CN101284455B - Thermal imaging method and element - Google Patents

Thermal imaging method and element Download PDF

Info

Publication number
CN101284455B
CN101284455B CN2007101817128A CN200710181712A CN101284455B CN 101284455 B CN101284455 B CN 101284455B CN 2007101817128 A CN2007101817128 A CN 2007101817128A CN 200710181712 A CN200710181712 A CN 200710181712A CN 101284455 B CN101284455 B CN 101284455B
Authority
CN
China
Prior art keywords
layer
imaging
thermal
image
color
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
CN2007101817128A
Other languages
Chinese (zh)
Other versions
CN101284455A (en
Inventor
J·C·巴特
B·D·布施
D·P·拜贝尔
F·R·科特雷尔
A·德扬
C·刘
S·J·特尔菲尔
J·E·托恩顿
W·T·维特林
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zink Imaging LLC
Original Assignee
Zink Imaging LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zink Imaging LLC filed Critical Zink Imaging LLC
Priority claimed from US10/151,432 external-priority patent/US6801233B2/en
Publication of CN101284455A publication Critical patent/CN101284455A/en
Application granted granted Critical
Publication of CN101284455B publication Critical patent/CN101284455B/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Landscapes

  • Heat Sensitive Colour Forming Recording (AREA)

Abstract

The present invention relates to color imaging system, wherein visiting at least two, optimally three different image layers, of the thermal imaging element from same surface of the imaging element at least partly independently through one or more thermal print heads by means of controlling the temperature of the thermal printing head(s) and time applied heat energy on the imaging layer. Each color of the thermal imaging element is all printed independently or printed according to selectable percentage relative to other colors. The present invention also relates to novel thermal imaging element.

