 is not limited to white Look also can present other color.
Priming coat 2 is in order to cover substrate metal plate 1 and bottom 3, preferably with 10～20 microns Thickness form. Adopt thickness less than 10 microns bottom 2, to substrate metal plate 1 He A little less than the screening capacity of bottom 3, what formation substrate metal plate 1 and bottom 3 colors mixed films Face. Otherwise, adopt thickness to surpass 20 microns priming coat 2, residual in filming during sintering Solvent sharply vaporize, the Pinhole-shaped that might be called as " overflowing " is filmed scarce Fall into.
Thermal hardening type polyester resin is the tree that generates by polymerization binary acid and polyalcohol Fat. Binary acid is aromatic binary carboxylic acid, aliphatic dicarboxylic acid or their acid Acid anhydride specifically, can independent or two or more mixing use phthalic acid, isophthalic Dioctyl phthalate, phthalic acid, terephthalic acid (TPA), maleic acid, maleic anhydride, rich horse Acid, adipic acid etc. In order to obtain good light resistance, particularly after polymerization, Preferably contain the phthalic acid and/or the phthalic acid that form 1,2-benzene dicarbonyl structure. The adipic acid that does not contain phenyl also is suitable as binary acid and uses.
For polyalcohol, can independent or two or more mixing make spent glycol, Diethylene glycol, triethylene glycol, propane diols, pentanediol, neopentyl glycol, trihydroxy methyl Ethane etc. In order to obtain good light resistance, preferably use the such aliphatic chain of pentanediol Long alcohol after the polymerization, more preferably uses formation 2,2-dimethyl trimethylene to construct Neopentyl glycol.
Thermal hardening type polyester resin used in the present invention can be adjusted to the number average molecule Amount 1000～10000. Number-average molecular weight is less than 1000 o'clock, owing to be not coated with at face Extend on the film 4, poor in processability, on the contrary number-average molecular weight surpasses 10000, because by The ratio of the crosslink part that melamine produces reduces, and causes branch by ultraviolet ray irradiation etc. easily Separate. Itself photostability height of the melamine that uses as curing agent can be by with poly-The ester mixed with resin improves the light resistance of resin.
Improve sunproof effect and adopt the above melamine of 20 weight portions to become significantly, as Fruit contains the excess quantity melamine that surpasses 150 weight portions, owing to crosslink density excessively increases, Adding films man-hour breaks easily. And glass transition temperature (Tg) is less than 20 ℃ The time, hardness of film reduces, and form easily with the filming of defective, otherwise vitrifying is turned to When temperature (Tg) surpassed 60 ℃, hardness excessively increased, the remarkable variation of processability.
If will adopt sublimable dye in advance transfer plate and the substrate metal of additional pattern Plate 1 contact and heating, the dyestuff of distillation is soaked in a transparent or translucent coating and is coated with In the film 4, just form sublimable dye and dying layer 5, present at thickness direction and dying Pattern. Transfer plate can adopt gravure, hectographic printing, serigraphy etc. to make. With In the small lot printing, can adopt the electronics of the computer graphical that does not need plate-making process to shine Phase method, electrostatic recording, ink jet method, sensible heat transfer printing etc.
The phenomenons such as distillation when sublimable dye refers to by heating, volatilization can be transferred to face The coating dyestuff on 4 of filming. In specification of the present invention, also comprising from liquid Use " distillation " under the implication of attitude volatilization. As sublimable dye, make suitably Using such as quinophthalone derivatives, anthraquinone derivative, azo is the dispersion dyestuffs such as pigment. The sublimable dye that uses in present processed through sublimation heat transfer printing, the sublimation transfer stamp etc. does not have Special restriction can be used for face and films in 4 the printing.