Description

Thermal imaging method and element
The application is to be on May 20th, 2002 applying date, and application number is 02815088.0, and denomination of invention is divided an application for the application for a patent for invention of " thermal imaging system ".
The cross-application of related application
The application requires the priority of series number of submitting to May 30 calendar year 2001 of temporary patent application formerly 60/294,486 and the series number of submitting on May 13rd, 2002 of temporary patent application formerly 60/364,198.
Technical field
Present invention relates in general to thermal imaging system, and more specifically relate to colored thermal imaging system, wherein visit at least two imaging layers of (address) thermal imaging element from same surface to the small part of thermal imaging element independently by a thermal printer head or a plurality of print head.
Background technology
Conventional colored thermal imaging method generally must employing independently be given body and be received the body material such as hot wax trans-printing method and dye diffusion thermal shift assay.Donor material generally comprises the colour imaging material that is coated on the substrate surface or becomes color imaging material, and this image forming material or to become color imaging material be to transfer to by the mode of heat to receive on the body material.In order to form coloured image, can adopt the donor material that comprises a plurality of in succession different colors or form the material piece of different color.If printing machine is furnished with magazine or the more than one hot head that is used interchangeably, can adopt different monochromes to the body band, carry out repeatedly color separation process, will successively be stacked each other then.Use comprises giving body member or using a plurality of complexity and costs that can improve this class print system to body member of a plurality of different color chips.Simpler way is, develops a kind of monolithic image forming material that whole colour imaging reactant system is integrated in one.
Many measures that are intended to realize colored direct heat printing are disclosed in the prior art.Such as, double-colored direct heat system is known, wherein the formation of first color is influenced by the formation of second color.United States Patent (USP) 3,895,173 disclose two looks hot record-paper, and it comprises two leuco dye systems, and one of them required activation temperature is than another height.If the leuco dye system that activation temperature is not lower just can not the higher leuco dye system of activation temperature.The direct heat imaging system is known, and it has adopted and has comprised two image-forming components that become chromatograph that are coated on the relative both side surface of transparent substrates.This image-forming component is by a plurality of print heads independent access from each side of image-forming component.Such thermal imaging system is referring to United States Patent (USP) 4,956,251.
It also is known that dyestuff is shifted the hot system that imaging method and direct heat imaging method be used in combination.In this type systematic, give body member and receive body member to contact with each other.The reception body member can receive the dyestuff from shifting to body member, and comprises that also direct heat becomes chromatograph.Thermal printer head in first time stroke with dyestuff from be transferred to the reception body member to body member, make then to body member with receive body and separate, then receive body member once more through the print head imaging with activation direct heat image forming material.Such hot system is referring to United States Patent (USP) 4,328,977.United States Patent (USP) 5,284,816 disclosed thermal imaging elements comprise substrate, and this substrate comprises direct heat in a side and becomes the chromatograph opposite side then to comprise the dyestuff transfer with receiving body member.
The thermal imaging system that the image-forming component that is adopted comprises the zone that separates on a plurality of spaces also is known, and these zones comprise the direct heat color forming composition that forms different color.United States Patent (USP) 5,618,063 and 5,644,352 disclosed thermal imaging systems scribble on the zones of different of substrate in order to form the prescription of two kinds of different colors.Similarly dichroic materials is referring to United States Patent (USP) 4,627,641.
Another kind of known thermal imaging system is the direct heat system that contains leuco dye, wherein activation image forming material and formation information is wiped by material is heated under another temperature then under a temperature.At United States Patent (USP) 5,663, in the 115 disclosed systems, utilize and realize reversible one-tenth chromatic effect to the transition process of amorphous or glassy phase from crystal.Image-forming component is heated to the fusing point of steroid developer, thereby forms colored amorphous phase, and should colour amorphous phase be heated to, make developer that crystallization take place once more and can wipe image than the low-melting temperature of material crystals.
The hot system that comprises one-tenth chromatograph that contains a kind of leuco dye that decolours and the layer that contains second leuco dye also is known, and it can form different colors.This first one-tenth chromatograph is painted at low temperatures, and the second layer then forms color under higher temperature, and ground floor also under this temperature decolorization takes place.In this type systematic, can form a kind of color or another color at the specified point place.United States Patent (USP) 4,020,232 disclose the method for passing through leuco dye/another kind of color of acid mechanism formation by leuco dye/a kind of color of alkali mechanism formation, and the reactant that adopts when wherein the first machine-processed formed color is formed another color neutralizes.The distortion of this type systematic can be referring to United States Patent (USP) 4,620,204; 5,710,094; 5,876,898 and 5,885,926.
In known direct heat imaging system, can independent access more than one layer becomes on chromatograph and make the most responsive one-tenth chromatograph be in other.After in distance sheet base layer farthest, forming image, make this layer be exposed to light and inactivation forms image then in the not too high one-tenth chromatograph of other sensitiveness.This type systematic is referring to United States Patent (USP) 4,250,511; 4,734,704; 4,833,488; 4,840,933; 4,965,166; 5,055,373; 5,729,274; With 5,916,680.
Continuous development along with the thermal imaging prior art, industry all is being devoted to develop the novel thermal imaging system that can satisfy novel performance need always, and some unfavorable characteristic of reduction or elimination known system, preferably can obtain this colored thermal imaging system, wherein can visit at least two different imaging layers of an image-forming component independently from same surface to small part, thereby every kind of color all can be printed separately or print according to optional percentage with respect to other color by a thermal printer head or a plurality of thermal printer head.
Summary of the invention
Therefore, the purpose of this invention is to provide colored thermal imaging system, it can be visited at least two different imaging layers of image-forming component independently by a thermal printer head or a plurality of thermal printer head from same surface to the small part of image-forming component.
Another object of the present invention provides colored thermal imaging system, and wherein every kind of color all can print separately or print according to selectable percentage with respect to other color.
Also purpose of the present invention provides colored thermal imaging system, wherein by controlling every layer of temperature that is applied and every layer of residing time under this temperature, visits at least two different imaging layers of image-forming component independently to small part.
A further object of the present invention provides colored thermal imaging system, wherein visit at least two different imaging layers of image-forming component independently from same surface to the small part of image-forming component, and visit one or more imaging layers from a relative side surface of image-forming component by a thermal printer head or a plurality of thermal printer head by a thermal printer head or a plurality of thermal printer head.
Another purpose of the present invention provides colored thermal imaging system, wherein visits at least two different imaging layers of image-forming component in one stroke independently to small part.
An also purpose of the present invention provides colored thermal imaging system, and it can provide branch colourity enough good image in the application-specific of this system of use.
A further object of the present invention provides novel thermal imaging element.
By colored thermal imaging system is provided, just can realize these and other objects and advantage, wherein visit at least two and preferred three imaging layers of thermal imaging element from same surface to the small part of image-forming component independently by a thermal printer head or a plurality of thermal printer head according to the present invention.Advanced thermal imaging system of the present invention is based on following: utilize two adjustable parameters, i.e. temperature and time is visited a plurality of imaging layers of thermal imaging element independently to small part.When adjusting these two parameters by the present invention,, under any particular case, all can obtain required result by the temperature of selecting thermal printer head and the duration that is applied to the heat energy on each imaging layer.According to the present invention, each color of colour imaging element can print separately or according to printing with the optional ratio of other color.Therefore as following specifically as described in, according to the present invention, temperature-time-domain is divided into a plurality of zones corresponding to different color, wish it is combined among the final printing.
The imaging layer of thermal imaging element changes on color, thereby produces required image in image-forming component.Color change can be a color from colourless to a certain, perhaps from coloured to colourless, perhaps from a kind of color to another kind of color.Used term " imaging layer " comprises all these embodiments in this paper full text (comprising claim).If color change is a color from colourless to a certain, by with the color amount in each image pixel from being colourless minimum density D basically MinChange over the highest maximal density D of formed color amount Max, just can obtain the image of the optical density (OD) grade difference (i.e. " tonal gradation " difference) of this color.If color change from coloured to colourless, by with the color amount of given pixel from D MaxBe reduced to D Min, can obtain different tonal gradations, wherein desirable D MinBasically be colourless.At this moment,, given pixel must be changed into lighter color from coloured in order to form image, but not necessarily colourless state.
For the beneficial effect that obtains to utilize time and temperature variable to be provided, there are many technology all can utilize according to the present invention.These technology comprise the thermal diffusion method that adds buried regions, chemical diffusion method or dissolution method, melting transition method and the chemical threshold method that cooperates the time-delay layer.In order to adjust a plurality of zones that are about to form every kind of required color in the image-forming component, independent use of these technology or combination with one another can be used together.
In preferred embodiments, thermal imaging element comprises two and preferred three different imaging layers by the same surface bears of substrate.In another embodiment preferred, thermal imaging element comprises by one or more image forming material layers of a surface bears of substrate and by one or more image forming material layers of the relative side surface of substrate carrying.According to imaging system of the present invention, the imaging layer of image-forming component can be visited independently via thermal printer head that contacts with the same surface of image-forming component or a plurality of print head to small part.In preferred embodiments, can utilize one or more thermal printer heads to visit two different imaging layers independently, and utilize another thermal printer head to visit one or more imaging layers independently by the relative side surface carrying of substrate from a relative side surface to the small part of image-forming component by a surface bears of substrate from a surface to the small part of image-forming component.The thermal printer head of the contact of a relative side surface with image-forming component can be each other over against arranging or staggered each other, thereby make any distinct area on the image-forming component produce carryover effects when separately thermal printer head contacts betwixt.
In another preferred embodiment, can adopt a thermal printer head in one stroke, to visit the two or more different imaging layers of image-forming component independently to small part, and optional second thermal printer head that adopts is visited one or more imaging layers, and it can be used in combination with first thermal printer head or following closely.
Description of drawings
In order to understand the present invention and other purpose and advantage and further feature thereof better, by accompanying drawing a plurality of embodiment preferred are carried out specific description, wherein:
Fig. 1 illustrates can be by the color of the double-colored direct heat print system printing of prior art;
Fig. 2 illustrates can be by the color of the double-colored direct heat printing of the present invention embodiment printing;
Fig. 3 illustrates the non-independent color dot that runs in the prior art direct heat print process and forms;
Fig. 4 illustrates can be by the color of prior art three look direct heat print systems and the printing of the present invention's three look direct heat printing embodiment;
Fig. 5 illustrates one embodiment of the invention;
Fig. 6 diagram further illustrates the present invention's embodiment shown in Figure 5;
Fig. 7 illustrates how to implement three look embodiments of the present invention;
Fig. 8 is the schematic side partial view that has utilized the double-colored image-forming component of the present invention of heat lag effect;
Fig. 9 is the schematic side partial view that has utilized the present invention's three look image-forming components of heat lag effect;
Figure 10 is the schematic side partial view that has utilized another three looks image-forming component of the present invention of heat lag effect;
Figure 11 is a schematic part lateral plan of implementing the hot stamping brush equipment that embodiment of the present invention adopted;
Figure 12 illustrates in prior art thermal imaging method process and apply voltage method on conventional thermal printer head;
Figure 13 illustrates when implementing thermal imaging system embodiment of the present invention and apply voltage method on conventional thermal printer head;
Figure 14 illustrates the another kind of method that applies voltage when implementing thermal imaging system embodiment of the present invention on conventional thermal printer head;
Figure 15 illustrates the developing time of two kinds of dyestuffs and the relation of temperature;
Figure 16 is the schematic part lateral plan that has utilized the colour imaging element of the present invention of chemical diffusion and dissolution method;
Figure 17 is the schematic part lateral plan of negativity colour imaging element of the present invention; And
Figure 18 is the schematic part lateral plan that has utilized the present invention's three look image-forming components of chemical diffusion and dissolution method.
The specific embodiment
As previously mentioned, according to colored thermal imaging system of the present invention, visit two or more colour imaging layers of thermal imaging element independently from same surface to the small part of image-forming component, thereby every kind of color can be printed or print according to selectable percentage with respect to other color separately, by selecting color based on two adjustable parameters, be temperature and time, can obtain these results.Temperature-time-domain is divided into a plurality of zones corresponding to different color, wishes it is made up.
In order to help the one skilled in the art to understand the implication of independent control color when relevant better with colored direct heat print process of the present invention, preferably at first consider the prior art thermal imaging system, it relates to and contain two thermal imaging elements that become chromatograph in white reflectivity substrate.For convenience of explanation, can consider like this that layer is blue or greenly to become chromatograph and another is the fuchsin quality layer, and the temperature threshold of blue or green layer is higher than magenta layer.If independent point on this image-forming component or zone apply the fixing thermal pulse of length, will form color according to the difference of pulse strength.The raising pulse strength can improve the maximum temperature in place, the thermal pulse present position imaging layer.Color temperature along with temperature surpasses pinkish red threshold value, the medium that is white in color at first can become magenta gradually, color temperature and becomes blueness gradually along with temperature surpasses blue or green threshold value then, promptly pinkish redly adds blue or green color.This color change process can be represented with 2 dimension chromatic graphs shown in Figure 1.
Shown in curvilinear path, along with the temperature in the magenta layer surpasses threshold temperature, color at first moves along pinkish red direction, along with the temperature in the blue or green layer surpasses threshold temperature, then moves towards blue or green direction then, promptly moves towards blue direction.Each point on the color locus is relevant with the thermal pulse intensity that produces this point, and each pulse strength is all relevant with the ratio of cyan with the magenta of fixing.If the intensity of the pulse that applied fixed and change its duration, also can produce similar color change process, prerequisite is that energy is wanted enough by force, the temperature of two dye coatings all is increased to be higher than its threshold value color temperature.At this moment, when pulse began, the temperature of two dye coatings progressively raise.Along with the prolongation in pulse duration, dye temperature at first surpasses pinkish red threshold value and surpasses blue or green threshold value then.Each pulse duration also is transformed into magenta again to blueness corresponding to the color of regulation along curvilinear path from white.The prior art thermal imaging system adopts regulating impulse amplitude or pulse duration, therefore only limits to reproduce the color that drops in the chrominance space on the curvilinear path basically.
The present invention is by visiting the different imaging layers of colored thermal imaging element independently to small part, in the thermal imaging method that is provided, formed color is not limited to the one dimension track but can selects in the whole zone of track both sides, shown in the shadow region of Fig. 2.
In aforesaid explanation, term " part independently " refers to the visit imaging layer.To what extent the independent access imaging layer is relevant with the image property that is commonly referred to as " branch colourity ".As previously mentioned, provide branch colourity enough good image in the various application that the objective of the invention is to suit at thermal imaging method of the present invention.Such as, the photographing imaging method requires branch colourity suitable with the branch colourity that conventional photographic exposure and development are obtained.According to printing time, the highest printing energy and other factors, can obtain various independent degree during the visit imaging layer.Term " independence " refers to this situation, and one becomes chromatograph after printing, generally can become to form very little in the chromatograph but general sightless optical density (OD) (density＜0.05) at other.Equally, the colored printing process of term " basically independent " refers to this situation, make look like in the involuntary visible density of catching color and producing of other one or more imaging layers and the photochrome between painted typical magnitude be in same magnitude (density＜0.2).In some cases, the color under this magnitude intersect to disturb and to be regarded as satisfying the photograph needs.Term " part independently " visit imaging layer refers to this situation, can make other one or more imaging layers catch color when printing maximal density in the anterior layer, and its density is higher than 0.2 but be no more than at about 1.0 o'clock." to small part independently " language comprises aforesaid all independent degree.
From the picture characteristics that is obtained separately, the difference between thermal imaging system of the present invention as can be seen and the prior art thermal imaging method.When two imaging layers can't independent access, have one or two in them and all can't not take place to print under the situation of serious colour contamination with another.Such as, think that the monolithic thermal imaging element that two kinds of colors is provided and designs is an example, color 1 and color 2, its painted temperature threshold is respectively T 1And T 2, T wherein 1＞T 2Consider to utilize heating element heater to heat and form a single color point from the upper surface of thermal element.Temperature T a bit reaches its peak T in place at certain Max, generally be the central authorities of heat affected zone.T far away more is just low more apart from this point, is reduced to far below T rapidly beyond heat affected zone 1Or T 2Temperature, shown in Fig. 3 a.Will be at local temperature T greater than T 2But less than T 1The zone in print out color 2 points (seeing Fig. 3 b) of " pure ".If T MaxSurpass T 1, so this point will with the color T of centre 1Mixed in together, thus again can't form color independently.
It should be noted that for printing color 1 point, require T Max＞T 1, and because T 1＞T 2, this must mean, has printed color 2 (seeing Fig. 3 c) too.Therefore, independent printing color 1 is impossible.The way that addresses this problem is to introduce the bleaching of color 2, as long as color 1 forms, this bleaching will play a role.If bleach, then be higher than T at T 1Heat affected zone in only color 1 be visible.But this can not be an independent access, and reason has two.The one, can't obtain any mixture of color 1 and color 2 according to this mode.The second, this can stay next annular section around 1 of each color, and the color 2 in this zone is without bleaching (seeing Fig. 3 d).
According to the present invention, for two kinds of colors of independent access in previous examples, can introduce time-delay mechanism, by this mechanism, the coloring process of second dye coating produces certain delay with respect to the coloring process of first dye coating.At this timing period, can on first dye coating, write down and can not make the second layer painted; And if the painted threshold temperature of the second layer is lower than the ground floor, just can on the second layer, writes down subsequently and can not surpass the threshold value of ground floor.
In one embodiment, the inventive method can form green grass or young crops or magenta fully independently.Therefore, in this embodiment, a kind of compound mode of temperature and time can make in vain-select any fuchsin density to become on the pinkish red axle may and can not produce any tangible cyan.The another kind of compound mode of temperature and time make in vain-select any blue or green density to become on the blue or green axle may and can not produce the painted existing picture of any tangible magenta.Two temperature-time compound mode is combined, just make that any green grass or young crops/pinkish red mixture of selection becomes possibility in closed area shown in Figure 2, independently blue or green and pinkish red control effect is provided thus.
In other embodiments of the present invention, when heat visit imaging layer, be not to be fully independently, but independent basically or only part is independently.From various considerations, comprise material property, print speed printing speed, energy consumption, material cost and other system requirements, its color of the system that is obtained intersects the existing picture of interference must be very serious.Though according to the present invention color being carried out independence or independently selects basically is to realize that the photographic quality printing is desirable, but this demand is very unimportant when printing some image such as manufacturing label or colored complimentary ticket, and in these cases, can sacrifice this demand based on economic consideration, such as improving print speed printing speed or reducing cost.
In these embodiments of the present invention, each imaging layer of colored thermal imaging element is not complete independent access, but basically or the part independently the visit, and from design, printing can cause forming the magenta of controlled amounts when blue or green, vice versa, therefore can not print out pure fully pinkish red or complete pure green grass or young crops.In fact, a color square frame is arranged all near each reference axis, the color that representative can't be printed, spendable color then falls into more limited zone, in shadow region shown in Figure 2.In these cases, though the range of choice that operational color kind analogy embodiment of the present invention is comprised will be lacked, the latter's color is selected can independently control fully, and however, it is still than superior in the very large prior art systems of limitation aspect the color selection.
Similarly consideration also is applicable to three look embodiments of the present invention.For these embodiments, chrominance space is three-dimensional, and generally is referred to as " look cube " shown in Figure 4.If the colored direct heat printed medium of prior art is applied the regular length thermal pulse that temperature increases gradually, will pass cube and produce color along the curvilinear path shown in the empty arrow.As figure shows, this track generally is a white from a kind of color, extends to another kind of color, generally is black, and the color kind of being passed by is simultaneously fixed.On the contrary, one embodiment of the invention are very advanced, and it can print any color in this three-dimensional color cubes.In other embodiments of the present invention, the access process that becomes chromatograph be basically or part independently, might be formed on the interior color of shaded area of Fig. 4, provide much bigger flexibility than prior art direct heat print system again aspect the selection of color.
For temperature and time parameter attribute of the present invention is described, with reference to Fig. 5, it illustrates one embodiment of the invention.Such as, thermal imaging element contains blue or green image forming material, and visual cyan zone C can be provided when it bears higher relatively temperature at short notice, and pinkish red image forming material, and it can provide visual pinkish red regional A when bearing lower temperature in the long time.Can utilize the combined effect of the length thermal pulse of different temperatures to select the ratio of every kind of color.Can see according to the present invention, because relate to two adjustable variablees and two or more image forming materials arranged, so control any specific color at least basically fully independently according to the present invention, require to specify unique substantially time and temperature range into every kind of color.
In conjunction with Fig. 6,, just be appreciated that and other relevant consideration of the colored thermal imaging system of the present invention by the following discussion that double-colored leuco dye system is done.Such as considering certain system, wherein color produces by leuco dye, and this dyestuff can combine with the acid developer material by thermal diffusion.Can't be limited to the developer response in the zone of a certain complete closed this moment, such as zone shown in Figure 5.Though be intended to utilize the temperature and time in the zone shown in Figure 5, image-forming component also can produce response in the temperature and time scope of broad.Refer now to Fig. 6, can see in this illustrative examples, regional A and C aim at the pinkish red zone of selecting with green grass or young crops of printing.But the compound mode of temperature and time makes pinkish red leuco dye diffuse to developer such as also being enough among area B and the E.And, with regard to the temperature among region D and the E-time compound mode, also can print cyan.Therefore, for according to the present invention's blue or green and pinkish red image forming material of control fully independently basically, pinkish red printing zone A preferably should be not overlapping with zone C, D or E, perhaps not with any other region overlapping that green grass or young crops is had response.On the contrary, blue or green printing zone C preferably should be not overlapping with regional A, B and E, perhaps not with any other region overlapping that magenta is produced response.Generally speaking, this means for the diffusion leuco dye system of example that the independent colored printing zone of selecting should be arranged along an inclined-plane, this inclined-plane is from the time of length tilts to higher temperature to the short time and from lower temperature.What know is, in the implementation process of reality, though selected printing zone shape may not be the rectangle shown in the schematic diagram, but its shape is the proterties control of physical method used when painted, and contains and satisfy the limited region overlapping that the required branch colourity of application-specific requires.