In spendable sublimable dye, yellow based dye has: the Kayaset Huang AG, Kayaset yellow TDN (above is Nippon Kayaku K. K's system), RTY 52, the bright orange 5G-E of yellow F3G-E, the Dianix of yellow 5R-E, Dianix of Dianix (with Upper be Mitsubishi chemical Co., Ltd's system), sandblast Huang 8040, DY108 be (above for basis is arranged KCC's system), the yellow E-of yellow EFG, Sumikaron of Sumikaron 4GL (above is Sumitomo Chemical Co's system), the bright orange SGGLPI of FORON (Sand society system), PS Huang-GG (dyestuff Co., Ltd. system is pressed in Mitsui east) etc.
Dark red is that sublimable dye has: Kayaset is red 026, Kayaset is red 130, The red B of Kayaset (above is Nippon Kayaku K. K's system), oil red DR-99, oil red DK-99 (above for this KCC system is arranged), the pink B of Diacelliton (Mitsubishi KCC's system), the red E-FBL of Sumikaron (Sumitomo Chemical Co The system), the red B of Latyl (Do Pont society system), the red 7B of Sudan (BASF society system), The red FB of Resolin, the red 7B of Ceres (above is Bayer society system) etc.
Cyanine is that sublimable dye has the blue FG of Kayalon Fast, Kaya1on indigo plant (above is Nippon Kayaku K. K for FR, Kayaset indigo plant 136, Kayaset indigo plant 906 System), oil blue 63 (this KCC system is arranged), HSB9, RTB31 (more than be three Water chestnut KCC system), the blue #1 (Sumitomo Chemical Co's system) of Disperse, MS indigo plant 50 (dyestuff Co., Ltd. system is pressed in Mitsui east), the blue GN of Ceres (Bayer society System), Duranol light blue 2G (ICI society system) etc.
Each color can be used with sublimable dye in independent or two or more mixing. Black Tone can get by the sublimable dye that suitable mixing yellow, peony, cyanine look are used Arrive. The preferred tool of sublimable dye with tone outside yellow, peony and the cyanine look The dyestuff that sublimation temperature more than 60 ℃ is arranged. When selecting sublimable dye, sublimation temperature High dye molecule amount is higher, from giving film good light resistance and heat resistance aspect Consideration is preferred.
If with state that substrate metal plate 1 contacts under the heating transfer plate, in the transfer plate Contained sublimable dye distillation shown in Fig. 1～3, is soaked at thickness direction A bright or translucent coating films 4. For this reason, be coated with in a transparent or translucent coating Be formed on the thickness direction basically the sublimable dye that all level dyeing on the film 4 and dying layer 5, obtain having relief printed patterns. Because resulting printed patterns only is not Film 4 top layer with denseization of sublimable dye at face, therefore, by wiping etc. no Can cause the printing attenuation, and, also can omit with transparent protective resin by hot transfer printing Give the operation of the hectographic printing layer behind the figure. Like this, because can be the figure of needs Case can be added when needed simply, adapts to the figure of the additional various patterns of various demands The small serial production transfiguration of steel plate is easy. And, do not need to store the figure with given pattern Therefore the shape steel plate has alleviated stock's burden. Because at transparent or semi-transparent resin layer And do not have the individualism dye coating between the metal level, do not resemble existing multilayer steel plates The middle splitting that occurs.
For prevent by see through that sublimable dye that sunshine or ultraviolet ray cause fades and Film 4 gloss reducing of face, face are filmed and can be added ultraviolet radiation absorption in 4 Agent. As ultra-violet absorber, preferably use in atmosphere, 5 ℃ of programming rates/ Minute heating condition under reduce benzo three below 10 % by weight 300 ℃ of lower weight Azoles system or triazine system. Specifically, non-volatile with respect to film 4 coating of face Part 100 weight portions add separately triazine system or mixed with the mixed proportion of 3～22 weight portions Close triazine system and BTA and be and add face to and film in 4. And, if mix 3.0 the following hindered amine of weight portion is light stabilizer, can further improve light resistance.
BTA is that ultra-violet absorber can be enumerated: the octyl group-3-[3-tert-butyl group-5-(2H-BTA-2-yl)-4-hydroxy phenyl] propionic ester is (by Ciba-Geigy company Provide with TINUVIN384), 2-[2-hydroxyl-3,5-two (α, α '-dimethylbenzyl Base) phenyl]-the 2H-BTA (carried with TINUVIN900 by Ciba-Geigy company Confession), the methyl-3-[3-tert-butyl group-5-(2H-BTA-2-yl)-4-hydroxy phenyl] third The polymer of acid esters and polyethylene glycol (molecular weight is about 300) is (by Ciba-Geigy company Provide with TINUVIN 1130), 2-[2 '-dihydroxy-3 '-(3 ", 4 ", 5 ", 6 "-and the tetrahydric phthalimide methyl)-5 '-aminomethyl phenyl]-BTA (by KYODOH drugmaker provides with Viosorb 590) etc.
Triazine is that ultra-violet absorber can be enumerated: for example 2-{4-[(2-hydroxyl-3-12 The alkoxyl propyl group)-oxygen]-the 2-hydroxy phenyl }-4,6-two (2,4-3,5-dimethylphenyl)-1,3,5-Triazine and 2-{4-[(2-hydroxyl-3-tridecane oxygen base propyl group)-oxygen]-the 2-hydroxy phenyl }-The mixture of 4,6-two (2,4-3,5-dimethylphenyl)-1,3,5-triazines is (by Ciba-Geigy Company provides with TINUVIN400) etc.
These ultra-violet absorbers can use separately, also can two or more mixing use. The combined amount of ultra-violet absorber is preferably adjusted to non-volatile part of 100 weights with respect to coating Amount part is 3～22 % by weight. Sunproof improvement is in the ultraviolet ray of adding more than 3 weight portions Particularly remarkable during absorbent, still, when combined amount surpassed 22 % by weight, that films was anti-The variation such as contaminative, processability, appearance of film. And also observable is by ultraviolet ray Filming that absorbent causes is painted.
In order further to improve film 4 light resistance of a transparent or translucent coating, root According to needs, preferably to mix as the ratio below 3 % by weight with respect to coating is non-volatile part Hindered amine is light stabilizer. Hindered amine is that light stabilizer can be enumerated following material.
Two (2,2,6,6-tetramethyl-4-piperidyl) sebacate (by Sankyo Co., Ltd with SANOL LS770 provides), two (1,2,2,6,6-pentamethyl-4-piperidyl) decanedioic acid Ester (being provided with SANOL LS765 by Sankyo Co., Ltd), 1-{2-[3-(3,5-Two-tert-butyl group-4-hydroxyphenyl) propionyloxy] ethyl }-4-[3-(3,5-, two-tert-butyl group-The 4-hydroxyphenyl) propiono oxygen]-2,2,6, the 6-tetramethyl piperidine (by Sankyo Co., Ltd with SANOL LS2626 provides), 4-benzoyl oxygen-2,2,6, the 6-tetramethyl piperidine (by Sankyo Co., Ltd provides with SANOL LS744), 8-acetyl group-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-thriazaspiro [4,5] decane-2,4-diones are (by three altogether Co., Ltd. provides with SANOL LS440), 2-[3,5-two-uncle-acrinyl-2-is just Butylmalonic acid two (1,2,2,6,6-pentamethyl-4-piperidyl)] ester is (by Ciba-Geigy Company provides with TINUVIN 144), succinic acid two (2,2,6,6-tetramethyl-4-piperidines Base) ester (being provided with TINUVIN780FF by Ciba-Geigy company), succinic acid two Methyl esters and 1-(2-hydroxyethyl)-4-hydroxyl-2,2,6, the condensation polymer of 6-tetramethyl piperidine (being provided with TINUVIN622LD by Ciba-Geigy company), poly-{ [6-(1,1,3,3-tetramethyl butyl) amino-1,3,5-triazines-2,4-two bases] [(2,2,6,6-four Methyl-4-piperidyl) imino group] hexa-methylene [2,2,6,6-tetramethyl-4-piperidyl] Asia Amino } (being provided with CHIMASSORB944LD by Ciba-Geigy company), N, N '-two (3-aminopropyl) ethylene diamine and 2,4-two [N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl) amino]-polycondensation of 6-chloro-1,3,5-triazines Thing (being provided with CHIMASSORB119FL by Ciba-Geigy company), two (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (by Ciba-Geigy company with TINUVIN292 provides), two (1-octyloxy-2,2,6,6-tetramethyls-4-piperidyl) Sebacate (being provided with TINUVIN123 by Ciba-Geigy company), HA-70G (being provided by Sankyo Co., Ltd), ADECA STAB LA-52, ADECA STAB LA-57, ADECA STAB LA-62, ADECA STAB LA-63, ADECA STAB LA-67, ADECA STAB LA-68, ADECA STAB LA-82 or ADECA STAB LA-87 are (by ASAHI DENKA KOGYO company provides).