The suitable schematic arrangement mode of the present invention three look DIFFUSION CONTROLLED leuco dye systems as shown in Figure 7, wherein expression be print respectively magenta, green grass or young crops and when yellow time-temperature makes up.
In a preferred embodiment of the invention, the selected temperature in quality zone generally is about 50 ℃～about 450 ℃.Become preferably about 0.01～about 100ms of the duration that applies heat energy on the chromatograph to image-forming component.
As previously mentioned, many imaging techniques can be used according to the present invention, comprise the thermal diffusion method that adds buried regions, chemical diffusion or dissolution method, melting transition method and the chemical threshold method that cooperates with the time-delay layer.
Refer now to Fig. 8, can see colored thermal imaging element, it utilizes hot time-lag action for each color definition printing zone to be formed to be arranged.The thermal diffusion that image-forming component 10 relies on by image-forming component is used for obtaining delay difference effect proposed by the invention.Image-forming component 10 comprises and is loaded with blue or green and pinkish red imaging layer 14 and 16 and the substrate 12 of wall 18 respectively.It should be noted that in each embodiment of the present invention, imaging layer itself can comprise two or more independently layers.Such as, when the imaging material was the leuco dye that uses with the developer material fit, leuco dye can be arranged in the different layers with the developer material.
If from blue or green imaging layer 14 top heating, the thermal break-through image-forming component arrives pinkish red imaging layer 16 to image-forming component 10 via thermal printer head.Blue or green imaging layer 14 almost is heated above its painted threshold temperature by thermal printer head immediately after applying heat, but pinkish red imaging layer 16 has one period comparatively significant period of delay before reaching its threshold temperature.If two imaging layers all begin to form color under same temperature, such as 120 ℃, and print head is heated to temperature with image-forming component 10 surfaces and is much higher than 120 ℃, so blue or green imaging layer 14 will almost begin to provide cyan immediately, pinkish red imaging layer 16 then begins to provide magenta after a period of time postpones, this depends on the thickness of wall 18.The activating chemical character of color is not very crucial in each layer.
For according to the invention provides the colored printing effect, each imaging layer is designed to activate under different temperature, is T such as blue or green imaging layer 14 5The pinkish red imaging layer 16 of " embedding " formula then is T 6Can obtain this effect like this, such as these imaging layers being designed to have different melt temperatures or to wherein introducing different hot solvents, these solvents are fusion and liquefaction image forming material under different temperature.Selected temperature T 5Compare T 6High.
If be applied to temperature on the image-forming component less than T 6, how long no matter apply, do not have color yet and form.Therefore, image forming material can be less than T 6Temperature under transport safely and store.If the printed element that contacts with layer 14 applies heat, make the temperature of imaging layer 16 be in T 5～T 6Between, it is colourless basically that so blue or green imaging layer 14 can keep, and pinkish red imaging layer 16 can form pinkish red color density after postponing after a while, and this time is relevant with the thickness of wall 18.If the printed element that contacts with imaging layer 14 is applied to temperature on the image-forming component just above T 5, so blue or green imaging layer 14 can begin to form color density immediately, and pinkish red imaging layer 16 also can form magenta density but just will be through delay after a while.In other words, moderate temperature may produce magenta and not produce cyan with the relative long time, and with regard to high-temperature and relative to regard to the time of lacking, and may produce cyan and did not produce any magenta.Thermal pulse and the time that time is short, temperature is high thermal pulse long, that temperature is medium is combined the magenta and the cyan that can obtain according to selected percentage combination.
What those skilled in the art will know that is, provides desirable differential effect in the mechanism described in Fig. 8 between two kinds of colors before, and wherein selected thermal printer head is in order from image-forming component 10 surfaces heat to be passed away effectively after heat applies.Be even more important during the firm end of this printed pixels in imaging layer 14.
The imaging layer 14 of image-forming component 10 and 16 can be chosen the color change that produces more than one wantonly.Such as, imaging layer 14 can be from the colourless yellow that is varied to red, and this is relevant with the heat that is applied.During imaging layer 16 beginnings can be coloured, becomes the colourless different color that becomes then then.One skilled in the art will appreciate that by adopting United States Patent (USP) 3,895,173 described image-forming mechanisms just can obtain these color change.
Except described two imaging layers of Fig. 8,, can adopt any known printing form for the 3rd imaging layer or additional imaging layer are provided.Such as, the 3rd imaging layer can pass through imagings such as ink jet printing method, thermal transfer, photograph method.Especially, image-forming component 10 can comprise the 3rd imaging layer, forms after the color in this layer, can fix by exposure method, and this is known in the prior art.In this embodiment, the 3rd imaging layer should be in image-forming component 10 near surfaces, and prints under the temperature lower than imaging layer 14 before printing imaging layer 14.The 3rd layer fix also can be carried out before printing imaging layer 14.
Substrate 12 can be the used any suitable material of thermal imaging element, such as polymeric material, and can be transparent or reflexive.
Any combination of materials that can the thermal induction variable color all can adopt.These materials can issue biochemical reaction in heat effect, perhaps because of physical mechanism contacts with each other, such as fusion or diffusion, perhaps by heat reaction rate are quickened.Reaction can be that chemistry is reversible or irreversible.
Such as, the leuco dye precursor can form color when contacting with the reactant thermal induction.This reactant can be Bronsted acid, referring to " Imaging Processes andMaterials ", and Neblette the 8th edition, J.Sturge, V.Walworth, A.Shepp compiles, Van Nostrand Reinhold, 1989, the 274-275 page or leaf, perhaps Lewis acid is referring to such as United States Patent (USP) 4,636,819.With the shared suitable dyestuff former of acid reaction agent such as referring to United States Patent (USP) 2,417,897, south african patent 68-00170, south african patent 68-00323 and Deutsche Bundespatent 2,259,409.Other example of this class dyestuff can be referring to " Synthesis and Properties of Phthalide-type Color Formers ", it is that Ina Fletcher and Rudolf Zink are at " Chemistry and Applicationsof Leuco Dyes ", Muthyala compiles, Plenum Press, New York delivers in 1997.This class dyestuff can comprise triarylmethane, diphenyl methane, xanthenes, thiazine or spiro-compound, such as crystal violet lactone, the colourless auramine of N-halogenophenyl, rhodamine B aniline lactams, 3-piperidines also-6-methyl-7-aniline fluorane, benzoyl leucomethylene blue, 3-methyl-spiral shell dinaphtho furans etc.Acid material can be phenol derivatives or aromatic derivant carboxylate, such as p-t-butyl phenol, 2, and two (p-hydroxybenzene) propane, 1 of 2-, two (p-hydroxybenzene) pentanes of 1-, P-hydroxybenzoic acid, 3,5-di-tert-butyl salicylic acid etc.This class thermal imaging material and various combination thereof are known at present, and to adopt the whole bag of tricks of these material preparation heat sensitivity recording elements also be known, and such as can be referring to United States Patent (USP) 3,539,375,4,401,717 and 4,415,633.
Forming the used reactant of coloured dyestuff from colourless precursor also can be electrophilic reagent, such as referring to United States Patent (USP) 4,745,046, alkali is such as referring to United States Patent (USP) 4,020,232, oxidant, such as referring to United States Patent (USP) 3,390,994 and 3,674,467, reducing agent, such as referring to United States Patent (USP) 4,042,392, chelating agent is such as referring to United States Patent (USP) 3,293,055, spiro-pyrans dyestuff, perhaps metal ion, such as referring to United States Patent (USP) 5,196,297, wherein thiolactone dyestuff and silver salt form complex and are formed with color substance.
Also can adopt back reaction, wherein coloring matter is because of becoming colourless with reactant generation effect.Therefore, can become colourlessly under the alkali effect such as protonated indicator dye, perhaps irreversible decolouring can take place because of the effect of alkali in the preformed dyestuff, such as referring to United States Patent (USP) 4,290,951 and 4,290,955, perhaps the electrophilic dyestuff can be bleached by the nucleophilic reagent effect, such as referring to United States Patent (USP) 5,258,274.
Also can adopt previous reaction that molecule is changed into the form that another kind has different color from a kind of coloured form.
Is what to separate such as used reactant in described many schemes before with dyestuff former, comes in contact under the effect of heat with dyestuff former then, perhaps can adopt the precursor of reactant itself.The reactant precursor can closely contact with dyestuff former.Can utilize the effect of heat from the reactant precursor, to discharge reactant.Therefore, such as United States Patent (USP) 5,401,619 disclose the method for heat release Bronsted acid from precursor molecule.But other example of heat release reaction agent can be referring to " Chemical Triggering ", G.J.Sabongi, PlenumPress, New York (1987).
Can adopt the material of two kinds of novel colored molecules of formation that are coupled together.This class material comprises the coupling agent that diazol collocation is suitable, such as referring to " Imaging Processes andMaterials ", 268-270 page or leaf and United States Patent (USP) 6,197,725, the perhaps suitable coupling agent of Oxybenzene diamine compound collocation, such as referring to United States Patent (USP) 2,967,784,2,995,465,2,995,466,3,076,721 and 3,129,101.
Other chemical stain method relates to monomolecular reaction, and it can form color from colourless precursor, make coloring matter produce color change, perhaps bleaching coloured material.The speed of this class reaction can be quickened because of being heated.Such as United States Patent (USP) 3,488,705 disclose the thermally labile type acylate of triarylmethane dye, and it can decompose and bleach when heating.United States Patent (USP) 3,745,009 the U.S. of mandate again review patent 29,168 and United States Patent (USP) 3,832,212 disclose temperature-sensitive takes a picture and use thermographic compound, and it contains-the heterocyclic nitrogen atom of OR group replacement, such as carbonate group, its bleaching principle is that nitrogen-oxygen key when heating equal cracking takes place or heterolytic fission is separated reaction and produced RO +Ion or RO ' free radical and dye base or dyestuff free radical, the back both further generating unit divide cracking.United States Patent (USP) 4,380,629 disclose the quasi-styrene based compound, and reversible or irreversible open loop and ring-closure reaction take place in it under the activation evergy effect, thereby produce painted or discoloration.United States Patent (USP) 4,720,449 disclose acylation reaction in the molecule, and it changes into coloured form with colourless molecule.United States Patent (USP) 4,243,052 discloses the pyrolytic reaction of quinophthalone precursor mixed carbonate ester, can be used for forming dyestuff.United States Patent (USP) 4,602,263 disclose heat can remove blocking group, can be used for making the color of dye coloring or change dyestuff.United States Patent (USP) 5,350,870 disclose acylation reaction in the molecule, can be used for producing color change.Other example of unimolecule dye-forming reaction is referring to " New Thermo-Response Dyes:Coloration by the Claisen Rearrangement andIntramolecular Acid-Base Reaction ", Masahiko Inouye, KikuoTsuchiya and Teijiro Kitao, Angew.Chem.Int.Ed.Engl.31,204-5 page or leaf (1992).
Formed coloring matter differs, and to establish a capital be dyestuff.Coloring matter also can be such as being materials such as metal or polymer.United States Patent (USP) 3,107,174 disclose by forming argent (it looks it is black) with the colourless mountain Yu acid silver of suitable reducing agent reduction under the effect of heat.United States Patent (USP) 4,242,440 disclose the thermal activation system, and wherein polyacetylene is as chromophore.
Also can adopt physical mechanism.It is known that phase transformation causes physical appearance to change.Phase transformation is such as causing light scattering property to change.The thermal activation diffusion takes place in dyestuff from the restricted area, change its covering power and apparent density thus, also referring to " A New ThermographicProcess ", Shoichiro Hoshino, Akira Kato and Yuzo Ando, Symposiumon Unconventional Photographic System, Washington D.C., on October 29th, 1964.
Imaging layer 14 and 16 can comprise any aforesaid image forming material, perhaps any other thermal activation developer, and its thickness is generally about 0.5～about 4.0 μ m, preferred about 2 μ m.When imaging layer 14 and 16 comprised more than one layer, the thickness of each group layer was generally about 0.1 μ m～about 3.0 μ m.Imaging layer 14 and 16 can comprise dispersion, enclosed liquid, amorphous or solid material or the solution of active material in polymer adhesive, the perhaps combination of any previous materials of solid material.
The thickness in intermediate layer 18 is generally about 5～about 30 μ m, preferably about 14-25 μ m.Intermediate layer 18 can comprise any suitable material, comprises inert material or produce the material of phase transformation when being heated, such as when layer comprises hot solvent.General suitable material comprises that polymeric material is such as polyvinyl alcohol.Intermediate layer 18 can comprise one or more suitable materials and can be made of one or more layers.Intermediate layer 18 can or be administered in the film laminated with imaging layer through moisture or solvent-laden solution coat.Intermediate layer 18 can be opaque or transparent.If the intermediate layer is opaque, substrate 12 is preferably transparent so, thereby can print the outer surface of image-forming component 10 with thermal printer head from a side.In particularly preferred embodiments, substrate 12 is transparent, and intermediate layer 18 is white.Only adopt a thermal printer head thus, only on a side of described sheet material, print, just obtained the effect of single sheets two-face printing.
Thermal imaging element of the present invention also can comprise hot back coating and the protective cowl surface layer that is arranged on the imaging layer outer surface.In the preferred embodiment of image-forming component shown in Figure 8, be included in barrier layer and protective cowl surface layer on the layer 14.The barrier layer can comprise water and preventing property of gas material.Barrier layer and finishing coat can provide UV anti-radiation protection effect by cooperation.
In another embodiment of image-forming component shown in Figure 8, imaging layer 16 is coated in the thin substrate 12, such as the PETG of the about 4.5 μ m of thickness.Deposit intermediate layer 18 and imaging layer 14 then.Substrate 12 can be opaque or transparent and can be coated with, laminated or extrude on layer 16.In this embodiment of the present invention, imaging layer 14 and 16 can be by one or more thermal printer heads by thin substrate 12 visits.
Refer now to Fig. 9, can see and adopt heat lag to do the three look thermal imaging elements according to the present invention of printing zone to be formed are arranged in order to limit color.Three look image-forming components 20 comprise substrate 22, are respectively blue or green, pinkish red and yellow imaging layer 24,26 and 28, and wall 30 and 32.Preferred interlayer 30 is thinner than intermediate layer 32, as long as it is identical with thermal conductivity to constitute its thermal capacity of material of two layers.Layer 24 activation temperature be than layer 26 height, and the latter is then than the activation temperature height of layer 28.
According to the preferred embodiments of the invention, a plurality of imaging layers of thermal imaging element are by the same surface bears of substrate, as shown in Figure 9, wherein three imaging layers are by the same surface bears of substrate 22, two imaging layers can be via one or more thermal printer heads from a surface of this element and be embodied as picture, and at least the three imaging layer is from the relative side surface imaging of substrate via thermal printer head independently.In the embodiment depicted in fig. 9, imaging layer 24 and 26 is via one or more and become thermal printer head imagings that the outer surface of chromatograph 24 contacts, forms chromatograph 28 and be the thermal printer head imaging that contacts by the outer surface with substrate 22.In the embodiment of the present invention, substrate 22 is thinner, and it is generally less than about 20 μ m and preferred about 5 μ m.
At this moment, because substrate 22 is thinner, preferably image-forming component is laminated in other substrate, such as the label card base-material.This laminate structures also can provide additional feature, and the structure such as imaging layer being designed to separate at once when taking laminate structures apart provides secured feature thus.Also can introduce ultraviolet ray and infrared ray secured feature to imaging layer.
The thermal imaging element of imaging is laminated in another substrate by inciting somebody to action, can provide many products to use.Base material can be any material that is loaded with adhesive.Therefore, imaging can be carried out on various materials, such as transparent or reflectivity sticking agent material, can be laminated in it transparent or the reflectivity carrier material on, so that the transparency or reflectivity product to be provided.
Figure 10 has illustrated and wherein two imaging layers has been arranged on the side of substrate, and an imaging layer is arranged on the opposite side of substrate according to colored thermal imaging element of the present invention.Refer now to Figure 10, can see, image-forming component 40 comprises substrate 42, first imaging layer 44, intermediate layer 46, second imaging layer 48, the 3rd imaging layer 50, optional white or reflective layer 52, back layer 53 and finishing coat 54.In this embodiment preferred, substrate 42 is transparent.Imaging layer and intermediate layer can comprise any material of above-mentioned these layers.Optional layer 52 can be any suitable reflective material or can comprise the Chinese white particle, such as titanium dioxide.Protective cowl surface layer and back layer 53 and 54 can comprise any suitable material, and these materials can provide lubricating function, heat-resisting, UV, water and oxygen barrier layers performance etc.This class material can comprise dissolving or be dispersed with suitable micromolecular polymer adhesive, and the one skilled in the art is very familiar to this.The activation temperature of imaging layer 48 is lower than imaging layer 44, and the activation temperature of imaging layer 50 and the identical of imaging 48 or than being high or low, and low as far as possible to satisfy the needs of room temperature and transportation stability.
In preferred embodiments, can utilize a thermal printer head to visit two imaging layers independently from a surface of image-forming component, and utilize another thermal printer head to visit one or more imaging layers independently by the relative side surface carrying of substrate from the relative side surface of image-forming component by a substrate surface carrying.This embodiment preferred of the present invention will more specifically illustrate with reference to image-forming component shown in Figure 10, though what will know is to utilize other suitable image-forming component to implement this embodiment.The thermal printer head of relative side surface contact with image-forming component can be each other over against arrangement.Perhaps, and preferably, each print head is staggered each other as shown in figure 11.And, can adopt two independently hot stamping brush motors, such as from Alps Electric Co.Ltd., Tokyo, the Alps MBL 25 that Japan obtains.But, preferably adopting this hot stamping brush equipment, wherein a part of parts are shared by two print stations such as drive motors and power supply.
Refer now to Figure 11, can see a volume thermal imaging element 55, such as image-forming component shown in Figure 10.Make this image-forming component by between first thermal printer head 56 and the bearing roller 57, subsequently by between second thermal printer head 58 and the bearing roller 59.First thermal printer head 56 to small part is visited first and second imaging layers 44 and 48 independently, and they can be respectively blue or green and pinkish red imaging layer, and second thermal printer head, 58 visits the 3rd imaging layer 50, it can be yellow imaging layer.
As previously mentioned, in advanced person's of the present invention polychrome thermal imaging method, two or more different thermal imaging element imaging layers are to be visited independently from same surface to the small part of image-forming component by a thermal printer head or a plurality of thermal printer head.In particularly preferred embodiment of the present invention, two or more different thermal imaging element imaging layers are visited to small part in an one way independently via a thermal printer head.Be applied to control signal on the conventional thermal printer head by manipulation, just can realize these methods, the heating element heater of this print head contacts with the image-forming component surface.Conventional thermal printer head is made of the linear array of heating element heater, and each all has corresponding electronic switch, and it can realize being communicated with between common electric voltage bus and ground wire.The temperature and time that common influence heat of the voltage of common bus and the shut-in time of electronic switch exposes.
For temperature controlling method when of the present invention of implementing is described, below the operation of thermal printer head is described more specifically.In the normal use of print head, print head is applied fixing voltage and by the time length that is controlled at when applying energy on the heating element heater imaging intensity regulated.Control system can disperse, in other words, will on image-forming component, print the used time interval of each pixel be divided into a plurality of discrete at interval inferior, and each inferior interim heating element heater both can be in activation and also can be in unactivated state.And, can control each inferior working cycles of interior heating at interval.Such as, if heating element heater therein an inferior interim be in state of activation, and should the Asia at interval working cycles be 50%, energy will account for this specific inferior at interval 50% during in be applied on the heating element heater.This method is seen Figure 12.
What Figure 12 represented is the application of print head, wherein that each pixel pressroom is equal at interval inferior every being divided into 7.With regard to shown in situation with regard to, this pixel inferior is in state of activation at interval at preceding 4, and inferiorly is in unactivated state at interval at back 3.In addition, the potential pulse working cycles that is applied is 50%, so in each activated inferior interval, voltage was opening and is closed condition in second half in the inferior interval of half.Because in the voltage that is applied, one of ordinary skill in the art will readily recognize that, the temperature-responsive of heating element heater can utilize the working cycles of common bus voltage and pulse to control temperature.In fact, if each inferior thermal time constant much shorter during at interval than the heating and cooling medium, the effect of the working cycles by changing pulse just can be simulated the influence of change common bus voltage so.
This just provides at least two kinds of possibilities for the mean power that control is applied on the print head.The firstth,, by handling the temperature of the Control of Voltage print head heating element heater on the common bus, in each inferior interval, make working cycles remain fixed in some predetermined value simultaneously.At this moment, mainly control temperature, and come the control time by the inferior number of selecting heater is activated at interval by the mode of selecting bus voltage.
Second kind of possibility be, comes the control heater temperature by handling inferior working cycles at interval, and bus voltage remains unchanged simultaneously.In order to make full use of this temperature-controlled process, require inferiorly to be shorter than the thermal time constant of image-forming component at interval, thereby make the average energy that the temperature-responsive in the imaging layer applied in inferior interim rather than follow voltage and fast transition.For the typical print head in this application, can lack 10 times or littler inferior blanking time than the thermal response time of image-forming component, therefore can satisfy this condition well.
Select anyly among these two kinds of control methods, perhaps two kinds of methods are combined, this concerns concrete design.Such as, in the multiple-pass system, each color layer all is to print in the independent stroke of image-forming component under print head, it is not so difficult to change the voltage that is applied on the print head common bus in the each run.Be easy to regulate the voltage that applied then to obtain optimum efficiency.On the other hand, for the one-stroke system, two or more color layers are successively to be recorded in each pixel place apace, and generally speaking this print head of operation is more convenient and economical under fixing voltage.At this moment, the inferior working cycles at interval of preferably passing through the regulation order realizes variations in temperature.
These two kinds of technology are seen Figure 13 and 14, and they are based on two kinds of imaging layer systems, and the high temperature that one of them imaging layer was applied by the short time activates, and the low temperature that another imaging layer is then applied for a long time activates.
Figure 13 has schematically illustrated by the activationary time that changes bus voltage and heater and realized the alternately method of record on two imaging layer.During beginning, at high temperature continue short time realization record, under the high-voltage pulse of a series of weak points, realize record then.Then, adopt the long action of low-voltage pulse of sequence to realize record at low temperatures for a long time.This sequence is order before and after becoming to repeat alternately between the chromatograph then.
Figure 14 has schematically illustrated and realized the alternately another kind of method of record on two imaging layer.At this moment, change is that pulsed operation circulates but not pulse voltage.Realize heating between high temperature, short time with the high short train pulse of working cycles.The low working cycles pulse long with sequence realizes the low temperature long-time heating.
Method shown in Figure 14 can form image in the present invention comprises the image-forming component of two imaging layers, below more specifically be described.Will be on thermal imaging element with the zone of print head heating element heater thermo-contact in form the single image pixel the time interval be divided into a plurality of instantaneous inferior (hereinafter referred to as little at interval inferior) at interval, as previously mentioned.Little inferior duration at interval can be equal to each other or not wait.In preferred embodiments, little inferior duration at interval equates.The time interval that also will form single pixel was divided into for first and second time intervals, and the very first time is shorter than second time interval at interval.The very first time is used for forming the image in the first one-tenth chromatograph of thermal imaging element (can be that high temperature becomes chromatograph) at interval, and second time interval was used for forming the image in the second one-tenth chromatograph of thermal imaging element (can be that low temperature becomes chromatograph).In the interval separately in the very first time interval and second time interval, can contain great majority or all aforesaid little inferior intervals.If this is inferior slightly all to be isometric at interval, contained little inferior interval, very first time interval was lacked than second time interval so.The length in second time interval preferably is very first time twice at interval at least.The very first time not necessarily was in before second time interval at interval.The very first time combines required whole time interval when also not taking the single pixel of printing with second time interval at interval, and this is possible.But when the very first time was combined with second time interval at interval, required most of the time at interval when preferably taking the single pixel of printing.
Activate the print head heating element heater by applying a current impulse at little inferior interval section.Apply time that current impulse continues this little inferior at interval in shared percentage (being working cycles) can be any value between about 1%～100%.In preferred embodiments, the working cycles in very first time interval is fixed value p 1, and be the second fixed value p in second time interval 2, and p 1＞p 2In preferred embodiments, p 1Near 100%.Preferred p 1More than or equal to p 2The twice of length.
At very first time interval with in second time interval, by from alternative little inferior sum at interval, selecting one group of specific little inferior interval, in this inferior slightly interval, apply current impulse, can in imaging layer, obtain different imaging degree (that is the different tonal gradation of image).By changing the size of printing points in the imaging layer, perhaps change the optical density (OD) of printing points in the imaging layer, perhaps combination changes the size and the optical density (OD) of point, can obtain different imaging degree.