These light stabilizers can use separately, also can two or more mixing use. Light is steady Decide agent when surpassing a large amount of mixing of 3.0 % by weight, the liter that face is filmed and soaked in 4 The effect that the light resistance of China's property dyestuff improves is saturated, also can't see further improvement, But there is deterioration to apply the tendency of outward appearance. The scope that light stabilizer preferably mixes is 0.5～1.5 % by weight.
A transparent or translucent coating is filmed and 4 can be passed through priming coat 2 (Fig. 1), and is logical Cross priming coat 2 and bottom 3 (Fig. 2), perhaps (Fig. 3) direct shape on substrate metal plate 1 Become. In either case, the tone of substrate metal plate 1 and priming coat 2 becomes base Ground patterns can be observed by dying resin bed 5. Therefore, can obtain matter with bottom material The printing of coated metal plate that unique feel is arranged of livelyization of amount style.
Embodiment
The manufacturing of the coated steel plates that uses in the transfer printing raw sheet
To thickness of slab be the galvanized steel plain sheet of 0.5mm carry out the degreasing surface adjust process after, execute Process with the application type chromate, take the coating weight coating white of dry film thickness as 14 microns Polyester based resin coating (Nippon Paint Co., Ltd's system) is up to 220 ℃ in the plate temperature Sintering is 1 minute under the temperature, forms white priming coat 2. Then, take dry film thickness as 18 The coating weight of micron applies transparent resin coating at white priming coat 2. At transparent resin On the coating, use number-average molecular weight 500～20000, glass transition temperature (Tg) to be 10～80 ℃, mixed 5～70 weight portions with respect to resin solid part 100 weight portions The Polyester resin lacquer of melamine. This Polyester resin lacquer can use and be selected from as binary Carboxylic acid is adipic acid, phthalic acid, M-phthalic acid, the terephthalic acid (TPA) of monomer A kind of or two kinds. And the embodiment of the invention 1～9,11,13,15,17 and the ratio Be the neopentyl glycol of monomer than having added in the example 1～7 as dihydroxylic alcohols.
Except the embodiment of the invention 9,19 and comparative example 7 and 9, face films 4 With clear dope in add the triazine system of 8 % by weight take the non-volatile composition of coating as benchmark Ultra-violet absorber and BTA are 1: 1 mixture of ultra-violet absorber. And And the hindered amine that adds 1.5 % by weight in whole transparent resin coating is that light is stable Agent.
The steel plate that applies transparent resin coating is up in the plate temperature under 230 ℃ the temperature and adds Heat 1 minute, formation face films 4 thus.
| The test sequence number | Molecular weight | Glass transition point (Tg) | Melamine content (weight section) | Binary acid | Have or not the interpolation neopentyl glycol | Ultra-violet absorber addition (% by weight) |
| 1 | 1000 | 35 | 70 | Adipic acid: phthalic acid=40: 60 | Have | 8 |
| 2 | 3000 | |||||
| 3 | 6000 | |||||
| 4 | 10000 | |||||
| 5 | 3000 | 22 | ||||
| 6 | 56 | |||||
| 7 | 35 | 20 | ||||
| 8 | 150 | |||||
| 9 | 70 | 0 | ||||
| 10 | Do not have | 8 | ||||
| 11 | M-phthalic acid: phthalic acid=60: 40 | Have | ||||
| 12 | Do not have | |||||
| 13 | Terephthalic acid (TPA): phthalic acid=80: 20 | Have | ||||
| 14 | Do not have | |||||
| 15 | Terephthalic acid (TPA): M-phthalic acid=50: 50 | Have | ||||
| 16 | Do not have | |||||
| 17 | Terephthalic acid (TPA)=100 | Have | ||||
| 18 | Do not have | |||||
| 19 | Do not have | 0 |
Table 2: the composition that the transparent area on each coated steel plates is filmed (comparative example)
| The test sequence number | Molecular weight | Glass transition point (Tg) | Melamine content (weight section) | The binary carboxylic | Have or not the interpolation neopentyl glycol | Ultra-violet absorber addition (% by weight) |
| 1 | 500 | 35 | 70 | Adipic acid: phthalic acid=40: 60 | Have | 8 |
| 2 | 15000 | 8 | ||||
| 3 | 3000 | 15 | ||||
| 4 | 70 | |||||
| 5 | 35 | 10 | ||||
| 6 | 200 | |||||
| 7 | 15000 | 70 | 0 | |||
| 8 | Terephthalic acid (TPA): M-phthalic acid=50: 50 | Do not have | 8 | |||
| 9 | 0 |
Hectographic printing
The sublimable dye printing ink that employing is made by the cyanine sublimable dye adopts printing ink Jet printers is at printing printing cyanine pattern. The transfer paper that obtains is fitted On the coated side of coated steel plates, in 160 ℃ temperature and 4 * 104Under the pressure of Pa Suppressed 150 seconds. After compacting is finished, peel off transfer paper from coated steel plates. Relatively in phase With the light resistance of the cyanine that distils under the condition, dark red, yellow sublimable dye, cyanine Light resistance is the poorest, therefore, take the light resistance of cyanine as benchmark, can clearly know Resin forms to sunproof impact.
The performance test of printing coated steel plates
Downcut test film from the coated steel plates that respectively prints of making, supply light fastness test, be coated with The test of being adjacent to property of film, workability test, anti-moisture test, stain resistance test, anti-The flaw test is used.
In light fastness test, be set in 63 ℃ サ Application シ ャ イ Application in test temperature Among カ-ボ Application ァ-Network ウ ェ ザ-メ-, in irradiation in 60 minutes, pass into 12 minutes clearly Under the condition of water, place test film 240 hours, measure the look of test film after 240 hours Transfer, by estimating light resistance with the aberration △ E of exposure experiment sheet not. That is after, 240 hours Aberration △ E is outdoor not being suitable for more than 10, be used for using for a long time more than 3 years , aberration △ E should be less than 7.
In the being adjacent to property test of filming, (put into JIS by the reticulate pattern Erichsen test The reticulate pattern of G3320 regulation is extruded 6mm), observe being accompanied by filming that adhesive band peels off Peel off situation. All peel off to film for punctuating and annotating 1, approach all peel off for punctuating and annotating 2, obviously peel off for estimate 3, slightly have peel off for punctuating and annotating 4, what do not peel off is Estimate 5, divide 5 sections evaluations being adjacent to property of filming.
In workability test, (clamp 1 and test at 20 ℃ the indoor 0～6t that impose Be 1t during the same thick plate of sheet) 180 degree bending machining, according to the degree research of bending A situation arises in the crack of filming. Film the crack do not take place and when 0～2t, film on That the crack takes place be ◎, take place during 3～4t the crack be zero, 5t the time generation crack be △, the generation crack is during 6t *, estimate with this. Usually, if evaluation point More than zero, can be used as pre-coated steel plate and use in practice.