Though preceding method is the explanation of doing with reference to via the single pixel of print head heating element heater printing, but those skilled in the art are readily appreciated that, print head can contain the linear array of many these class heating element heaters, and thermal imaging element can translation under this linear array, direction is vertical with described linear array, thereby can form the single pixel image image that formation is made of one-row pixels in thermal imaging element in the required time interval by the single heating element.And, those skilled in the art are clear that very much, can form image in one or two imaging layer by the required inherent thermal imaging element of the time interval of single heating element formation single image pixel, image in first imaging layer is that the energy that is applied at interval the very first time by aforementioned regulation forms, and the image that forms in second imaging layer then is the energy formation that applied in second time interval by aforementioned regulation.Therefore, under print head, just can form two images, the i.e. one stroke of print head during translation one time when thermal imaging element.In fact, the energy that applies in the very first time interval can make the heating of second imaging layer, and the energy that applies in second time interval can make the heating of first imaging layer.Those skilled in the art know, must carry out suitable adjustment to the energy that applies in two time intervals, to offset these influences and to offset other influence, such as the non-heat effect intentionally of thermal history and adjacent heating element.
When reality is implemented, pulse number can with being very different shown in Figure 13 and 14.In typical print system, the pixel pressroom is every being 1-100ms, and little inferior gap length can be 1-100ms.Therefore generally can there be hundreds of little Asia at interval at the pixel pressroom every interior.
Little inferior interior at interval working cycles generally changes along with the difference of pulse, and in another preferred embodiment, can utilize this technology to regulate the mean power that is applied on the heating element heater, to obtain good printing effect.
Certainly, those skilled in the art know, if wish in one stroke, to visit independently two above imaging layers of image-forming component, little inferior effective number and duty cycle range at interval must be divided into corresponding therewith plurality purpose compound mode, each can both be on an imaging layer prints independently to small part.
In particularly preferred embodiment of the present invention, by three kinds of different imaging layers of the same surface bears of thermal imaging element substrate be by a thermal printer head in one stroke from the same surface visit of image-forming component.Specifying of this embodiment with reference to Fig. 9.Substrate 22 can be aforesaid any material.Imaging layer 28 comprises fusible leuco dye, about 90 ℃～about 140 ℃ of its fusing points, and developer material, and its fusing point is in same scope, and optional comprises that fusing point is in the hot solvent of same scope.In this embodiment, the thickness of layer 28 is about 1～4 μ m, and is coated with aqueous dispersion.The thickness in intermediate layer 32 is about 5～about 25 μ m, and comprises water-soluble inert material, and it can be aforementioned any suitable water-soluble intermediate layer material.Second imaging layer 26 comprises leuco dye and developer material, and the fusing point of every kind of material is about 150～about 280 ℃, and optional comprises that fusing point is in the hot solvent of same scope.The thickness of second imaging layer is about 1～about 4 μ m, and is coated with aqueous dispersion.Second intermediate layer 30 comprises water-soluble inert material, and it can be any aforesaid water-soluble intermediate layer material, and its thickness is about 3～about 10 μ m.The 3rd imaging layer 24 comprises: a) fusible leuco dye, and its fusing point is at least 150 ℃, preferred 250 ℃, and the developer material, its fusing point is at least 250 ℃, preferred 300 ℃, and the optional hot solvent that comprises; Perhaps b) at the molecule (suitable material is the following leuco dye II that specifies) that in about 0.1～about 2ms, forms color under at least 300 ℃ the temperature by the unimolecule mode.The thickness of the 3rd imaging layer is about 1～about 4 μ m, and obtains through coating from aqueous dispersion.This particularly preferred thermal imaging element further comprises finishing coat, and I is described such as following examples.
As previously mentioned, Fig. 8-10 relates to thermal imaging element, and thermal diffusion is to be used for the technology of distribution time-temperature field.Distribute other technology of thermal imaging element time-temperature field to utilize phase transformation according to the present invention.Phase transformation perhaps can realize by introduce hot solvent in dye coating such as being the result that natural fusion of dyestuff itself or glass change.Dye coating is remained under the fixing temperature T, when measuring dyestuff and reach the required time t of a certain optical density (OD), finds the available Arrhenius curve representation of relation between the temperature and time usually:
log(t)～(-A+B/T)
Wherein A and B are constants, can pass through determination of test method.When carrying out in the temperature range of measuring at melting transition, can find that generally slope B is considerably beyond away from common discovery the in the zone that changes mutually.Therefore, normal dye coating (is the dye coating that imaging does not relate to phase transformation, such as taking place under the situation of diffusion controlled reaction) with the Arrhenius curve of fusion dye coating with very steep angle of intersection, shown in the blue or green dyestuff of Figure 15, i.e. 3-(1-normal-butyl-2 methyl indole-3-yl)-3-(4-dimethyl amine-2-aminomethyl phenyl)-2-benzo [c] furanone that obtains from Hilton-Davis Company, it and Lewis acid developer 3,5-di-tert-butyl zinc salicylate salt cooperates, and the rosaniline dyes of natural fusion, the i.e. solvent red 40 that obtains from Yamamoto Chemical Company, it and acid developer are from Nippon Kayku Company, and two (3-pi-allyl-4-hydroxy phenyl) sulfones that Ltd. obtains cooperate.Article two, curve is represented every kind of dyestuff density was reached for 0.1 required time.This relation itself can be brushed the benchmark of system according to one embodiment of the invention as colored hot stamping, with regard to Fig. 5, show to be lower than when intersecting temperature that the painted speed of blue or green dyestuff is faster than rosaniline dyes, and be higher than when intersecting temperature, the painted speed of rosaniline dyes is faster than blue or green dyestuff.For shown in two kinds of dyestuffs for, can see that do not produce magenta in order to print cyan and be infected with, it is capable that the required time will be higher than 1s/.In order to overcome this restriction, can change dyestuff or its environment, joining is moved in the short time zone.But, from the consideration of time, by by before Fig. 8 described " embedding " rosaniline dyes layer, can make system even more suit the requirements.
Another distributes the technology of thermal imaging element time-temperature field to see Figure 16 according to the present invention.This technology has adopted colored thermal imaging element 60 of the present invention, and it comprises the pinkish red image forming material 62 of one deck, and in this embodiment, leuco dye and fusing point are T 7Acid developer material layer 64 relevant, and blue or green image forming material layer 66 is T with fusing point 8Acid developer material layer 68 relevant.Image-forming component 60 also comprises the first and second time-delay layers, be respectively 70 and 72, and fusing point is T 9Fixation material layer 74.Image-forming component 60 also comprises and layer 64 or layer 68 adjacent substrate (not shown).
Known have many leuco dyes irreversibly to form color when contacting with the developer that suits.Adopt such dyestuff, the effect of fixation material layer 74 is that the color forming process in two imaging layers 62 and 66 one of them layers is stopped but not reverse.But this fixation material must be respectively by time- delay layer 70 and 72, by diffusion or dissolving, to stop the color forming process in the imaging layer.As shown in this example, one of them layer of delaying time, time-delay layer 70, thinner than another time-delay layer 72, so the fixation material to reach time of blue or green imaging layer more late than the time that reaches pinkish red imaging layer 62.Therefore, between the formation of two kinds of colors, introduce delay inequality according to the present invention.
With before leuco dye mixes, developer layer 64 and 68 must fusions at the developer material.By selecting the material in the developer layer, make its fusion under different temperature, just can between the formation of two kinds of colors, introduce temperature difference according to the present invention.In the illustration embodiment, T 7Compare T 8Low, such as T 7=120 ℃ and T 8=140 ℃.In embodiments of the invention, various possibilities are provided.Be lower than 120 ℃ if image-forming component is heated to temperature, developer layer 64 and 68 all can fusion and is not had color and form so.And, be enough to fusion fixation material as long as be applied to the thermal energy of image-forming component, because the T of fusing point fixation layer 9Be lower than the fusing point T of developer layer respectively 7And T 8(such as T 9=100 ℃), so the fixation material diffusion takes place and finally make two imaging layer fixation by time- delay layer 70 and 72, can not form any color thereby apply temperature subsequently more yet.
Be heated to temperature T as pixel spare 60 7With T 8Between the time, so the developer material of layer in 64 will fusion and beginning mix with pinkish red leuco dye precursor and form color.Color formation amount depends primarily on developer layer 64 and is being higher than T 7Temperature under the time length that keeps.After the exposure of this heat, the temperature of image-forming component is reduced to is lower than T 7And keep this temperature to arrive, therefore avoided forming any further color until the fixation material.Temperature as pixel spare is being lower than T 7The time of following maintenance, the fixation material can also arrive blue or green imaging layer 66 when longer, can avoid this layer further to form any color thus.In this way, formed red color amount is selectable, and can not form any cyan.
By similar mode, just can select blue or green formation amount and can not form any magenta according to the present invention.During beginning, image-forming component is heated to temperature is higher than T 9But be lower than T 7,, prevent to form subsequently any color thus so that the fixation material arrives pinkish red imaging layer 62 and makes its inactivation.Then, temperature is increased to is higher than T 8, developer material layer 68 mixed with blue or green leuco dye precursor and begin to form cyan.Blue or green color formation amount depends primarily on image-forming component and is being higher than T 8Temperature under the time length that keeps.What know is, this process also can make the developer material fusion in the layer 64 but can not form magenta, because the rosaniline dyes precursor is before this by fixation.Then, the temperature of image-forming component 60 is reduced to is lower than T 7And keep this temperature to arrive layer 66, thereby prevent to form any further green grass or young crops until the fixation material.
In order to print green grass or young crops and magenta, be applied to thermal pulse sequence on the image-forming component 60 and will make and when aforementioned each step is combined, can produce green grass or young crops and magenta respectively.During beginning, image-forming component 60 is heated to temperature is higher than T 7To produce the magenta of optional density.Then temperature is reduced to and is lower than T 7, the duration is enough to make pinkish red precursor layer 62 fixation, temperature is elevated to be higher than T then 8Producing the cyan of optional density, and then once temperature is reduced to and is lower than T 7With the blue or green precursor layer 66 of fixation.
As previously mentioned, in order in layer, to realize color change, can adopt many different irreversible chemical reactions.Used coloring material fixing agent depends on selected mechanism when realizing this color change under any particular case.Such as, this mechanism can relate to two kinds of procrypsis materials because of coupling forms coloured dyestuff.At this moment, color-fixing agent can react with one of two kinds of dyestuff former molecules, thereby forms colourless product, can stop any dyestuff of further formation thus.
Also can construct the double-colored image-forming component scheme of negativity of the present invention, as shown in figure 17 according to identity principle.In this embodiment, at first that dye coating is painted, make it keep this state then, remove non-adjacent decoloring reaction agent layer and before arriving by the time-delay layer, thermal activation has taken place early than color-fixing agent.Refer now to Figure 17, can see, negativity thermal imaging element 80 of the present invention comprises first imaging layer 82, such as the rosaniline dyes layer, second imaging layer 84 is such as blue or green dye coating, the first and second time- delay layers 86 and 88, fixation layer 90 and the first and second decolorizer layers 92 and 94.Image-forming component 80 also can comprise and layer 92 or layer 94 adjacent substrate (not shown).
Such as, by contacting with alkali, irreversible decolouring can take place in pinkish red and blue or green dyestuff, referring to United States Patent (USP) 4,290, and 951 and 4,290,955.If reactant layer 90 contain acid material and select this sour purpose be in and decoloring layer 92 and 94 in base material, what know is, when acid arrives when containing dye coating early than alkali, alkali just can't make magenta or blue or green dye decolored, and work as alkali early than arriving before the acid, irreversible decoloring reaction will take place.As the explanation of doing with regard to embodiment shown in Figure 8 before, can utilize any other printing machinery to obtain the 3rd color, comprise by Fig. 9 just and 10 and describedly brush the 3rd color from the hot stamping of the image-forming component back side.
What Figure 18 represented is the present invention's three look thermal imaging elements.Refer now to Figure 18, can see image-forming component 100, it comprises those layers that image-forming component shown in Figure 16 60 is included, and the identical Reference numeral of these layers usefulness is represented.Image-forming component 100 also comprises cushion 102, yellow dye precursor layer 104 and the 3rd acid developer layer 106, wherein the fusing point T of developer material 10Compare T 7And T 8High.Before pressing just after the required green grass or young crops and pinkish red color density of the described formation of Figure 16, the temperature of image-forming component is elevated to is higher than T 10To form the yellow dye of optional density.It should be noted, if T 10, write down after the yellow image at the temperature height that its length of life often runs into than image-forming component 100, not necessarily can make yellow dye precursor inactivation.Image-forming component 100 also can comprise and layer 64 or layer 106 adjacent substrate (not shown).
When selecting the layer size of the image-forming component shown in Figure 16 and 18, preferably make time-delay layer 70 thin as far as possible, but thin too many unlike dye coating 62.Time-delay layer 72 generally is about 2～3 times of time-delay layer 70 thickness.
What know is, is implementing according to preceding method when of the present invention, and what relied on is the diffusion or the course of dissolution of chemical substance, but not the diffusion process of heat.Though thermal-diffusion constant is under normal circumstances comparatively insensitive to temperature, chemical diffusion constant inverse general and temperature is exponential relationship, and is therefore more responsive to the variation of environment temperature.And if select dissolving as the time decision mechanism, numerical simulation shows that the time-delay process is quite crucial under normal conditions, because in case the time-delay layer is broken, coloring process will very fast generation.
Any chemical reaction that irreversibly forms color all meets the requirement of aforesaid fixation mechanism substantially.The material that irreversibly forms color comprises, two kinds of materials formation dyestuff that is coupled together.Can realize fixation mechanism by introducing the 3rd reactant, this reactant is preferential to be become the generation coupling of one of dye materials and forms colourless product with two.
Except preceding method, also can adopt chemical threshold to come distribution time-temperature field by colored thermal imaging system according to the present invention.As this machine-processed example, can consider the leuco dye reaction, in this reaction, dyestuff activates when contacting with acid.If except dyestuff, medium also contains alkalescence than the obvious stronger material of this dyestuff, this material adds acid so and just can not produce any visual color change because of acid does not change color when protonated in this mixture, unless the stronger material of all alkalescence is all protonated.This basic matterial has been stipulated the threshold doseag that must surpass for acid before any coloring process manifests.Can be undertaken by various technology when adding acid, such as adding the acid developer crystal dispersion of melting and diffusion at high temperature, the pure acid developer layer that can spread or mix when perhaps being added on heating with dye coating.
When reaching the required acid amount of activation dyestuff, delay that must be for some time.By in image-forming component, adding alkali, can adjust the length of this time significantly.As previously mentioned, when having the alkali that is added, the amount that increases acid comes neutralization bases to need a period of time.Surpass after this time period, image-forming component will be painted.Can see that same technology can be used according to opposite order.By increasing the background content of acid, can prolong the delay effect that dyestuff is activated by alkali.
In this specific embodiment, it should be noted that acid or the diffusion of alkaline developer material in containing dye coating generally turn over a head in developer layer by dyestuff diffusion takes place realizes.In the case, almost can begin to form color immediately, because in the residing environment of dyestuff itself that diffusion takes place, the content of developer material is considerably beyond the necessary threshold content of this dyestuff of activation.Therefore, preferably take measures to suppress the diffusion of dyestuff in developer layer.Such as, on dyestuff,, just can realize this purpose, dyestuff is combined on the polymer or with dyestuff is combined on the ionic bond in conjunction with long strand.
Embodiment
Mode with embodiment is further detailed thermal imaging system of the present invention with reference to certain preferred embodiment now, what need know is, these embodiment only are intended to illustrate, and the present invention is not limited to material described here, amount, step and method parameter etc.All umbers and percentage are all based on weight, unless point out in addition.
In the embodiment of the following stated, adopted following material:
Leuco dye I, 3, two (1-normal-butyl-2-methyl-indol-3-yl)-2-benzo [c] furanones of 3-(red 40, from Yamamoto Chemical Industry Co.Ltd., Wakayama, Japan obtains);
Leuco dye II, 7-(1-butyl-2-Methyl-1H-indole-3-yl)-7-(4-diethylamino-2-aminomethyl phenyl)-7H-furans be [3,4-b] pyridine-5-ketone (from Hilton-DavisCo., Cincinnati, OH acquisition) also;
Leuco dye III, 1-(2,4-two chloro-phenyl amino formoxyls)-3,3-dimethyl-2-oxo-1-phenoxy group butyl]-(4-diethylamino phenyl) carbamic acid isobutyl, according to United States Patent (USP) 5,350,870 preparations;
Leuco dye IV, the yellow I-3R of Pergascrip t, from Ciba SpecialtyChemicals Corporation, Tarrytown, NY obtains;
Acid developer I, two (3-pi-allyl-4-hydroxy phenyl) sulfone, from Nippon Kayku Co.Ltd., Tokyo, Japan obtains;
Acid developer II, PHS-E, the trade mark of poly-(hydroxy styrenes), from TriQuest, LP obtains, and it is ChemFirst Inc., Jackson, the subsidiary of MS;
Acid developer III, 3,5-di-tert-butyl zinc salicylate salt, from Aldrich ChemicalCo., Milwaukee, WI obtains;
Acid developer IV, 3-octyl group-5-cresotinic acid zinc salt is according to following examples 7 described preparations;
Airvol 205, the trade mark of poly-(vinyl alcohol), and from Air Products and Chemicals, Inc., Allentown, PA obtains;
Airvol 350, the trade mark of poly-(vinyl alcohol), and from Air Products and Chemicals, Inc., Allentown, PA obtains;
Airvol 540, the trade mark of poly-(vinyl alcohol), and from Air Products and Chemicals, Inc., Allentown, PA obtains;
Genflo 305, latex adhesive, and from Omnova Solutions, Fairlawn, OH obtains;
Genflo 3056, latex adhesive, and from Omnova Solutions, Fairlawn, OH obtains;
Glascol C44, aqueous polymer dispersion, from Ciba Specialty ChemicalsCorporation, Tarrytown, NY obtains;
Joncryl 138, adhesive, and from S.C.Johnson, Racine, WI obtains;
Irganox 1035, antioxidant, and from Ciba Specialty ChemicalsCorporation, Tarrytown, NY obtains;
Aerosol-OT, surfactant, from Dow Chemical, Midland, MI obtains;
Dowfax 2A1, surfactant, from Dow Chemical Corporation, Midland, MI obtains;
Ludox HS40, cataloid, from DuPont Corporation, Wilmington, DE obtains;
Nipa Proxel, bactericide, from Nipa Inc., Wilmington, DE obtains;
Pluronic 25R2, surfactant, from BASF, Ludwigshaven, Germany obtains;
Tamol 731, polymeric surfactant (polymer carboxylic acid sodium salt), and from Rohm andHaas Company, Philadelphia, PA obtains;
Triton X-100, surfactant, from Dow Chemical Corporation, Midland, MI obtains;
Zonyl FSN, surfactant, from DuPont Corporation, Wilmingtion, DE obtains;
Zonyl FSA, surfactant, from DuPont Corporation, Wilmingtion, DE obtains;
Hymicron ZK-349, the trade mark of zinc stearate, from Cytech Products, Inc., Elizabethtown, KY obtains;
Klebosol 30V-25, silica dispersion, from Clariant Corporation, Muttenz, Switzerland obtains;
Titanium dioxide, pigment, from DuPont Corporation, Wilmington, DE obtains;
Glyoxal, from Aldrich Chemical Co., Milwaukee, WI obtains;
Melinex 534, white PETG sheet base, and the about 96 μ m of thickness, from DuPont Corporation, Wilmington, DE obtains;
Cronar 412, transparent PETG sheet base, and the about 102 μ m of thickness, from DuPont Corporation, Wilmington, DE obtains.
Example I
Be prepared as follows such as double-colored image-forming component shown in Figure 8, and further comprised the finishing coat that is deposited on the blue or green one-tenth chromatograph:
A. according to being prepared as follows pinkish red imaging layer:
Employing has been equipped with the attritor of bead, with the procrypsis rosaniline dyes, leuco dye I, be dispersed in the aqueous mixture that comprises Airvol 205 (4.5% total solids content), surfactant Pluronic25R2 (1.5% total solids content), Aerosol-OT (5.0% total solids content) and deionized water, stir 18h down at 2 ℃.The average grain granularity of the dispersion that is obtained is about 0.28 μ m, and total solids content is 19.12%.
Employing has been equipped with the attritor of bead, acid developer I is dispersed in the aqueous mixture that comprises Airvol 205 (7.0% total solids content), Pluronic 25R2 (1.5% total solids content) and deionized water, and stirs 18h down at 2 ℃.The average grain granularity of the dispersion that is obtained is about 0.42 μ m, and total solids content is 29.27%.
Utilize aforementioned dispersion to make pinkish red coating fluid according to the percentage of the following stated.Adopt the Meyer excellent spreader that winds the line to be applied on the Melinex 534 coating composition of preparation thus, carry out drying then.The regulation coating thickness is 2.9 μ m.
Composition Percentage solids content in the dry film
Leuco dye I ?10.74％
Acid developer I ?42.00％
Genflo?3056 ?47.05％
Zonyl?FSN ?0.21％
B. according to following heat insulation intermediate layer is deposited on the pinkish red imaging layer:
The coating fluid for preparing the intermediate layer according to percentage as described below.Adopt the Meyer excellent spreader that winds the line to be coated on the pinkish red imaging layer image intermediate layer coating composition of so preparation, final thickness is 13.4 μ m, carries out drying then in air.
Composition Percentage solids content in the dry film
Glascol?C44 ?99.50％
Zonyl?FSA ?0.50％
C. according to following blue or green imaging layer C1-C3 is deposited on the thermal insulation layer:
The blue or green developer layer of C1.
The attritor that employing has been equipped with bead is dispersed in acid developer III in the aqueous mixture that comprises Airvol 205 (6.0% total solids content), Aerosol-OT (4.5% total solids content), Triton X-100 (0.5% total solids content) and deionized water, at room temperature stirs 18h.The average grain granularity of the dispersion that is obtained is about 0.24 μ m, and total solids content is 25.22%.
Adopt aforementioned dispersion to prepare blue or green developer coating fluid according to the percentage of the following stated.Utilize the Meyer excellent spreader that winds the line to be coated on the end face in imaging intermediate layer the blue or green developer coating composition of preparation thus, specific thickness is 1.9 μ m, carries out drying then in air.
Composition Percentage solids content in the dry film
Joncryl?138 ?9.50％
Acid developer III ?89.50％
Zonyl?FSN ?1.00％
The blue or green intermediate layer of C2.
Percentage according to the following stated prepares blue or green intermediate layer coating fluid.Adopt the Meyer excellent spreader that winds the line to be coated on the end face of blue or green developer layer the blue or green intermediate layer coating composition of preparation thus, specific thickness is 2.0 μ m, carries out drying then in air.
Composition Percentage solids content in the dry film
Arivol?205 ?99.00％
Zonyl?FSN ?1.00％
The blue or green dye coating of C3.
Employing has been equipped with the attritor of bead, with the blue or green dyestuff of procrypsis, leuco dye II, be dispersed in the aqueous mixture that comprises Airvol 205 (7.0% total solids content), Aerosol-OT (1.0% total solids content), Triton X-100 (0.2% total solids content) and deionized water, at room temperature stir 18h.The average grain granularity of the dispersion that is obtained is about 0.58 μ m, and total solids content is 26.17%.
Adopt aforementioned dispersion to prepare blue or green developer coating fluid according to the percentage of the following stated.Utilize the Meyer excellent spreader that winds the line to be coated on the imaging intermediate layer the blue or green developer coating composition of preparation thus, specific thickness is 0.6 μ m, carries out drying then in air.
Composition Percentage solids content in the dry film
Leuco dye II ?59.5％
Joncryl?138 ?39.5％
Zonyl?FSN ?1.0％
D. according to following the protective cowl surface layer is deposited on the blue or green one-tenth chromatograph:
Coating grease boot surface layer on blue or green dye coating.Finishing coat is prepared according to the percentage of the following stated.Utilize the Meyer excellent spreader that winds the line to be coated on the blue or green dye coating cover coating composition of preparation thus, specific thickness is 1.0 μ m, carries out drying then in air.
Composition Percentage solids content in the dry film
Glyoxal ?9.59％
Hymicron?ZK-349 ?31.42％
Klebosol?30V-25 ?23.53％
Zonyl?FSA ?3.89％
Airvol?540 ?31.57％
6 layers of image-forming component that employing is equipped with KST-87-12MPC8 type laboratory test platform printing machine (Kyocera Corporation, 6 Takedatobadono-cho, Fushimi-ku, Kyoto, the Ja pan) printshop of heat head to obtain.
Adopted following printing parameter:
Print head width: 3.41in
Every in number of pixels: 300
Resistance size: 69.7 * 80 μ m
Resistance: 3536Ohm
Linear velocity: 8ms/ is capable
Print speed printing speed: 0.42in/s
Pressure: 1.5-2lb/ linear inch
Dot pattern: rectangle grid.
The blue or green layer of printing under the condition of high-energy/short time.In order to obtain color gradient, pulse width is elevated to maximum 1.3ms (account for single file total time about 16.3%) through 20 isometric steps from 0, makes the voltage that is applied on the print head keep 27.0V simultaneously.
Adopt low-yield/long-time condition to come the printed matter red beds.Pulse width is brought up to the full 8ms single file time through 20 isometric steps from 0, makes the voltage that is applied on the print head keep 14.5V simultaneously.
After the printing, adopt from GretagMacbeth AG Regensdorf, the reflection density of each printing zone of spectrophotometer measurement of Switzerland.The results are shown in Table I and Table II.What Table I was represented is the relation of a blue or green layer printing density and a heat energy that is applied.Also provided the fuchsin density that is obtained.Table I also comprises the ratio (C/M) between green grass or young crops and the fuchsin density.What equally, Table II was represented is the relation of a magenta layer printing density and a heat energy that is applied.Provided the ratio (M/C) between pinkish red and the blue or green density.
C/M in the Table I than and Table II in M/C than being to indicate that a kind of color is printed in differential but not tolerance that whether another kind of color achieves success.But, have two reasons to make these numerical value can't reflect the discrimination of layer fully.At first, contain the contribution that produces because of following medium substrate absorption light in the density measurement.(such as, even when not having printing density, also there are the remnants of 0.04 density unit to absorb.) its two, every kind of dyestuff all partially absorbs beyond himself color wave band.Therefore, the ratio of the measurement optical density (OD) of blue or green and magenta is different from the ratio of painted blue or green dyestuff and painted rosaniline dyes.
For the approximate absorption of revising substrate, can from each density measurement value, deduct the not optical density (OD) of heated medium.The outer absorption of wave band of revising every kind of dyestuff is more complicated.Here with the general example of three look image-forming components (constituting) as modification method by three kinds of dye coatings.
At first, by measuring three kinds of dyestuffs separately density in three each wave bands of color wave band, and, characterize wave band thus and absorb outward at these density of substrate density correction.Adopted three monochromatic samples, and each sample all comprises the specific area concentration a of a kind of dyestuff 0 j, wherein j=C, M or Y depend on that dyestuff is respectively green grass or young crops, magenta or Huang.
The result of this measurement is as follows:
? Blue or green dyestuff Rosaniline dyes Yellow dye
Blue or green density 0.75 ?0.02 ?0.00
Fuchsin density 0.26 ?0.63 ?0.04
Yellow density 0.14 ?0.11 ?0.38
The density that writes down in this matrix is designated as d Ij, wherein i and j are color-values C, M and Y, such as value d CMIt is the fuchsin density of blue or green dye sample.
If what obtained is not residing illuminating colour area concentration when writing down these data, the density of this dyestuff just is directly proportional with this area concentration so.Particularly, if the painted green grass or young crops of sample, magenta and yellow dye area concentration are a C, a MAnd a Y, under same printing condition, can observe following density measurement D so C, D MAnd D Y
D C＝(a C/a C 0)d CC+(a M/a M 0)d MC+(a Y/a Y 0)d YC
D M＝(a C/a C 0)d CM+(a M/a M 0)d MM+(a Y/a Y 0)d YM
D Y＝(a C/a C 0)d CY+(a M/a M 0)d MY+(a Y/ Y 0)d YY
Can be in such a way with the matrix notation of its standard of writing into:
D C D M D Y = d CC d MC d YC d CM d MM d YM d CY d MY d YY a c / a c 0 a M / a M 0 a Y / a Y 0
If measure the density D of sample C, D MAnd D Y, can adopt this equational inverse to try to achieve the area concentration of illuminating colour in the sample so, itself and standard sample are compared.
a c / a c 0 a M / a M 0 a Y / a Y 0 = d CC d MC d YC d CM d MM d YM d CY d MY d YY - 1 D C D M D Y
More accurate each layer of representative of this tittle be because of applying the coloring degree that heat causes, and not with the spectral absorption of dyestuff is overlapping obscures in these layers.Therefore, their more accurate representatives can to what extent be write down on a layer and do not influenced another.
Be intended in an independent color layer, produce optical density (OD) and but in another color layer, form undesirable optical density (OD), this result's the order of severity can be defined as " intersect and disturb ".Such as, if a certain medium comprises blue or green layer and magenta layer,, can represent blue or green relative intersection to disturb with following formula if attempt record on magenta layer so:
Figure S2007101817128D00321
When attempting to write down on blue or green layer, the equation that pinkish red intersection is disturbed similarly.
These intersection interference values are recorded in last row of Table I and Table II.Following embodiment has also provided similar value, but only when density measurement is enough big (density＞0.1) just produce significative results, and only at be from image-forming component same surface visit layer.
Table I
Apply energy (J/cm 2) Blue or green printing density Pinkish red printing density C/M Intersect and disturb (magenta)
0.00 0.04 0.04 1.00 ?
0.18 0.04 0.04 1.00 ?
0.35 0.04 0.04 1.00 ?
0.53 0.04 0.04 1.00 ?
0.71 0.04 0.04 1.00 ?
0.88 0.04 0.04 1.00 ?
1.06 0.04 0.04 1.00 ?
1.24 0.04 0.04 1.00 ?
1.41 0.04 0.05 0.80 ?
1.59 0.05 0.05 1.00 ?
1.77 0.06 0.05 1.20 ?
1.94 0.1 0.06 1.67 ?
2.12 0.15 0.08 1.88 ?
2.29 0.2 0.1 2.00 ?
2.47 0.29 0.12 2.42 0.01
2.65 0.34 0.15 2.27 0.04
2.82 0.43 0.22 1.95 0.14
3.00 0.5 0.29 1.72 0.22
3.18 0.62 0.35 1.77 0.22
3.35 0.6 0.42 1.43 0.37
3.53 0.61 0.47 1.30 0.45
Table II
Apply energy (J/cm 2) Blue or green printing density Pinkish red printing density M/C Intersect and disturb (green grass or young crops)
0 0.04 0.04 1.00 ?
0.30 0.04 0.04 1.00 ?
0.60 0.04 0.05 1.25 ?
0.90 0.04 0.05 1.25 ?
1.21 0.04 0.05 1.25 ?
1.51 0.04 0.05 1.25 ?
1.81 0.04 0.05 1.25 ?
2.11 0.04 0.05 1.25 ?
2.41 0.05 0.06 1.20 ?
2.71 0.05 0.1 2.00 0.14
3.02 0.05 0.15 3.00 0.07
3.32 0.06 0.22 3.67 0.08
3.62 0.07 0.29 4.15 0.09
3.92 0.09 0.42 4.67 0.10
4.22 0.1 0.54 5.40 0.09
4.52 0.13 0.69 5.31 0.11
4.83 0.16 0.97 6.06 0.10
5.13 0.22 1.32 6.00 0.11
5.43 0.26 1.56 6.00 0.12
5.73 0.31 1.69 5.45 0.14
6.03 0.34 1.74 5.12 0.15
Example II
This embodiment has illustrated such as double-colored image-forming component shown in Figure 8.It is yellow that end face becomes chromatograph to produce, utilization be United States Patent (USP) 5,350,870 described unimolecule thermal response mechanism.One-tenth chromatograph under it produces magenta, utilization be acid developer and pinkish red leuco dye.
A. according to being prepared as follows pinkish red imaging layer:
Dispersion according to previous embodiment I part A described preparation leuco dye I and acid developer I.
Employing has been equipped with the attritor of bead, acid developer I is dispersed in the aqueous mixture that comprises Airvol 205 (2% total solids content), Dowfax 2A1 (2% total solids content), Irganox1035 (5% total solids content) and deionized water, and stirs 24h down at 10-15 ℃.The about 0.52 μ m of the average grain granularity of the dispersion that is obtained, and total solids content is 22.51%.
Utilize aforementioned dispersion to make pinkish red coating fluid according to the percentage of the following stated.Adopt the Meyer excellent spreader that winds the line to be applied on the Melinex 534 coating composition of preparation thus, carry out drying then.The regulation coating thickness is 3 μ m.
Composition Percentage solids content in the dry film
Leuco dye I ?24.18％
Acid developer I ?47.49％
Acid developer II ?11.63％
Joncryl?138 ?16.16％
Zonyl?FSN ?0.54％
B. according to example I part B is described before heat insulation intermediate layer is deposited on the pinkish red imaging layer, but coating layer thickness is 16.1 μ m.
C. according to following Huang Cheng's picture is deposited upon on the thermal insulation layer:
Employing has been equipped with the attritor of bead, leuco dye III is dispersed in the aqueous mixture that comprises Airvol 205 (4.54% total solids content), Aerosol-OT (2.73% total solids content), Pluronic 25R2 (1.82% total solids content) and deionized water, at room temperature stirs 18h.The average grain granularity of the dispersion that is obtained is about 0.49 μ m, and total solids content is 25.1%.
Percentage according to the following stated adopts the yellow coating of aforementioned dispersion preparation fluid.Utilize the Meyer excellent spreader that winds the line to be coated on the heat insulation intermediate layer the yellow coating composition of preparation thus, specific thickness is 3 μ m, carries out drying then in air.
Composition Percentage solids content in the dry film
Leuco dye III ?70％
Genflo?3056 ?22.95％
Airvol?205 ?7％
Zonyl?FSN ?0.05％
D. according to following the protective cowl surface layer is deposited on Huang Cheng's chromatograph:
The grease boot surface layer is coated on the xanthochromia bed of material.Percentage according to the following stated prepares finishing coat.Utilize the Meyer excellent spreader that winds the line to be coated on the xanthochromia bed of material cover coating composition of preparation thus, specific thickness is 1.0 μ m, carries out drying then in air.
Composition Percentage solids content in the dry film
Glyoxal ?8.39％
Hymicron?ZK-349 ?31.77％
Klebosol?30R?25 ?23.77％
Zonyl?FSA ?0.92％
Zonyl?FSN ?3.22％
Airvol?540 ?31.93％
Employing is equipped with KST-87-12MPC8 type laboratory test platform printing machine (Kyocera Corporation, 6 Takeda tobadono-cho, Fushimi-ku, Kyoto, Japan) 4 layers of image-forming component of printshop acquisition of heat head.Adopted following printing parameter:
Print head width: 3.41in
Every in number of pixels: 300
Resistance size: 69.7 * 80 μ m
Resistance: 3536Ohm
Linear velocity: 8ms/ is capable
Print speed printing speed: 0.42in/s
Pressure: 1.5-2lb/ linear inch
Dot pattern: rectangle grid.
The yellow layer of printing under the condition of high-energy/short time.In order to obtain color gradient, pulse width is elevated to maximum 1.65ms (account for single file total time about 20.6%) through 21 isometric steps from 0, makes the voltage that is applied on the print head keep 29.0V simultaneously.
Adopt low-yield/long-time condition to come the printed matter red beds.Pulse width is brought up to 99.5% of the 8ms single file time through 21 isometric steps from 0, makes the voltage that is applied on the print head keep 16V simultaneously.
After the printing, adopt the reflection density of each printing zone of Gretag Macbeth spectrophotometer measurement.The results are shown in Table III and Table IV.What Table III was represented is the relation that yellow layer prints the energy that is applied with the heat head.Also provided the fuchsin density that is obtained.Table III also comprises the ratio (Y/M) and the interference that intersects between Huang and the fuchsin density.What equally, Table IV was represented is the relation of a magenta layer printing density and a heat energy that is applied.Ratio (M/Y) and the interference that intersects between pinkish red and the yellow density have been provided.
Table III
Apply energy (J/cm 2) Yellow printing density Pinkish red printing density Y/M Intersect and disturb (magenta)
0.00 0.07 0.09 0.78 ?
0.26 0.07 0.09 0.78 ?
0.52 0.06 0.09 0.67 ?
0.78 0.06 0.09 0.67 ?
1.04 0.06 0.09 0.67 ?
1.30 0.07 0.09 0.78 ?
1.56 0.06 0.09 0.67 ?
1.82 0.06 0.09 0.67 ?
2.08 0.08 0.09 0.89 ?
2.34 0.11 0.10 1.10 ?
2.60 0.17 0.10 1.70 ?
2.86 0.24 0.11 2.18 0.01
3.12 0.34 0.12 2.83 0.01
3.38 0.48 0.14 3.43 0.02
3.64 0.58 0.16 3.63 0.03
3.90 0.68 0.19 3.58 0.06
4.16 0.83 0.23 3.61 0.08
4.41 0.94 0.26 3.62 0.09
4.67 1.08 0.32 3.38 0.13
4.93 1.13 0.38 2.97 0.18
5.19 1.19 0.40 2.98 0.18
Table IV
Apply energy (J/cm 2) Pinkish red printing density Yellow printing density M/Y Intersect and disturb (Huang)
0.00 0.10 0.08 1.25 ?
0.38 0.10 0.09 1.11 ?
0.76 0.10 0.09 1.11 ?
1.15 0.10 0.09 1.11 ?
1.53 0.10 0.08 1.25 ?
1.91 0.10 0.08 1.25 ?
2.29 0.10 0.07 1.43 ?
2.67 0.10 0.07 1.43 ?
3.05 0.10 0.07 1.43 ?
3.44 0.10 0.09 1.11 ?
3.82 0.10 0.08 1.25 ?
4.20 0.11 0.08 1.38 ?
4.58 0.14 0.1 1.40 ?
4.96 0.23 0.13 1.77 ?
5.35 0.40 0.18 2.22 0.22
5.73 0.61 0.25 2.44 0.17
6.11 0.88 0.34 2.59 0.17
6.49 1.17 0.44 2.66 0.17
6.87 1.42 0.53 2.68 0.17
7.26 1.65 0.65 2.54 0.20
7.64 1.68 0.74 2.27 0.26
EXAMPLE III
This embodiment has illustrated such as double-colored image-forming component shown in Figure 8, and has further comprised the finishing coat that is deposited on the blue or green one-tenth chromatograph.In this embodiment, the thermal insulation layer 18 of Fig. 8 is opaque, and substrate 12 is transparent.Therefore can utilize the hot head that only is positioned on image-forming component one side, utilize the image-forming component described in this embodiment to print opaque image-forming component independently from both sides.
A. according to the dispersion of following examples IV portion C described preparation leuco dye I and acid developer I.
According to the described dispersion acid developer of example II part A II before.
Percentage according to the following stated utilizes aforementioned dispersion to make pinkish red coating fluid.The coating composition of preparation thus is applied to (Cronar 412) on the transparent polyester sheet base, carries out drying then.The regulation coating weight is 3.3g/m 2
Composition Percentage solids content in the dry film
Leuco dye I ?21.91％
Acid developer I ?52.71％
Airvol?205 ?14.35％
Acid developer II ?10.54％
Zonyl?FSN ?0.49％
B. according to following heat insulation intermediate layer is deposited on the pinkish red imaging layer:
Percentage preparation coating fluid intermediate layer according to the following stated.The image intermediate layer coating composition of preparation thus is applied on the pinkish red imaging layer, and specific thickness is 8.95 μ m.
Composition Percentage solids content in the dry film
Glascol?C44 ?99.50％
Zonyl?FSA ?0.50％
C. according to following opaque layer is deposited on the thermal insulation layer:
According to being prepared as follows titanium dioxide dispersion:
Employing has been equipped with the attritor of bead, titanium dioxide is dispersed in the aqueous mixture that comprises Tamol731 (3.86% total solids content), Ludox HS40 (3.85% total solids content), minute quantity (750ppm) Nipa Proxel and deionized water, and at room temperature stirs 18h.Its total solids content is 50.2%.
Adopt the percentage manufacturing coating fluid of the dispersion of so preparation according to the following stated.To be coated with fluid and be coated on the thermal insulation layer, specific thickness is 12.4 μ m.
Composition Percentage solids content in the dry film
Titanium dioxide ?81.37％
Joncryl?138 ?18.08％
Zonyl?FSN ?0.54％
D. according to following blue or green imaging layer D1-D3 is deposited on the thermal insulation layer:
The blue or green developer layer of D1.
According to the described dispersion acid developer of following examples IV part E1 III.
Percentage according to the following stated adopts aforementioned dispersion to prepare blue or green developer coating fluid.The blue or green developer coating composition of preparation thus is coated on the end face in imaging intermediate layer, and specific thickness is 1.74 μ m.
Composition Percentage solids content in the dry film
Acid developer III ?80.84％
Joncryl?138 ?18.54％
Zonyl?FSN ?0.62％
The blue or green intermediate layer of D2.
Percentage according to the following stated prepares blue or green intermediate layer coating fluid.The blue or green intermediate layer coating composition of preparation thus is coated on the end face of blue or green developer layer, and specific thickness is 1.0 μ m.
Composition Percentage solids content in the dry film
Airvol?205 ?99.00％
Zonyl?FSN ?1.00％
The blue or green dye coating of D3.
According to the blue or green dyestuff of the described dispersion procrypsis of following examples 4 part E3, dyestuff II.
Percentage according to the following stated adopts this dispersion to prepare blue or green developer coating fluid.The blue or green developer coating composition of preparation thus is coated on the blue or green intermediate layer, and specific thickness is 0.65 μ m.
Composition Percentage solids content in the dry film
Dyestuff II ?59.30％
Joncryl?138 ?39.37％
Zonyl?FSN ?1.33％
E. according to following the protective cowl surface layer is deposited on the blue or green one-tenth chromatograph:
The grease boot surface layer is coated on the blue or green dye coating.Prepare finishing coat according to the described percentage of Table VI.The cover coating composition of preparation thus is coated on the blue or green dye coating, and specific thickness is 1.1 μ m.
Composition Percentage solids content in the dry film
Hymicron?ZK-349 ?31.77％
Klebosol?30R?25 ?23.77％
Airvol?540 ?31.93％
Glyoxal ?8.39％
Zonyl?FSA ?0.92％
Zonyl?FSN ?3.22％
Image-forming component according to example II described printshop acquisition before.Blue or green image can be seen and pinkish red image can be seen from behind from substrate front surface.Therefore, obtain blue or green image optical density (OD) from the top surface of image-forming component, and obtain pinkish red image optical density (OD) from the bottom of image-forming component.
Blue or green layer prints under the condition of high-energy/short time.In order to obtain color gradient, pulse width is elevated to maximum 1.41ms (account for single file total time about 18.5%) through 20 isometric steps from 0, makes the voltage that is applied on the print head keep 29.0V simultaneously.
Adopt low-yield/long-time condition to come the printed matter red beds.Pulse width is brought up to the full 8ms single file time through 20 isometric steps from 0, makes the voltage that is applied on the print head keep 14.5V simultaneously.
After the printing, adopt the reflection density of each printing zone of Gretag Macbeth spectrophotometer measurement.The results are shown in Table V and Table VI.What Table V was represented is the relation of blue or green layer printing and the heat head energy that applies.Also provided the fuchsin density that is obtained.Also comprise the ratio (C/M) and the interference that intersects between green grass or young crops and the fuchsin density in the Table V.What equally, Table VI was represented is the relation of a magenta layer printing and a heat energy that is applied.Provided the ratio (M/C) between pinkish red and the blue or green density, also had to intersect and disturb.
Table V
Apply energy (J/cm 2) Blue or green printing density Pinkish red printing density C/M Intersect and disturb (magenta)
0.00 0.08 0.08 1.00 ?
0.23 0.08 0.08 1.00 ?
0.47 0.08 0.08 1.00 ?
0.70 0.08 0.08 1.00 ?
0.93 0.08 0.08 1.00 ?
1.17 0.08 0.08 1.00 ?
1.40 0.08 0.08 1.00 ?
1.64 0.08 0.08 1.00 ?
1.87 0.08 0.09 0.89 ?
2.10 0.08 0.08 1.00 ?
2.34 0.09 0.09 1.00 ?
2.57 0.09 0.09 1.00 ?
2.80 0.1 0.09 1.11 ?
3.04 0.11 0.10 1.10 ?
3.27 0.13 0.10 1.30 ?
3.51 0.22 0.13 1.69 0.03
3.74 0.27 0.15 1.80 0.04
3.97 0.35 0.18 1.94 0.04
4.21 0.36 0.20 1.80 0.10
4.44 0.42 0.24 1.75 0.15
4.67 0.51 0.28 1.82 0.14
Table VI
Apply energy (J/cm 2) Blue or green printing density Pinkish red printing density M/C Intersect and disturb (green grass or young crops)
0.00 0.08 0.11 1.38 ?
0.31 0.08 0.11 1.38 ?
0.63 0.08 0.11 1.38 ?
0.94 0.08 0.11 1.38 ?
1.25 0.08 0.11 1.38 ?
1.57 0.08 0.11 1.38 ?
1.88 0.08 0.11 1.38 ?
2.20 0.08 0.11 1.38 ?
2.51 0.08 0.11 1.38 ?
2.82 0.08 0.11 1.38 ?
3.14 0.08 0.11 1.38 ?
3.45 0.08 0.11 1.38 ?
3.76 0.08 0.11 1.38 ?
4.08 0.08 0.12 1.50 ?
4.39 0.09 0.12 1.33 ?
4.70 0.09 0.13 1.44 ?
5.02 0.10 0.18 1.80 0.27
5.33 0.12 0.25 2.08 0.27
5.65 0.13 0.36 2.77 0.18
5.96 0.16 0.59 3.69 0.14
6.27 0.19 0.76 4.00 0.14
EXAMPLE IV
According to being prepared as follows, and further comprising and be deposited on the blue or green finishing coat that becomes on the chromatograph such as three look image-forming components shown in Figure 9:
A. according to being prepared as follows yellow imaging layer:
Similar approach used when leuco dye I dispersion is provided in the following portion C is disperseed the procrypsis yellow dye, and leuco dye IV makes that the concentration of dyestuff is 20.0%.
In the 4oz glass jar that contains 10g Mullite pearl, acid developer IV (10g) is dispersed in the aqueous mixture that comprises Tamol 731 (7.06% aqueous solution of 7.08g) and 32.92g deionized water, at room temperature stir 16h.The concentration of developer is 20.0%.
Percentage according to the following stated utilizes aforementioned dispersion to make yellow coating fluid.The coating composition of preparation thus is applied on the Melinex 534, carries out drying then.The regulation coating weight is 2.0g/m 2
Composition Percentage solids content in the dry film
Leuco dye IV ?41.44％
Acid developer IV ?41.44％
Joncryl?138 ?16.57％
Zonyl?FSN ?0.55％
B. according to following heat insulation intermediate layer is deposited on the yellow imaging layer:
The intermediate layer preparation of coating fluid is according to the described percentage of Table II.What image intermediate layer coating composition will prepare thus is applied on the yellow imaging layer, and the regulation coating weight is 9.0g/m 2
Composition Percentage solids content in the dry film
Glascol?C44 ?99.50％
Zonyl?FSA ?0.50％
C. according to being prepared as follows pinkish red imaging layer:
In containing the 4oz glass jar of Mullite pearl, leuco dye I (15.0g) is dispersed in the aqueous mixture that comprises Airvol 205 (20% aqueous solution of 3.38g), Triton X-100 (0.6g 5% aqueous solution), Aerosol-OT (15.01g 19% aqueous solution) and deionized water (31.07g), at room temperature stirs 16h.The total content of dyestuff is 20.00%.
In the 4oz glass jar that contains 10g Mullite pearl, acid developer I (10g) is dispersed in the aqueous mixture that comprises Tamol 731 (7.06% aqueous solution of 7.08g) and 32.92g deionized water, at room temperature stir 16h.The concentration of developer is 20.0%.
According to the described dispersion acid developer of example II part A II before.
Percentage according to the following stated utilizes aforementioned dispersion to make pinkish red coating fluid.The coating composition of preparation thus is applied on the heat insulation intermediate layer, carries out drying then.The regulation coating weight is 1.67g/m 2
Composition Percentage solids content in the dry film
Leuco dye I ?24.18％
Acid developer I ?47.50％
Joncryl?138 ?16.16％
Acid developer II ?11.63％
Zonyl?FSN ?0.54％
D. according to following heat insulation intermediate layer is deposited on the pinkish red imaging layer:
Percentage preparation coating fluid intermediate layer according to the following stated.The image intermediate layer coating composition of preparation thus is applied on the pinkish red imaging layer in three strokes, and the regulation coating weight is 13.4g/m 2
Composition Percentage solids content in the dry film
Glascol?C44 ?99.50％
Zonyl?FSA ?0.50％
E. according to following blue or green imaging layer E1-E3 is deposited on the thermal insulation layer:
The blue or green developer layer of E1.
In the 4oz. glass jar that contains 10g Mullite pearl, acid developer III (10g) is dispersed in the aqueous mixture that comprises Tamol 731 (7.06% aqueous solution of 7.08g) and 32.92g deionized water, at room temperature stir 16h.The concentration of developer is 20.0%.
Percentage according to the following stated adopts aforementioned dispersion to prepare blue or green developer coating fluid.The blue or green developer coating composition of preparation thus is coated on the end face in heat insulation intermediate layer, and specific thickness is 1.94g/m 2
Composition Percentage solids content in the dry film
Acid developer III ?89.5％
Joncryl?138 ?9.5％
Zonyl?FSN ?1.0％
The blue or green intermediate layer of E2.
Percentage according to the following stated prepares blue or green intermediate layer coating fluid.The blue or green intermediate layer coating composition of preparation thus is coated on the end face of blue or green developer layer, and specific thickness is 1.0g/m 2
Composition Percentage solids content in the dry film
Airvol?205 ?99.00％
Zonyl?FSN ?1.00％
The blue or green dye coating of E3.
In containing the 4oz. glass jar of Mullite pearl, leuco dye II (15.0g) is dispersed in the aqueous mixture that comprises Airvol 350 (9.5% aqueous solution of 11.06g), Airvol 205 (20% aqueous solution of 2.25g), Aerosol-OT (2.53g 19% aqueous solution), Triton X-100 (1.49g 5% aqueous solution) and deionized water (52.61g), at room temperature stirs 16h.The concentration of dyestuff is 20.0%.
Percentage according to the following stated adopts aforementioned dispersion to prepare blue or green developer coating fluid.The blue or green coating composition of preparation thus is coated on the blue or green intermediate layer, and the regulation coating weight is 0.65g/m 2
Composition Percentage solids content in the dry film
Leuco dye II ?59.30％
Joncryl?138 ?39.37％
Zonyl?FSN ?1.33％
F. according to following the protective cowl surface layer is deposited on the blue or green one-tenth chromatograph:
The grease boot surface layer is coated on the blue or green dye coating.Finishing coat is according to the described percentage preparation of Table VI.The cover coating composition of preparation thus is coated on the blue or green dye coating, and the regulation coating weight is 1.1g/m 2
Composition Percentage solids content in the dry film
Hymicron?ZK-349 ?31.77％
Klebosol?30R?25 ?23.77％
Airvol?540 ?31.93％
Glyoxal ?8.39％
Zonyl?FSA ?0.92％
Zonyl?FSN ?3.22％
Employing is equipped with KST-87-12MPC8 type laboratory test platform printing machine (Kyocera Corporation, 6 Takeda tobadono-cho, Fushimi-ku, Kyoto, Japan) image-forming component of printshop acquisition of heat head.Adopted following printing parameter:
Print head width: 3.41in
Every in number of pixels: 300
Resistance size: 69.7 * 80 μ m
Resistance: 3536Ohm
Linear velocity: 8ms/ is capable
Print speed printing speed: 0.42in/s
Pressure: 1.5-2lb/ linear inch
Dot pattern: rectangle grid.
Blue or green layer prints under the condition of high-energy/short time.In order to obtain color gradient, pulse width is elevated to maximum 1.31ms (account for single file total time about 16.4%) through 10 isometric steps from 0, makes the voltage that is applied on the print head keep 29.0V simultaneously.
Adopt low-yield/long-time condition to come the printed matter red beds.Pulse width is brought up to 99.5% of the 8ms single file time through 10 isometric steps from 0, makes the voltage that is applied on the print head keep 15V simultaneously.
Adopted low-down energy/very long time during printing Huang layer.According to a part of printing condition of following change:
Linear velocity: 15.23ms/ is capable
Pulse width: 15.23ms
Print speed printing speed: 0.0011in./s
The printing line number: 1600, the single step maximal density.
After the printing, adopt the reflection density of each printing zone of Gretag Macbeth spectrophotometer measurement.The results are shown in Table VII, VIII and Table I X.What Table VII was represented is the relation that blue or green layer prints the energy that is applied with the heat head.Also provide magenta and the yellow density that is obtained and intersected and disturbed the result.What equally, Table VIII was represented is the relation of a magenta layer printing density and a heat energy that is applied.Density that Table I X represents is obtained when being the yellow layer of printing and the relation between voltage that is applied and the energy.
Table VII
? Blue or green printing density Pinkish red printing density Yellow printing density Intersect and disturb (magenta) Intersect and disturb (Huang)
0.00 0.06 0.07 0.17 ? ?
0.41 0.06 0.07 0.17 ? ?
0.83 0.06 0.07 0.17 ? ?
1.24 0.05 0.07 0.16 ? ?
1.65 0.06 0.07 0.16 ? ?
2.07 0.06 0.07 0.18 ? ?
2.48 0.07 0.08 0.19 ? ?
2.89 0.12 0.09 0.19 -0.03 0.15
3.30 0.19 0.12 0.21 0.03 0.12
3.72 0.19 0.14 0.22 0.18 0.17
4.13 0.33 0.17 0.24 0.02 0.07
Table VIII
Apply energy (J/cm 2) Blue or green printing density Pinkish red printing density Yellow printing density Intersect and disturb (green grass or young crops) Intersect and disturb (Huang)
0.00 0.05 0.07 0.16 ? ?
0.67 0.05 0.07 0.16 ? ?
1.34 0.05 0.07 0.17 ? ?
2.01 0.05 0.07 0.18 ? ?
2.68 0.06 0.07 0.18 ? ?
3.36 0.06 0.08 0.18 ? ?
4.03 0.08 0.12 0.19 ? ?
4.70 0.08 0.24 0.22 0.16 0.17
5.37 0.10 0.38 0.25 0.14 0.11
6.04 0.16 0.63 0.33 0.18 0.12
6.71 0.20 0.91 0.42 0.16 0.13
Table I X
Apply voltage (V) Apply energy (J/cm 2) Blue or green printing density Pinkish red printing density Yellow printing density
7.5 639 0.06 0.26 0.73
7 557 0.06 0.23 0.70
This embodiment shows, can adopt the heat head to print out three kinds of all colors independently from the image-forming component the same side according to structure shown in Figure 9.
EXAMPLE V
This embodiment has illustrated such as three look image-forming components shown in Figure 10.It is yellow that end face becomes chromatograph to produce, utilization be United States Patent (USP) 5,350,870 described unimolecule thermal response mechanism.The intermediate image layer produces magenta, utilization be that acid developer, acidity help developer and pinkish red leuco dye.Under the one-tenth chromatograph produce cyan, utilization be acid developer and blue or green leuco dye.Between magenta layer and blue or green layer, employing be thick transparent PETG sheet base, the about 102 μ m of thickness (Cronar 412).Under blue or green imaging layer, with thick opaque white color layer as the masking layer.Image-forming component is (yellow and pinkish red) and bottom (green grass or young crops) visit from the top.But, because there is opaque layer, so all three kinds of colors only can be seen from the top.Therefore, can obtain coloured image.
A. according to being prepared as follows pinkish red imaging layer:
Dispersion according to previous embodiment I part A described preparation leuco dye I and acid developer I.
According to the dispersion of the described preparation acid developer of example II part A III before.
Utilize aforementioned dispersion to make pinkish red coating fluid according to the percentage of the following stated.Adopt the Meyer excellent spreader that winds the line, the coating composition of preparation thus is applied to a side that is primed with gelatin on the transparent PETG sheet base, the about 102 μ m of the thickness of this sheet base (Cronar 412) carry out drying then.The regulation coating thickness is 3 μ m.
Composition Percentage solids content in the dry film
Leuco dye I ?24.18％
Acid developer I ?47.49％
Acid developer III ?11.63％
Joncryl?138 ?16.16％
Zonyl?FSN ?0.54％
B. according to example II part B is described before heat insulation intermediate layer is deposited on the pinkish red imaging layer.
C. according to following Huang Cheng's picture is deposited upon on the thermal insulation layer:
According to the described preparation leuco dye of example II portion C III dispersion before.Percentage according to the following stated adopts the yellow coating of this dispersion preparation fluid.Yellow coating composition that excellent spreader will prepare thus is coated on the heat insulation intermediate layer to utilize Meyer to wind the line, and specific thickness is 3 μ m, carries out drying then in air.
Composition Percentage solids content in the dry film
Leuco dye III ?70％
Genflo?3056 ?22.95％
Airvol?205 ?7％
Zonyl?FSN ?0.05％
D. according to following the protective cowl surface layer is deposited on the yellow imaging layer:
The grease boot surface layer is coated on the xanthochromia bed of material.Percentage according to the following stated prepares finishing coat.Cover coating composition that excellent spreader will prepare thus is coated on the xanthochromia bed of material to utilize Meyer to wind the line, and specific thickness is 1.0 μ m, carries out drying then in air.
Composition Percentage solids content in the dry film
Glyoxal ?8.39％
Hymicron?ZK-349 ?31.77％
Klebosol 30R?25 ?23.77％
Zonyl?FSA ?0.92％
Zonyl?FSN ?3.22％
Airvol?540 ?31.93％
E. according to being prepared as follows blue or green imaging layer:
Employing has been equipped with the attritor of bead, leuco dye II is dispersed in the aqueous mixture that comprises Airvol 205 (2.7% total solids content), Airvol 350 (6.3% total solids content), Triton X-100 (0.18% total solids content), Aerosol-OT (0.9% total solids content) and deionized water, at room temperature stirs 18h.The total solids content of this dispersion is 20%.
According to the dispersion of the described preparation acid developer of example I part A I before.
Adopt the percentage preparation blue or green coating fluid of aforementioned dispersion according to the following stated.Utilize the Meyer excellent spreader that winds the line, the coating composition of preparation thus is coated on the surface of a relative side with coating A-D on the transparent PETG sheet base, in air, carry out drying then.The specific thickness of coating is 2 μ m.
Composition Percentage solids content in the dry film
Leuco dye II ?28.38％
Acid developer I ?41.62％
Genflo?3056 ?22.90％
Airvol?205 ?7％
Zonyl?FSN ?0.1％
F. masking opaque layer.
Employing has been equipped with the attritor of bead, titanium dioxide is dispersed in the aqueous mixture that comprises Tamol731 (3.86% total solids content), Ludox HS40 (3.85% total solids content), minute quantity (750ppm) Nipa Proxel and deionized water, and at room temperature stirs 18h.The total solids content of this dispersion is 50.2%.
Adopt the percentage manufacturing coating fluid of aforementioned dispersion according to the following stated.Coating composition that excellent spreader will prepare thus is coated on the blue or green imaging layer to utilize Meyer to wind the line, and specific thickness is 15 μ m, carries out drying then in air.
Composition Percentage solids content in the dry film
Titanium dioxide 81.37％
Joncryl?138 18.08％
Zonyl?FSN 0.54％
G. according to part D is described before the protective cowl surface layer is deposited on the opaque layer.
Employing is equipped with KST-87-12MPC8 type laboratory test platform printing machine (Kyocera Corporation, 6 Takedatobadono-cho, Fushimi-ku, Kyoto, Japan) image-forming component of printshop acquisition of heat head.Adopted following printing parameter:
Print head width: 3.41in
Every in number of pixels: 300
Resistance size: 69.7 * 80 μ m
Resistance: 3536Ohm
Linear velocity: 8ms/ is capable
Print speed printing speed: 0.42in/s
Pressure: 1.5-2lb/ linear inch
Dot pattern: rectangle grid.
Under the condition of high-energy/short time, print yellow layer from the front.In order to obtain color gradient, pulse width is elevated to maximum 1.65ms (account for single file total time about 20.6%) through 21 isometric steps from 0, makes the voltage that is applied on the print head keep 29.0V simultaneously.
Adopt low-yield/long-time condition to come the printed matter red beds, it is also visited from the front.Pulse width is brought up to 99.5% of the 8ms single file time through 21 isometric steps from 0, makes the voltage that is applied on the print head keep 16V simultaneously.
(the sheet base is loaded with a side of opaque layer) prints blue or green layer from the back side under the condition of high-energy/short time.In order to obtain color gradient, pulse width is elevated to maximum 1.65ms (account for single file total time about 20.6%) through 21 isometric steps from 0, makes the voltage that is applied on the print head keep 29.0V simultaneously.
After the printing, adopt the reflection density of each printing zone of Gretag Macbeth spectrophotometer measurement.The results are shown in Table among X, XI and the XII.What Table X was represented is the relation of a yellow layer printing density and a heat energy that is applied.The magenta and the blue or green density that are obtained have also been provided.Also comprise the ratio (Y/M) between Huang and the fuchsin density in the Table X and intersect and disturb the result.What equally, Table X I represented is the relation of a magenta layer printing density and a heat energy that is applied.The ratio (M/Y) and the interference result of intersecting between pinkish red and the yellow density have been provided.In Table X II, also provided the relation of a blue or green layer printing density and heat energy that is applied.Provided the ratio (C/M) between green grass or young crops and the fuchsin density.
Table X
Apply energy (J/cm 2) Yellow printing density Pinkish red printing density Blue or green printing density Y/M Intersect and disturb (magenta)
0.00 0.11 0.11 0.08 1.00 ?
0.26 0.11 0.11 0.08 1.00 ?
0.52 0.11 0.11 0.08 1.00 ?
0.78 0.12 0.11 0.08 1.09 ?
1.04 0.11 0.11 0.08 1.00 ?
1.30 0.11 0.11 0.08 1.00 ?
1.56 0.12 0.11 0.08 1.09 ?
1.82 0.12 0.11 0.08 1.09 ?
2.08 0.13 0.11 0.08 1.18 ?
2.34 0.15 0.11 0.08 1.36 ?
2.60 0.21 0.12 0.08 1.75 -0.01
2.86 0.28 0.12 0.08 2.33 -0.05
3.12 0.36 0.13 0.08 2.77 -0.03
3.38 0.46 0.15 0.08 3.07 0.01
3.64 0.63 0.17 0.08 3.71 0.01
3.90 0.79 0.20 0.08 3.95 0.03
4.16 0.98 0.24 0.08 4.08 0.05
4.41 1.12 0.27 0.08 4.15 0.06
4.67 1.24 0.30 0.09 4.13 0.06
4.93 1.36 0.33 0.09 4.12 0.07
5.19 1.44 0.36 0.09 4.00 0.08
Table X I
Apply energy (J/cm 2) Pinkish red printing density Yellow printing density Blue or green printing density M/Y Intersect and disturb (Huang)
0.00 0.11 0.11 0.07 1.00 ?
0.38 0.11 0.11 0.08 1.00 ?
0.76 0.11 0.11 0.07 1.00 ?
1.15 0.11 0.11 0.08 1.00 ?
1.53 0.11 0.11 0.08 1.00 ?
1.91 0.11 0.11 0.08 1.00 ?
2.29 0.11 0.11 0.08 1.00 ?
2.67 0.11 0.11 0.07 1.00 ?
3.05 0.11 0.11 0.07 1.00 ?
3.44 0.11 0.12 0.07 0.92 ?
3.82 0.11 0.12 0.07 0.92 ?
4.20 0.12 0.13 0.07 0.92 ?
4.58 0.13 0.14 0.07 0.93 ?
4.96 0.17 0.16 0.07 1.06 ?
5.35 0.24 0.19 0.08 1.26 0.47
5.73 0.39 0.25 0.09 1.56 0.34
6.11 0.60 0.34 0.10 1.76 0.31
6.49 0.86 0.44 0.12 1.95 0.28
6.87 1.16 0.55 0.13 2.11 0.25
7.26 1.50 0.71 0.15 2.11 0.27
7.64 1.54 0.81 0.16 1.90 0.33
Table X II
Apply energy (J/cm 2) Blue or green printing density Pinkish red printing density Yellow printing density C/M
0.00 0.07 0.11 0.11 0.64
0.26 0.07 0.11 0.11 0.64
0.52 0.07 0.11 0.11 0.64
0.78 0.07 0.11 0.11 0.64
1.04 0.07 0.11 0.11 0.64
1.30 0.07 0.11 0.11 0.64
1.56 0.07 0.11 0.11 0.64
1.82 0.07 0.11 0.11 0.64
2.08 0.07 0.11 0.11 0.64
2.34 0.07 0.11 0.11 0.64
2.60 0.08 0.11 0.11 0.73
2.86 0.10 0.11 0.11 0.91
3.12 0.16 0.13 0.12 1.23
3.38 0.24 0.15 0.13 1.60
3.64 0.33 0.17 0.14 1.94
3.90 0.43 0.21 0.15 2.05
4.16 0.57 0.26 0.18 2.19
4.41 0.90 0.42 0.27 2.14
4.67 1.09 0.53 0.33 2.06
4.93 1.06 0.52 0.33 2.04
5.19 1.03 0.51 0.32 2.02
Example VI
This embodiment has illustrated such as three look image-forming components shown in Figure 10.The end face imaging layer produces cyan, and the intermediate image layer produces magenta, and the bottom imaging layer produces yellow.All three layers have all adopted acid developer, and leuco dye.Pinkish red and between yellow layer, employing be thick transparent PETG sheet base, the about 102 μ m (Cronar412) of thickness.Under yellow imaging layer, make the masking layer with thick opaque white color layer.(blue or green and pinkish red) and bottom (Huang) visit image-forming component from the top.But, because there is opaque layer, so only can see all three kinds of colors from the top.Therefore, can obtain coloured image.
A. according to being prepared as follows the fuchsin quality layer:
According to the dispersion of EXAMPLE IV portion C described preparation leuco dye I and acid developer I before.According to the dispersion of the described preparation acid developer of example II part A II before.
Utilize aforementioned dispersion to make pinkish red coating fluid according to the percentage of the following stated.The coating composition of preparation thus is applied on the Cronar 412, carries out drying then.The regulation coating weight is 2.0g/m 2
Composition Percentage solids content in the dry film
Leuco dye I ?241?8％
Acid developer I ?47.50％
Joncryl?138 ?16.16％
Acid developer III ?11.63％
Zonyl?FSN ?0.54％
B. according to following heat insulation intermediate layer is deposited on the pinkish red imaging layer:
Percentage according to the following stated prepares intermediate layer coating fluid.The image intermediate layer coating composition of preparation thus is applied on the pinkish red imaging layer in three strokes, and the regulation coating weight is 13.4g/m 2
Composition Percentage solids content in the dry film
Glascol C44 ?99.50％
Zonyl?FSA ?0.50％
C. according to following blue or green imaging layer C1-C3 is deposited on the thermal insulation layer:
The blue or green developer layer of C1.
According to the dispersion of the described preparation acid developer of EXAMPLE IV part E1 III before.
Adopt aforementioned dispersion to prepare blue or green developer coating fluid according to the percentage of the following stated.The blue or green developer coating composition of preparation thus is coated on the end face in heat insulation intermediate layer, and specific thickness is 2.1g/m 2, carry out drying then.
Composition Percentage solids content in the dry film
Joncryl?138 ?10.0％
Acid developer III ?89.5％
Zonyl?FSN ?0.50％
The blue or green intermediate layer of C2.
Percentage according to the following stated prepares blue or green intermediate layer coating fluid.The blue or green intermediate layer coating composition of preparation thus is coated on the end face of blue or green developer layer, and specific thickness is 1.0g/m 2
Composition Percentage solids content in the dry film
Airvol?205 ?99.00％
Zonyl FSN ?1.00％
The blue or green dye coating of C3.
According to the described dispersion leuco dye of EXAMPLE IV part E3 II before.
Adopt the percentage preparation blue or green coating fluid of aforementioned dispersion according to the following stated.The blue or green coating composition of preparation thus is coated on the blue or green intermediate layer, and the regulation coating weight is 0.65g/m 2
Composition Percentage solids content in the dry film
Leuco dye II ?59.30％
Joncryl?138 ?39.37％
Zonyl?FSN ?1.33％
D. according to following the protective cowl surface layer is deposited on the blue or green imaging layer:
The grease boot surface layer is coated on the blue or green dye coating.Finishing coat is according to the percentage preparation of the following stated.The cover coating composition of preparation thus is coated on the blue or green dye coating, and the regulation coating weight is 1.1g/m 2
Composition Percentage solids content in the dry film
Hymicron?ZK-349 ?31.77％
Klebosol?30R?25 ?23.77％
Airvol?540 ?31.93％
Glyoxal ?8.39％
Zonyl?FSA ?0.92％
Zonyl?FSN ?3.22％
E. the described program of EXAMPLE IV part A is deposited upon Huang Cheng's picture on the reverse side of transparent substrates before adopting, except dry-coated amount is 1.94g/m 2
F. according to following White-opalescent is deposited upon on Huang Cheng's chromatograph:
According to the described preparation titanium dioxide dispersion of EXAMPLE V part F before.
The dispersion preparation that forms from the percentage according to the following stated is coated with fluid.The coating composition of so preparation is coated on the top of Huang Cheng's chromatograph, and the regulation coating weight is 10.76g/m 2
Composition Percentage solids content in the dry film
Titanium dioxide ?89.70％
Joncryl?138 ?9.97％
Zonyl?FSN ?0.33％
G. according to part D is described before the protective cowl surface layer is deposited on the opaque layer.
Employing is equipped with KST-87-12MPC8 type laboratory test platform printing machine (Kyocera Corporation, 6 Takedatobadono-cho, Fushimi-ku, Kyoto, Japan) image-forming component of printshop acquisition of heat head.Adopted following printing parameter:
Print head width: 3.41in
Every in number of pixels: 300
Resistance size: 69.7 * 80 μ m
Resistance: 3536Ohm
Linear velocity: 8ms/ is capable
Print speed printing speed: 0.42in/s
Pressure: 1.5-2lb/ linear inch
Dot pattern: rectangle grid.
Under the condition of high-energy/short time, print blue or green layer from the front.In order to obtain color gradient, pulse width is elevated to maximum 1.25ms (account for single file total time about 16.4%) through 21 isometric steps from 0, makes the voltage that is applied on the print head keep 29.0V simultaneously.
Adopt low-yield/long-time condition to come the printed matter red beds, it is also visited from the front.Pulse width is brought up to 99.5% of the 8ms single file time through 21 isometric steps from 0, makes the voltage that is applied on the print head keep 14.5V simultaneously.
With the time conditions of lower energy/long from the back side the yellow layer of (the sheet base is loaded with a side of opaque layer) printing.Pulse width is elevated to 99.5% of the 8ms single file time through 21 isometric steps from 0, makes the voltage that is applied on the print head keep 14.5V simultaneously.
After the printing, adopt the reflection density of each printing zone of Gretag Macbeth spectrophotometer measurement.The results are shown in Table among XIII, XIV and the XV.What Table X III represented is the relation of a blue or green layer printing density and a heat energy that is applied.The magenta and the yellow density that are obtained have also been provided.Also comprise the ratio (C/M) between green grass or young crops and the fuchsin density among the Table X III and intersect and disturb the result.What equally, Table X IV represented is the relation of a magenta layer printing density and a heat energy that is applied.The ratio (M/C) and the interference result of intersecting between pinkish red and the blue or green density have been provided.In Table X V, also provided the relation of a yellow layer printing density and heat energy that is applied.Provided the ratio (Y/M) between Huang and the fuchsin density.
Table X III
Apply energy (J/cm 2) Blue or green printing density Pinkish red printing density Yellow printing density C/M Intersect and disturb (magenta)
1.57 0.07 0.10 0.23 0.70 ?
1.83 0.08 0.10 0.23 0.80 ?
2.09 0.08 0.11 0.25 0.73 ?
2.34 0.08 0.10 0.23 0.80 ?
2.60 0.11 0.11 0.23 1.00 ?
2.85 0.12 0.12 0.23 1.00 ?
3.11 0.16 0.13 0.24 1.23 -0.01
3.36 0.20 0.14 0.25 1.43 -0.04
3.62 0.26 0.16 0.26 1.63 -0.03
3.87 0.28 0.17 0.27 1.65 -0.01
4.13 0.36 0.20 0.28 1.80 0.00
Table X IV
Apply energy (J/cm 2) Pinkish red printing density Blue or green printing density Yellow printing density M/C Intersect and disturb (green grass or young crops)
3.14 0.10 0.07 0.20 1.43 ?
3.45 0.11 0.09 0.22 1.22 ?
3.76 0.11 0.09 0.22 1.22 ?
4.08 0.12 0.10 0.22 1.20 ?
4.39 0.13 0.10 0.21 1.30 ?
4.70 0.16 0.11 0.23 1.45 ?
5.02 0.21 0.11 0.24 1.91 0.39
5.33 0.30 0.14 0.24 2.14 0.36
5.65 0.43 0.16 0.26 2.69 0.27
5.96 0.57 0.17 0.29 3.35 0.20
6.27 0.60 0.18 0.29 3.33 0.20
Table X V
Apply energy (J/cm 2) Yellow printing density Pinkish red printing density Blue or green printing density Y/M
0.00 0.23 0.10 0.07 2.30
0.63 0.23 0.10 0.07 2.30
1.25 0.24 0.10 0.08 2.40
1.88 0.22 0.10 0.08 2.20
2.51 0.22 0.10 0.07 2.20
3.14 0.23 0.10 0.08 2.30
3.76 0.32 0.10 0.07 3.20
4.39 0.57 0.12 0.07 4.75
5.02 0.85 0.18 0.07 4.72
5.65 0.95 0.25 0.07 3.80
6.27 0.98 0.33 0.08 2.97
Example VII A
This embodiment has illustrated the preparation of 3-methyl-5-n-octyl salicylic acid zinc salt.
The preparation of 3-methyl-5-normal-butyl MEXORYL SAM methyl esters:
In the 1L flask, aluminium chloride (98g) is suspended in the carrene (150ml), and in ice bath, makes this mixture be cooled to 5 ℃.During 1h, in this stirred mixture, add 3-cresotinic acid methyl esters (50g) and the caprylyl chloride (98g) that is in the 150ml carrene.Reactant stirs 30min again under 5 ℃, at room temperature stir 3h then.Reactant is poured in the ice that 500g contains the 50ml concentrated hydrochloric acid.Separate organic layer, then with twice in 50ml dichloromethane extraction water-bearing layer.With saturated sodium bicarbonate aqueous solution washing carrene, with dried over mgso, filter and flash to oil then, be frozen into the pale brown look crystal of 90g. 1H and 13C NMR spectrum shows the product that meets expection.
The preparation of the positive MEXORYL SAM of 3-methyl-5-:
The positive MEXORYL SAM methyl esters of 3-methyl-5-(according to aforementioned preparation, 90g) is dissolved in 200ml ethanol and the 350ml water.In this solution, add 100g 50% sodium hydrate aqueous solution, stir this solution 6h down at 85 ℃ then.In ice bath, cool off reactant, and slowly add 50% aqueous hydrochloric acid solution, reach 1 up to the pH value.Filtering-depositing, (5 * 50ml) washings and under low pressure at 45 ℃ of following dry 6h obtain 80g light brown yellow product with water. 1H and 13C NMR spectrum shows the product structure that meets expection.
The salicylic preparation of 3-methyl 5-n-octyl:
In the 1L flask, 16g mercury chloride (II) is dissolved in 8ml concentrated hydrochloric acid and the 200ml water.Add 165g Mossy zinc and this solution one oscillates.Strain water and Xiang Xinzhong and add 240ml concentrated hydrochloric acid, 100ml water and the positive MEXORYL SAM of 3-methyl-5-(according to aforementioned preparation, 80g).The mixture 24h that under agitation refluxes, every 6h replenish and add 50ml concentrated hydrochloric acid (3 times).From zinc, drain reactant while hot and cool off it, product is solidified.Filter and collect product, wash it (2 * 100ml water), and be dissolved in the 300ml hot ethanol.Add 50ml water and frozen soln, obtain white crystal.Cross filter solid, wash (3 * 100ml water) and, obtain the 65g product under low pressure at 45 ℃ of following dry 8h. 1H and 13C NMR spectrum shows and meets the expection product structure.
The preparation of 3-methyl-5-n-octyl salicylic acid zinc salt:
In the 4L beaker, under agitation in the solution of 14.5g 50% sodium hydrate aqueous solution and 200ml water, add 3-methyl-5-n-octyl salicylic acid (according to aforementioned preparation, 48g).To wherein adding 1L water and solution being heated to 65 ℃.Under agitation in this hot solution, add 24.5g and be in zinc chloride in the 40ml water.There is colloidal solid to be precipitated out.Drain solution and remaining solid is dissolved in 95% ethanol of 300ml.With 500ml water heat of dilution solution and freezing it.Filtration product and washing (3 * 500ml water) obtain the 53g pale solid.
Example VII A I
This embodiment has illustrated that every side all deposits three look image-forming components of finishing coat, and utilizes two thermal printer heads to write down the method for multicolour in single stroke on this element.It is yellow that end face becomes chromatograph to produce, utilization be United States Patent (USP) 5,350,870 described unimolecule thermal response mechanism.The intermediate coupler layer produces magenta, utilization be that acid developer, acidity help developer and pinkish red leuco dye.The bottom becomes chromatograph to produce cyan, utilization be acid developer and blue or green leuco dye.Pinkish red and between blue or green layer, employing be thick transparent PETG sheet base, the about 102 μ m of thickness (Cronar 412).Under blue or green imaging layer, make the masking layer with thick opaque white color layer.(yellow and pinkish red) and bottom (green grass or young crops) visit image-forming component from the top.But because there is opaque layer, so only can see all three kinds of colors from the top.Therefore, can obtain coloured image.
A. according to being prepared as follows the fuchsin quality layer:
According to the dispersion of example I part A described preparation leuco dye I and acid developer I before.
According to the dispersion of the described preparation acid developer of example II part A II before.
Utilize aforementioned dispersion to make pinkish red coating fluid according to the percentage of the following stated.Use the Meyer rod to be coated with method, the coating composition for preparing thus is applied to a side that is primed with gelatin on the transparent PETG sheet base, the about 102 μ m of the thickness of sheet base (Cronar 412) carry out drying then.The regulation coating thickness is 3.06 μ m.
Composition Percentage solids content in the dry film
Leuco dye I ?12.08％
Acid developer I ?28.70％
Acid developer III ?15.14％
Genflo?3056 ?37.38％
Airvol?205 ?6.38％
Zonyl?FSN ?0.32％
B. according to following heat insulation intermediate layer is deposited on the pinkish red imaging layer:
B1. the percentage according to the following stated prepares intermediate layer coating fluid.Image intermediate layer coating composition that excellent spreader will prepare thus is applied on the imaging layer to utilize Meyer to wind the line, and specific thickness is 6.85 μ m, carries out drying then in air.
Composition Percentage solids content in the dry film
Glascol?C44 ?99.78％
Zonyl?FSN ?0.22％
B2. the second heat insulation intermediate layer with same specification is coated on first intermediate layer, carries out drying then.
B3. last, the 3rd heat insulation intermediate layer of same specification is coated on second intermediate layer, carry out drying then.Three heat insulation intermediate layers are combined, and add thermal insulation layer, and total specific thickness is 20.55 μ m.
C. according to following Huang Cheng's picture is deposited upon on the 3rd thermal insulation layer:
According to the dispersion of the described preparation leuco dye of example II portion C III before.Utilize this dispersion to make yellow coating fluid according to the percentage of the following stated.Yellow coating composition that excellent spreader will prepare thus is applied on the heat insulation intermediate layer to utilize Meyer to wind the line, and specific thickness is 3.21 μ m, carries out drying then in air.
Composition Percentage solids content in the dry film
Leuco dye III ?49.42％
Airvol?205 ?11.68％
Genflo?3056 ?38.00％
Zonyl?FSN ?0.90％
D. according to following the protective cowl surface layer is deposited on the yellow imaging layer:
The grease boot surface layer is coated on the xanthochromia bed of material.Percentage according to the following stated prepares finishing coat.Cover coating composition that excellent spreader will prepare thus is coated on the xanthochromia bed of material to utilize Meyer to wind the line, and specific thickness is 1.46 μ m, carries out drying then in air.
Composition Percentage solids content in the dry film
Glyoxal ?8.54％
Hymicron?ZK-349 ?31.95％
Klebosol?30R?25 ?23.89％
Zonyl?FSA ?0.98％
Zonyl?FSN ?2.44％
Airvol?540 ?32.20％
E. according to being prepared as follows blue or green imaging layer:
Employing has been equipped with the attritor of bead, leuco dye II is dispersed in the aqueous mixture that comprises Airvol 205 (2.7% total solids content), Airvol 350 (6.3% total solids content), Triton X-100 (0.18% total solids content), Aerosol-OT (0.9% total solids content) and deionized water, at room temperature stirs 18h.The total solids content of this dispersion is 20%.
According to the dispersion of the described preparation acid developer of example I part A I before.
Adopt the percentage preparation blue or green coating fluid of aforementioned dispersion according to the following stated.Utilize the Meyer excellent spreader that winds the line, the coating composition of preparation thus is coated on a side relative with layer A-D on the transparent PETG sheet base, in air, carry out drying then.The regulation coating thickness is 3.01 μ m.
Composition Percentage solids content in the dry film
Leuco dye II ?18.94％
Acid developer I ?51.08％
Genflo?3056 ?22.86％
Airvol?205 ?7.01％
Zonyl?FSN ?0.10％
F. masking opaque layer.
Employing has been equipped with the attritor of bead, titanium dioxide is dispersed in the aqueous mixture that comprises Tamol731 (3.86% total solids content), Ludox HS40 (3.85% total solids content), minute quantity (750ppm) Nipa Proxel and deionized water, and at room temperature stirs 18h.The total solids content of this dispersion is 50.2%.
Adopt the percentage manufacturing coating fluid of aforementioned dispersion according to the following stated.Coating composition that excellent spreader will so prepare is coated on the blue or green imaging layer to utilize Meyer to wind the line, and specific thickness is 15 μ m, carries out drying then in air.
Composition Percentage solids content in the dry film
Titanium dioxide ?88.6?1％
Airvol?205 ?11.08％
Zonyl?FSN ?0.32％
G. according to part D is described before the protective cowl surface layer is deposited on the opaque layer.
Employing is equipped with KST-87-12MPC8 type laboratory test platform printing machine (Kyocera Corporation, 6 Takedatobadono-cho, Fushimi-ku, Kyoto, Japan) image-forming component of printshop acquisition of heat head.Adopted following printing parameter:
Print head width: 4.16in
Every in number of pixels: 300
Resistance size: 70 * 80 μ m
Resistance: 3900Ohm
Linear velocity: 10.7ms/ is capable
Print speed printing speed: 0.31in/s
Pressure: 1.5-2lb/ linear inch
Dot pattern: rectangle grid.
Under the condition of high-energy/short time, print yellow layer from the front.In order to obtain color gradient, pulse width is elevated to maximum 1.99ms (account for single file total time about 18.2%) through 10 isometric steps from 0, makes the voltage that is applied on the print head keep 26.5V simultaneously.120 inferior intervals are arranged, and each inferior working cycles at interval is 95% in this pulse width.
Adopt low-yield/long-time condition to come the printed matter red beds, it is also visited from the front.Pulse width is brought up to the 8.5ms single file time (account for single file total time about 79%) through 10 isometric steps from 0, makes the voltage that is applied on the print head keep 26.5V simultaneously.525 inferior intervals are arranged, and each inferior working cycles at interval is 30% in this pulse width.
Different with before embodiment is, yellow pulse and pinkish red pulse are interlaced, and are provided in one stroke by a print head, thereby a print head can synchronously print two kinds of colors.By between 30% pinkish red used working cycles of yellow used 95% working cycles of printing and printing, switching, select high-energy or low-yield thus.The voltage constant of print head is 26.5V,
(the sheet base is loaded with a side of opaque titanium dioxide layer) prints blue or green layer from the back side under low-yield/long-time condition.In order to obtain color gradient, pulse width is elevated to maximum 10.5ms (account for single file total time about 98%) through 10 isometric steps from 0, makes the voltage that is applied on the print head keep 21.0V simultaneously.
Except the gradation that prints every layer of three dye coating, also printed the level of paired color scheme, and the level of all three kinds of color scheme.
After the printing, adopt the reflection density of each printing zone of Gretag Macbeth spectrophotometer measurement.Record yellow, pinkish red and blue or green layer the results are shown in Table XVI, XVII and XVIII.
What Table X VI represented is the relation of a blue or green layer printing density and a heat energy that is applied.The magenta and the yellow density that are obtained have also been provided.What equally, Table X VII represented is the relation of a magenta layer printing density and a heat energy that is applied.The ratio (M/Y) and the interference result of intersecting between pinkish red and the yellow density have been provided.In Table X VIII, also provided the relation of a yellow layer printing density and heat energy that is applied.Provide the ratio (Y/M) between Huang and the fuchsin density and intersected and disturbed the result.
Table X VI
Apply energy (J/cm 2) Blue or green printing density Pinkish red printing density Yellow printing density
1.79 0.10 0.12 0.20
2.07 0.11 0.12 0.20
2.35 0.11 0.12 0.19
2.63 0.12 0.13 0.19
2.92 0.17 0.13 0.20
3.20 0.25 0.15 0.20
3.48 0.34 0.18 0.22
3.76 0.56 0.25 0.25
4.05 0.82 0.35 0.29
4.33 1.07 0.43 0.33
4.61 1.17 0.45 0.34
Table X VII
Apply energy (J/cm 2) Blue or green printing density Pinkish red printing density Yellow printing density M/Y Intersect and disturb Huang
3.07 0.11 0.13 0.20 0.65 ?
3.40 0.10 0.13 0.20 0.65 ?
3.74 0.10 0.13 0.20 0.65 ?
4.08 0.10 0.14 0.22 0.64 ?
4.42 0.10 0.16 0.22 0.73 ?
4.75 0.10 0.21 0.24 0.88 ?
5.09 0.11 0.33 0.27 1.22 0.18
5.43 0.11 0.53 0.31 1.71 0.11
5.77 0.13 0.80 0.38 2.10 0.10
6.10 0.14 0.97 0.43 2.25 0.10
6.45 0.14 1.02 0.45 2.27 0.11
Table X VIII
Apply energy (J/cm 2) Blue or green printing density Pinkish red printing density Yellow printing density Y/M Intersect and disturb magenta
1.82 0.11 0.13 0.20 1.53 ?
2.07 0.11 0.13 0.22 1.69 ?
2.33 0.11 0.13 0.27 2.08 ?
2.58 0.10 0.13 0.31 2.38 ?
2.84 0.11 0.14 0.36 2.57 ?
3.09 0.10 0.15 0.48 3.20 ?
3.35 0.11 0.17 0.59 3.47 0.00
3.60 0.11 0.19 0.71 3.74 0.01
3.86 0.11 0.20 0.76 3.80 0.02
4.11 0.11 0.21 0.88 4.19 0.01
4.37 0.11 0.21 0.84 4.00 0.02
Simultaneously when two enterprising line items of color layer, what obtained the results are shown in Table XIX, XX and XXI.That Table X IX represents is the result who utilizes a thermal printer head to print simultaneously on yellow and magenta layer.The printing that is obtained is red.Table X X represents is the result of printing simultaneously on blue or green and yellow layer, has obtained green printing, is the result who prints on blue or green and magenta layer and Table X XI represents, acquisition be the printing of blueness.
Table X IX
Apply energy (J/cm 2) Blue or green printing density Pinkish red printing density Yellow printing density
4.89 0.10 0.12 0.20
5.47 0.11 0.14 0.23
6.08 0.11 0.17 0.28
6.66 0.11 0.27 0.38
7.26 0.12 0.40 0.50
7.84 0.13 0.80 0.65
8.45 0.15 1.20 0.84
9.03 0.18 1.60 1.11
9.63 0.19 1.71 1.26
10.21 0.19 1.69 1.39
10.82 0.20 1.62 1.42
Table X X
Apply energy (J/cm 2) Blue or green printing density Pinkish red printing density Yellow printing density
3.61 0.11 0.13 0.20
4.14 0.11 0.13 0.20
4.69 0.12 0.13 0.22
5.21 0.13 0.14 0.27
5.76 0.17 0.15 0.32
6.29 0.31 0.19 0.43
6.84 0.46 0.26 0.55
7.36 0.67 0.33 0.57
7.91 0.92 0.43 0.67
8.44 1.23 0.54 0.84
8.99 1.36 0.58 0.93
Table X XI
Apply energy (J/cm 2) Blue or green printing density Pinkish red printing density Yellow printing density
4.86 0.11 0.12 0.19
5.47 0.11 0.13 0.24
6.10 0.12 0.13 0.20
6.71 0.13 0.15 0.21
7.34 0.15 0.17 0.22
7.95 0.32 0.26 0.25
8.58 0.51 0.42 0.31
9.19 0.69 0.76 0.39
9.82 0.88 1.01 0.47
10.43 1.40 1.27 0.59
11.06 1.49 1.31 0.61
Table X XII is illustrated in the color density that is obtained when printing in the one stroke on all three kinds of color layers.The printing that is obtained is a black.
Table X XII
Apply energy (J/cm 2) Blue or green printing density Pinkish red printing density Yellow printing density
6.68 0.11 0.13 0.20
7.54 0.11 0.14 0.24
8.43 0.11 0.17 0.29
9.29 0.11 0.23 0.37
10.18 0.18 0.43 0.43
11.04 0.29 0.81 0.71
11.93 0.41 1.21 0.94
12.79 0.64 1.59 1.12
13.68 0.89 1.81 1.38
14.54 1.17 1.79 1.46
15.43 1.29 1.71 1.55
Though the present invention has been carried out specific description with reference to various preferred embodiments, but the present invention is not limited to this, and those skilled in the art know, various changes and modification all be possible and also belong to spirit of the present invention and the claims scope within.