In anti-moisture test, according to JIS Z0208, will set 49 ℃ of test temperatures Moistening test duration 500 hours. Observe after the test and film, do not take place to bubble Be zero, detect foaming for *, estimate moisture-proof with this.
In the anti-pollution test, on coated surface, draw red line and black with oil-based ink Line after 24 hours, is used methyl alcohol wiping red line and black line 20 ℃ of lower placements. No Vestige for punctuating and annotating 5, have some vestiges residual for punctuating and annotating 3, vestige is significantly for commenting Point 1 carries out the stain resistance evaluation with this. Usually, red according to what draw with oil-based ink Line can be used as pre-coated steel plate and uses in practice for punctuating and annotating 2 when above.
In the flaw resistance test, according to JIS K5400-8.4, with pencil (Mitsubishi's connection Close Mitsubishi Pencil K. K's system) cause flaw at coated surface, not cause flaw The pencil hardness of boundary is estimated flaw resistance.
By the investigation result of table 3 as seen, adopt printing of coated metal plate of the present invention, can Satisfy light resistance, the being adjacent to property of filming, processability, flaw resistance, stain resistance and anti-All moist characteristics. Wherein, phthalic acid and/or neopentyl glycol make as monomer The time spent light resistance is the best.
In contrast to this, adopt the printing of coated metal plate of comparative example, light resistance, film In being adjacent to property, processability, flaw resistance and the stain resistance one or several are not good (table 4). That is, adopt in the test number 1 of the little mylar of molecular weight the subsides of filming Sigma compactness and poor in processability, otherwise, the test number of the mylar that the employing molecular weight is big 2, in 7～9, the light resistance deficiency. And, the low examination of glass transition temperature (Tg) The coated surface of testing numbering 3 produces flaw, the high test of glass transition temperature (Tg) easily The poor in processability of numbering 4. And then, the light resistance of the poor test number 5 of melamine and Low contamination resistance, on the contrary the processability of the test number 6 that melamine content is many exists asks Topic.
Table 3: each prints the characteristic (embodiment of the invention) of coated steel plates
| Test number | The aberration △ E of light resistance after 240 hours | The being adjacent to property of filming | Processability | Flaw resistance | Stain resistance | Moisture- | |
| Red | Black | ||||||
| 1 | 3.5 | 5 | ○ |
| 5 | 5 | ○ |
| 2 | 5.0 | 5 | ◎ |
| 5 | 5 | ○ |
| 3 | 5.8 | 5 | ◎ |
| 5 | 5 | ○ |
| 4 | 6.3 | 5 | ◎ |
| 4 | 5 | ○ |
| 5 | 5.5 | 5 | ◎ |
| 4 | 5 | ○ |
| 6 | 4.4 | 5 | ○ |
| 5 | 5 | ○ |
| 7 | 6.8 | 5 | ◎ |
| 4 | 5 | ○ |
| 8 | 2.9 | 5 | ○ |
| 5 | 5 | ○ |
| 9 | 9.7 | 5 | ◎ |
| 5 | 5 | ○ |
| 10 | 6.4 | 5 | ◎ |
| 5 | 5 | ○ |
| 11 | 5.2 | 5 | ◎ |
| 5 | 5 | ○ |
| 12 | 6.7 | 5 | ◎ |
| 5 | 5 | ○ |
| 13 | 5.5 | 5 | ◎ |
| 5 | 5 | ○ |
| 14 | 7.0 | 5 | ◎ |
| 5 | 5 | ○ |
| 15 | 6.3 | 5 | ◎ |
| 5 | 5 | ○ |
| 16 | 7.9 | 5 | ◎ |
| 5 | 5 | ○ |
| 17 | 6.5 | 5 | ◎ |
| 5 | 5 | ○ |
| 18 | 8.1 | 5 | ◎ |
| 5 | 5 | ○ |
| 19 | 9.6 | 5 | ◎ |
| 5 | 5 | ○ |
Table 4: each prints the characteristic (comparative example) of coated steel plates
| Test number | The aberration △ E of light resistance after 240 hours | The being adjacent to property of filming | Processability | Flaw resistance | Stain resistance | Moisture- | |
| Red | Black | ||||||
| 1 | 3.2 | 3 | × |
| 5 | 5 | ○ |
| 2 | 11.0 | 5 | ◎ |
| 4 | 5 | ○ |
| 3 | 6.1 | 5 | ◎ |
| 4 | 5 | ○ |
| 4 | 4.2 | 4 | × |
| 5 | 5 | ○ |
| 5 | 10.5 | 5 | ◎ | F | 3 | 4 | ○ |
| 6 | 2.6 | 5 | △ |
| 5 | 5 | ○ |
| 7 | 13.1 | 5 | ◎ |
| 4 | 5 | ○ |
| 8 | 12.4 | 5 | ◎ |
| 4 | 5 | ○ |
| 9 | 15.3 | 5 | ◎ |
| 4 | 5 | ○ |
As discussed above, sublimable dye hectographic printing of the present invention is with being coated with Cover metallic plate on the substrate metal plate directly or by priming coat and bottom setting by tool There is the thermmohardening type of specified molecular weight, glass transition temperature (Tg) and melamine content poly-The face that the ester resin consists of is filmed. Light resistance and processability that face is filmed are excellent Very, being sublimated property dyes easily, therefore, can obtain good bright-coloured of light resistance The printing of coated metal plate of the printed patterns that certain depth is arranged. Make as mentioned above The printing of coated metal plate is applicable to the production of the many kinds of small lot, and it is excellent to can be used as aesthetic appearance Good fluorescent color advertising display plate, decorate with interior finish material, decoration flooring board Material, decoration are with outside table package material, elevator door material, household electrical appliance external application plate, the article Use as patterned steel plate in wide spectrum with plate etc.
Claims (4)
1. sublimable dye hectographic printing metallic sheet that light resistance is good, it is characterized in that: the face that is provided with on metal sheet surface is filmed, this face film by with number-average molecular weight be 1000～10000, glass transition temperature (Tg) is 20～60 ℃, be that the thermal hardening type polyester resin of 20～150 weight portions is that the transparent or translucent coating of Main Ingredients and Appearance is made with respect to resin solid part 100 weight portion melamine resins.
2. sublimable dye hectographic printing metallic sheet as claimed in claim 1, it is characterized in that: it is 1 of monomer that the part of the thermal hardening type polyester resin molecular configuration that face is filmed contains from dicarboxylic acids, 2-benzene-dicarbonyl structure and/or be 2 of monomer from glycol, 2-dimethyl trimethylene structure.
3. sublimable dye hectographic printing metallic sheet as claimed in claim 1 is characterized in that: the independent or compound triazine that contains was that ultra-violet absorber and BTA are ultra-violet absorber during face was filmed.