Claims (16)

1. colored thermal imaging method comprises:
(a) utilize one or more thermal printer heads that design in order in first imaging layer, to form image, described one or more by controlling for the temperature that in described first imaging layer, forms the thermal printer head that image designs and the time interval that on described first imaging layer, applies heat energy, visit first imaging layer of described thermal imaging element independently from surface to the small part of thermal imaging element, this thermal imaging element comprises at least two different imaging layers, and one of them is second imaging layer for described first imaging layer with another;
(b) utilize one or more thermal printer heads that design in order in described second imaging layer, to form image, described one or more by controlling for the temperature that in described second imaging layer, forms the thermal printer head that image designs and the time interval that on described second imaging layer, applies heat energy, visit described second imaging layer of described thermal imaging element independently from same surface to the small part of described thermal imaging element;
Wherein the described temperature of the described thermal printer head in the step (b) is than the described temperature height of the described thermal printer head in the step (a), and the described time interval in the step (b) is shorter than the described time interval in the step (a); And
Wherein at least one described imaging layer comprises the compound that forms color in the molecule.
2. the colored thermal imaging method of claim 1, the temperature that wherein is applied to the heat energy of described first and second imaging layers is 50 ℃～450 ℃, the duration is 0.01～100ms.
3. the colored thermal imaging method of claim 1, wherein at least one described imaging layer further comprises hot solvent.
4. the colored thermal imaging method of claim 1, wherein a plurality of described imaging layers include hot solvent, and every kind of hot solvent has different fusing points.
5. the colored thermal imaging method of claim 1, wherein to rise be colourless at least one described imaging layer at the beginning, is formed with color image then therein.
6. the colored thermal imaging method of claim 1, wherein to rise be coloured at least one described imaging layer at the beginning, forms the lighter image of color then therein.
7. the colored thermal imaging method of claim 1, wherein at least one described imaging layer rises and is first color at the beginning, forms the image of second color then therein.
8. the colored thermal imaging method of claim 1, wherein in the zone of described imaging layer and heating element heater thermo-contact, form image pixel in the required time interval, on at least one heating element heater of described one or more print heads, provide one or more current impulses, this print head designs in order to form image in described imaging layer, and control is applied to the heat energy on each described imaging layer thus.
9. the colored thermal imaging method of claim 1, first voltage that at least one described print head, applies during wherein by formation image in described first imaging layer, control the heat energy that on described first imaging layer, applies via at least one described print head that designs in order in described first imaging layer, to form image, and second voltage that at least one described print head, applies during by formation image in described second imaging layer, control the heat energy that applies on described second imaging layer via at least one described print head that designs in order to form image in described second imaging layer, described first and second voltages are identical basically.
10. thermal imaging element comprises:
(a) substrate, it has first and second facing surfaces;
(b) by first and second imaging layers of the described first surface carrying of described substrate, described first imaging layer is than the described first surface of the more approaching described substrate of described second imaging layer, and the activation temperature of described first imaging layer is lower than described second imaging layer; And
(c) intermediate layer between described first and second imaging layers, wherein said intermediate layer is included in the material that undergoes phase transition when applying heat.
11. the thermal imaging element of claim 10, the thickness in wherein said intermediate layer are 1～40 μ m.
12. the thermal imaging element of claim 11, the thickness in wherein said intermediate layer are 14～25 μ m.
13. the thermal imaging element of claim 10, at least one in wherein said first and second imaging layers comprise the compound that forms color in the molecule.
14. the thermal imaging element of claim 10, wherein said intermediate layer comprises inert material.
15. the thermal imaging element of claim 10, the thickness of at least one in wherein said first and second imaging layers are 2 μ m.
16. the thermal imaging element of claim 10, wherein said first and second imaging layers thickness separately is 0.5～4.0 μ m.
CN2007101817128A 2001-05-30 2002-05-20 Thermal imaging method and element Expired - Lifetime CN101284455B (en)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US29448601P 2001-05-30 2001-05-30
US60/294486 2001-05-30
US36419802P 2002-03-13 2002-03-13
US60/364198 2002-03-13
US10/151432 2002-05-20
US10/151,432 US6801233B2 (en) 2001-05-30 2002-05-20 Thermal imaging system