4. the printing of coated metal plate that light resistance is good, it is characterized in that: the face that is provided with on metal sheet surface is filmed, this face film by with number-average molecular weight be 1000～10000, glass transition temperature (Tg) is 20～60 ℃, be that the thermal hardening type polyester resin of 20～150 weight portions is that the transparent or translucent coating of Main Ingredients and Appearance is made with respect to resin solid part 100 weight portion melamine resins, and the face of colored pattern is filmed and is arranged on metal sheet surface by soaking into of sublimable dye.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP250599/2000 | 2000-08-22 | ||
| JP2000250599A JP3464971B2 (en) | 2000-08-22 | 2000-08-22 | Printed metal plate with excellent light resistance |
| JP250599/00 | 2000-08-22 | ||
| JP313637/00 | 2000-10-13 | ||
| JP313637/2000 | 2000-10-13 | ||
| JP2000313637A JP3464974B2 (en) | 2000-10-13 | 2000-10-13 | Painted metal plate for sublimation dye transfer printing with excellent light resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1340416A true CN1340416A (en) | 2002-03-20 |
| CN1239317C CN1239317C (en) | 2006-02-01 |
Family
ID=26598209
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011307064A Expired - Fee Related CN1239317C (en) | 2000-08-22 | 2001-08-21 | Coated metal plate for excellent-light resistance sublimable dye transfer printing and printing of coated metal plate |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR100749308B1 (en) |
| CN (1) | CN1239317C (en) |
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| CN100351080C (en) * | 2002-11-14 | 2007-11-28 | 松下冷机株式会社 | Metallic decorative sheet with sublimation-transferred pattern, heat-insulating panel and outer wall for refrigerator both employing the same, and processes for producing these |
| CN100595080C (en) * | 2004-07-15 | 2010-03-24 | 三菱电机株式会社 | Decorative member |
| CN1839036B (en) * | 2003-09-08 | 2010-08-25 | 东洋制罐株式会社 | Resin-coated metal plate and drawn can using the same |
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| CN102414020A (en) * | 2009-05-11 | 2012-04-11 | 新日本制铁株式会社 | Surface-treated metal material and manufacturing method therefor |
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| JP4056963B2 (en) * | 2002-11-14 | 2008-03-05 | 松下冷機株式会社 | Method of manufacturing metal decorative plate with sublimation transfer pattern and metal decorative plate, method of manufacturing heat insulating panel and heat insulating panel, method of manufacturing refrigerator door and refrigerator door |
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| JP2976395B2 (en) * | 1990-10-16 | 1999-11-10 | 川崎製鉄株式会社 | Painted steel sheet with excellent workability and stain resistance |
| JP3210474B2 (en) * | 1993-04-06 | 2001-09-17 | 日本ユピカ株式会社 | Resin composition for paint and paint |
| JP2776300B2 (en) * | 1995-05-31 | 1998-07-16 | 日本電気株式会社 | Audio signal processing circuit |
| JPH11148047A (en) * | 1997-11-14 | 1999-06-02 | Kansai Paint Co Ltd | Coating composition |
| JP4160188B2 (en) * | 1998-11-10 | 2008-10-01 | 関西ペイント株式会社 | Matte painted metal plate |
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2001
- 2001-08-21 CN CNB011307064A patent/CN1239317C/en not_active Expired - Fee Related
- 2001-08-21 KR KR1020010050220A patent/KR100749308B1/en not_active IP Right Cessation
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100351080C (en) * | 2002-11-14 | 2007-11-28 | 松下冷机株式会社 | Metallic decorative sheet with sublimation-transferred pattern, heat-insulating panel and outer wall for refrigerator both employing the same, and processes for producing these |
| CN1839036B (en) * | 2003-09-08 | 2010-08-25 | 东洋制罐株式会社 | Resin-coated metal plate and drawn can using the same |
| CN100595080C (en) * | 2004-07-15 | 2010-03-24 | 三菱电机株式会社 | Decorative member |
| CN1760497B (en) * | 2004-10-15 | 2010-10-06 | 上海振兴铝业有限公司 | Weatherproof color shape bars in aluminium alloy, and manufacturing method |
| CN102414020A (en) * | 2009-05-11 | 2012-04-11 | 新日本制铁株式会社 | Surface-treated metal material and manufacturing method therefor |
| CN102414020B (en) * | 2009-05-11 | 2016-04-20 | 新日铁住金株式会社 | Surface-treated metal material and manufacture method thereof |
| CN102971152A (en) * | 2010-01-22 | 2013-03-13 | 奥克蒂技术有限责任公司 | Imaging process for flooring material |
| CN108859463A (en) * | 2018-07-02 | 2018-11-23 | 天津恒丰达塑业股份有限公司 | Transfer article and its manufacturing method for sublimation transfer |
| CN112176765A (en) * | 2020-09-18 | 2021-01-05 | 江阴万邦新材料有限公司 | High-transfer-precision thermal sublimation dye adsorption coating formula |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20020015656A (en) | 2002-02-28 |
| KR100749308B1 (en) | 2007-08-14 |
| CN1239317C (en) | 2006-02-01 |
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