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
CNB028150880A Division CN100354136C (en) 2001-05-30 2002-05-20 Thermal imaging system

Publications (2)

Publication Number Publication Date
CN101284455A CN101284455A (en) 2008-10-15
CN101284455B true CN101284455B (en) 2011-07-06

Family

ID=40056966

Family Applications (2)

Application Number Title Priority Date Filing Date
CNA2007101817113A Pending CN101284464A (en) 2001-05-30 2002-05-20 Thermal imaging system
CN2007101817128A Expired - Lifetime CN101284455B (en) 2001-05-30 2002-05-20 Thermal imaging method and element

Family Applications Before (1)

Application Number Title Priority Date Filing Date
CNA2007101817113A Pending CN101284464A (en) 2001-05-30 2002-05-20 Thermal imaging system

Country Status (1)

Country Link
CN (2) CN101284464A (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8716178B2 (en) * 2009-12-22 2014-05-06 Ncr Corporation One-ply two-sided thermal imaging labels
CN113474174B (en) * 2018-11-15 2023-10-31 津克控股有限责任公司 Ordering of color forming layers in direct thermal print media

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4665410A (en) * 1985-04-20 1987-05-12 Ricoh Company, Ltd. Multi-color thermosensitive recording material
US5699100A (en) * 1994-02-16 1997-12-16 Fuji Photo Film Co., Ltd. Direct color thermal printing method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4665410A (en) * 1985-04-20 1987-05-12 Ricoh Company, Ltd. Multi-color thermosensitive recording material
US5699100A (en) * 1994-02-16 1997-12-16 Fuji Photo Film Co., Ltd. Direct color thermal printing method

Also Published As

Publication number Publication date
CN101284455A (en) 2008-10-15
CN101284464A (en) 2008-10-15

Similar Documents

Publication Publication Date Title
CN100354136C (en) Thermal imaging system
CN102202905B (en) Print head pulsing techniques for multicolor printers
JP3306609B2 (en) Thermochromic color memory composition
JP3396787B2 (en) Thermochromic color memory microcapsule pigment
US4940689A (en) Display material
JP2002234119A (en) Reversibly thermally color changeable light shutting- off-light pervious laminate
CN101284455B (en) Thermal imaging method and element
JP2015024582A (en) Method of arranging adhesive layer on reversible thermochromic laminate and reversible thermochromic pasted body
JP2001030404A (en) Metallic gloss style thermally discoloring laminate
CN218711814U (en) Double-color thermal sensitive paper
JP2001105731A (en) Thermally reversibly recording material and thremally reversibly recording medium using the same
JPH03231888A (en) Reversible thermal color-changeable material and copy preventing paper using the same
JPH03224788A (en) Reversible thermal color changeable material and copy preventing paper using the same
JPH0648026A (en) Reversible thermal recording medium
JPH11291630A (en) Fixing method thermal recording body
JPH1024652A (en) Reversible thermal recording material

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CX01 Expiry of patent term
CX01 Expiry of patent term

Granted publication date: 20110706